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Sample records for zn isotope compositions

  1. Origin of isotopically light Zn in lunar samples through vaporization and the Zn isotope composition of the Moon

    NASA Astrophysics Data System (ADS)

    Kato, C.; Valdes, M. C.; Dhaliwal, J.; Day, J. M.; Moynier, F.

    2013-12-01

    the surface of the Moon. This represents secondary effects and mixing with exogenous Zn, explaining the higher abundance of Zn in highland rocks, relative to mare basalts. The pyroclastic green glass (15426) has a higher measured Zn concentration (~50ppm) compared with mare basalts, but is still depleted in Zn relative to most terrestrial basalts (typically >50 to 100 ppm). 15426 is also isotopically light (δ66Zn= -0.98), which is similar to previous measurements of Zn composition made for high-Ti pyroclastic glass beads (74220). We interpret the composition of the lunar pyroclastic glasses to reflect lava fountaining and coating of the surface of the beads by a volatile rich and isotopically light vapor. Thus, we conclude that mare basalts, which are isotopically heavier than the Earth, best represent the lunar silicate composition.

  2. Isotope variations of dissolved Zn in the Rio Grande watershed, USA: The role of adsorption on Zn isotope composition

    NASA Astrophysics Data System (ADS)

    Szynkiewicz, Anna; Borrok, David M.

    2016-01-01

    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.

  3. Zinc isotope fractionation during mantle melting and constraints on the Zn isotope composition of Earth's upper mantle

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    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.

  4. Zn isotopic heterogeneity in the mantle: A melting control?

    NASA Astrophysics Data System (ADS)

    Doucet, Luc S.; Mattielli, Nadine; Ionov, Dmitri A.; Debouge, Wendy; Golovin, Alexander V.

    2016-10-01

    We present new Zn elemental and isotope data on seventeen fertile and refractory mantle peridotite xenoliths. Eleven fertile peridotites are garnet and spinel lherzolites from Vitim and Tariat (Siberia and Mongolia) and represent some of the most pristine fertile peridotites available. Six refractory peridotites are spinel harzburgites from the Udachnaya kimberlite (Siberian craton) that are nearly pristine residues of high-degree polybaric melting at high pressure (7-4 GPa). Geochemical data suggest that Zn isotopic compositions in the peridotites have not been affected by post-melting processes such as metasomatism, contamination by the host-magmas or alteration. The fertile peridotites have uniform Zn concentrations (59 ± 2 ppm) and Zn isotopic compositions with δ66Zn (relative to JMC-Lyon-03-0749l) = +0.30 ± 0.03‰ consistent with the Bulk Silicate Earth estimates of δ66Zn = +0.28 ± 0.05‰ (Chen et al., 2013). The refractory peridotites have Zn concentrations ranging from 30 to 48 ppm and δ66Zn from + 0.10 ± 0.01 ‰ to + 0.18 ± 0.01 ‰ with an average of + 0.14 ± 0.03 ‰. Our data suggest that the lithospheric mantle has a heterogeneous Zn isotopic composition. Modeling of Zn isotope partitioning during partial melting of fertile mantle suggests that high degrees of melt extraction (>30%) may significantly fractionate Zn isotopes (up to 0.16‰) and that during mantle melting, Zn concentrations and isotopic compositions are mainly controlled by the stability of clinopyroxene and garnet within the melting residue. Because the stability of clinopyroxene and garnet is mainly pressure dependent we suggest that both the depth and the degrees of melt extraction may control Zn isotope fractionation during mantle melting.

  5. Kinetic control on Zn isotope signatures recorded in marine diatoms

    NASA Astrophysics Data System (ADS)

    Köbberich, Michael; Vance, Derek

    2017-08-01

    not only limits diatom growth, but also affects the Zn uptake physiology of diatoms. Uptake of heavy isotopes occurs under Fe-limiting conditions that drive extremely low Zn uptake rates. On the other hand, more rapid Zn uptake rates result in biomass that is indistinguishable from the external bioavailable free Zn pool. These experimental results can, in principle, explain the range of Zn isotopic compositions found in the real surface ocean, given the geographically variable interplay between Fe-limitation, Zn uptake rates, and the degree of organic complexation of oceanic Zn.

  6. The role of soil biogeochemistry in wine taste: Soil factors influencing grape elemental composition, photosynthetic biomarkers and Cu/Zn isotopic signature of Vitis vinifera

    NASA Astrophysics Data System (ADS)

    Blotevogel, Simon; Oliva, Priscia; Darrozes, José; Viers, Jérôme; Audry, Stéphane; Courjault-Radé, Pierre; Orgogozo, Laurent; Le Guedard, Marina; Schreck, Eva

    2015-04-01

    Understanding the influence of soil composition in wine taste is of great economic and environmental interest in France and around the world. Nevertheless the impact of soil composition on wine taste is still controversially discussed. Since inorganic soil components do not have a proper taste and do not enter the plant anyway, their influence needs to be induced by nutrient absorption and its impact on plant functioning and grape composition. Indeed recent development of geological tracers of origin proof the existence of soil chemical and isotopic signatures in wine. However, type and scale of the impact of soil composition on wine taste are not well understood yet, and little experimental evidence exists due to the complexity of mechanisms involved. Thus, to provide evidence for the impact of soil composition on grape composition and potentially wine taste, we studied soil and plant material from two relevant vineyards (Soave, Italia). On those two directly adjacent vineyards, two different wines are produced with the same plant material and cultivation techniques. The vineyards only differ by their underlying bedrock - limestone versus basaltic rock - and thus present suitable conditions for investigating the impact of soil composition on grapes and wine. Pedological and mineralogical parameters were analyzed for the two vineyards whereas chemical extractions (citrate, CaCl2) were performed to determine nutrient bioavailability in both soils. Elemental compositions were determined by ICP-MS analyses in different compartments (soils, vine leaves and grapes). Isotopic fractionation of Cu and Zn was investigated in various samples as source tracers and in order to better understand fractionation mechanisms involved. Finally, plant health was studied using the Omega-3 biomarker which determines the fatty acid composition in vine leaves, directly involved in photosynthetic processes. Results show that the vineyards are characterized by two different soil types due

  7. Study of the dynamics of Zn, Fe, and Cu in the soil-plant system during leaf litter decomposition using isotopic compositions

    NASA Astrophysics Data System (ADS)

    Pichat, S.; Fekiacova, Z.

    2013-12-01

    Litter decomposition is a key process in the cycle of the elements in the soil-plant system. We have investigated the dynamics of three essential micronutrients (Zn, Fe, and Cu) in the vegetal cover, litter, organic horizons, and upper soil horizon (0-2 and 5-10 cm) using both element concentrations and isotopic compositions. The study was conducted on the O3HP (Oak Observatory at the Haute-Provence Observatory) experimental field site in southern France. O3HP is located far from pollution sources. It has been a fallow land for 70 years with the tree cover represented mainly by oak trees (Quercus pubescens). The soil is a thin layer of Calcisol developed under Mediterranean climate. The area has been subdivided in four zones as a function of plant cover. The results for two of these zones, dominated by respectively Poaceae and Genista hispanica, are reported here. We found that the concentrations of the three elements increase from the Ol to the Of horizon. Copper concentration in the Of horizon is close to that of the soil, whereas it is lower for Fe and Zn. For isotopic compositions, the behavior of the three elements is, however, different, which suggests different processes of redistribution for these elements. An enrichment in light Fe isotopes was observed from the Ol to the Of horizon, the latter having an isotopic composition similar to that of the soil. Zinc isotopic compositions are also similar in the Of horizon and the soil but they are isotopically heavier than in the Ol horizon. For Cu, the O horizons are isotopically heavier than the soil, with Of being the heaviest horizon. In addition, for Cu and Zn, the profiles in the O-horizons in the Poaceae-dominated and Genista hispanica-dominated areas are similar but their values are offset, suggesting an influence of the vegetal cover. The increase in concentration for Cu, Zn and Fe with age/depth in the O horizons is in agreement with what is commonly observed in litter-bag experiments, e.g. 1,2. Two

  8. The Cd and Zn Isotope Compositions of PM10 in the Atmosphere of Paris: New Tools for Discrimination and Tracking of the Origin of Metallic Pollution

    NASA Astrophysics Data System (ADS)

    Petelet-Giraud, E.; Widory, D.; Innocent, C.; Quetel, C.; Le Bihan, O.; Fraboulet, I.; Forti, L.; Joos, E.; Goupil, G.; Canard, E.

    2008-12-01

    Due to their relatively high concentration in urban environments (from 10 to more than 50 μg.m-3), atmospheric particles (PM10) have potential damaging effects on the Public Health. Hence, the development of measures dealing with fine particulate matter is considered a priority by the EU Clean Air For Europe (CAFE) Program. Still, the origin of these airborne particles is subject to debate, as classical chemical methods showed their limitations. Recent studies have shown that stable isotopes of elements such as carbon, nitrogen or lead could be of great help in the search of new particle air pollution tracking tools. We will present here preliminary results on the pioneer use of stable isotope compositions of cadmium, zinc and mercury to help decipher the different possible origins of PM10 pollution in the atmosphere of Paris (France). Main potential sources were characterized: (1) waste incineration, (2) road traffic, (3) central heating and (4) coal-fired power plants. Results show that the use of cadmium (d114Cd) and zinc (d66Zn) isotopes, and the combination of both provides a reliable and precise tool for discriminating the different families of particle vectors. The isotope systematic of mercury (d200Hg) is more difficult to apprehend due to the low levels encountered (mercury is mainly present under gaseous form, but is still observed at low concentrations in particles), but does show significant variations between the different sources. Daily cumulative air samples were taken on three different locations, covering different scenarios in Paris city: 1) background pollution in Paris, 2) under the plume of a major pollution source and 3) Paris vicinity. Corresponding chemical and isotope analyses help identify the main vectors for the three elements (Cd, Zn and Hg) considered as well as assess their respective contributions to the levels of pollution observed.

  9. A Zn isotope perspective on the rise of continents.

    PubMed

    Pons, M-L; Fujii, T; Rosing, M; Quitté, G; Télouk, P; Albarède, F

    2013-05-01

    Zinc isotope abundances are fairly constant in igneous rocks and shales and are left unfractionated by hydrothermal processes at pH < 5.5. For that reason, Zn isotopes in sediments can be used to trace the changing chemistry of the hydrosphere. Here, we report Zn isotope compositions in Fe oxides from banded iron formations (BIFs) and iron formations of different ages. Zinc from early Archean samples is isotopically indistinguishable from the igneous average (δ(66) Zn ~0.3‰). At 2.9-2.7 Ga, δ(66) Zn becomes isotopically light (δ(66) Zn < 0‰) and then bounces back to values >1‰ during the ~2.35 Ga Great Oxygenation Event. By 1.8 Ga, BIF δ(66) Zn has settled to the modern value of FeMn nodules and encrustations (~0.9‰). The Zn cycle is largely controlled by two different mechanisms: Zn makes strong complexes with phosphates, and phosphates in turn are strongly adsorbed by Fe hydroxides. We therefore review the evidence that the surface geochemical cycles of Zn and P are closely related. The Zn isotope record echoes Sr isotope evidence, suggesting that erosion starts with the very large continental masses appearing at ~2.7 Ga. The lack of Zn fractionation in pre-2.9 Ga BIFs is argued to reflect the paucity of permanent subaerial continental exposure and consequently the insignificant phosphate input to the oceans and the small output of biochemical sediments. We link the early decline of δ(66) Zn between 3.0 and 2.7 Ga with the low solubility of phosphate in alkaline groundwater. The development of photosynthetic activity at the surface of the newly exposed continents increased the oxygen level in the atmosphere, which in turn triggered acid drainage and stepped up P dissolution and liberation of heavy Zn into the runoff. Zinc isotopes provide a new perspective on the rise of continents, the volume of carbonates on continents, changing weathering conditions, and compositions of the ocean through time. © 2013 Blackwell Publishing Ltd.

  10. Zinc isotope fractionation during magmatic differentiation and the isotopic composition of the bulk Earth

    USGS Publications Warehouse

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

    2013-01-01

    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.).

  11. Zinc Isotopic Compositions of Spinel Peridotites

    NASA Astrophysics Data System (ADS)

    Chen, S.; Huang, F.

    2015-12-01

    Zn isotope geochemistry has shown great potential in exploring planetary differentiation and volatilization history [1,2,3,4]. However, the zinc isotopic composition of the mantle and its fractionation mechanism in high-temperature processes are still unclear. In order to understand Zn isotope composition of the mantle, here we measured Zn isotope data for mantle rocks and minerals, including coexisting olivine, orthopyroxene (Opx), clinopyroxene (Cpx) and spinel from peridotite xenoliths in the Hannuoba (China), Vitim (Siberia), Tariat (central Mongolia), and Dariganga (SE Mongolia). As an accessary mineral, spinels in our study have high Zn contents (500-1400 ppm), accounting for 18%-40% of the total Zn budget in peridotites. Spinels have higher δ66Zn ranging from 0.17 to 0.30‰ than other mantle minerals. For most samples, the δ66Zn of olivines vary from -0.03‰ to 0.19‰, indistinguishable to the value of the coexisting Opx (0.05‰ to 0.20‰). However, we also observed large fractionation between these two minerals, which may reflect disequilibrium fractionation due to kinetic processes. Finally, δ66Zn for peridotites are 0.12-0.21‰, slightly lighter than that of basalts (~0.25±0.05‰), revealing that Zn isotopes can be slightly fractionated during mantle melting. [1] Luck et al., (2005) Geochimica Cosmo Acta, 69, 5351-5363. [2] Paniello et al., (2012) Nature, 490, 376-379. [3] Chen et al., (2013) Meteoritics Planet Sci, 48, 2441-2450. [4] Day and Moynier, (2014) Phil. Transac. of the Royal Society B, 372, 20130259

  12. Atomic Weights and Isotopic Compositions

    National Institute of Standards and Technology Data Gateway

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

  13. Calibrating NIST SRM 683 as A New International Reference Standard for Zn Isotopes

    NASA Astrophysics Data System (ADS)

    Yang, Y.; Zhang, X.; Yu, H.; Huang, F.

    2017-12-01

    Zinc isotopes have been widely applied in the cosmochemical, geochemical, and environmental studies (Moynier et al. 2017). Obtaining precise Zn isotopic data for inter-laboratory comparison is a prerequisite to these applications. Currently, the JMC3-0749L is the primary reference standard for Zn isotopes (Albarède 2004), but it is not commercially available now. Thus, it is necessary to calibrate a new international primary reference standard for Zn isotopic analysis. Chen et al. (2016) showed that NIST SRM 683 (a pure Zn metal nugget of 140 grams) has a δ66ZnJMC of 0.12‰, which is falling within the range of natural Zn isotopic compositions, and it may a good candidate for the next generation of international reference standard (Chen et al. 2016). In order to further examine whether NIST SRM 683 has a homogeneous Zn isotopic composition, we measured more NIST SRM 683 by double-spike methods using MC-ICPMS (Conway et al. 2013). The metal nuggets of NIST SRM 683 were intensively sampled by micro-drilling. Zinc isotope analyses for two nuggets show that they have δ66Zn of 0.14 ± 0.02‰ (2SD, N = 32) and 0.13 ± 0.02‰ (2SD, N = 33), respectively. These values are similar to those of two Zn metal nuggets (0.11 ± 0.02‰ vs. 0.12 ± 0.02‰) reported previously by Chen et al. (2016). We fully dissolved one nugget, producing pure Zn solution with identical Zn isotopic composition with the drilling samples. All results strongly support that NIST SRM 683 is homogeneous in Zn isotopic compositions which could be an ideal candidate for the next reference for Zn isotopes. Tests on more metal nuggets will be performed in a few months for further confirming the Zn isotope compositions and homogeneity. Reference: Albarède et al., 2004. 'The stable isotope geochemistry of copper and zinc', Reviews in Mineralogy and Geochemistry, 55: 409-27. Chen et al., 2016. 'Zinc Isotopic Compositions of NIST SRM 683 and Whole-Rock Reference Materials', Geostandards and

  14. The origin of volatile element depletion in early solar system material: Clues from Zn isotopes in chondrules

    NASA Astrophysics Data System (ADS)

    Pringle, Emily A.; Moynier, Frédéric; Beck, Pierre; Paniello, Randal; Hezel, Dominik C.

    2017-06-01

    Volatile lithophile elements are depleted in the different planetary materials to various degrees, but the origin of these depletions is still debated. Stable isotopes of moderately volatile elements such as Zn can be used to understand the origin of volatile element depletions. Samples with significant volatile element depletions, including the Moon and terrestrial tektites, display heavy Zn isotope compositions (i.e. enrichment of 66Zn vs. 64Zn), consistent with kinetic Zn isotope fractionation during evaporation. However, Luck et al. (2005) found a negative correlation between δ66Zn and 1/[Zn] between CI, CM, CO, and CV chondrites, opposite to what would be expected if evaporation caused the Zn abundance variations among chondrite groups. We have analyzed the Zn isotope composition of multiple samples of the major carbonaceous chondrite classes: CI (1), CM (4), CV (2), CO (4), CB (2), CH (2), CK (4), and CK/CR (1). The bulk chondrites define a negative correlation in a plot of δ66Zn vs 1/[Zn], confirming earlier results that Zn abundance variations among carbonaceous chondrites cannot be explained by evaporation. Exceptions are CB and CH chondrites, which display Zn systematics consistent with a collisional formation mechanism that created enrichment in heavy Zn isotopes relative to the trend defined by CI-CK. We further report Zn isotope analyses of chondrite components, including chondrules from Allende (CV3) and Mokoia (CV3), as well as an aliquot of Allende matrix. All chondrules are enriched in light Zn isotopes (∼500 ppm on 66Zn/64Zn) relative to the bulk, contrary to what would be expected if Zn were depleted during evaporation, on the other hand the matrix has a complementary heavy isotope composition. We report sequential leaching experiments in un-equilibrated ordinary chondrites, which show sulfides are isotopically heavy compared to silicates and the bulk meteorite by ca. +0.65 per mil on 66Zn/64Zn. We suggest isotopically heavy sulfides were

  15. Zn isotopes in hydrothermal sulfides and their oxidation products along the south mid-Atlantic ridge: evidence of hydrothermal fluid deposition

    NASA Astrophysics Data System (ADS)

    Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Lei, Jijiang; Wang, Hao; Li, Zhenggang

    2018-04-01

    Significant Zn isotope fractionation occurs during seafloor hydrothermal activities. Therefore, exploring variations in Zn isotope composition affected by hydrothermal fluids and oxidative processes would help to better understand hydrothermal fluid cycling and sulfide deposition on mid-ocean ridges. In this paper, the Zn isotope compositions of different types of sulfides and their oxidation products obtained from hydrothermal fields on the South Mid-Atlantic Ridge (13-15°S) were analyzed using a Neptune plus MC-ICP-MS. The δ66Zn ratios range from -0.14‰ to +0.38‰, and the average δ66Zn ratio is +0.12±0.06‰ ( n=21, 2 SD) for all the studied sulfides and oxidation products. The Cu-rich sulfides have a slightly heavier Zn isotope composition (average δ66Zn=+0.19±0.07‰, n=6) than the Zn-rich sulfides (average δ66Zn=-0.02±0.06‰, n=5). The Zn isotope compositions of the oxidation products are similar to those of the Cu-rich sulfides, with an average δ66Zn ratio of 0.14±0.06‰ ( n=10, 2 SD). The Zn isotope compositions of all the samples are generally within the ranges of sulfides from hydrothermal fields on other mid-ocean ridges, such as the East Pacific Rise (9°N, 21°N) and the Trans-Atlantic Geotraverse. However, the average Zn isotope composition indicates the presence of significantly lighter Zn isotopes relative to those reported in the literature (average δ66Zn=+0.39‰). The significant enrichment of the Zn-rich sulfides with light Zn isotopes reveals that kinetic fractionation likely occurs during mineral deposition. Furthermore, the Zn isotope compositions of the sulfides and their oxidation products (average δ66Zn=+0.12‰) are significantly lighter than the average Zn isotope composition of the ocean (δ66Zn=+0.5‰), which could further constrain the modern Zn isotope cycle in the ocean by serving as a sink for light Zn isotopes.

  16. Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

    NASA Astrophysics Data System (ADS)

    Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

    2014-06-01

    The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during

  17. Tracing Cd, Zn and Pb pollution sources in bivalves using isotopes

    NASA Astrophysics Data System (ADS)

    Shiel, A. E.; Weis, D. A.; Orians, K. J.

    2010-12-01

    In a multi-tracer study, Cd, Zn and Pb isotopes (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are evaluated as tools to distinguish between natural and anthropogenic sources of these metals in bivalves from western Canada (British Columbia), the eastern USA, Hawaii and France. High Cd concentrations found in BC oysters have elicited economic and health concerns. The source of these high Cd levels is unknown but thought to be largely natural. High Cd levels in BC oysters are largely attributed to the natural upwelling of Cd-rich intermediate waters in the North Pacific as the δ114/110Cd (-0.69 to -0.09‰) and δ66/64Zn (0.28 to 0.36‰) values of BC oysters fall within the range reported for North Pacific seawater. Different contributions from anthropogenic sources account for the variability of Cd isotopic compositions of BC oysters; the lightest of these oysters are from the BC mainland. These oysters also have Pb isotopic compositions that reflect primarily anthropogenic sources (e.g., leaded and unleaded automotive gasoline and smelting of Pb ores, potentially historical). On the contrary, USA East Coast bivalves exhibit relatively light Cd isotopic compositions (δ114/110Cd = -1.20 to -0.54‰; lighter than reported for North Atlantic seawater) due to the high prevalence of industry on this coast. The Pb isotopic compositions of these bivalves indicate contributions from the combustion of coal. The large variability of environmental health among coastal areas in France is reflected in the broad range of Cd isotopic compositions exhibited by French bivalves (δ114/110Cd = -1.08 to -0.20‰). Oysters and mussels from the Marennes-Oléron basin and Gironde estuary have the lightest Cd isotopic compositions of the French oysters consistent with significant historical Cd emissions from the now-closed proximal Zn smelter. In these bivalves, significant declines in the Cd levels between 1984/7 and 2004/5 are not accompanied by a significant shift in the Cd

  18. The Luanchuan Mo-W-Pb-Zn-Ag magmatic-hydrothermal system in the East Qinling metallogenic belt, China: Constrains on metallogenesis from C-H-O-S-Pb isotope compositions and Rb-Sr isochron ages

    NASA Astrophysics Data System (ADS)

    Cao, Hua-Wen; Zhang, Shou-Ting; Santosh, M.; Zheng, Luo; Tang, Li; Li, Dong; Zhang, Xu-Huang; Zhang, Yun-Hui

    2015-11-01

    The Luanchuan Mo-W-Pb-Zn-Ag polymetallic ore district is located in the East Qinling metallogenic belt on the southern margin of the North China Craton. Two ore fields (Nannihu and Yuku) are recognized in the district, and three types of deposits are identified from the two ore fields as follows: (1) the 6 proximal porphyry-skarn type Mo-W deposits occurring at the inner contact zone of the granite porphyries, (2) the 3 middle skarn-hydrothermal type Zn deposits, and (3) the 8 distal hydrothermal type Pb-Zn-Ag deposits at the periphery of the porphyry. We present C-H-O isotope compositions of hydrothermal quartz and calcite, S-Pb isotope compositions of sulfide minerals, and sphalerite Rb-Sr isochron ages from the 17 deposits. The geochemical and geochronological data from the two ore fields all show systematic temporal and spatial variation, and primarily lead to the following inferences. (1) The temperatures and salinities of the ore-forming fluids decreased during mineralization. The ore-forming fluids gradually evolved from magmatic water to mixed magmatic-meteoric water. (2) The metallogenic components were primarily derived from igneous rocks, with increasing proportions of the materials from the ore-bearing rocks. (3) The mineralization ages of these deposits are close (147-136 Ma), which correspond to the emplacement of the granite intrusions. (4) The three types of deposits and the ore-related late Mesozoic intrusives constitute a unified magmatic-hydrothermal-mineralization system. Finally, we also suggest exploration strategies for the Luanchuan ore district.

  19. Constraints of C-O-S isotope compositions and the origin of the Ünlüpınar volcanic-hosted epithermal Pb-Zn ± Au deposit, Gümüşhane, NE Turkey

    NASA Astrophysics Data System (ADS)

    Akaryali, Enver; Akbulut, Kübra

    2016-03-01

    The Eastern Pontide Orogenic Belt (EPOB) constitutes one of the best examples of the metallogenic provinces in on the Alpine-Himalayan belt. This study focuses on the genesis of the Ünlüpınar Pb-Zn ± Au deposit in the southern part of the Eastern Pontide Orogenic Belt. The main lithological units in the study area are the Early Carboniferous Kurtoğlu Metamorphic Complex the Late Carboniferous Köse Granitoid and the Early-Middle Jurassic Şenköy Formation. The studied deposit is hosted by the Şenköy Formation, which consists predominantly of basaltic-andesitic rocks and associated pyroclastic rocks that are calc-alkaline in composition. Silicic, sulfidic, argillic, chloritic, hematitic, carbonate and limonite are the most obvious alteration types observed in the deposit site. Ore microscopy studies exhibit that the mineral paragenesis in deposits includes pyrite, chalcopyrite, sphalerite, galena, gold, quartz and calcite. Electron microprobe analyses conducted on sphalerite indicate that the Zn/Cd ratio varies between 84 and 204, and these ratios point at a hydrothermal deposit related to granitic magmas. Fluid inclusion studies in calcite and quartz show that the homogenization temperature of the studied deposit ranges between 90-160 °C and 120-330 °C respectively. The values of sulfur isotope analysis of pyrite, sphalerite and galena minerals vary between 1.6‰ and 5.7‰, and the results of oxygen and carbon isotope analysis range between 8.4‰ and 18‰ and -5‰ and -3.6‰, respectively. The average formation temperature of the ore was calculated as 264 °C with a sulfur isotope geothermometer. All of the data indicate that the Ünlüpınar deposit is an epithermal vein-type mineralization that was formed depending on the granitic magmatism.

  20. Use of Zn isotopes as a probe of anthropogenic contamination and biogeochemical processes in the Seine River, France

    NASA Astrophysics Data System (ADS)

    Chen, J.; Gaillardet, J.; Louvat, P.; Birck, J.

    2009-05-01

    Metal contamination is a major issue of human impact on the aqueous environment. River water is particularly susceptible to contamination for both dissolved and particulate loads, displaying a major challenge in understanding the dominant sources and pathways of metals in polluted drainage basins. Recent improvements in mass spectrometry allow isotopic measurements of "non-traditional" metals (Zn, Cu, Fe, etc.), making their isotopes a new potential device to investigate contamination of metals under dissolved and particulate forms in rivers. We focus here on Zn isotope geochemistry in the largely anthropized Seine River (France). A new protocol of two-column separation of Zn from dilute aqueous solution has been developed and proven to be reproducible and satisfactory for accurate measurement of Zn isotopic ratios in water samples by MC-ICP-MS (2σ = 0.04‰). Preliminary results show a total variation of 0.65‰ for δ66Zn in dissolved phases of the Seine basin, and a light isotope enrichment in anthropogenic sources compared to other water samples. The determined conservative behavior of Zn in river water makes its isotopes an effective probe of anthropogenic contamination. The natural and anthropogenic inputs were clearly identified and calculated based on Zn isotope compositions for dissolved loads. Suspended particular matters (SPM) display different Zn isotope compositions compared to dissolved loads, with a total δ66Zn variation of 0.22‰. Zn concentrations and its isotope compositions in SPM reveal inverse relationships as function of the distance from the headwater and the SPM content for geographical and temporal samples, respectively. The δ66Zn data in SPM are interpreted as reflecting the mixture of natural and anthropogenic particles. The correlation between dissolved and particulate δ66Zn shows that adsorption processes are not the dominant process making Zn enrichment in SPM. We report here for the first time systematic δ66Zn data in waters of

  1. Evidences for Cu and Zn Isotope Fractionation in Sediments and Particulate Suspended Matter of the Scheldt Estuary

    NASA Astrophysics Data System (ADS)

    Petit, J.; Mattielli, N.; de Jong, J.; Chou, L.

    2004-05-01

    observed. Results show that variations in Cu and Zn isotopic composition are smaller in SPM (δ 66Zn varying from 0.35 to 0.17 and δ 65Cu from -0.13 to 0.18) than in sediments. Cu and Zn isotopic signatures of sediments show a clear trend of lighter isotopes removal from the MTZ seaward with δ 66Zn varying from 0.21 at 2 psu to 1.11 per mil at 33 psu (and δ 65Cu = -0.37 to 0.24). In contrast, Zn isotopic compositions in SPM are more homogeneous with average δ 66Zn of 0.24 ± 0.18 over all the transect. Cu isotopic composition in SPM are very constant downstream of the MTZ with average δ 65Cu =-0.06 ± 0.08 but become more scattered within MTZ (varying from -0.04 to 0.18). These preliminary results pinpoint important variations in Cu and Zn isotopic compositions within estuarine systems and contrasted isotopic signatures in Cu and Zn between SPM and sediments. Results suggest the important role of early diagenesis in the isotope geochemistry of heavy metals in estuarine environment. This study provides a stepping stone for further investigation of interacting processes involved in controlling the cycling of metals in the Scheldt estuary. (1) Zhu et al., Earth Planet. Sci. Lett. 200 (2002), 47-62 (2) Pichat et al., Earth Planet. Sci. Lett. 6598 (2003), 1-12 (3) Maréchal et al., Geochem. Geophys. Geosyt., 1 (2000), GC000029

  2. Transpiration flow controls Zn transport in Brassica napus and Lolium multiflorum under toxic levels as evidenced from isotopic fractionation

    NASA Astrophysics Data System (ADS)

    Couder, Eléonore; Mattielli, Nadine; Drouet, Thomas; Smolders, Erik; Delvaux, Bruno; Iserentant, Anne; Meeus, Coralie; Maerschalk, Claude; Opfergelt, Sophie; Houben, David

    2015-11-01

    Stable zinc (Zn) isotope fractionation between soil and plant has been used to suggest the mechanisms affecting Zn uptake under toxic conditions. Here, changes in Zn isotope composition in soil, soil solution, root and shoot were studied for ryegrass (Lolium multiflorum L.) and rape (Brassica napus L.) grown on three distinct metal-contaminated soils collected near Zn smelters (total Zn 0.7-7.5%, pH 4.8-7.3). The Zn concentrations in plants reflected a toxic Zn supply. The Zn isotopic fingerprint of total soil Zn varied from -0.05‰ to +0.26 ± 0.02‰ (δ66Zn values relative to the JMC 3-0749L standard) among soils, but the soil solution Zn was depleted in 66Zn, with a constant Zn isotope fractionation of about -0.1‰ δ66Zn unit compared to the bulk soil. Roots were enriched with 66Zn relative to soil solution (δ66Znroot - δ66Znsoil solution = Δ66Znroot-soil solution = +0.05 to +0.2 ‰) and shoots were strongly depleted in 66Zn relative to roots (Δ66Znshoot-root = -0.40 to -0.04 ‰). The overall δ66Zn values in shoots reflected that of the bulk soil, but were lowered by 0.1-0.3 ‰ units as compared to the latter. The isotope fractionation between root and shoot exhibited a markedly strong negative correlation (R2 = 0.83) with transpiration per unit of plant weight. Thus, the enrichment with light Zn isotopes in shoot progressed with increasing water flux per unit plant biomass dry weight, showing a passive mode of Zn transport by transpiration. Besides, the light isotope enrichment in shoots compared to roots was larger for rape than for rye grass, which may be related to the higher Zn retention in rape roots. This in turn may be related to the higher cation exchange capacity of rape roots. Our finding can be of use to trace the biogeochemical cycles of Zn and evidence the tolerance strategies developed by plants in Zn-excess conditions.

  3. Textural, compositional, and sulfur isotope variations of sulfide minerals in the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Implications for Ore Formation

    USGS Publications Warehouse

    Kelley, K.D.; Leach, D.L.; Johnson, C.A.; Clark, J.L.; Fayek, M.; Slack, J.F.; Anderson, V.M.; Ayuso, R.A.; Ridley, W.I.

    2004-01-01

    The Red Dog Zn-Pb deposits are hosted in organic-rich mudstone and shale of the Mississippian Kuna Formation. A complex mineralization history is defined by four sphalerite types or stages: (1) early brown sphalerite, (2) yellow-brown sphalerite, (3) red-brown sphalerite, and (4) late tan sphalerite. Stages 2 and 3 constitute the main ore-forming event and are volumetrically the most important. Sulfides in stages 1 and 2 were deposited with barite, whereas stage 3 largely replaces barite. Distinct chemical differences exist among the different stages of sphalerite. From early brown sphalerite to later yellow-brown sphalerite and red-brown sphalerite, Fe and Co content generally increase and Mn and Tl content generally decrease. Early brown sphalerite contains no more than 1.9 wt percent Fe and 63 ppm Co, with high Mn (up to 37 ppm) and Tl (126 ppm), whereas yellow-brown sphalerite and red-brown sphalerite contain high Fe (up to 7.3 wt %) and Co (up to 382 ppm), and low Mn (<27 ppm) and Tl (<37 ppm). Late tan sphalerite has distinctly lower Fe (< 0.9 wt %) and higher Tl (up to 355 ppm), Mn (up to 177 ppm), and Ge (426 ppm), relative to earlier sphalerite. Wide ranges in concentrations of Ag, Cu, Pb, and Sb characterize all sphalerite types, particularly yellow-brown sphalerite and red-brown sphalerite, and most likely reflect submicroscopic inclusions of galena, chalcopyrite and/or tetrahedrite in the sphalerite. In situ ion microprobe sulfur isotope analyses show a progression from extremely low ??34S values for stage 1 (as low as -37.20???) to much higher values for yellow-brown sphalerite (mean of 3.3???; n = 30) and red-brown sphalerite (mean of 3.4; n = 20). Late tan sphalerite is isotopically light (-16.4 to -27.2???). The textural, chem ical, and isotopic data indicate the following paragenesis: (1) deposition of early brown sphalerite with abundant barite, minor pyrite, and trace galena immediately beneath the sea floor in unconsolidated mud; (2) deposition

  4. Two mineralization events in the Baiyinnuoer Zn-Pb deposit in Inner Mongolia, China: Evidence from field observations, S-Pb isotopic compositions and U-Pb zircon ages

    NASA Astrophysics Data System (ADS)

    Jiang, Si-Hong; Chen, Chun-Liang; Bagas, Leon; Liu, Yuan; Han, Ning; Kang, Huan; Wang, Ze-Hai

    2017-08-01

    The Xing-Mong Orogenic Belt (XMOB) is located in the eastern part of the Central Asian Orogenic Belt (CAOB) and has experienced multiple tectonic events. The Baiyinnuoer Pb-Zn deposit may be a rare case that documents two periods of mineralization in the tectonically complex XMOB. There are two types of Pb-Zn mineralization in the deposit: (1) skarn-type ore, hosted by the skarn in the contact zone between marble and granodiorite and within the marble and (2) vein-type ore, hosted by crystal tuff and feldspar porphyry. This study revealed that the host rocks, mineral assemblages, mineralization occurrences, S-Pb isotopes, and ages between the two types of ore are notably different. Zircon U-Pb dating indicates that the granodiorite was emplaced in the Early Triassic (244 ± 1 to 242 ± 1 Ma), the crystal tuff was deposited in the Early Cretaceous (140 ± 1 to 136 ± 1 Ma), and the feldspar porphyry was intruded in the Early Cretaceous (138 ± 2 to 136 ± 2 Ma). The first skarn mineralization occurred at ∼240 Ma and the second vein-type Pb-Zn mineralization took place between 136 and 129 Ma. Thus the Triassic orebodies were overprinted by Early Cretaceous mineralization. The sphalerite and galena from the skarn mineralization have higher δ34S values (-4.7 to +0.3‰) than the sphalerite, galena and aresenopyrite from the vein-type mineralization (-7.5 to -4.2‰), indicating different sulfur sources or ore-forming processes for the two types of mineralization. The Pb isotopic compositions of the two types of ore are very similar, suggesting similar lead sources. Geochemistry and Nd-Pb-Hf isotopic systematics of the igneous rocks in the region show that the Triassic granodiorite was generated from hybridization of mafic and felsic magmas due to strong crust-mantle interaction under the collisional setting that resulted following the closure of the Paleo-Asian Ocean and the collision of North China and Siberian cratons at the end of the Permian; while the

  5. Interaction between zinc and freshwater and marine diatom species: Surface complexation and Zn isotope fractionation

    NASA Astrophysics Data System (ADS)

    Gélabert, A.; Pokrovsky, O. S.; Viers, J.; Schott, J.; Boudou, A.; Feurtet-Mazel, A.

    2006-02-01

    quantitative reproduction of all adsorption experiments. Although Zn adsorption constants on carboxylate groups are almost the same, Zn surface adsorption capacities are very different among diatom species which is related to the systematic differences in their cell wall composition and thickness. Measurements of Zn isotopic composition ( 66Zn/( 64Zn)) performed using a multicollector ICP MS demonstrated that irreversible incorporation of Zn in cultured diatom cells produces enrichment in heavy isotope compared to growth media (Δ 66Zn(solid-solution) = 0.27 ± 0.05, 0.08 ± 0.05, 0.21 ± 0.05, and 0.19 ± 0.05‰ for TW, SC, NMIN, and AMIN species, respectively). Accordingly, an enrichment of cells in heavy isotopes (Δ 66Zn(solid-solution) = 0.43 ± 0.1 and 0.27 ± 0.1‰ for NMIN and AMIN, respectively) is observed following short-term Zn sorption on freshwater cells in nutrient media at pH ˜ 7.8. Finally, diatoms frustules are enriched in heavy isotopes compared to solution during Zn adsorption on silica shells at pH ˜ 5.5 (Δ 66Zn(solid-solution) = 0.35 ± 0.10‰). Measured isotopes fractionation can be related to the structure and stability of Zn complexes formed and they provide a firm basis for using Zn isotopes for biogeochemical tracing.

  6. Elemental and isotopic behaviour of Zn in Deccan basalt weathering profiles: Chemical weathering from bedrock to laterite and links to Zn deficiency in tropical soils.

    PubMed

    Suhr, Nils; Schoenberg, Ronny; Chew, David; Rosca, Carolina; Widdowson, Mike; Kamber, Balz S

    2018-04-01

    Zinc (Zn) is a micronutrient for organisms and essential for plant growth, therefore knowledge of its elemental cycling in the surface environment is important regarding wider aspects of human nutrition and health. To explore the nature of Zn cycling, we compared its weathering behaviour in a sub-recent regolith versus an ancient laterite profile of the Deccan Traps, India - an area of known soil Zn deficiency. We demonstrate that progressive breakdown of primary minerals and the associated formation of phyllosilicates and iron oxides leads to a depletion in Zn, ultimately resulting in a loss of 80% in lateritic residues. This residue is mainly composed of resistant iron oxides and hydroxides ultimately delivering insufficient amounts of bio-available Zn. Moreover, (sub)-tropical weathering in regions experiencing extended tectonic quiescence (e.g., cratons) further enhance the development of old and deep soil profiles that become deficient in Zn. This situation is clearly revealed by the spatial correlation of the global distribution of laterites, cratons (Africa, India, South America and Australia) and known regions of Zn deficient soils that result in health problems for humans whose diet is derived from such land. We also investigate whether this elemental depletion of Zn is accompanied by isotope fractionation. In the saprolitic horizons of both weathering profiles, compositions of δ 66 Zn JMC-Lyon lie within the "crustal average" of +0.27±0.07‰ δ 66 Zn JMC-Lyon . By contrast, soil horizons enriched in secondary oxides show lighter isotope compositions. The isotopic signature of Zn (Δ 66 Zn sample-protolith up to ~ -0.65‰) during the formation of the ferruginous-lateritic weathering profile likely resulted from a combination of biotically- and kinetically-controlled sorption reactions on Fe-oxyhydroxides. Our findings suggest that oxide rich soil types/horizons in (sub)-tropical regions likely exert a control on riverine Zn isotope compositions such

  7. Investigating the effects of abyssal peridotite alteration on Si, Mg and Zn isotopes

    NASA Astrophysics Data System (ADS)

    Savage, P. S.; Wimpenny, J.; Harvey, J.; Yin, Q.; Moynier, F.

    2013-12-01

    Around 1/3 of Earth's divergent ridge system is now classified as "slow" spreading [1], exposing ultramafic rocks (abyssal peridotites) at the seafloor. Such material is often highly altered by serpentinisation and steatisation (talc formation). It is crucial to understand such processes in order to access the original composition of the mantle, and to quantify any impact on ocean composition. Here we examine the effect of both serpentinisation and steatisation on Si, Mg and Zn isotopes. Hydrothermal alteration and seafloor weathering are both sources of oceanic Si [2] and weathering of abyssal peridotites is a source of oceanic Mg [3]; hence isotopic fractionation as a result of seafloor alteration could affect oceanic Si and Mg isotope composition. Zinc isotopes can provide complimentary information; the magnitude and direction of fractionation is highly dependent on complexing ligand [4] and can provide compositional information on the fluids driving metasomatism. For this study, two cores from the well-characterised abyssal peridotites recovered on ODP Leg 209 were examined [5]. Hole 1274a peridotites exhibit variable serpentinisation at ~200°C, whereas samples from Hole 1268a have been comprehensively serpentinised and then subsequently steatised to talc facies at ~350°C, by a low Mg/Si, low pH fluid. The Si, Mg and Zn isotope compositions of 1274a samples are extremely homogeneous, identical to that of pristine mantle rocks (BSE) i.e., serpentinisation at this locality was predominantly isochemical [5]. In contrast, samples from 1268a show greater isotopic variability. In all samples, Mg is enriched in the heavier isotopes relative to BSE, consistent with formation of isotopically heavy secondary phases [6]. For Si, serpentinised samples are slightly enriched in the lighter isotopes compared to BSE, again consistent with the behaviour of Si during formation of secondary phases [7]. Within the steatised samples, some exhibit enrichments in the lighter Si

  8. Grosnaja ABCs: Magnesium isotope compositions

    NASA Technical Reports Server (NTRS)

    Goswami, J. N.; Srinivasan, G.; Ulyanov, A. A.

    1993-01-01

    Three CAI's from the Grosnaja CV3 chondrite were analyzed for their magnesium isotopic compositions by the ion microprobe. The selected CAI's represent three distinct types: GR4(compact Type A), GR7(Type B) and GR2(Type C). Petrographic studies indicate that all three Grosnaja inclusions were subjected to secondary alterations. The Type A CAI GR4 is primarily composed of melilite with spinel and pyroxene occurring as minor phases. The rim of the inclusion does not exhibit distinct layered structure and secondary alteration products (garnet, Fe-rich olivine and Na-rich plagioclase) are present in some localized areas near the rim region. The average major element compositions of different mineral phases in GR4 are given. Preliminary REE data suggest a depletion of HREE relative to LREE by about a factor of 3 without any clear indication of interelement fractionation. The CAI GR7 has textural and minerological characteristics similar to Type B inclusions. The REE data show a pattern that is similar to Group 6 with enrichment in Eu and Yb. In addition, a depletion of HREE compared to LREE is also evident in this object. Melilite composition shows a broad range of akermanite content (Ak(sub 15-55)). Detailed petrographic study is in progress. GR2 is a anorthite-rich Type C inclusion with large plagioclase laths intergrown with Ti-rich pyroxene. The average plagioclase composition is close to pure anorthite (An99).

  9. Determining provenance of marine metal pollution in French bivalves using Cd, Zn and Pb isotopes

    NASA Astrophysics Data System (ADS)

    Shiel, Alyssa E.; Weis, Dominique; Cossa, Daniel; Orians, Kristin J.

    2013-11-01

    Cadmium, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) have been used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from the coastlines of France (English Channel, Atlantic and Mediterranean coasts). The Cd isotopic signatures (δ114Cd = -1.08‰ to -0.52‰) exhibited by bivalves from the coastlines of France, excluding those from NE France, are within the range of those exhibited by bivalves from the USA East coast (δ114Cd = -1.20‰ to -0.54‰). This indicates the high prevalence of industry, as well as the low natural contributions of Cd from North Atlantic waters in both regions. Thus, the significance of anthropogenic Cd sources is similar. These significant anthropogenic contributions are identified for bivalves with a large range in tissue Cd concentrations. Importantly, French bivalves from the Gironde estuary and Marennes-Oléron basin (regions of historic and modern importance for oyster farming, respectively) exhibited the highest Cd levels of the study. Their Cd isotopic signatures indicate historical smelting emissions remain the primary Cd source despite the cessation of local smelting activities in 1986 and subsequent remedial efforts. No significant variability is observed in the δ66Zn values of the French bivalves (∼0.53‰), with the exception of the much heavier compositions exhibited by oysters from the polluted Gironde estuary (1.19-1.27‰). Lead isotopes do not fractionate during processing like Cd and Zn. They can, therefore, be used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as metal sources to French bivalves. Cadmium and Zn isotopes are successfully used here as tracers of anthropogenic processing emissions and are combined with Pb isotope "fingerprinting" techniques to identify metal sources.

  10. Zn and C isotopic evidence of climatic change during the Marinoan

    NASA Astrophysics Data System (ADS)

    Thiemens, M. M.; Moynier, F.; Koeberl, C.; Thiemens, M. H.; Shaheen, R.; Gyollai, I.; Popp, F.; Chong, K.

    2011-12-01

    The "Snowball Earth" events of the Cryogenian period are renowned for their remarkable chemical and isotopic signatures left in the geological record. Through analysis of post Marinoan glaciation cap carbonates from Namibia, specifically from Fransfontein, the Khowarib Valley, and Naraachamspos, a multi isotopic study was undertaken. We analyzed the δ 13C of chemically isolated calcite and dolomite. A moderate depletion of 13C in calcite (δ 13C<0% V-PDB) associated with global glaciations was observed, confirming the event. Associated dolomites also show a 13C depletion, but at a much lower magnitude. Zinc is a trace element that is necessary for all forms of life. Zn does not undergo redox cycling under normal environmental conditions, and biological uptake is one of the few processes that produces isotopic fractionation. This fractionation is in the range of 0.1 permil for the 66Zn/64Zn ratio (δ 66Zn in permil deviation), however with the advent of multi-collection inductively-coupled plasma mass spectrometry (MC-ICP-MS) such variations have become resolvable. We also have measured the Zinc composition of multiple species of lab cultured archaea, and found that the cells are enriched in the light isotopes of Zn compared to the culture medium. By measuring Zn levels in the Cap Carbonates, we seek corroboration for the carbon depletion we find during the glaciation. Zinc should undergo a similarly significant alteration at the mass extinction from climatic shifts inherent to a worldwide glaciation. We find the samples to be relatively consistent, with a δ 66Zn of approximately 0.30 to 0.40 in most places, with a δ 68Zn of double that, values typical of terrestrial rocks. Several sites have a much larger fractionation, with δ 66Zn of up to 0.90 in the Khowarib Valley, and up to 1.06 in the clays at the entrance to the South Valley. These isotopic compositions may be indicative of the massive climatic event leading to the formation of the cap carbonates.

  11. Isotopic composition of zinc, copper, and iron in lunar samples

    NASA Astrophysics Data System (ADS)

    Moynier, F.; Albarède, F.; Herzog, G. F.

    2006-12-01

    We determined by ICP-MS the concentrations and isotopic ratios of Fe, Cu, and Zn in the Ti-rich lunar basalt 74275, in the lunar orange glass 74220, and in up to 10 lunar soils, namely, 14163, 15231, 64501, 66041, 68841, 69941, 70011, 72501, 75081, and 76501. Two analyses of zinc in lunar basalt 74275 give δ 66Zn = 0.17‰ and 0.75‰, values within the range of those measured in terrestrial basalts; copper in lunar basalt 74275 has δ 65Cu ˜ +1.4‰, which is isotopically heavier than values observed in terrestrial basalts. In the orange glass, we measured δ 56Fe = -0.24‰, δ 65Cu = -0.42‰, and δ 66Zn ˜ -3.6‰. These values of δ are more negative than those obtained for 74275 and for typical lunar basalts, but for Cu, comparable to those observed in terrestrial sulfides and meteorites. In lunar soils we found 0.11‰ ⩽ δ 56Fe ⩽ 0.51‰, 2.6‰ ⩽ δ 65Cu ⩽ 4.5‰, and 2.2‰ ⩽ δ 66Zn ⩽ 6.4‰. Insofar as we can generalize from a small sample set, S, Fe, Cu, Zn, and Cd show similar trends in isotopic fractionation on the Moon. Lunar basalts have nearly terrestrial isotopic ratios. Relative to the lunar basalt 74275, the pyroclastic glass 74220 is enriched in the lighter isotopes of Fe, Cu, and Zn, and the soils are enriched in the heavier isotopes of Fe, Cu, and Zn. The patterns in the basalts are likely inherited from the source material; the light-isotope enrichments seen in the orange glass originated during lava fountaining or, less probably, during partial condensation of vapor; and the heavy-isotope enrichments in the lunar soils were likely created by a combination of processes that included micrometeorite vaporization and sputtering. In the orange glass, the light-isotope enrichments (relative to lunar basalts) of Zn are larger than those of Cu. If these enrichments reflect accurately the isotopic composition of the gas, they suggest that Cu is more volatile than Zn in the liquid from which the gas derived. A simple model built on

  12. Isotopic compositions of the elements, 2001

    USGS Publications Warehouse

    Böhlke, J.K.; De Laeter, J. R.; De Bievre, P.; Hidaka, H.; Peiser, H.S.; Rosman, K.J.R.; Taylor, P.D.P.

    2005-01-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the “best measurement” of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E)">Ar(E)Ar(E) and its uncertainty U[Ar(E)]">U[Ar(E)]U[Ar(E)] recommended by CAWIA in 2001.

  13. Isotopic Compositions of the Elements, 2001

    NASA Astrophysics Data System (ADS)

    Böhlke, J. K.; de Laeter, J. R.; De Bièvre, P.; Hidaka, H.; Peiser, H. S.; Rosman, K. J. R.; Taylor, P. D. P.

    2005-03-01

    The Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry completed its last review of the isotopic compositions of the elements as determined by isotope-ratio mass spectrometry in 2001. That review involved a critical evaluation of the published literature, element by element, and forms the basis of the table of the isotopic compositions of the elements (TICE) presented here. For each element, TICE includes evaluated data from the "best measurement" of the isotope abundances in a single sample, along with a set of representative isotope abundances and uncertainties that accommodate known variations in normal terrestrial materials. The representative isotope abundances and uncertainties generally are consistent with the standard atomic weight of the element Ar(E) and its uncertainty U[Ar(E)] recommended by CAWIA in 2001.

  14. Li-Zn-Pb multi isotopic characterization of the Loire River Basin, France

    NASA Astrophysics Data System (ADS)

    Millot, R.; Desaulty, A.; Widory, D.; Bourrain, X.

    2013-12-01

    The Loire River in France is approximately 1010 km long and drains an area of 117 800 km2. Upstream, the Loire River flows following a south to north direction from the Massif Central down to the city of Orléans, 650 km from its source. The Loire River is one of the main European riverine inputs to the Atlantic Ocean. Over time, its basin has been exposed to numerous sources of anthropogenic metal pollutions, such as metal mining, industry, agriculture and domestic inputs. The Loire River basin is thus an excellent study site to develop new isotope systematics for tracking anthropogenic sources of metal pollutions (Zn and Pb) and also to investigate Li isotope tracing that can provide key information on the nature of weathering processes at the Loire River Basin scale. Preliminary data show that Li-Zn-Pb concentrations and isotopic compositions span a wide range in river waters of the Loire River main stream and the main tributaries. There is a clear contrast between the headwaters upstream and rivers located downstream in the lowlands. In addition, one of the major tributaries within the Massif Central (the Allier River) is clearly influenced by inputs resulting from mineralizations and thermomineral waters. The results showed that, on their own, each of these isotope systematics reveals important information about the geogenic or anthropogenic origin Li-Zn-Pb. Considered together, they are however providing a more integrated understanding of the overall budgets of these elements at the scale of the Loire River Basin.

  15. Dynamics of Zn in an urban wetland soil-plant system: Coupling isotopic and EXAFS approaches

    NASA Astrophysics Data System (ADS)

    Aucour, Anne-Marie; Bedell, Jean-Philippe; Queyron, Marine; Magnin, Valérie; Testemale, Denis; Sarret, Géraldine

    2015-07-01

    Plants play a key role in the stabilization of metals in contaminated environments. Studies have been performed on Zn uptake and storage mechanisms, mainly for Zn hyperaccumulating plants, though less is known about Zn stabilization in the rhizosphere of non-accumulating plants. This study was focused on the dynamics of Zn in a whole soil-litter-plant system and the processes controlling Zn mobilization and stabilization. The site studied was an infiltration basin receiving urban stormwater, in which Phalaris arundinacea (reed canary grass) developed spontaneously. A combination of chemical extractions (CaCl2, DTPA), EXAFS spectroscopy and Zn stable isotope measurements was applied for the water inlet, soil, plant organs and decaying biomass. Zn speciation changed from the water inlet to the soil. In the soil, Zn was present as Zn-layered double hydroxide (Zn-LDH), tetrahedral and octahedral sorbed Zn species. The formation of Zn-LDH participates in Zn stabilization. Tetrahedral Zn species, which were partly DTPA exchangeable, were enriched in heavy isotopes, whereas octahedral Zn (Zn-LDH and sorbed species) were enriched in light isotopes. Based on a linear model between δ66Zn and Zn speciation, δ66Zn for pure tetrahedral and octahedral end-members were estimated at ca. 0.33‰ and 0.04‰, respectively. In the plant, a mixture of octahedral Zn (attributed to aqueous Zn-organic acid complexes present in the symplasm), and tetrahedral Zn (attributed to apoplasmic Zn-cell wall complexes) was observed in all organs. Large enrichment in light isotopes from the soil to the plant Δ66Zn (of ca. -0.6‰) was observed. The stem was enriched in light isotopes versus roots and, to a lesser extent, versus leaves. The results suggest that Zn was taken up via a low-affinity transport system and that Zn was sequestrated in the stem symplasm after transit through leaves. Finally, intense Zn exchanges were observed between the decaying biomass and the soil, with the sorption of

  16. Heterogeneous distribution of Zn stable isotopes in mice and applications to medical sciences

    NASA Astrophysics Data System (ADS)

    Moynier, F.; Fujii, T.; Shaw, A.; Le Borgne, M.

    2013-12-01

    Zinc is required for the function of more than 300 enzymes involved in many metabolic pathways, and is a vital micronutrient for living organisms. To investigate if Zn isotopes could be used to better understand metal homeostasis, as well as a biomarker for diseases, we assessed the distribution of natural Zn isotopes in various mouse tissues. We found that, with respect to Zn isotopes, most mouse organs are isotopically distinct and that the total range of variation within one mouse encompasses the variations observed in the Earth's crust. Therefore, biological activity must have a major impact on the distribution of Zn isotopes in inorganic materials. The most striking aspect of the data is that red blood cells and bones are enriched by ~0.5 per mil in 66Zn relative to 64Zn when compared to serum, and up to ~1 per mil when compared to the brain and liver. This fractionation is well explained by the equilibrium distribution of isotopes between different bonding environments of Zn in different organs. Differences in gender and genetic background did not appear to affect the isotopic distribution of Zn. Together, these results suggest that potential use of Zn isotopes as a tracer for dietary Zn, and for detecting disturbances in Zn metabolism due to pathological conditions.

  17. Magnesium isotopic composition of the mantle

    NASA Astrophysics Data System (ADS)

    Teng, F.; Li, W.; Ke, S.; Marty, B.; Huang, S.; Dauphas, N.; Wu, F.; Helz, R. L.

    2009-12-01

    Studies of Mg isotopic composition of the Earth not only are important for understanding its geochemistry but also can shed light on the accretion history of the Earth as well as the evolution of the Earth-Moon system. However, to date, the Mg isotopic composition of the Earth is still poorly constrained and highly debated. There is uncertainty in the magnitude of Mg isotope fractionation at mantle temperatures and whether the Earth has a chondritic Mg isotopic composition or not. To constrain further the Mg isotopic composition of the mantle and investigate the behavior of Mg isotopes during igneous differentiation, we report >200 high-precision (δ26Mg < 0.1‰, 2SD) analyses of Mg isotopes on 1) global mid-ocean ridge basalts covering major ridge segments of the world and spanning a broad range in latitudes, chemical and radiogenic isotopic compositions; 2) ocean island basalts from Hawaiian (Koolau, Kilauea and Loihi) and French Polynesian volcanoes (Society island and Cook Austral chain); 3) olivine grains from Hawaiian volcanoes (Kilauea, Koolau and Loihi) and 4) peridotite xenoliths from Australia, China, France, Tanzania and USA. Global oceanic basalts and peridotite xenoliths have a limited (<0.2 ‰) variation in Mg isotopic composition, with an average δ26Mg = -0.25 relative to DSM3. Olivines from Hawaiian lavas have δ26Mg ranging from -0.43 to +0.03, with most having compositions identical to basalts and peridotites. Therefore, the mantle’s δ26Mg value is estimated to be ~ -0.25 ± 0.1 (2SD), different from that reported by Wiechert and Halliday (2007; δ26Mg = ~ 0) but similar to more recent studies (δ26Mg = -0.27 to -0.33) (Teng et al. 2007; Handler et al. 2009; Yang et al., 2009). Moreover, we suggest the Earth, as represented by the mantle, has a Mg isotopic composition similar to chondrites (δ26Mg = ~-0.33). The need for a model such as that of Wiechert and Halliday (2007) that involves sorting of chondrules and calcium

  18. Zn isotope study of atmospheric emissions and dry depositions within a 5 km radius of a Pb-Zn refinery

    NASA Astrophysics Data System (ADS)

    Mattielli, Nadine; Petit, Jérôme C. J.; Deboudt, Karine; Flament, Pascal; Perdrix, Esperanza; Taillez, Aurélien; Rimetz-Planchon, Juliette; Weis, Dominique

    The present paper examines the use of zinc isotopes as tracers of atmospheric sources and focuses on the potential fractionation of Zn isotopes through anthropogenic processes. In order to do so, Zn isotopic ratios are measured in enriched ores and airborne particles associated with pyrometallurgical activities of one of the major Pb-Zn refineries in France. Supporting the isotopic investigation, this paper also compares morphological and chemical characteristics of Zn particles collected on dry deposition plates ("environmental samples") placed within a 5 km radius of the smelter, with those of Zn particles collected inside the plant ("process samples"), i.e. dust collected from the main exhaust system of the plant. To ensure a constant isotopic "supply", the refinery processed a specific set of ores during the sampling campaigns, as agreed with the executive staff of the plant. Enriched ores and dust produced by the successive Zn extraction steps show strong isotope fractionation (from -0.66 to +0.22‰) mainly related to evaporation processes within the blast furnaces. Dust from the main chimney displays a δ 66Zn value of -0.67‰. Application of the Rayleigh equation to evaluate the fractionation factor associated with the Zn vapor produced after a free evaporation gives a range of αore/vapor from 1.0004 to 1.0008. The dry deposits, collected on plates downwind of the refinery, display δ 66Zn variations of up to +0.7‰. However, it is to be noted that between 190 and 1250 m from the main chimney of the refinery, the dry deposits show a high level of large (>10 μm) Zn, S, Fe and O bearing aggregates characterized by positive δ 66Zn values (+0.02 to +0.19‰). These airborne particles probably derive from the re-suspension of slag heaps and local emissions from the working-units. In contrast, from 1720 to 4560 m, the dry deposits are comprised of small (PM10) particles, including spherical Zn-bearing aggregates, showing negative δ 66Zn values (-0.52 to -0

  19. The quadrupole moments of Cd and Zn isotopes - an apology

    NASA Astrophysics Data System (ADS)

    Haas, H.; Barbosa, M. B.; Correia, J. G.

    2016-12-01

    In 2010 we presented an update of the nuclear quadrupole moments (Q) for the Cd and Zn isotopes, based essentially on straightforward density functional (DF) calculations (H. Haas and J.G. Correia, Hyperfine Interact 198, 133-137 (2010)). It has been apparent for some years that the standard DF procedure obviously fails, however, to reproduce the known electric-field gradient (EFG) for various systems, typical cases being Cu2O, As and Sb, and the solid halogens. Recently a cure for this deficiency has been found in the hybrid DF technique. This method is now applied to solid Cd and Zn, and the resultant quadrupole moments are about 15 % smaller than in our earlier report. Also nuclear systematics, using the recently revised values of Q for the long-lived 11/2 isomers in111Cd to129Cd, together with earlier PAD data for107,109Cd, leads to the same conclusion. In addition, EFG calculations for the cadmium dimethyl molecule further support the new values: Q(111Cd, 5/2+) = .683(20) b, Q(67Zn, gs) = .132(5) b. This implies, that the value for the atomic EFG in the 3it {P}1 state of Zn must be revised, as it has been for Cd.

  20. The carbon isotopic composition of ecosystem breath

    NASA Astrophysics Data System (ADS)

    Ehleringer, J.

    2008-05-01

    At the global scale, there are repeatable annual fluctuations in the concentration and isotopic composition of atmospheric carbon dioxide, sometimes referred to as the "breathing of the planet". Vegetation components within ecosystems fix carbon dioxide through photosynthesis into stable organic compounds; simultaneously both vegetation and heterotrophic components of the ecosystem release previously fixed carbon as respiration. These two-way fluxes influencing carbon dioxide exchange between the biosphere and the atmosphere impact both the concentration and isotopic composition of carbon dioxide within the convective boundary layer. Over space, the compounding effects of gas exchange activities from ecosystems become reflected in both regional and global changes in the concentration and isotopic composition of atmospheric carbon dioxide. When these two parameters are plotted against each other, there are significant linear relationships between the carbon isotopic composition and inverse concentration of atmospheric carbon dioxide. At the ecosystem scale, these "Keeling plots" intercepts of C3-dominated ecosystems describe the carbon isotope ratio of biospheric gas exchange. Using Farquhar's model, these carbon isotope values can be translated into quantitative measures of the drought-dependent control of photosynthesis by stomata as water availability changes through time. This approach is useful in aggregating the influences of drought across regional landscapes as it provides a quantitative measure of stomatal influence on photosynthetic gas exchange at the ecosystem-to-region scales. Multi-year analyses of the drought-dependent trends across terrestrial ecosystems show a repeated pattern with water stress in all but one C3-ecosystem type. Ecosystems that are dominated by ring-porous trees appear not to exhibit a dynamic stomatal response to water stress and therefore, there is little dependence of the carbon isotope ratio of gas exchange on site water balance

  1. Nickel isotopic composition of the mantle

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    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.

  2. Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

    NASA Astrophysics Data System (ADS)

    Bigalke, Moritz; Weyer, Stefan; Kobza, Jozef; Wilcke, Wolfgang

    2010-12-01

    Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ 65Cu, δ 66Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g -1 Cu and 2084 μg g -1 Zn in the organic horizons. The δ 65Cu values varied little (-0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ 66Zn IRMM values were isotopically lighter in ash (-0.41‰) and organic horizons (-0.85‰ to -0.47‰) than in bedrock (-0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ 66Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ 66Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ 66Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources

  3. Triple oxygen isotope composition of photosynthetic oxygen

    NASA Astrophysics Data System (ADS)

    van der Meer, Anne; Kaiser, Jan

    2013-04-01

    The measurement of biological production rates is essential for our understanding how marine ecosystems are sustained and how much CO2 is taken up through aquatic photosynthesis. Traditional techniques to measure marine production are laborious and subject to systematic errors. A biogeochemical approach based on triple oxygen isotope measurements in dissolved oxygen (O2) has been developed over the last few years, which allows the derivation of gross productivity integrated over the depth of the mixed layer and the time-scale of O2 gas exchange (Luz and Barkan, 2000). This approach exploits the relative 17O/16O and 18O/16O isotope ratio differences of dissolved O2 compared to atmospheric O2 to work out the rate of biological production. Two parameters are key for this calculation: the isotopic composition of dissolved O2 in equilibrium with air and the isotopic composition of photosynthetic oxygen. Recently, a controversy has emerged in the literature over these parameters (Kaiser, 2011) and one of the goals of this research is to provide additional data to resolve this controversy. In order to obtain more information on the isotopic signature of biological oxygen, laboratory experiments have been conducted to determine the isotopic composition of oxygen produced by different phytoplankton cultures.

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

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.

    2004-01-01

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

  5. Calcium Isotopic Composition of Bulk Silicate Earth

    NASA Astrophysics Data System (ADS)

    Kang, J.; Ionov, D. A.; Liu, F.; Zhang, C.; Zhang, Z.; Huang, F.

    2016-12-01

    Ca isotopes are used to study the accretion history of the Earth and terrestrial planets, but, Ca isotopic composition of the Bulk Silicate Earth (BSE) remains poorly constrained [1]. To better understand the Ca isotopic composition of BSE, we analyzed 22 well studied peridotite xenoliths from Tariat (Mongolia), Vitim (southern Siberia) and Udachnaya (Siberian Craton). These samples include both fertile and highly depleted garnet and spinel peridotites that show no or only minor post-melting metasomatism or alteration. Ca isotope measurements were done on a Triton-TIMS using double spike method at the Guangzhou Institute of Geochemistry, CAS. The data are reported as δ44/40Ca (relative to NIST SRM 915a). Results for geostandards are consistent with those from other laboratories. 2 standard deviations of SRM 915a analyses are 0.13‰ (n=48). δ44/40Ca of both and fertile and refractory peridotites range from 0.79 to 1.07‰ producing an average of 0.93±0.12‰ (2SD). This value defines the Ca isotopic composition of the BSE, which is consistent with the average δ44/40Ca of oceanic basalts ( 0.90‰)[2,3]. [1] Huang et al (2010) EPSL 292; [2] Valdes et al (2014) EPSL 394; [3]DePaolo (2004) RMG 55.

  6. The oxygen isotope composition of Almahata Sitta

    NASA Astrophysics Data System (ADS)

    Rumble, Douglas; Zolensky, Michael E.; Friedrich, Jon M.; Jenniskens, Peter; Shaddad, Muawia H.

    2010-10-01

    Eleven fragments of the meteorite Almahata Sitta (AHS) have been analyzed for oxygen isotopes. The fragments were separately collected as individual stones from the meteorite's linear strewn field in the Nubian Desert. Each of the fragments represents a sample of a different and distinct portion of asteroid 2008 TC3. Ten of the fragments span the same range of values of δ18O, δ17O, and Δ17O, and follow the same trend along the carbonaceous chondrite anhydrous minerals (CCAM) line as monomict and polymict members of the ureilite family of meteorites. The oxygen isotope composition of fragment #25 is consistent with its resemblance petrographically to an H5 ordinary chondrite. Our results demonstrate that a single small asteroidal parent body, asteroid 2008 TC3, only 4 m in length, encompassed the entire range of variation in oxygen isotope compositions measured for monomict and polymict ureilites.

  7. The Chlorine Isotope Composition of Martian Meteorites

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Shearer, C. K.; Agee, C.; Burger, P. V.; McKeegan, K. D.

    2014-11-01

    The Cl isotope composition of martian meteorites range from -3.8 to +8.6 per mil. Ol-phyric shergottites are lightest; crustally contaminated samples are heaviest, basaltic shergottites are in-between. The system is explained as two component mixing.

  8. Cu-Zn isotope constraints on the provenance of air pollution in Central Europe: Using soluble and insoluble particles in snow and rime.

    PubMed

    Novak, Martin; Sipkova, Adela; Chrastny, Vladislav; Stepanova, Marketa; Voldrichova, Petra; Veselovsky, Frantisek; Prechova, Eva; Blaha, Vladimir; Curik, Jan; Farkas, Juraj; Erbanova, Lucie; Bohdalkova, Leona; Pasava, Jan; Mikova, Jitka; Komarek, Arnost; Krachler, Michael

    2016-11-01

    Copper (Cu) and zinc (Zn) isotope ratios can be used to fingerprint sources and dispersion pathways of pollutants in the environment. Little is known, however, about the potential of δ 65 Cu and δ 66 Zn values in liquid and solid forms of atmospheric deposition to distinguish between geogenic, industrial, local and remote sources of these potentially toxic base metals. Here we present Cu-Zn deposition fluxes at 10 mountain-top sites in the Czech Republic, a region affected by extremely high industrial emission rates 25 years ago. Additionally, we monitored isotope composition of Cu and Zn in vertical and horizontal atmospheric deposition at two sites. We compared δ 65 Cu and δ 66 Zn values in snow and rime, extracted by diluted HNO 3 and concentrated HF. Cu and Zn isotope signatures of industrial pollution sources were also determined. Cu and Zn deposition fluxes at all study sites were minute. The mean δ 65 Cu value of atmospheric deposition (-0.07‰) was higher than the mean δ 65 Cu value of pollution sources (-1.17‰). The variability in δ 65 Cu values of atmospheric deposition was lower, compared to the pollution sources. The mean δ 66 Zn value of atmospheric deposition (-0.09‰) was slightly higher than the mean δ 66 Zn value of pollution sources (-0.23‰). The variability in δ 66 Zn values of atmospheric deposition was indistinguishable from that of pollution sources. The largest isotope differences (0.35‰) were observed between the insoluble and soluble fractions of atmospheric deposition. These differences may result from different sources of Cu/Zn for each fraction. The difference in isotope composition of soluble and insoluble particles appears to be a promising tool for pollution provenance studies in Central Europe. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Multi isotopic characterization (Li-Cu-Zn-Pb) of waste waters pollution in a small watershed (Loire River basin, France)

    NASA Astrophysics Data System (ADS)

    Millot, R.; Desaulty, A. M.; Perret, S.; Bourrain, X.

    2016-12-01

    The goal of this study is to use multi-isotopic signature to track the pollution in surface waters, and to understand the complex processes causing the metals mobilization and transport in the environment. In the present study, we investigate waste water releases from a hospital water treatment plant and its potential impact in a small river basin near Orléans in France (Egoutier watershed: 15 km²and 5 km long). We decided to monitor this small watershed which is poorly urbanized in the Loire river basin. Its spring is located in a pristine area (forested area), while it is only impacted some kilometers further by the releases rich in metals coming from a hospital water treatment plant. A sampling of these liquid effluents as well as dissolved load and sediment from upstream to downstream was realized and their concentrations and isotopic data were determined. Isotopic ratios were measured using a MC-ICP-MS at BRGM, after a specific protocol of purification for each isotopic systematics. Lithium isotopic compositions are rather homogeneous in river waters along the main course of the stream. The waste water signal is very different from the natural background with significant heavy lithium contribution (high δ7Li). Lead isotopic compositions are rather homogenous in river waters and sediments with values close to geologic background. For Zn, the sediments with high concentrations and depleted isotopic compositions (low δ66Zn), typical of an anthropic pollution, are strongly impacted. The analyses of Cu isotopes in sediments show the impact of waster waters, but also isotopic fractionations due to redox processes in the watershed. To better understand these processes controlling the release of metals in water, sequential extractions on sediments are in progress under laboratory conditions and will provide important constraints for metal distribution in this river basin.

  10. Combining XAS speciation and Zn isotopes to track past eutrophication in lake sediments : The example of Baldeggersee (Switzerland)

    NASA Astrophysics Data System (ADS)

    Noël, V. S.; Voegelin, A.; Jouvin, D.; Louvat, P.; gelabert, A.; Mueller, B.; Benedetti, M. F.; Juillot, F.

    2011-12-01

    and occupancy of the related catchment, these results emphasize the great potential of such a combination of molecular level speciation and Zn isotopes in lake sediments cores to track paleo-climatic or paleo-environmental conditions in lake catchments. Lotter A.F., Sturm M., Teranes J.L. and Wehrli B. (1997) Varve fromation since 1885 and high-resolution varve analyses in hypertrophic Baldeggersee (Switzerland) Aquatic Sciences 59, 304-325. Morel F. M. M. and Price N. M. (2003) The biogeochemical cycles of trace metals in the oceans. Science 300, 944-947. Peel K., Weiss D., Sigg L. (2010) Zinc isotope composition of settling particles as a proxy for biogeochemical processes in lakes: Insights from the eutrophic Lake Greifen, Switzerland. Limnol. Oceanogr., 54(5), 1699-1708. Wehrli, B.; Lotter, A.F.; Schaller, T.; Sturm, M. (1997) High-resolution varve studies in Baldeggersee (Switzerland): Project overview and limnological background data. Aquatic Sciences 59, 285-294).

  11. Isotopic Composition of Oxygen in Lunar Zircons

    NASA Technical Reports Server (NTRS)

    Nemchin, A. A.; Whitehouse, M. J.; Pidgeon, R. T.; Meyer, C.

    2005-01-01

    The recent discovery of heavy oxygen in zircons from the Jack Hills conglomerates Wilde et al. and Mojzsis et al. was interpreted as an indication of presence of liquid water on the surface of Early Earth. The distribution of ages of Jack Hills zircons and lunar zircons appears to be very similar and therefore analysis of oxygen in the lunar grains may provide a reference frame for further study of the early history of the Earth as well as give additional information regarding processes that operated on the Moon. In the present study we have analysed the oxygen isotopic composition of zircon grains from three lunar samples using the Swedish Museum of Natural History CAMECA 1270 ion microprobe. The samples were selected as likely tests for variations in lunar oxygen isotopic composition. Additional information is included in the original extended abstract.

  12. Chemical composition and Zn bioavailability of the soil solution extracted from Zn amended variable charge soils.

    PubMed

    Zampella, Mariavittoria; Adamo, Paola

    2010-01-01

    A study on variable charge soils (volcanic Italian and podzolic Scottish soils) was performed to investigate the influence of soil properties on the chemical composition of soil solution. Zinc speciation, bioavailability and toxicity in the soil solution were examined. The soils were spiked with increasing amounts of Zn (0, 100, 200, 400 and 1000 mg/kg) and the soil solutions were extracted using rhizon soil moisture samplers. The pH, total organic carbon (TOC), base cations, anions, total Zn and free Zn2+ in soil solution were analysed. A rapid bioassay with the luminescent bacterium Escherichia coli HB101 pUCD607 was performed to assess Zn toxicity. The influence of soil type and Zn treatments on the chemical composition of soil solution and on Zn toxicity was considered and discussed. Different trends of total and free Zn concentrations, base cations desorption and luminescence of E. coli HB101 pUCD607 were observed. The soil solution extracted from the volcanic soils had very low total and free Zn concentrations and showed specific Zn2+/Ca2+ exchange. The soil solution from the podzolic soil had much higher total and free Zn concentrations and showed no evidence of specific Zn2+/Ca2+ exchange. In comparison with the subalkaline volcanic soils, the acidic podzol showed enhanced levels of toxic free Zn2+ and consequently stronger effects on E. coli viability.

  13. Synthesis of isotopically modified ZnO nanoparticles and their potential as nanotoxicity tracers

    USGS Publications Warehouse

    Dybowska, A.D.; Croteau, M.-N.; Misra, S.K.; Berhanu, D.; Luoma, S.N.; Christian, P.; O'Brien, P.; Valsami-Jones, E.

    2011-01-01

    Understanding the behavior of engineered nanoparticles in the environment and within organisms is perhaps the biggest obstacle to the safe development of nanotechnologies. Reliable tracing is a particular issue for nanoparticles such as ZnO, because Zn is an essential element and a common pollutant thus present at elevated background concentrations. We synthesized isotopically enriched (89.6%) with a rare isotope of Zn (67Zn) ZnO nanoparticles and measured the uptake of 67Zn by L. stagnalis exposed to diatoms amended with the particles. Stable isotope technique is sufficiently sensitive to determine the uptake of Zn at an exposure equivalent to lower concentration range (<15 ??g g-1). Without a tracer, detection of newly accumulated Zn is significant at Zn exposure concentration only above 5000 ??g g-1 which represents some of the most contaminated Zn conditions. Only by using a tracer we can study Zn uptake at a range of environmentally realistic exposure conditions. ?? 2010 Elsevier Ltd. All rights reserved.

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

    PubMed

    Fekiacova, Z; Cornu, S; Pichat, S

    2015-06-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. The isotopic composition of cosmic ray calcium

    NASA Technical Reports Server (NTRS)

    Krombel, K. E.; Wiedenbeck, M. E.

    1985-01-01

    Data from the high energy cosmic ray experiment on the international sun earth explorer 3 (ISEE-3) spacecraft have been used to study the isotopic composition of cosmic ray calcium at an energy of approx. 260 MeV/amu. The arriving calcium is found to consist of (32 + or - 6)%. A propagation model consistent with both the light and the subiron secondary element abundances was used for the interpretation of the observed calcium composition. The measured 42Ca+43Ca+44Ca abundance is consistent with the calculated secondary production, while the 40Ca abundance implies a source ratio of 40Ca/Fe = (7.0 + or - 1.7)%.

  16. The estuarine geochemical reactivity of Zn isotopes and its relevance for the biomonitoring of anthropogenic Zn and Cd contaminations from metallurgical activities: Example of the Gironde fluvial-estuarine system, France

    NASA Astrophysics Data System (ADS)

    Petit, Jérôme C. J.; Schäfer, Jörg; Coynel, Alexandra; Blanc, Gérard; Chiffoleau, Jean-François; Auger, Dominique; Bossy, Cécile; Derriennic, Hervé; Mikolaczyk, Mathilde; Dutruch, Lionel; Mattielli, Nadine

    2015-12-01

    geochemical reactivity of Zn in the estuary rather than signatures of past metallurgical contaminations in the watershed as recorded in contaminated river sediments. The study also shows that the isotopic composition of Zn is strongly fractionated by its geochemical reactivity in the Gironde Estuary, representative of meso-macrotidal estuarine systems.

  17. Sulfur Isotope Composition of Putative Primary Troilite in Chondrules

    NASA Technical Reports Server (NTRS)

    Tachibana, Shogo; Huss, Gary R.

    2002-01-01

    Sulfur isotope compositions of putative primary troilites in chondrules from Bishunpur were measured by ion probe. These primary troilites have the same S isotope compositions as matrix troilites and thus appear to be isotopically unfractionated. Additional information is contained in the original extended abstract.

  18. The Oxygen Isotopic Composition of the Sun

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.; Kallio, A.; Heber, V. S.; Jarzebinski, G.; Mao, P.; Coath, C.; Kunihiro, T.; Wiens, R. C.; Judith, A.; Burnett, D. S.

    2010-12-01

    An accurate and precise determination of the oxygen isotopic composition of the Sun is the highest priority scientific goal of the Genesis Mission [1] as such data would provide a baseline from which one could interpret the oxygen isotopic anomalies found at all spatial scales in inner solar system materials. We have measured oxygen isotope compositions of implanted solar wind in 40 spots along a radial traverse of the Genesis SiC target sample 60001 by depth profiling with the UCLA MegaSIMS [2]. Mass-dependent fractionation induced by the solar wind concentrator [3] ion optics was corrected by comparison of the concentrator 22Ne/20Ne with that measured in a bulk solar wind target (diamond-like carbon on Si, [4]). The solar wind captured at L1 has an isotopic composition of (δ18O, δ17O) ≈ (-99, -79)‰, a value which is far removed from the terrestrial mass fractionation line. Profiles from the central portion of the target, where solar concentrations are highest and background corrections minimal, yield a mean Δ17O = -28.3 ± 1.8 ‰ indicating that the Earth and other planetary materials from the inner solar system are highly depleted in 16O relative to the solar wind. A mass-dependent fractionation of ~ -20%/amu in the acceleration of solar wind is required if we hypothesize that the photospheric oxygen isotope value, which represents the bulk starting composition of the solar system, is on the 16O-mixing line characteristic of refractory phase in primitive meteorites [5]. With this assumption, our preferred value for the bulk solar oxygen isotope composition is δ18O ≈ δ17O ≈ -57‰. A mechanism is required to fractionate oxygen isotopes in a non-mass-dependent manner to deplete 16O by ~6 to 7% in the rocky materials of the solar nebula. As oxygen is the third most abundant element in the solar system, and the most abundant in the terrestrial planets, this mechanism must operate on a large scale. Isotope-selective photochemistry, for example as in

  19. THE NITROGEN ISOTOPIC COMPOSITION OF METEORITIC HCN

    SciTech Connect

    Pizzarello, Sandra, E-mail: pizzar@asu.edu

    2014-12-01

    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 organicmore » 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.« less

  20. Oxygen Isotopic Compositions of Solar Corundum Grains

    NASA Astrophysics Data System (ADS)

    Makide, Kentaro; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.

    2009-11-01

    Oxygen is one of the major rock-forming elements in the solar system and the third most abundant element of the Sun. Oxygen isotopic composition of the Sun, however, is not known due to a poor resolution of astronomical spectroscopic measurements. Several Δ17O values have been proposed for the composition of the Sun based on (1) the oxygen isotopic measurements of the solar wind implanted into metallic particles in lunar soil (< -20‰ by Hashizume & Chaussidon and ~ +26‰ by Ireland et al.), (2) the solar wind returned by the Genesis spacecraft (-27‰ ± 6‰ by McKeegan et al.), and (3) the mineralogically pristine calcium-aluminum-rich inclusions (CAIs) (-23.3‰ ± 1.9‰ by Makide et al. and -35‰ by Gounelle et al.). CAIs are the oldest solar system solids, and are believed to have formed by evaporation, condensation, and melting processes in hot nebular region(s) when the Sun was infalling (Class 0) or evolved (Class 1) protostar. Corundum (Al2O3) is thermodynamically the first condensate from a cooling gas of solar composition. Corundum-bearing CAIs, however, are exceptionally rare, suggesting either continuous reaction of the corundum condensates with a cooling nebular gas and their replacement by hibonite (CaAl12O19) or their destruction by melting together with less refractory condensates during formation of igneous CAIs. In contrast to the corundum-bearing CAIs, isolated micrometer-sized corundum grains are common in the acid-resistant residues from unmetamorphosed chondrites. These grains could have avoided multistage reprocessing during CAI formation and, therefore, can potentially provide constraints on the initial oxygen isotopic composition of the solar nebula, and, hence, of the Sun. Here we report oxygen isotopic compositions of ~60 micrometer-sized corundum grains in the acid-resistant residues from unequilibrated ordinary chondrites (Semarkona (LL3.0), Bishunpur (LL3.1), Roosevelt County 075 (H3.2)) and unmetamorphosed carbonaceous

  1. Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

    NASA Technical Reports Server (NTRS)

    Becker, H.; Walker, R. J.

    2003-01-01

    Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

  2. Copper and Zinc isotope composition of CR, CB and CH-like meteorites.

    NASA Astrophysics Data System (ADS)

    Russell, S.; Zhu, X.; Guo, Y.; Mullane, E.; Gounelle, M.; Mason, T.; Coles, B.

    2003-04-01

    Copper and zinc isotopes have recently been shown to be variable in isotopic composi-tion among terrestrial and extraterrestrial materials [1-3]. For this study, we have se-lected samples (bulk meteorite and chondrule separates) from the CR meteorite clan: Bencubbin (CB), Renazzo (CR2), NWA 801 (CR2), and HaH237 (CH-like). These meteorites were selected because meteorites from this clan have experienced very little alteration since their initial formation [4] and for their extremely high refrac-tory/volatile element ratios. The latter characteristic may allow a test of the correlation observed by [2] between element ratios and Cu isotope composition. Measurements were performed on NHM/IC Micromass Isoprobe and Oxford Nu MC-ICP-MS using techniques described elsewhere [1,5]. Each of the meteorites measured so far for Cu and Zn are isotopically light compared to the terrestrial mantle. This suggests that the terrestrial value may have been altered from the pristine solar system value, or else there were multiple early solar system components. Zinc isotopic com-positions lie on a fractionation line and range from δ66ZnNIST = -1.4±0.1ppm (bulk NWA801) to -1.9±0.1ppm (separated chondrule, NWA 801). Copper isotope compositions vary from δ65CuNIST976 = -1.5±0.1ppm (bulk Renazzo) to -3.1±0.1ppm (separated chondrule, NWA 801). Two chondrules from NWA 801 have differing Cu isotope values (-3.1±0.1 and -2.0±0.1ppm) and both are lighter than the bulk meteorite (-1.9±0.1ppm), suggesting a lack of equilibration with respect to Cu in this meteorite. The light values for the two separated chondrules, compared the bulk meteorite, hints that chondrules may be isotopically lighter than co-existing matrix, metal and sulphides with respect to Cu. The copper isotope compositions are not as isotopically light as expected for the high refractory/volatile element ratio observed in these chondrites. Thus a model to account for the Cu isotopes in chondrites may require greater com

  3. Investigation of Cu-, Zn- and Fe-containing human brain proteins using isotopic-enriched tracers by LA-ICP-MS and MALDI-FT-ICR-MS

    NASA Astrophysics Data System (ADS)

    Becker, J. Susanne; Zoriy, Miroslav; Pickhardt, Carola; Przybylski, Michael; Becker, J. Sabine

    2005-04-01

    Identification of metal-containing proteins and determination of Cu, Fe, Zn concentration in very small protein volumes is of increasing importance in protein research. Proteins containing metal ions were analyzed directly and simultaneously in separated protein spots in two-dimensional gels (2D gels) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as an element mass spectrometric technique. In order to study the formation of proteins containing Cu, Zn and Fe in a human brain sample, isotopic-enriched tracers (54Fe, 65Cu and 67Zn) were doped to two-dimensional gels of separated Alzheimer-diseased brain proteins after two-dimensional (2D) gel electrophoresis. The protein spots were screened systematically by LA-ICP-MS with respect to these metal ion intensities. 54Fe/56Fe, 65Cu/63Cu and 67Zn/64Zn isotope ratios in metal-containing proteins were measured directly by LA-ICP-MS. The isotope ratio measurements obtained by LA-ICP-MS indicate certain protein spots with a natural isotope composition of Cu, Zn and/or Fe. These proteins already contained the metal investigated in the original proteins and are stable enough to survive the reducing conditions during gel electrophoresis. On the other hand, proteins with a changed isotope ratio of metals in comparison to the isotope ratio in nature demonstrate the accumulation of tracers within the protein complexes during the tracer experiments in 2D gels. The identification of singular protein spots from Alzheimer-diseased brain separated by 2D gel electrophoresis was attempted by biopolymer mass spectrometry using MALDI-FTICR-MS after excision from the 2D gel and tryptic digestion.

  4. Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits

    PubMed Central

    Wen, Hanjie; Zhu, Chuanwei; Zhang, Yuxu; Cloquet, Christophe; Fan, Haifeng; Fu, Shaohong

    2016-01-01

    Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ114/110Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ114/110Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits. PMID:27121538

  5. Evolution of nuclear structure in neutron-rich odd-Zn isotopes and isomers

    NASA Astrophysics Data System (ADS)

    Wraith, C.; Yang, X. F.; Xie, L.; Babcock, C.; Bieroń, J.; Billowes, J.; Bissell, M. L.; Blaum, K.; Cheal, B.; Filippin, L.; Garcia Ruiz, R. F.; Gins, W.; Grob, L. K.; Gaigalas, G.; Godefroid, M.; Gorges, C.; Heylen, H.; Honma, M.; Jönsson, P.; Kaufmann, S.; Kowalska, M.; Krämer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Nowacki, F.; Otsuka, T.; Papuga, J.; Sánchez, R.; Tsunoda, Y.; Yordanov, D. T.

    2017-08-01

    Collinear laser spectroscopy was performed on Zn (Z = 30) isotopes at ISOLDE, CERN. The study of hyperfine spectra of nuclei across the Zn isotopic chain, N = 33- 49, allowed the measurement of nuclear spins for the ground and isomeric states in odd-A neutron-rich nuclei up to N = 50. Exactly one long-lived (>10 ms) isomeric state has been established in each 69-79Zn isotope. The nuclear magnetic dipole moments and spectroscopic quadrupole moments are well reproduced by large-scale shell-model calculations in the f5pg9 and fpg9d5 model spaces, thus establishing the dominant term in their wave function. The magnetic moment of the intruder Iπ = 1 /2+ isomer in 79Zn is reproduced only if the νs1/2 orbital is added to the valence space, as realized in the recently developed PFSDG-U interaction. The spin and moments of the low-lying isomeric state in 73Zn suggest a strong onset of deformation at N = 43, while the progression towards 79Zn points to the stability of the Z = 28 and N = 50 shell gaps, supporting the magicity of 78Ni.

  6. Magnesium isotopic composition of the Earth and chondrites

    NASA Astrophysics Data System (ADS)

    Teng, Fang-Zhen; Li, Wang-Ye; Ke, Shan; Marty, Bernard; Dauphas, Nicolas; Huang, Shichun; Wu, Fu-Yuan; Pourmand, Ali

    2010-07-01

    To constrain further the Mg isotopic composition of the Earth and chondrites, and investigate the behavior of Mg isotopes during planetary formation and magmatic processes, we report high-precision (±0.06‰ on δ 25Mg and ±0.07‰ on δ 26Mg, 2SD) analyses of Mg isotopes for (1) 47 mid-ocean ridge basalts covering global major ridge segments and spanning a broad range in latitudes, geochemical and radiogenic isotopic compositions; (2) 63 ocean island basalts from Hawaii (Kilauea, Koolau and Loihi) and French Polynesia (Society Island and Cook-Austral chain); (3) 29 peridotite xenoliths from Australia, China, France, Tanzania and USA; and (4) 38 carbonaceous, ordinary and enstatite chondrites including 9 chondrite groups (CI, CM, CO, CV, L, LL, H, EH and EL). Oceanic basalts and peridotite xenoliths have similar Mg isotopic compositions, with average values of δ 25Mg = -0.13 ± 0.05 (2SD) and δ 26Mg = -0.26 ± 0.07 (2SD) for global oceanic basalts ( n = 110) and δ 25Mg = -0.13 ± 0.03 (2SD) and δ 26Mg = -0.25 ± 0.04 (2SD) for global peridotite xenoliths ( n = 29). The identical Mg isotopic compositions in oceanic basalts and peridotites suggest that equilibrium Mg isotope fractionation during partial melting of peridotite mantle and magmatic differentiation of basaltic magma is negligible. Thirty-eight chondrites have indistinguishable Mg isotopic compositions, with δ 25Mg = -0.15 ± 0.04 (2SD) and δ 26Mg = -0.28 ± 0.06 (2SD). The constancy of Mg isotopic compositions in all major types of chondrites suggest that primary and secondary processes that affected the chemical and oxygen isotopic compositions of chondrites did not significantly fractionate Mg isotopes. Collectively, the Mg isotopic composition of the Earth's mantle, based on oceanic basalts and peridotites, is estimated to be -0.13 ± 0.04 for δ 25Mg and -0.25 ± 0.07 for δ 26Mg (2SD, n = 139). The Mg isotopic composition of the Earth, as represented by the mantle, is similar to chondrites

  7. Geochemistry of CI chondrites: Major and trace elements, and Cu and Zn Isotopes

    NASA Astrophysics Data System (ADS)

    Barrat, J. A.; Zanda, B.; Moynier, F.; Bollinger, C.; Liorzou, C.; Bayon, G.

    2012-04-01

    In order to check the heterogeneity of the CI chondrites and determine the average composition of this group of meteorites, we analyzed a series of six large chips (weighing between 0.6 and 1.2 g) of Orgueil prepared from five different stones. In addition, one sample from each of Ivuna and Alais was analyzed. Although the sizes of the chips used in this study were “large”, our results show evidence for minor chemical heterogeneity in Orgueil, particularly for alkali elements and U. After removal of one outlier sample, the spread of the results is considerably reduced. For most of the 46 elements analyzed in this study, the average composition calculated for Orgueil is in very good agreement with previous CI estimates. This average, obtained with a “large” mass of samples, is analytically homogeneous and is suitable for normalization purposes. Finally, the Cu and Zn isotopic ratios are homogeneously distributed within the CI parent body with a spread of less than 100 ppm per atomic mass unit (amu).

  8. Coulomb Excitation of Neutron-Rich Zn Isotopes: First Observation of the 21+ State in Zn80

    NASA Astrophysics Data System (ADS)

    van de Walle, J.; Aksouh, F.; Ames, F.; Behrens, T.; Bildstein, V.; Blazhev, A.; Cederkäll, J.; Clément, E.; Cocolios, T. E.; Davinson, T.; Delahaye, P.; Eberth, J.; Ekström, A.; Fedorov, D. V.; Fedosseev, V. N.; Fraile, L. M.; Franchoo, S.; Gernhauser, R.; Georgiev, G.; Habs, D.; Heyde, K.; Huber, G.; Huyse, M.; Ibrahim, F.; Ivanov, O.; Iwanicki, J.; Jolie, J.; Kester, O.; Köster, U.; Kröll, T.; Krücken, R.; Lauer, M.; Lisetskiy, A. F.; Lutter, R.; Marsh, B. A.; Mayet, P.; Niedermaier, O.; Nilsson, T.; Pantea, M.; Perru, O.; Raabe, R.; Reiter, P.; Sawicka, M.; Scheit, H.; Schrieder, G.; Schwalm, D.; Seliverstov, M. D.; Sieber, T.; Sletten, G.; Smirnova, N.; Stanoiu, M.; Stefanescu, I.; Thomas, J.-C.; Valiente-Dobón, J. J.; van Duppen, P.; Verney, D.; Voulot, D.; Warr, N.; Weisshaar, D.; Wenander, F.; Wolf, B. H.; Zielińska, M.

    2007-10-01

    Neutron-rich, radioactive Zn isotopes were investigated at the Radioactive Ion Beam facility REX-ISOLDE (CERN) using low-energy Coulomb excitation. The energy of the 21+ state in Zn78 could be firmly established and for the first time the 2+→01+ transition in Zn80 was observed at 1492(1) keV. B(E2,21+→01+) values were extracted for Zn74,76,78,80 and compared to large scale shell model calculations. With only two protons outside the Z=28 proton core, Zn80 is the lightest N=50 isotone for which spectroscopic information has been obtained to date. Two sets of advanced shell model calculations reproduce the observed B(E2) systematics. The results for N=50 isotones indicate a good N=50 shell closure and a strong Z=28 proton core polarization. The new results serve as benchmarks to establish theoretical models, predicting the nuclear properties of the doubly magic nucleus Ni78.

  9. Isotopic Composition of Barium in Single Presolar Silicon Carbide Grains

    NASA Technical Reports Server (NTRS)

    Savina, M. R.; Tripa, C. E.; Pellin, M. J.; Davis, A. M.; Clayton, R. N.; Lewis, R. S.; Amari, S.

    2002-01-01

    We have measured Ba isotope distributions in individual presolar SiC grains. We find that the Ba isotopic composition in mainstream SiC grains is consistent with models of nucleosynthesis in low to intermediate mass asymptotic giant branch (AGB) stars. Additional information is contained in the original extended abstract.

  10. Hercynian Pb-Zn mineralization types in the Alcudia Valley mining district (Spain) and their reflect in Pb isotopic signatures

    NASA Astrophysics Data System (ADS)

    García de Madinabeitia, S.; Santos Zalduegui, J. F.; Palero, F.; Gil Ibarguchi, J. I.; Carracedo, M.

    2003-04-01

    More than 450 ore deposits indexed within the Alcudia Valley of the Central-Iberian Zone (Spain) may be grouped by their tectonic and lithologic characteristics (1,2) as follows: type A of rare stratabound mineralizations, and types B, C, D and E represented by abundant Hercynian veins (post-Namurian). 86 new Pb isotope analyses of galenas from the four vein types reveal that types B and C have similar isotopic ratios with values of μ_2 = 10.07, ω_2 = 40.6 and a mean model age of 564 Ma. Types D and E have μ_2 and ω_2 values of 9.79 and 38.5, respectively, but differ each other with respect to their model ages, 600 Ma (type D) and 335 Ma (type E). The observed variations appear to be related to the geochemical features of the metasedimentary host-rocks of the mineralizations where two distinct types of Pb isotopic ratios have been reported (3): one with μ_2 and ω_2 comparable to those of the D and E types and another with a more radiogenic composition, close to those of the B and C types of galenas. Nägler et al. have suggested partial rehomogeneization of Pb isotopic composition within the metasediments at ca. 330 Ma, that is, prior to the mineralization events, but the extent of this process and its effects on the ore bodies isotopic features is not evident. The origin of the more abundant E type ore bodies has been related to the Hercynian granitic rocks in the area (2, and references therein). Other plutons within this sector of the Central Iberian Zone (e.g., Linares, etc.; cf. accompanying Abstract) associate ore bodies whose Pb isotopic composition is very similar to that of the E type galenas from the Alcudia Valley. The isotopic data obtained thus point to a related or common source material for the various types of granites within the area studied. Yet, the Pb isotopic composition of other mineralizations (B, C, D), likewise located in Hercynian veins, allow to consider different types of Pb-Zn ore bodies and point therefore to different sources of

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

    PubMed

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

    2015-01-01

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

  12. Pb-Zn-Cd-Hg multi isotopic characterization of the Loire River Basin, France

    NASA Astrophysics Data System (ADS)

    Millot, R.; Widory, D.; Innocent, C.; Guerrot, C.; Bourrain, X.; Johnson, T. M.

    2012-12-01

    The contribution of human activities such as industries, agriculture and domestic inputs, becomes more and more significant in the chemical composition (major ions and pollutants such as metals) of the dissolved load of rivers. Furthermore, this influence can also be evidenced in the suspended solid matter known to play an important role in the transport of heavy metals through river systems. Human factors act as a supplementary key process. Therefore the mass-balance for the budget of catchments and river basins include anthropogenic disturbances. The Loire River in central France is approximately 1010 km long and drains an area of 117,800 km2. Initially, the Loire upstream flows in a south to north direction originating in the Massif Central, and continues up to the city of Orléans, 650 km from the source. In the upper basin, the bedrock is old plutonic rock overlain by much younger volcanic rocks. The Loire River then follows a general east to west direction to the Atlantic Ocean. The intermediate basin includes three major tributaries flowing into the Loire River from the left bank: the Cher, the Indre and the Vienne rivers; the main stream flows westward and its valley stretches toward the Atlantic Ocean. Here, the Loire River drains the sedimentary series of the Paris Basin, mainly carbonate deposits. The lower Loire basin drains pre-Mesozoic basement of the Armorican Massif and its overlying Mesozoic to Cenozoic sedimentary deposits. The Loire River is one of the main European riverine inputs to the Atlantic ocean. Here we are reporting concentration and isotope data for heavy metals Zn-Cd-Pb-Hg in river waters and suspended sediments from the Loire River Basin. In addition, we also report concentration and isotope data for these metals for the different industrial sources within the Loire Basin, as well as data for biota samples such as mussels and oysters from the Bay of Biscay and North Brittany. These organisms are known to be natural accumulators of

  13. The silicon isotope composition of the upper continental crust

    NASA Astrophysics Data System (ADS)

    Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Halliday, Alex N.

    2013-05-01

    The upper continental crust (UCC) is the major source of silicon (Si) to the oceans and yet its isotopic composition is not well constrained. In an effort to investigate the degree of heterogeneity and provide a robust estimate for the average Si isotopic composition of the UCC, a representative selection of well-characterised, continentally-derived clastic sediments have been analysed using high-precision MC-ICPMS. Analyses of loess samples define a narrow range of Si isotopic compositions (δ30Si = -0.28‰ to -0.15‰). This is thought to reflect the primary igneous mineralogy and predominance of mechanical weathering in the formation of such samples. The average loess δ30Si is -0.22 ± 0.07‰ (2 s.d.), identical to average granite and felsic igneous compositions. Therefore, minor chemical weathering does not resolvably affect bulk rock δ30Si, and loess is a good proxy for the Si isotopic composition of unweathered, crystalline, continental crust. The Si isotopic compositions of shales display much more variability (δ30Si = -0.82‰ to 0.00‰). Shale Si isotope compositions do not correlate well with canonical proxies for chemical weathering, such as CIA values, but do correlate negatively with insoluble element concentrations and Al/Si ratios. This implies that more intensive or prolonged chemical weathering of a sedimentary source, with attendant desilicification, is required before resolvable negative Si isotopic fractionation occurs. Shale δ30Si values that are more positive than those of felsic igneous rocks most likely indicate the presence of marine-derived silica in such samples. Using the data gathered in this study, combined with already published granite Si isotope analyses, a weighted average composition of δ30Si = -0.25 ± 0.16‰ (2 s.d.) for the UCC has been calculated.

  14. Isotopic compositions of the elements 2013 (IUPAC Technical Report)

    USGS Publications Warehouse

    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

    2016-01-01

    The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) 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.

  15. Rubidium Isotope Composition of the Earth and the Moon: Evidence for the Origin of Volatile Loss During Planetary Accretion

    NASA Astrophysics Data System (ADS)

    Pringle, E. A.; Moynier, F.

    2016-12-01

    The Earth-Moon system has a variety of chemical and isotopic characteristics that provide clues to understanding the mechanism of lunar formation. One important observation is the depletion in moderately volatile elements in the Moon compared to the Earth. This volatile element depletion may be a signature of volatile loss during the Moon-forming Giant Impact. Stable isotopes are powerful tracers of such a process, since volatile loss via evaporation enriches the residue in heavy isotopes. However, early studies searching for the fingerprint of volatile loss failed to find any resolvable variations [1]. Recent work has now revealed heavy isotope enrichments in the Moon relative to the Earth for the moderately volatile elements Zn [2,3] and K [4]. The purely lithophile nature of Rb (in contrast to the chalcophile/lithophile nature of Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to study the origin of lunar volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. The Rb isotope compositions of terrestrial rocks define a narrow range, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). There is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. In particular, eucrites are significantly enriched in 87Rb (up to several per mil) relative to chondrites. Similarly, lunar basalts are enriched in 87Rb compared to terrestrial basalts, by 200 ppm for 87Rb/85Rb. These data are the first measurements of a resolvable difference in Rb isotope composition between the Earth and the Moon. The variations in Rb isotope composition between the Earth and the Moon are consistent with Rb isotope fractionation due to evaporation. References: [1] Humayun & Clayton GCA 1995. [2] Paniello et al. Nature 2012. [3] Kato et al. Nat. Comm. 2015. [4] Wang and Jacobsen Nature in press.

  16. Controls on the barium isotope compositions of marine sediments

    NASA Astrophysics Data System (ADS)

    Bridgestock, Luke; Hsieh, Yu-Te; Porcelli, Donald; Homoky, William B.; Bryan, Allison; Henderson, Gideon M.

    2018-01-01

    The accumulation of barium (Ba) in marine sediments is considered to be a robust proxy for export production, although this application can be limited by uncertainty in BaSO4 preservation and sediment mass accumulation rates. The Ba isotope compositions of marine sediments could potentially record insights into past changes in the marine Ba cycle, which should be insensitive to these limitations, enabling more robust interpretation of sedimentary Ba as a proxy. To investigate the controls on the Ba isotope compositions of marine sediments and their potential for paleo-oceanographic applications, we present the first Ba isotope compositions results for sediments, as well as overlying seawater depth profiles collected in the South Atlantic. Variations in Ba isotope compositions of the sediments predominantly reflect changes in the relative contributions of detrital and authigenic Ba sources, with open-ocean sediments constraining the isotope composition of authigenic Ba to be δ 138/134Ba ≈ + 0.1 ‰. This value is consistent with the average isotope composition inferred for sinking particulate Ba using simple mass balance models of Ba in the overlying water column and is hypothesized to reflect the removal of Ba from the upper water column with an associated isotopic fractionation of Δ diss-part 138/134Ba ≈ + 0.4 to +0.5. Perturbations to upper ocean Ba cycling, due to changes in export production and the supply of Ba via upwelling, should therefore be recorded by the isotope compositions of sedimentary authigenic Ba. Such insights will help to improve the reliable application of Ba accumulation rates in marine sediments as a proxy for past changes in export production.

  17. Antimony isotopic composition in river waters affected by ancient mining activity.

    PubMed

    Resongles, Eléonore; Freydier, Rémi; Casiot, Corinne; Viers, Jérôme; Chmeleff, Jérôme; Elbaz-Poulichet, Françoise

    2015-11-01

    In this study, antimony (Sb) isotopic composition was determined in natural water samples collected along two hydrosystems impacted by historical mining activities: the upper Orb River and the Gardon River watershed (SE, France). Antimony isotope ratio was measured by HG-MC-ICP-MS (Hydride Generation Multi-Collector Inductively Coupled Plasma Mass Spectrometer) after a preconcentration and purification step using a new thiol-cellulose powder (TCP) procedure. The external reproducibility obtained for δ(123)Sb measurements of our in-house Sb isotopic standard solution and a certified reference freshwater was 0.06‰ (2σ). Significant isotopic variations were evident in surface waters from the upper Orb River (-0.06‰≤δ(123)Sb≤+0.11‰) and from the Gardon River watershed (+0.27‰≤δ(123)Sb≤+0.83‰). In particular, streams that drained different former mining sites exploited for Sb or Pb-Zn exhibited contrasted Sb isotopic signature, that may be related to various biogeochemical processes occurring during Sb transfer from rocks, mine wastes and sediments to the water compartment. Nevertheless, Sb isotopic composition appeared to be stable along the Gardon River, which might be attributed to the conservative transport of Sb at distance from mine-impacted streams, due to the relative mobile behavior of Sb(V) in natural oxic waters. This study suggests that Sb isotopic composition could be a useful tool to track pollution sources and/or biogeochemical processes in hydrologic systems. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Zinc and copper behaviour at the soil-river interface: New insights by Zn and Cu isotopes in the organic-rich Rio Negro basin

    NASA Astrophysics Data System (ADS)

    Guinoiseau, Damien; Gélabert, Alexandre; Allard, Thierry; Louvat, Pascale; Moreira-Turcq, Patricia; Benedetti, Marc F.

    2017-09-01

    The complex behaviour of Zn and Cu at the soil-river interface was investigated in soil and riverine water samples from the Rio Negro basin, a secondary tributary of the Rio Amazonas, using their stable isotope compositions. This acidic and organic river drains two types of intensely weathered terrains: podzols in its upstream part, and lateritic soils downstream. Bulk soil particles, suspended particulate matter (SPM) as well as colloidal fractions were sampled across the whole basin during low and high water stages. In the basin, Zn and Cu are mostly exported from lateritic soils and transported by organic colloids where significant losses are observed in the downstream part of the river. The use of δ66Zn and δ65Cu measurements reveals distinct stories for these two metals in suspended sediments and colloids. In the colloids, the constant δ66Zncoll across the basin is induced by the same weak association mode between Zn and organic ligands, regardless of the origin of the water. By contrast, in SPM, the speciation of Zn and thus δ66ZnSPM differ according to the type of drained soils. Zn is associated with organic complexes in particles exported with water draining podzol whereas Zn2+ is incorporated in the structure of the remaining kaolinite clays in lateritic output. The stronger reactivity of Cu than Zn with organic ligands induces its complete complexation. Copper is controlled by refractory particulate organic matter (POM) and by reactive colloidal organic matter; the latter being enriched in 65Cu due to stronger binding interactions than in POM. While the Cu content remains constant in the upstream part of the Rio Negro, downstream, the decrease of SPM and colloidal Cu fluxes is associated with a constant δ65CuSPM and with an increase of δ65Cucoll at the Rio Negro outlet. Geochemical mass balance modelling, based on SPM, Cu and Zn fluxes in SPM and their associated isotopic signatures, confirms distinct host phases for Zn and Cu, and identifies the

  19. Nanofibrillated Cellulose-Assisted Synthesis of Fiber-Like ZnO-ZnFe2O4 Composites with Enhanced Visible-Light-Driven Photocatalytic Activity

    NASA Astrophysics Data System (ADS)

    Cai, Aijun; Guo, Aiying; Du, Liqiang; Chang, Yongfang; Wang, Xiuping

    2018-05-01

    In this article, fiber-like ZnO-ZnFe2O4 composites are obtained by using nanofibrillated cellulose as a biotemplate. The as-prepared composites exhibit strong absorbance in the visible-light region. The ZnO-ZnFe2O4 composites exhibit a similar bandgap (1.88 eV) compared with the ZnFe2O4 (1.85 eV). The ZnO-ZnFe2O4 composites can be easily collected by an external magnet, which contributes to improving the utilization efficiency of the photocatalysts. The photocatalytic activity of the ZnO-ZnFe2O4 catalysts was evaluated by photodegrading rhodamine B (RhB) under visible-light irradiation. Compared with ZnO and ZnFe2O4, the ZnO-ZnFe2O4 catalysts show higher photocatalytic activity due to the efficient electron-hole separation.

  20. The ruthenium isotopic composition of the oceanic mantle

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

    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.

  1. Aerosol carbon isotope composition over Baltic Sea

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

    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 <1 µm during stormy weather when air mass trajectory prevailed from the western direction. These measurements revealed that simplified isotope mixing model can not be applied for the aerosol source apportionment (Masalaite et al., 2015) in the perturbed marine environment. Additionally, concentration of bacteria and fungi were measured in size segregated and PM10 aerosol fraction. We were able to relate aerosol source δ13C end members with the abundance of bacteria and fungi over Baltic Sea combining air mass trajectories, stable isotope data, fungi and bacteria concentrations. Ceburnis, D., Garbaras, A

  2. Iron isotope composition of depleted MORB

    NASA Astrophysics Data System (ADS)

    Labidi, J.; Sio, C. K. I.; Shahar, A.

    2015-12-01

    In terrestrial basalts, iron isotope ratios are observed to weakly fractionate as a function of olivine and pyroxene crystallization. However, a ~0.1‰ difference between chondrites and MORB had been reported (Dauphas et al. 2009, Teng et al. 2013 and ref. therein). This observation could illustrate an isotope fractionation occurring during partial melting, as a function of the Fe valence in melt versus crystals. Here, we present high-precision Fe isotopic data measured by MC-ICP-MS on well-characterized samples from the Pacific-Antarctic Ridge (PAR, n=9) and from the Garrett Transform Fault (n=8). These samples allow exploring the Fe isotope fractionation between melt and magnetite, and the role of partial melting on Fe isotope fractionation. Our average δ56Fe value is +0.095±0.013‰ (95% confidence, n=17), indistinguishable from a previous estimate of +0.105±0.006‰ (95% confidence, n=43, see ref. 2). Our δ56Fe values correlate weakly with MgO contents, and correlate positively with K/Ti ratios. PAC1 DR10 shows the largest Ti and Fe depletion after titanomagnetite fractionation, with a δ56Fe value of +0.076±0.036‰. This is ~0.05‰ below other samples at a given MgO. This may illustrate a significant Fe isotope fractionation between the melt and titanomagnetite, in agreement with experimental determination (Shahar et al. 2008). GN09-02, the most incompatible-element depleted sample, has a δ56Fe value of 0.037±0.020‰. This is the lowest high-precision δ56Fe value recorded for a MORB worldwide. This basalt displays an incompatible-element depletion consistent with re-melting beneath the transform fault of mantle source that was depleted during a first melting event, beneath the ridge axis (Wendt et al. 1999). The Fe isotope observation could indicate that its mantle source underwent 56Fe depletion after a first melting event. It could alternatively indicate a lower Fe isotope fractionation during re-melting, if the source was depleted of its Fe3

  3. Controls on the Transition Metal Isotopic Composition of Seawater: Diatom Culture Experiments

    NASA Astrophysics Data System (ADS)

    Vance, D.; Archer, C.; Kennaway, G.; Cox, E.; Statham, P. J.

    2004-12-01

    Many transition metals are essential micronutrients for marine phytoplankton. As a result the expectation is that biological processes play an important, perhaps a dominant, role in their marine isotope geochemistry. These observations raise the prospect of using isotope records to trace transition metal micronutrient usage in the past oceans, an issue that is of importance to the efficiency of the biological pump and atmospheric carbon dioxide. As such, the characterisation of trace metal isotopic fractionations associated with marine primary productivity are an important scientific goal. Here we report fractionations associated with Fe, Cu and Zn sequestration by diatoms, one of the main primary producers in the oceans. Axenic unialgal cultures of Thalassiosira weissflogii and Thalassiosira pseudonana were established in artificial seawater + F/2 medium at 18° C on a 16:8 light:dark cycle. The cultures were filtered to separate diatom material from residual media and analysed for Zn, Cu and Fe concentrations and isotope composition using techniques described elsewhere1,2. Aliquots of the starting medium were also measured for each batch of cultures. The diatom organic material shows small, but consistent and resolvable, positive fractionations (0.1-0.3 per mil) for Fe, Cu and Zn relative to the starting medium. In the case of all three metals, but particularly for Zn (70-95% depending on experiment size), the diatoms had sequestered a large proportion of the available metal, suggesting that the fractionation factor for metal usage by the diatoms is much greater than 1.0001 to 1.0003. Time-series experiments are under way to determine the exact magnitude of the fractionation factor. The mass-balance is supported by the fact that the residual medium is around -0.4 per mil for Zn. The fact that diatoms incorporate trace metals that are isotopically heavier than the nutrient pool is a surprising result, the expectation having been that, as with carbon, the

  4. The Effects of Core Composition on Iron Isotope Fractionation During Planetary Differentiation

    NASA Astrophysics Data System (ADS)

    Elardo, S. M.; Shahar, A.; Caracas, R.; Mock, T. D.; Sio, C. K. I.

    2018-05-01

    High pressure and temperature isotope exchange experiments and density functional theory calculations show how the composition of planetary cores affects the fractionation of iron isotopes during planetary differentiation.

  5. Isotopic compositions of cometary matter returned by Stardust.

    PubMed

    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

    2006-12-15

    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.

  6. Verification of the isotopic composition of precipitation simulated by a regional isotope circulation model over Japan.

    PubMed

    Tanoue, Masahiro; Ichiyanagi, Kimpei; Yoshimura, Kei

    2016-01-01

    The isotopic composition (δ(18)O and δ(2)H) of precipitation simulated by a regional isotope circulation model with a horizontal resolution of 10, 30 and 50 km was compared with observations at 56 sites over Japan in 2013. All simulations produced reasonable spatio-temporal variations in δ(18)O in precipitation over Japan, except in January. In January, simulated δ(18)O values in precipitation were higher than observed values on the Pacific side of Japan, especially during an explosively developing extratropical cyclone event. This caused a parameterisation of precipitation formulation about the large fraction of precipitated water to liquid detrained water in the lower troposphere. As a result, most water vapour that transported from the Sea of Japan precipitated on the Sea of Japan side. The isotopic composition of precipitation was a useful verification tool for the parameterisation of precipitation formulation as well as large-scale moisture transport processes in the regional isotope circulation model.

  7. Magnesium isotope evidence that accretional vapour loss shapes planetary compositions

    PubMed Central

    Hin, Remco C.; Coath, Christopher D.; Carter, Philip J.; Nimmo, Francis; Lai, Yi-Jen; Pogge von Strandmann, Philip A.E.; Willbold, Matthias; Leinhardt, Zoë M.; Walter, Michael J.; Elliott, Tim

    2017-01-01

    It has long been recognised that Earth and other differentiated planetary bodies are chemically fractionated compared to primitive, chondritic meteorites and by inference the primordial disk from which they formed. An important question has been whether the notable volatile depletions of planetary bodies are a consequence of accretion1, or inherited from prior nebular fractionation2. The isotopic compositions of the main constituents of planetary bodies can contribute to this debate3–6. Using a new analytical approach to address key issues of accuracy inherent in conventional methods, we show that all differentiated bodies have isotopically heavier magnesium compositions than chondritic meteorites. We argue that possible magnesium isotope fractionation during condensation of the solar nebula, core formation and silicate differentiation cannot explain these observations. However, isotopic fractionation between liquid and vapour followed by vapour escape during accretionary growth of planetesimals generates appropriate residual compositions. Our modelling implies that the isotopic compositions of Mg, Si and Fe and the relative abundances of the major elements of Earth, and other planetary bodies, are a natural consequence of substantial (~40% by mass) vapour loss from growing planetesimals by this mechanism. PMID:28959965

  8. Calcium Isotopic Compositions of Forearc Sediments from DSDP Site 144

    NASA Astrophysics Data System (ADS)

    Zhang, Z.; Zhu, H.; Nan, X.; Li, X.; Huang, F.

    2016-12-01

    It is important to investigate calcium isotopic compositions of reservoirs of the Earth for better application of Ca isotopes into studies of a variety of geochemical problems. Because Ca isotopic compositions for igneous rocks and carbonates are increasingly reported, this maybe bring new requirements on carefully understanding the isotopic compositions of subducted marine sediments. Marine sediments mainly contains carbonates and clays, controlling the compositions of slab-derived materials which are added to the mantle wedge. Obviously, it could have different elemental and calcium isotopic compositions with marine carbonate. Thus, it could also put biases on calcium isotopic signatures of basalts resulted from recycling oceanic carbonate into the mantle. Here, we report calcium isotopic compositions of 17 sediment samples from Deep Sea Drilling Project (DSDP) site 144 (09°27.23' N, 54°20.52' W) which is located about 400 km north of Surinam on the northern flank of the Demerara Rise with a water depth of 2957 meters. These samples have CaO contents ranging from 14.56 wt.% to 41.46 wt.% with an average of 29.61 ± 18.21 (2SD), δ44/40Ca ranges from 0.19 to 0.58 (relative to SRM915a) with an average of 0.40 ± 0.22 (2SD). These carbonate-rich sediments can be used to represent an endmember with high CaO content and low δ44/40Ca, which could modify chemical composition of the upper mantle and subduction zone lavas if they are recycled to the convective mantle during subduction. The positive linear correlation between CaO and δ44/40Ca in the sediments cannot be explained by a simple mixing between marine carbonate and clay. Instead, δ44/40Ca of these samples roughly increase from the Upper Cretaceous to the Early Oligocene, which might reflect the evolution of calcium isotopic compositions of seawater through time.

  9. Chemical and isotopic compositions in acid residues from various meteorites

    NASA Technical Reports Server (NTRS)

    Kano, N.; Yamakoshi, K.; Matsuzaki, H.; Nogami, K.

    1993-01-01

    We are planning to carry out systematic isotopic investigations of Ru, Mg, etc., in primordial samples. The investigations will be pursued in the context of a study of the pre-history of the solar system. It is hoped that the study will yield direct evidence for processes of nucleosynthesis in the pre-solar stage and detection of extinct radioactive nuclides. In this paper, we present the results of chemical compositions of acid residues obtained from three types of meteorites: Canyon Diablo (IA), Allende (CV3), and Nuevo Mercuro (H5); and the preliminary results of Ru isotopic compositions.

  10. Carbon isotopic composition of individual Precambrian microfossils

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

    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.

  11. Stable isotopic compositions in Australian precipitation

    NASA Astrophysics Data System (ADS)

    Liu, Jianrong; Fu, Guobin; Song, Xianfang; Charles, Stephen P.; Zhang, Yinghua; Han, Dongmei; Wang, Shiqin

    2010-12-01

    Stable deuterium (δD) and oxygen-18 (δ18O) isotopes in 1962 to 2002 precipitation from the seven Australian stations of the Global Network of Isotopes in Precipitation (GNIP) were used to investigate isotope characteristics including temporal and spatial distributions across different regions of Australia. On the basis of 1534 samples, the local meteoric water line (LMWL) was established as δD = 7.10δ18O + 8.21. δ18O showed a depletion trend from north and south to central Australia (a continental effect) and from west to east. Precipitation amount effects were generally greater than temperature effects, with quadratic or logarithmic correlations describing δ/T and δ/P better than linear relationships. Nonlinear stepwise regression was used to determine the significant meteorological control factors for each station, explaining about 50% or more of the δ18O variations. Geographical control factors for δ18O were given by the relationship δ18O (‰) = -0.005 longitude (°) - 0.034 latitude (°)-0.003 altitude (m) - 4.753. Four different types of d-excess patterns demonstrated particular precipitation formation conditions for four major seasonal rainfall zones. Finally, wavelet coherence (WTC) between δ18O and SOI confirmed that the influence of ENSO decreased from east and north to west Australia.

  12. A Novel Ionic Polymer Metal ZnO Composite (IPMZC)

    PubMed Central

    Kim, Sang-Mun; Tiwari, Rashi; Kim, Kwang J.

    2011-01-01

    The presented research introduces a new Ionic Polymer-Metal-ZnO Composite (IPMZC) demonstrating photoluminescence (PL)-quenching on mechanical bending or application of an electric field. The newly fabricated IPMZC integrates the optical properties of ZnO and the electroactive nature of Ionic Polymer Metal Composites (IPMC) to enable a non-contact read-out of IPMC response. The electro-mechano-optical response of the IPMZC was measured by observing the PL spectra under mechanical bending and electrical regimes. The working range was measured to be 375–475 nm. It was noted that the PL-quenching increased proportionally with the increase in curvature and applied field at 384 and 468 nm. The maximum quenching of 53.4% was achieved with the membrane curvature of 78.74/m and 3.01% when electric field (12.5 × 103 V/m) is applied. Coating IPMC with crystalline ZnO was observed to improve IPMC transduction. PMID:22163869

  13. Stable isotope composition of cocoa beans of different geographical origin.

    PubMed

    Perini, Matteo; Bontempo, Luana; Ziller, Luca; Barbero, Alice; Caligiani, Augusta; Camin, Federica

    2016-09-01

    The isotopic profile (δ(13) C, δ(15) N, δ(18) O, δ(2) H, δ(34) S) was used to characterise a wide selection of cocoa beans from different renowned production areas (Africa, Asia, Central and South America). The factors most influencing the isotopic signatures of cocoa beans were climate and altitude for δ(13) C and the isotopic composition of precipitation water for δ(18) O and δ(2) H, whereas δ(15) N and δ(34) S were primarily affected by geology and fertilisation practises. Multi-isotopic analysis was shown to be sufficiently effective in determining the geographical origin of cocoa beans, and combining it with Canonical Discriminant Analysis led to more than 80% of samples being correctly reclassified. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  14. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    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.

  15. Converting isotope ratios to diet composition - the use of mixing models - June 2010

    EPA Science Inventory

    One application of stable isotope analysis is to reconstruct diet composition based on isotopic mass balance. The isotopic value of a consumer’s tissue reflects the isotopic values of its food sources proportional to their dietary contributions. Isotopic mixing models are used ...

  16. H-Isotopic Composition of Apatite in Northwest Africa 7034

    NASA Technical Reports Server (NTRS)

    McCubbin, F. M.; Barnes, J. J.; Santos, A. R.; Boyce, J. W.; Anand, M.; Franchi, I. A.; Agee, C. B.

    2016-01-01

    Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to estimates of Mars' bulk crust composition [1]. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the crustal composition of components that cannot be measured directly by remote sensing. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034.

  17. Fe Isotope Composition of Neoproterozoic Post-Glacial "Cap Dolostones"

    NASA Astrophysics Data System (ADS)

    Halverson, G. P.

    2005-12-01

    The largest variations in the Fe isotope composition in the geological record are found in sedimentary rocks, presumably as the result of redox transformations of iron during mineral precipitation, microbial processing, and diagenesis (Johnson et al., Cont. Min. Petrol., 2003). Systematic trends in the variability of the Fe isotope composition of sulfide minerals formed in ancient marine black shales broadly mirror patterns in sulfur isotope data (Δ33S, Δ34S), which are consistent with geological and other geochemical evidence for the progressive oxidation of the earth's surface during the Precambrian (Rouxel et al., Science, 2005). Therefore, the record of the Fe isotope composition of minerals formed in the marine environment appears to be a promising proxy for the redox evolution of the ocean. We have developed a method to extract the marine Fe isotope composition from carbonates in an attempt to establish higher resolution records of changes in marine redox changes than permitted by black shale geochemistry. We have applied this method to the study of ca. 635 Ma iron-rich dolostones, which are found in Neoproterozoic successions worldwide and immediately post-date a purported snowball (Marinoan) glaciation during which time the deep ocean is thought to have become anoxic (Hoffman et al., Science, 1998), allowing its Fe isotopic composition to evolve towards the composition of relatively light (δ57Fe vs. IRMM-14 ~ -0.6‰) hydrothermal iron (Beard et al., Geology, 2003). Fe isotope compositions were measured relative to IRMM-14 in medium-resolution mode on a Neptune MC-ICP-MS with a long-term external (2σ) reproducibility of < 0.04‰/amu. Preliminary data on dolomite samples from Svalbard, northern Namibia and northwest Canada show a range in δ57Fe values from -0.65 to 0.04‰, similar to the range found in siderite and Fe-rich dolomite in ancient BIFs (Johsnon et al., 2003) and to values for the Namibian cap dolostone reported by Leighton et al

  18. Magnesium Isotopic Composition of Kamchatka Sub-Arc Mantle Peridotites

    NASA Astrophysics Data System (ADS)

    Hu, Y.; Teng, F. Z.; Ionov, D. A.

    2016-12-01

    Subduction of the oceanic slab may add a crustal isotopic signal to the mantle wedge. The highly variable Mg isotopic compositions (δ26Mg) of the subducted oceanic crust input[1] and arc lava output[2] imply a distinctive Mg isotopic signature of the mantle wedge. Magnesium isotopic data on samples from the sub-arc mantle are still limited, however. To characterize the Mg isotopic composition of typical sub-arc mantle, 17 large and fresh spinel harzburgite xenoliths from Avacha volcano were analyzed. The harzburgites were formed by 30% melt extraction at ≤ 1 2 GPa and fluid fluxing condition, and underwent possible fluid metasomatism as suggested by distinctively high orthopyroxene mode in some samples, the presence of accessory amphibole and highly variable Ba/La ratios[3]. However, their δ26Mg values display limited variation from -0.32 to -0.21, which are comparable to the mantle average at -0.25 ± 0.07[4]. The overall mantle-like and homogenous δ26Mg of Avacha sub-arc peridotites are consistent with their similar chemical compositions and high MgO contents (> 44 wt%) relative to likely crustal fluids. Furthermore, clinopyroxene (-0.24 ± 0.10, 2SD, n = 5), a late-stage mineral exsolved from high-temperature, Ca-rich residual orthopyroxene, is in broad Mg isotopic equilibrium with olivine (-0.27 ± 0.04, 2SD, n = 17) and orthopyroxene (-0.22 ± 0.06, 2SD, n = 17). Collectively, this study finds that the Kamchatka mantle wedge, as represented by the Avacha peridotites, has a mantle-like δ26Mg, and low-degree fluid-mantle interaction does not cause significant Mg isotope fractionation in sub-arc mantle peridotites. [1] Wang et al., EPSL, 2012 [2] Teng et al., PNAS, 2016 [3] Ionov, J. Petrol., 2010, [4] Teng et al., GCA, 2010.

  19. Tin isotope fractionation during magmatic processes and the isotope composition of the bulk silicate Earth

    NASA Astrophysics Data System (ADS)

    Wang, Xueying; Amet, Quentin; Fitoussi, Caroline; Bourdon, Bernard

    2018-05-01

    Tin is a moderately volatile element whose isotope composition can be used to investigate Earth and planet differentiation and the early history of the Solar System. Although the Sn stable isotope composition of several geological and archaeological samples has been reported, there is currently scarce information about the effect of igneous processes on Sn isotopes. In this study, high-precision Sn isotope measurements of peridotites and basalts were obtained by MC-ICP-MS with a double-spike technique. The basalt samples display small variations in δ124/116Sn ranging from -0.01 ± 0.11 to 0.27 ± 0.11‰ (2 s.d.) relative to NIST SRM 3161a standard solution, while peridotites have more dispersed and more negative δ124Sn values ranging from -1.04 ± 0.11 to -0.07 ± 0.11‰ (2 s.d.). Overall, basalts are enriched in heavy Sn isotopes relative to peridotites. In addition, δ124Sn in peridotites become more negative with increasing degrees of melt depletion. These results can be explained by different partitioning behavior of Sn4+ and Sn2+ during partial melting. Sn4+ is overall more incompatible than Sn2+ during partial melting, resulting in Sn4+-rich silicate melt and Sn2+-rich residue. As Sn4+ has been shown experimentally to be enriched in heavy isotopes relative to Sn2+, the effect of melting is to enrich residual peridotites in relatively more compatible Sn2+, which results in isotopically lighter peridotites and isotopically heavier mantle-derived melts. This picture can be disturbed partly by the effect of refertilization. Similarly, the presence of enriched components such as recycled oceanic crust or sediments could explain part of the variations in Sn isotopes in oceanic basalts. The most primitive peridotite analyzed in this study was used for estimating the Sn isotope composition of the BSE, with δ124Sn = -0.08 ± 0.11‰ (2 s.d.) relative to the Sn NIST SRM 3161a standard solution. Altogether, this suggests that Sn isotopes may be a powerful probe of

  20. The Chlorine Isotope Composition of Earth’s Mantle

    NASA Astrophysics Data System (ADS)

    Bonifacie, M.; Jendrzejewski, N.; Agrinier, P.; Humler, E.; Coleman, M.; Javoy, M.

    2008-03-01

    Chlorine stable isotope compositions (δ37Cl) of 22 mid-ocean ridge basalts (MORBs) correlate with Cl content. The high-δ37Cl, Cl-rich basalts are highly contaminated by Cl-rich materials (seawater, brines, or altered rocks). The low-δ37Cl, Cl-poor basalts approach the composition of uncontaminated, mantle-derived magmas. Thus, most or all oceanic lavas are contaminated to some extent during their emplacement. MORB-source mantle has δ37Cl ≤ 1.6 per mil (‰), which is significantly lower than that of surface reservoirs (~ 0‰). This isotopic difference between the surface and deep Earth results from net Cl isotopic fractionation (associated with removal of Cl from the mantle and its return by subduction over Earth history) and/or the addition (to external reservoirs) of a late volatile supply that is 37Cl-enriched.

  1. Structural, Optical, and Photocatalytic Properties of Quasi-One-Dimensional Nanocrystalline ZnO, ZnOC:nC Composites, and C-doped ZnO

    NASA Astrophysics Data System (ADS)

    Shalaeva, E. V.; Gyrdasova, O. I.; Krasilnikov, V. N.; Melkozerova, M. A.; Baklanova, I. V.; Buldakova, L. Yu.

    Various thermolysis rotes of zinc glicolate complexes are considered for the synthesis of quasi-one-dimensional nanostructured aggregates ZnO and Zn-O-C used as photocatalysts. Structural features of quasi-one-dimensional aggregates Zn-O-C and ZnO are investigated in detail. Transmission electron microscopy, Raman spectroscopy, and electron paramagnetic resonance spectroscopy methods demonstrate that the aggregates Zn-O-C have either composite structure (ZnO crystallites in amorphous carbon matrix) or a C-doped ZnO single-phase structure depending on heat treatment conditions, and that all the aggregates exhibit as a rule a tubular morphology, a nanocrystalline structure with a high specific surface area, and a high concentration of singly charged oxygen vacancies. The mechanism of the nanocrystalline structure formation is discussed and the effect of thermolysis condition on the formation of the textured structure of aggregates is investigated. The results of examination of the photocatalytic and optical absorption properties of the synthesized aggregates are presented. The photocatalytic activity for the hydroquinone oxidation reaction under ultraviolet and visible light increases in the series: the reference ZnO powder, quasi-one-dimensional ZnO, quasi-one-dimensional aggregates C-doped ZnO, and this tendency correlates with the reduction of the optical gap width. As a result of our studies, we have arrived at an important conclusion that thermal treatment of ZnO:nC composites allows a C-doped ZnO with high catalytic activity. This increasing photoactivity of C-doped ZnO aggregates is attributed to the optimal specific surface area and electron-energy spectrum restructuring to be produced owing to the presence of singly charged oxygen vacancies and carbon dissolved in the ZnO lattice.

  2. Magnesium Isotopic Compositions of Continental Basalts From Various Tectonic Settings

    NASA Astrophysics Data System (ADS)

    Yang, W.; Li, S.; Tian, H.; Ke, S.

    2016-12-01

    Recycled sedimentary carbonate through subduction is the main light Mg isotopic reservoir in Earth's deep interior, thus Mg isotopic variation of mantle-derived melts provides a fresh perspective on investigating deep carbon cycling. Here we investigate Mg isotopic compositions of continental basalts from various tectonic settings: (1) The Cenozoic basalts from eastern China, coinciding with the stagnant Pacific slab in the mantle transition zone revealed by seismic tomography; (2) The Cenozoic basalts from Tengchong area, southwestern China, which comprises a crucial part of the collision zone between the Indian and Eurasian plates; (3) The Permian basalts from Emeishan large igneous province, related to a mantle plume. The Cenozoic basalts from both eastern China and Tengchong area exhibit light Mg isotopic compositions (δ26Mg = -0.60 to -0.30‰ and -0.51 to -0.33‰), suggesting recycled sedimentary carbonates in their mantle sources. This is supported by their low Fe/Mn, high CaO/Al2O3, low Hf/Hf* and low Ti/Ti* ratios, which are typical features of carbonated peridotite-derived melt. The Tengchong basalts also show high 87Sr/86Sr, high radiogenic Pb and upper crustal-like trace element pattern, indicating contribution of recycled continental crustal materials. By contrast, all Emeishan basalts display a mantle-like Mg isotopic composition, with δ26Mg ranging from -0.35 to -0.19‰. Since the Emeishan basalts derived from a mantle plume, their mantle-like Mg isotopic composition may indicate limited sedimentary carbonated recycled into the lower mantle. This is consistent with a recent experimental study which concluded that direct recycling of carbon into the lower mantle may have been highly restricted throughout most of the Earth's history.

  3. Mechanisms controlling the silicon isotopic compositions of river waters

    NASA Astrophysics Data System (ADS)

    Georg, R. B.; Reynolds, B. C.; Frank, M.; Halliday, A. N.

    2006-09-01

    It has been proposed that silicon (Si) isotopes are fractionated during weathering and biological activity leading to heavy dissolved riverine compositions. In this study, the first seasonal variations of stable isotope compositions of dissolved riverine Si are reported and compared with concomitant changes in water chemistry. Four different rivers in Switzerland were sampled between March 2004 and July 2005. The unique high-resolution multi-collector ICP-MS Nu1700, has been used to provide simultaneous interference-free measurements of 28Si, 29Si and 30Si abundances with an average limiting precision of ± 0.04‰ on δ 30Si. This precision facilitates the clarification of small temporal variations in isotope composition. The average of all the data for the 40 samples is δ 30Si = + 0.84 ± 0.19‰ (± 1σ SD). Despite significant differences in catchment lithologies, biomass, climate, total dissolved solids and weathering fluxes the averaged isotopic composition of dissolved Si in each river is strikingly similar with means of + 0.70 ± 0.12‰ for the Birs,+ 0.95 ± 0.22‰ for the Saane,+ 0.93 ± 0.12‰ for the Ticino and + 0.79 ± 0.19‰ for the Verzasca. However, the δ 30Si undergoes seasonal variations of up to 0.6‰. Comparisons between δ 30Si and physico-chemical parameters, such as the concentration of dissolved Si and other cations, the discharge of the rivers, and the resulting weathering fluxes, permits an understanding of the processes that control the Si budget and the fate of dissolved Si within these rivers. The main mechanism controlling the Si isotope composition of the mountainous Verzasca River appears to be a two component mixing between the seepage of soil/ground waters, with heavier Si produced by clay formation and superficial runoff associated with lighter Si during high discharge events. A biologically-mediated fractionation can be excluded in this particular river system. The other rivers display increasing complexity with increases

  4. What is the iron isotope composition of the Moon?

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    It is difficult to estimate the bulk chemical and isotopic composition of the Moon because of severe limitations in our sampling. As a result, there is currently a debate on the bulk Fe isotope composition of the Moon despite the constraints on the lunar accretion modes or differentiation processes it may provide. For this, a proper mass balance estimation of essential planetary reservoirs is required. For instance, the dichotomy in δ57Fe between low- and high-Ti mare basalt varieties as a consequence of differences in degree of fractional crystallization of their respective lunar mantle sources should be rigorously tested. To investigate this, we performed new iron isotope measurements of 33 bulk lunar mare basalts and highland rocks, including KREEP-related materials. The new data show significant Fe isotope differences between high-Ti and low-Ti mare basalts, yielding mean δ57FeIRMM-014=0.277±0.020‰ and δ57FeIRMM-014=0.127±0.020‰, respectively. Assuming that lunar basalts mirror the iron isotope composition of their respective mantle protoliths, the estimated relative proportion of the low-Ti and high-Ti mantle source suggests that the lunar upper mantle should be close to δ57Fe=0.14±0.03‰. At present, it is unclear whether the bulk lunar Fe isotope composition is indistinguishable from that of the Earth (δ57FeIRMM-014=0.10±0.03‰), when estimated solely from mare basalts data, or if it is twice as heavy relative to chondrites, as initially proposed. A large scatter at δ57Fe=0.08±0.19‰ for ferroan anorthosites, Mg-suite rocks and a KREEP basalt imparts more complexities for global isotopic view of the Moon. A better understanding of the cause of Fe isotope heterogeneity among the lunar highland rocks will likely allow to better estimate the bulk Moon composition, and possibly to improve our knowledge about the genesis of the lunar crust itself.

  5. Nano ZnO-activated carbon composite electrodes for supercapacitors

    NASA Astrophysics Data System (ADS)

    Selvakumar, M.; Krishna Bhat, D.; Manish Aggarwal, A.; Prahladh Iyer, S.; Sravani, G.

    2010-05-01

    A symmetrical (p/p) supercapacitor has been fabricated by making use of nanostructured zinc oxide (ZnO)-activated carbon (AC) composite electrodes for the first time. The composites have been characterized by field emission scanning electron microscopy (FESEM) and X-ray diffraction analysis (XRD). Electrochemical properties of the prepared nanocomposite electrodes and the supercapacitor have been studied using cyclic voltammetry (CV) and AC impedance spectroscopy in 0.1 M Na 2SO 4 as electrolyte. The ZnO-AC nanocomposite electrode showed a specific capacitance of 160 F/g for 1:1 composition. The specific capacitance of the electrodes decreased with increase in zinc oxide content. Galvanostatic charge-discharge measurements have been done at various current densities, namely 2, 4, 6 and 7 mA/cm 2. It has been found that the cells have excellent electrochemical reversibility and capacitive characteristics in 0.1 M Na 2SO 4 electrolyte. It has also been observed that the specific capacitance is constant up to 500 cycles at all current densities.

  6. Inelastic scattering of neutron-rich Ni and Zn isotopes off a proton target

    NASA Astrophysics Data System (ADS)

    Cortés, M. L.; Doornenbal, P.; Dupuis, M.; Lenzi, S. M.; Nowacki, F.; Obertelli, A.; Péru, S.; Pietralla, N.; Werner, V.; Wimmer, K.; Authelet, G.; Baba, H.; Calvet, D.; Château, F.; Corsi, A.; Delbart, A.; Gheller, J.-M.; Gillibert, A.; Isobe, T.; Lapoux, V.; Louchart, C.; Matsushita, M.; Momiyama, S.; Motobayashi, T.; Niikura, M.; Otsu, H.; Péron, C.; Peyaud, A.; Pollacco, E. C.; Roussé, J.-Y.; Sakurai, H.; Santamaria, C.; Sasano, M.; Shiga, Y.; Takeuchi, S.; Taniuchi, R.; Uesaka, T.; Wang, H.; Yoneda, K.; Browne, F.; Chung, L. X.; Dombradi, Zs.; Franchoo, S.; Giacoppo, F.; Gottardo, A.; Hadynska-Klek, K.; Korkulu, Z.; Koyama, S.; Kubota, Y.; Lee, J.; Lettmann, M.; Lozeva, R.; Matsui, K.; Miyazaki, T.; Nishimura, S.; Olivier, L.; Ota, S.; Patel, Z.; Sahin, E.; Shand, C. M.; Söderström, P.-A.; Stefan, I.; Steppenbeck, D.; Sumikama, T.; Suzuki, D.; Vajta, Zs.; Wu, J.; Xu, Z.

    2018-04-01

    Proton inelastic scattering of Ni,7472 and Zn,8076 ions at energies around 235 MeV/nucleon was performed at the Radioactive Isotope Beam Factory and studied using γ -ray spectroscopy. Angular integrated cross sections for direct inelastic scattering to the 21+ and 41+ states were measured. The Jeukenne-Lejeune-Mahaux folding model, extended beyond 200 MeV, was used together with neutron and proton densities stemming from quasiparticle random-phase approximation (QRPA) calculations to interpret the experimental cross sections and to infer neutron to proton matrix element ratios. In addition, coupled-channels calculations with a phenomenological potential were used to determine deformation lengths. For the Ni isotopes, correlations favor neutron excitations, thus conserving the Z =28 gap. A dominance of proton excitation, on the other hand, is observed in the Zn isotopes, pointing to the conservation of the N =50 gap approaching 78Ni. These results are in agreement with QRPA and large-scale shell-model calculations.

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

    PubMed Central

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

    2012-01-01

    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 CH4 and CO2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth. PMID:22392985

  8. Isotope composition and volume of Earth's early oceans.

    PubMed

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

    2012-03-20

    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.

  9. Size effect of ZnO nanorods on physicochemical properties of plasticized starch composites.

    PubMed

    Guz, L; Famá, L; Candal, R; Goyanes, S

    2017-02-10

    This work demonstrates that the size of ZnO nanorods (ZnONR) with similar aspect ratio determines several physicochemical and microbiological properties of thermoplastic starch composites (TPS/ZnONR) at a given concentration of ZnONRs. A combination of sol-gel and hydrothermal methods was developed to synthesize ZnONR with different sizes but similar aspect ratios. Starch composites containing 1wt.% of ZnONR were prepared by casting. Composites with smaller size nanorods (ZnONR-S) showed more efficiency in shielding UVA radiation and had a higher solubility and water vapor permeability than those with larger nanorods (ZnONR-L). Mechanical properties, biodegradability and antibacterial activity were also influenced by the size of the ZnONR. X-ray diffraction analysis showed that composites with ZnONR-S maintained the typical B-V type starch structure, intensifying the V-type starch structure peaks, while composite with ZnONR-L induced the formation of an amorphous structure, preventing starch retrogradation during storage. Properties affected by nanorods size are fundamental in determining composite applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. The Chlorine Isotopic Composition Of Lunar UrKREEP

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-01-01

    Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

  11. Isotopic composition of hydrogen in insoluble organic matter from cherts

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.

    1991-01-01

    Robert (1989) reported the presence of unusually enriched hydrogen in the insoluble HF-HCl residue extracted from two chert samples of Eocene and Pliocene ages. Since the presence of heavy hydrogen might be due to the incorporation of extraterrestrial materials, we desired to reexamine the same samples to isolate the D-rich components. Our experiments did not reveal any D-rich components, but the hydrogen isotope composition of the insoluble residue of the two chert samples was well within the range expected for terrestrial organic matter. We also describe a protocol that needs to be followed in the hydrogen isotope analysis of any insoluble organic matter.

  12. Single-neutron orbits near 78Ni: Spectroscopy of the N = 49 isotope 79Zn

    DOE PAGES

    Orlandi, R.; Mücher, D.; Raabe, R.; ...

    2014-12-09

    Single-neutron states in the Z=30, N=49 isotope 79Zn have been populated using the 78Zn(d, p) 79Zn transfer reaction at REX-ISOLDE, CERN. The experimental setup allowed the combined detection of protons ejected in the reaction, and of γ rays emitted by 79Zn. The analysis reveals that the lowest excited states populated in the reaction lie at approximately 1 MeV of excitation, and involve neutron orbits above the N=50 shell gap. From the analysis of γ -ray data and of proton angular distributions, characteristic of the amount of angular momentum transferred, a 5/2 + configuration was assigned to a state at 983more » keV. Comparison with large-scale-shell-model calculations supports a robust neutron N=50 shell-closure for 78Ni. Finally, these data constitute an important step towards the understanding of the magicity of 78Ni and of the structure of nuclei in the region.« less

  13. The Chlorine Isotopic Composition Of Lunar UrKREEP

    NASA Technical Reports Server (NTRS)

    Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

    2016-01-01

    Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. Numerous studies have examined the abundances and isotopic compositions of volatiles in lunar apatite, Ca5(PO4)3(F,Cl,OH). In particular, apatite has been used as a tool for assessing the sources of H2O in the lunar interior. However, current models for the Moon's formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. For ex-ample, in the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs (Rare Earth Elements), and P, collectively called KREEP, and in its primitive form - urKREEP, given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon (BSM). In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes in lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

  14. C-isotope composition of fossil sedges and grasses

    NASA Astrophysics Data System (ADS)

    Kurschner, Wolfram M.

    2010-05-01

    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.

  15. Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

    SciTech Connect

    Mathavan, T., E-mail: tjmathavan@gmail.com; Divya, A.; Benial, A. Milton Franklin

    2016-05-23

    Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

  16. Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

    NASA Astrophysics Data System (ADS)

    Mathavan, T.; Divya, A.; Archana, J.; Ramasubbu, A.; Benial, A. Milton Franklin; Jothirajan, M. A.

    2016-05-01

    Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

  17. Two-proton transfer reactions on even Ni and Zn isotopes

    SciTech Connect

    Boucenna, A.; Kraus, L.; Linck, I.

    New levels strongly excited by 112-MeV {sup 12}C ions on even Ni and Zn isotopes are {ital J}{sup {pi}} assigned on kinematical and geometrical arguments, crude shell-model calculations, and distorted-wave Born approximation angular-distribution analysis. These tentative assignments are supported by the Bansal-French model. Because of the contribution of additional collective effects, the two-proton transfer reaction spectra are less selectively fed than those obtained with the analogous two-neutron transfer reactions induced on the same targets in a similar energy range.

  18. Two-proton transfer reactions on even Ni and Zn isotopes

    NASA Astrophysics Data System (ADS)

    Boucenna, A.; Kraus, L.; Linck, I.; Chan, Tsan Ung

    1990-10-01

    New levels strongly excited by 112-MeV 12C ions on even Ni and Zn isotopes are Jπ assigned on kinematical and geometrical arguments, crude shell-model calculations, and distorted-wave Born approximation angular-distribution analysis. These tentative assignments are supported by the Bansal-French model. Because of the contribution of additional collective effects, the two-proton transfer reaction spectra are less selectively fed than those obtained with the analogous two-neutron transfer reactions induced on the same targets in a similar energy range.

  19. Dolomite clumped isotope constraints on the oxygen isotope composition of the Phanerozoic Sea

    NASA Astrophysics Data System (ADS)

    Ryb, U.; Eiler, J. M.

    2017-12-01

    The δ18O value of the Phanerozoic Sea has been debated several decades, largely motivated by an 8‰ increase in δ18O of sedimentary carbonates between the Cambrian and the present. Some previous studies have interpreted this increase to be a primary depositional signal, resulting from an increase in the 18O content of ocean water over time, or from a decrease in ocean temperature increasing the oxygen isotope fractionation between seawater and carbonates. In contrast, other studies have interpreted lower δ18O compositions as the products of diagenetic alteration at elevated burial temperatures. Here, we show that the Phanerozoic dolomite δ18O record overlaps with that of well-preserved calcite fossils, and use carbonate clumped isotope measurements of Cambrian to Pleistocene dolomites to calculate their formation temperatures and the isotopic compositions of their parent-waters. The observed variation in dolomite δ18O is largely explained by dolomite formation at burial temperatures of up to 158°C. The δ18O values of dolomite parent-waters range -2 to +12‰ and are correlated with formation temperatures. Such correlation is consistent with the modification of seawater (0±2‰, VSMOW) toward isotopically heavier compositions through water-rock reactions at elevated burial temperatures. The similarity between the dolomite and calcite δ18O records, and published clumped isotope-based calculations of water compositions, suggests that like dolomite, temporal variations of the calcite δ18O record may also be largely driven by diagenetic alteration. Finally, the relationship we observe between temperature of dolomitization and d18O of dolomite suggests platform carbonates generally undergo dolomitization through reaction with modified marine waters, and that there is no evidence those waters were ever significantly lower in d18O than the modern ocean.

  20. Chemical and boron isotopic composition of tourmaline from the Mariinsky emerald deposit, Central Urals, Russia

    NASA Astrophysics Data System (ADS)

    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.

    2018-04-01

    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.

  1. Investigation of ZnO Nanowire Interfaces for Multi-Scale Composites

    DTIC Science & Technology

    2012-03-06

    growth of zinc oxide ( ZnO ) nanowires on the surface of the...through the growth of zinc oxide ( ZnO ) nanowires on the surface of the reinforcing fibers. The nanowires functionally grade the interface, improve bonding...bulk composite. This has been accomplished through the growth of zinc oxide ( ZnO ) nanowires on the surface of the reinforcing fibers. ZnO

  2. Pb isotope compositions of modern deep sea turbidites

    NASA Astrophysics Data System (ADS)

    Hemming, S. R.; McLennan, S. M.

    2001-01-01

    Modern deep sea turbidite muds and sands collected from Lamont piston cores represent a large range in age of detrital sources as well as a spectrum of tectonic settings. Pb isotope compositions of all but three of the 66 samples lie to the right of the 4.56 Ga Geochron, and most also lie along a slope consistent with a time-integrated κ ( 232Th/ 238U) between 3.8 and 4.2. Modern deep sea turbidites show a predictable negative correlation between both Pb and Sr isotope ratios and ɛNd and ɛHf, clearly related to the age of continental sources. However, the consistency between Pb and Nd isotopes breaks down for samples with very old provenance ( ɛNd<-20) that are far less radiogenic than predicted by the negative correlation. The correlations among Sr, Nd and Hf isotopes also become more scattered in samples with very old provenance. The unradiogenic Pb isotopic character of modern sediments with Archean Nd model ages is consistent with a model where Th and U abundances of the Archean upper crust are significantly lower than the post-Archean upper crust.

  3. The mercury isotope composition of Arctic coastal seawater

    NASA Astrophysics Data System (ADS)

    Štrok, Marko; Baya, Pascale Anabelle; Hintelmann, Holger

    2015-11-01

    For the first time, Hg isotope composition of seawater in the Canadian Arctic Archipelago is reported. Hg was pre-concentrated from large volumes of seawater sampling using anion exchange resins onboard the research vessel immediately after collection. Elution of Hg was performed in laboratory followed by isotope composition determination by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). For comparison, seawater from two stations was shipped to the laboratory and processed within it. Results showed negative mass-dependent fractionation in the range from -2.85 to -1.10‰ for δ202Hg, as well as slightly positive mass-independent fractionation of odd Hg isotopes. Positive mass-independent fractionation of 200Hg was also observed. Samples that were pre-concentrated in the laboratory showed different Hg isotope signatures and this is most probably due to the abiotic reduction of Hg in the dark by organic matter during storage and shipment after sampling. This emphasizes the need for immediate onboard pre-concentration.

  4. Pb isotopic constraints on the formation of the Dikulushi Cu-Pb-Zn-Ag mineralisation, Kundelungu Plateau (Democratic Republic of Congo)

    NASA Astrophysics Data System (ADS)

    Haest, Maarten; Schneider, Jens; Cloquet, Christophe; Latruwe, Kris; Vanhaecke, Frank; Muchez, Philippe

    2010-04-01

    Base metal-Ag mineralisation at Dikulushi and in other deposits on the Kundelungu Plateau (Democratic Republic of Congo) developed during two episodes. Subeconomic Cu-Pb-Zn-Fe polysulphide ores were generated during the Lufilian Orogeny (c. 520 Ma ago) in a set of E-W- and NE-SW-oriented faults. Their lead has a relatively unradiogenic and internally inhomogeneous isotopic composition (206Pb/204Pb = 18.07-18.49), most likely generated by mixing of Pb from isotopically heterogeneous clastic sources. These sulphides were remobilised and enriched after the Lufilian Orogeny, along reactivated and newly formed NE-SW-oriented faults into a chalcocite-dominated Cu-Ag mineralisation of high economic interest. The chalcocite samples contain only trace amounts of lead and show mostly radiogenic Pb isotope signatures that fall along a linear trend in the 207Pb/204Pb vs. 206Pb/204Pb diagram (206Pb/204Pb = 18.66-23.65; 207Pb/204Pb = 15.72-16.02). These anomalous characteristics reflect a two-stage evolution involving admixture of both radiogenic lead and uranium during a young fluid event possibly c. 100 Ma ago. The Pb isotope systematics of local host rocks to mineralisation also indicate some comparable young disturbance of their U-Th-Pb systems, related to the same event. They could have provided Pb with sufficiently radiogenic compositions that was added to less radiogenic Pb remobilised from precursor Cu-Pb-Zn-Fe polysulphides, whereas the U most likely originated from external sources. Local metal sources are also suggested by the 208Pb/204Pb-206Pb/204Pb systematics of combined ore and rock lead, which indicate a pronounced and diversified lithological control of the immediate host rocks on the chalcocite-dominated Cu-Ag ores. The Pb isotope systematics of polysulphide mineralisation on the Kundelungu Plateau clearly record a diachronous evolution.

  5. Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

    USGS Publications Warehouse

    Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.

    2008-01-01

    Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

  6. Fossil black smoker yields oxygen isotopic composition of Neoproterozoic seawater.

    PubMed

    Hodel, F; Macouin, M; Trindade, R I F; Triantafyllou, A; Ganne, J; Chavagnac, V; Berger, J; Rospabé, M; Destrigneville, C; Carlut, J; Ennih, N; Agrinier, P

    2018-04-13

    The evolution of the seawater oxygen isotopic composition (δ 18 O) through geological time remains controversial. Yet, the past δ 18 O seawater is key to assess past seawater temperatures, providing insights into past climate change and life evolution. Here we provide a new and unprecedentedly precise δ 18 O value of -1.33 ± 0.98‰ for the Neoproterozoic bottom seawater supporting a constant oxygen isotope composition through time. We demonstrate that the Aït Ahmane ultramafic unit of the ca. 760 Ma Bou Azzer ophiolite (Morocco) host a fossil black smoker-type hydrothermal system. In this system we analyzed an untapped archive for the ocean oxygen isotopic composition consisting in pure magnetite veins directly precipitated from a Neoproterozoic seawater-derived fluid. Our results suggest that, while δ 18 O seawater and submarine hydrothermal processes were likely similar to present day, Neoproterozoic oceans were 15-30 °C warmer on the eve of the Sturtian glaciation and the major life diversification that followed.

  7. Alkali elemental and potassium isotopic compositions of Semarkona chondrules

    USGS Publications Warehouse

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

    2005-01-01

    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.

  8. Nonstoichiometric Zn Ferrite and ZnFe2O4/Fe2O3 Composite Spheres: Preparation, Magnetic Properties, and Chromium Removal

    NASA Astrophysics Data System (ADS)

    Hang, Chun-Liang; Yang, Li-Xia; Sun, Chang-Mei; Liang, Ying

    2018-03-01

    Monodisperse and porous nonstoichiometric Zn ferrite can be prepared by a solvothermal method. Such non-Zn ferrite was used to be the precursor for synthesis of ZnFe2O4/Fe2O3 composite via calcination at 600°C for 3 h in air. X-ray powder diffractometer (XRD) and Energy Dispersive Spectrometer (EDS) proved the nonstoichiometry of Zn ferrite synthesized by solvothermal method and the formation of ZnFe2O4/Fe2O3 composite via calcination. TEM image showed that non-Zn ferrite spheres with wormlike nanopore structure were made of primary nanocrystals. BET surface area of non-Zn ferrite was much higher than that of ZnFe2O4/Fe2O3 composite. Saturation magnetization of non-Zn ferrites was significantly higher than that of ZnFe2O4/Fe2O3 composites. Calcination of non-Zn ferrite resulted in the formation of large amount of non-magnetic Fe2O3,which caused a low magnetization of composite. Because of higher BET surface area and higher saturation magnetization, non-Zn ferrite presented better Cr6+ adsorption property than ZnFe2O4/Fe2O3 composites.

  9. The vanadium isotope compositions of subduction zone lavas

    NASA Astrophysics Data System (ADS)

    Tian, S.; Huang, F.

    2017-12-01

    Vanadium is a redox sensitive element with multiple oxidation states, and thus it has the potential to trace redox-related processes. With the advancement of analytical method for V isotopes, we are now able to recognize V isotope fractionation for igneous rocks. Subduction zones are critical zones on the Earth for the interaction between crust and mantle where undergo complex geological processes. However, V isotope data of subduction zone lavas are still rare except those reported in [1]. To investigate the V isotope variations of subduction zones and discuss the potential to apply V to trace mantle redox state. In this contribution, we report δ51V for three subduction zone lavas from Kamchatka, Lesser Antilles, and Aleutians which are characterized by well-documented magmatic evolutionary series. 47 arc lava samples have been analyzed and the δ51V data of them range from -0.91‰ to -0.53‰ (2sd = 0.10 ‰). Among these samples, primitive arc basalts with MgO > 6 wt. % have an average δ51V of -0.80 ± 0.15‰ (2sd, n = 20), broadly consistent with δ51V data of MORB [2, 3]. Within the single arc of Kamchatka, δ51V data of primitive basalts from the arc front to the back-arc is almost constant, suggesting limited influences of mantle melting and source heterogeneity on V isotopes. δ51V data of these samples show no correlation with Ba/Nb, suggesting that fluids have little impact on V isotopes. On the other hand, δ51V data of the more involved samples with MgO < 6 wt. % are negatively correlated with MgO contents, indicating that the 50V preferentially enters crystalline minerals, which produces heavier V isotope compositions of residual melts. Distinct to the observation showing 2‰ fractionation reported in [1], the magnitude of V isotope fractionation in arc lavas is much smaller (0.38‰) in this study. Future works are needed for better understanding the V isotope fractionation mechanisms of subduction zone lavas. [1]Prytulak et al., 2017, Geochem

  10. NBL CRM 112-A: A new certified isotopic composition

    NASA Astrophysics Data System (ADS)

    Thomas, R. B.; Essex, R. M.; Mason, P.

    2007-12-01

    NBL CRM 112-A Uranium Metal Assay Standard is commonly used as a natural uranium isotopic reference material within the earth science mass spectrometry community. The metal is from the same parent material as NBS SRM 960, the uranyl nitrate solution, CRM 145, and the high-purity uranyl nitrate solution CRM 145-B. Because CRM 112-A has not yet been certified for isotopic composition, it has been assumed that this material has a natural 235U/238U (0.0072527), and the δ234U has been determined by measurement (e.g. -37.1‰; Cheng et al., 2000). These values have been widely used to calibrate the concentration of spikes and standards, and to correct measurements for instrument or mass bias. New, preliminary, isotopic measurements on CRM 145 and CRM 112-A performed at New Brunswick Laboratory suggest that these reference materials have a slightly lower 235U/238U and δ234U than have been commonly used. If this is the case, then data using the accepted values may be slightly biased. The significance of this bias will depend on the uncertainty of the measurement, how the CRM 112-A data is used to correct measurement data, the cited values that were used to correct the data, and the final certified values of the CRM. This fall, New Brunswick Laboratory is certifying the isotopic composition of the CRM 112-A metal using high precision thermal ionization mass spectrometry techniques. Upon completion of certification, the new CRM 112- A standard with certified isotopic ratios will provide the earth science community with a well characterized and traceable reference for calibrating and correcting their mass spectrometry measurement systems.

  11. Magnesium stable isotope composition of Earth's upper mantle

    NASA Astrophysics Data System (ADS)

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

    2009-05-01

    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

  12. Controls on the iron isotopic composition of global arc magmas

    NASA Astrophysics Data System (ADS)

    Foden, John; Sossi, Paolo A.; Nebel, Oliver

    2018-07-01

    We determined the iron isotope composition of 130 mafic lavas from 15 arcs worldwide with the hypothesis that the results would reflect the relatively high oxidation state of arc magmas. Although this expectation was not realized, this Fe isotope data set reveals important insights into the geodynamic controls and style of the melting regimes in the sub-arc mantle. Samples are from oceanic arcs from the circum-Pacific, the Indonesian Sunda-Banda islands, Scotia and the Lesser Antilles as well as from the eastern Pacific Cascades. Their mean δ57Fe value is +0.075 ± 0.05‰, significantly lighter than MORB (+0.15 ± 0.03‰). Western Pacific arcs extend to very light δ57Fe (Kamchatka = -0.11 ± 0.04‰). This is contrary to expectation, because Fe isotope fractionation factors (Sossi et al., 2016, 2012) and the incompatibility of ferric versus ferrous iron during mantle melting, predict that melts of more oxidized sources will be enriched in heavy Fe isotopes. Subducted oxidation capacity flux may correlate with hydrous fluid release from the slab. If so, a positive correlation between each arc's thermal parameter (ϕ) and δ57Fe is predicted. On the contrary, the sampled arcs mostly contribute to a negative array with the ϕ value. High ϕ arcs, largely in the western Pacific, have primary magmas with lower δ57Fe values than the low ϕ, eastern Pacific arcs. Arcs with MORB-like Sr-, Nd- and Pb-isotopes, show a large range of δ57Fe from heavy MORB-like values (Scotia or the Cascades) to very light values (Kamchatka, Tonga). Although all basalts with light δ57Fe values have MORB-like Pb-, Nd- and Sr-isotope ratios some, particularly those from eastern Indonesia, have heavier δ57Fe and higher Pb- and Sr- and lower Nd-isotope ratios reflecting sediment contamination of the mantle wedge. Because basalts with MORB-like radiogenic isotopes range all the way from heavy to light δ57Fe values this trend is process-, not source composition-driven. Neither the slab

  13. BOREAS TE-5 CO2 Concentration and Stable Isotope Composition

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

    The BOREAS TE-5 team collected measurements in the NSA and SSA on gas exchange, gas composition, and tree growth. This data set contains measurements of the concentration and stable carbon (C-13/C-12 and oxygen (O-18/O-16) isotope ratios of atmospheric CO2 in air samples collected at different heights within forest canopies. The data were collected to determine the influence of photosynthesis and respiration by the forest ecosystems on the concentration and stable isotope ratio of atmospheric CO2 These measurements were collected at the SSA during each 1994 IFC at OJP, OBS, and OA sites. Measurements were also collected at the NSA during each 1994 IFC at the OJP, T6R5S TE UBS, and T2Q6A TE OA sites. The stable isotope ratios are expressed using standard delta notation and in units of per mil. The isotope ratios are expressed relative to the international standard, PDB, for both carbon and oxygen samples. The data are stored in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Activity Archive Center (DAAC).

  14. Fe, Zn, and Cd stable isotopes from the eastern tropical South Pacific from GEOTRACES cruise GP16 - Methods and data

    NASA Astrophysics Data System (ADS)

    Helgoe, J. M.; Townsend, E.; John, S.

    2014-12-01

    A new method has been developed for the rapid analysis of metal concentrations and stable isotope ratios using a prepFAST automated sample processing robot. Although concentrations and isotopes are processed separately, similar methods are used for both. Initially all seawater is acidified to pH 2. Then Nobias resin with EDTA/IDA functional groups is added to either 10mL of sample for concentrations or ~1L samples for isotopes. Fe binds to the resin at low pH, and the pH is subsequently raised to allow Zn and Cd to bind. For concentration analyses, all subsequent chemistry is automated on the prepFAST including removal of seawater, rinsing of resin, and elution of resin into acid. For isotope samples these extraction techniques are performed manually, but the subsequent purification of Fe, Zn, and Cd by anion exchange chromatography is automated using the prepFAST. With these new methods, samples from the US GEOTRACES cruise GP16, in the eastern tropical South Pacific, are being analyzed. High concentrations of dissolved Fe are observed near the continental shelf and near submarine hydrothermal vents. Interestingly, isotope data show that dissolved Fe near the continental shelf generally has a δ56Fe close to 0 ‰. This δ56 Fe signature is suggestive of a non-reductive dissolution source for Fe, as Fe(II) released by reductive dissolution is typically closer to -2 ‰. Preliminary data show nutrient-type profiles for Zn and Cd, with Zn matching Si and Cd having a similar distribution to P. An increase in dissolved Zn near hydrothermal vents suggests a possible hydrothermal zinc source to the deep ocean. Continuing analysis of isotope data will reveal more about the source and biogeochemical cycling of these three chemically and biologically important trace metals throughout the eastern tropical Pacific Ocean.

  15. Isotope-Labeled Composition B for Tracing Detonation Signatures

    NASA Astrophysics Data System (ADS)

    Manner, Virginia; Podlesak, David; Huber, Rachel; Amato, Ronald; Giambra, Anna; Bowden, Patrick; Hartline, Ernest; Dattelbaum, Dana

    2017-06-01

    To better understand how solid carbon forms and evolves during detonation, we have prepared Composition B with 13 C and 15 N-labeled 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and 2,4,6-trinitrotoluene (TNT) in order to trace the formation of soot from the carbon and nitrogen atoms in these explosives. Isotope-labeling of explosives has been performed in the recent past for a variety of reasons, including environmental remediation and reaction mechanism studies. Because it is expensive and time consuming to prepare these materials, and our detection equipment only requires trace amounts of isotopes, we have prepared fully-labeled materials and substituted them into unlabeled RDX and TNT at less than the 1% level. We will discuss the preparation and full characterization of this labeled Composition B, the detonation tests performed, along with the results of the post-detonation soot analysis. Various detonation models predict differing amounts and forms of carbon and nitrogen; these isotopically-labeled precursors have allowed these models to be tested.

  16. Using trace element content and lead isotopic composition to assess sources of PM in Tijuana, Mexico

    NASA Astrophysics Data System (ADS)

    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.

    2016-05-01

    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.

  17. Perchlorate in the Great Lakes: isotopic composition and origin.

    PubMed

    Poghosyan, Armen; Sturchio, Neil C; Morrison, Candice G; Beloso, Abelardo D; Guan, Yunbin; Eiler, John M; Jackson, W Andrew; Hatzinger, Paul B

    2014-10-07

    Perchlorate is a persistent and mobile contaminant in the environment with both natural and anthropogenic sources. Stable isotope ratios of oxygen (δ(18)O, Δ(17)O) and chlorine (δ(37)Cl) along with the abundance of the radioactive isotope (36)Cl were used to trace perchlorate sources and behavior in the Laurentian Great Lakes. These lakes were selected for study as a likely repository of recent atmospheric perchlorate deposition. Perchlorate concentrations in the Great Lakes range from 0.05 to 0.13 μg per liter. δ(37)Cl values of perchlorate from the Great Lakes range from +3.0‰ (Lake Ontario) to +4.0‰ (Lake Superior), whereas δ(18)O values range from -4.1‰ (Lake Superior) to +4.0‰ (Lake Erie). Great Lakes perchlorate has mass-independent oxygen isotopic variations with positive Δ(17)O values (+1.6‰ to +2.7‰) divided into two distinct groups: Lake Superior (+2.7‰) and the other four lakes (∼+1.7‰). The stable isotopic results indicate that perchlorate in the Great Lakes is dominantly of natural origin, having isotopic composition resembling that measured for indigenous perchlorate from preindustrial groundwaters of the western USA. The (36)Cl/Cl ratio of perchlorate varies widely from 7.4 × 10(-12) (Lake Ontario) to 6.7 × 10(-11) (Lake Superior). These (36)ClO4(-) abundances are consistent with an atmospheric origin of perchlorate in the Great Lakes. The relatively high (36)ClO4(-) abundances in the larger lakes (Lakes Superior and Michigan) could be explained by the presence of (36)Cl-enriched perchlorate deposited during the period of elevated atmospheric (36)Cl activity following thermonuclear bomb tests in the Pacific Ocean.

  18. Does burial diagenesis reset pristine isotopic compositions in paleosol carbonates?

    NASA Astrophysics Data System (ADS)

    Bera, M. K.; Sarkar, A.; Tandon, S. K.; Samanta, A.; Sanyal, P.

    2010-11-01

    Sedimentological study of early Oligocene continental carbonates from the fluvial Dagshai Formation of the Himalayan foreland basin, India resulted in the recognition of four different types namely, soil, palustrine, pedogenically modified palustrine and groundwater carbonates. Stable oxygen and carbon isotopic ( δ18O and δ13C) analyses of fabric selective carbonate microsamples show that although the pristine isotopic compositions are largely altered during deep-burial diagenesis, complete isotopic homogenization does not occur. δ18O and δ13C analyses of ~ 200 calcrete and palustrine carbonates from different stratigraphic horizons and comparison with δ18O of more robust bioapatite (fossil vertebrate tooth) phase show that dense micrites (~ > 70% carbonate) invariably preserve the pristine δ18O value (mean) of ~ - 9.8‰, while altered carbonates show much lower δ18O value ~ - 13.8‰. Such inhomogeneity causes large intra-sample and intra-soil profile variability as high as > 5‰, suggesting that soils behave like a closed system where diagenetic overprinting occurs in local domains. A simple fluid-rock interaction model suggests active participation of clay minerals to enhance the effect of fluid-rock ratio in local domains during diagenesis. This places an upper limit of 70% micrite concentration above which the effect of diagenetic alteration is minimal. Careful sampling of dense micritic part of the soil carbonate nodules, therefore, does provide pristine isotopic composition and it is inappropriate, as proposed recently, to reject the paleoclimatic potential of all paleosol carbonates affected by burial diagenesis. Based on pristine δ13C value of - 8.8 ± 0.2‰ in soil carbonates an atmospheric CO 2 concentration between ~ 764 and ~ 306 ppmv is estimated for the early Oligocene (~ 31 Ma) Dagshai time. These data show excellent agreement between two independent proxy records (viz. soil carbonate and marine alkenone) and support early Oligocene

  19. Oxygen isotope composition of mafic magmas at Vesuvius

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

    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

  20. Helium-carbon isotopic composition of thermal waters from Tunisia

    NASA Astrophysics Data System (ADS)

    Fourré, E.; Aiuppa, A.; di Napoli, R.; Parello, F.; Gaubi, E.; Jean-Baptiste, P.; Allard, P.; Calabrese, S.; Ben Mammou, A.

    2010-12-01

    Tunisia has numerous thermo-mineral springs. Previous studies have shown that their chemical composition and occurrence are strongly influenced by the regional geology, however little work has been conducted to date to investigate the isotopic composition of volatiles associated with these geothermal manifestations. Here, we report the results of an extensive survey of both natural hot springs and production wells across Tunisia aimed at investigating the spatial distribution of the 3He/4He ratio and associated carbon isotopic compositions. With respect to helium isotopes, not unexpectedly, the lowest 3He/4He values (0.01-0.02 Ra) are associated with the old groundwaters of the “Continental Intercalaire” aquifer of the stable Saharan Platform. The 3He/4He values are equal to the crustal production ratio, with no detectable amount of mantle-derived 3He, in agreement with previous studies of helium isotopes in sedimentary basin, which conclude that tectonically-stable regions are essentially impermeable to mantle volatiles. The low 3He/4He domain extends to the entire Atlasic domain of central Tunisia. This Atlasic domain also displays the highest helium concentrations : along the Gafsa Fault, helium concentrations of 1777 and 4723 x 10-8 cm3STP/g (the highest value of our data set) are observed in the production wells of Sidi Ahmed Zarrouk. This emphasizes the role of deep tectonic features in channelling and transporting deep crustal volatiles to shallow levels. The eastern margin of Tunisia displays higher 3He/4He values indicative of a substantial mantle volatile input. The highest value is recorded in the carbo-gaseous mineral water of Ain Garci (2.4 Ra). This northeastern part of the African plate commonly referred to as the Pelagian block extends from Tunisia to Sicily and is characterized by strong extensional tectonics (Pantelleria rift zone) and present-day magmatic activity. This lithospheric stretching and decompressional mantle melts production in

  1. Zn isotope fractionation in the komatiitic and tholeiitic lava flows of Fred's flow and Theo's flow (Ontario, Canada)

    NASA Astrophysics Data System (ADS)

    Mattielli, N. D.; Haenecour, P.; Debaille, V.

    2010-12-01

    Komatiites are subvolcanic or volcanic ultramafic rocks characterized by a high MgO content (>18 wt%) usually but not systematically associated to a spinifex texture. Komatiites are nearly exclusively Archean in age and essentially found in the greenstone belts of the oldest cratons, although some rare Proterozoic and Cretaceous examples are also known. Komatiitic flows are commonly associated with tholeiitic lavas, which have many petrological, textural and geochemical similarities with komatiites. We present new high-precision MC-ICPMS Zinc isotopic data for the komatiitic lavas of Fred’s flow and the associated tholeiitic lavas of Theo’s flow from Munro Township in the 2.7 Ga Abitibi greenstone belt (Ontario, Canada). Zinc isotopes show a significant shift between Fred’s flow (mean δ66Zn = +0.30±0.04‰ (2SD)) and Theo’s flow samples (mean δ66Zn = +0.39±0.03‰ (1)). In addition, the two flows show a systematic shift in δ66Zn between the ultrabasic level at the bottom of the sequence (= +0.51± 0.04‰ and +0.47±0.04‰ for Fred’s Flow and Theo’s Flow, respectively) and the rest of the pile (Δ = 0.21±0.01‰). According to the literature, processes of secondary alteration may cause Zn isotope fractionation. However, petrographic data indicate a slight alteration fingerprint while the geochemical study (whole rock and in-situ) shows no remobilization of HFSE and REE by secondary alteration (low-grade metamorphism and/or hydrothermal alteration). In addition, if similar levels of alteration affected the two lava flows, the alteration process cannot explain the difference of δ66Zn between Fred’s and Theo’s flows. Alternatively, this isotopic difference can be interpreted as reflecting either source effects or mineral fractionation related to spinel crystallization. The correlation between the δ66Zn values and the Cr bulk concentrations may suggest fractionation effects of Zn isotopes by the crystallization of spinel minerals. However, the

  2. The Dissolved Ca Isotope Composition of Himalayan-Tibetan Waters

    NASA Astrophysics Data System (ADS)

    Tipper, E. T.; Galy, A.; Bickle, M. J.

    2004-12-01

    Determining the relative proportions of carbonate versus silicate weathering in the Himalaya is important for understanding the long-term atmospheric CO2 budget and the marine Sr isotope record. 87Sr/86Sr is not a straightforward proxy of carbonate to silicate weathering in the Himalaya and up to 50% of the dissolved Ca may be removed by the precipitation of secondary calcite. Ca isotopes have the potential to constrain the relative inputs of carbonates to silicates and incongruent dissolution processes in the weathering environment. Ca is the major cation carried by rivers. Thirty four Himalayan rock and water samples from the Nepal Himalaya and Tibet have been analysed for 44/42Ca and 43/42Ca on a Nu-Instruments Multiple Collector -ICP-MS. Unlike the 44/40Ca ratio the 44/42Ca is not susceptible to excess 40Ca production from the decay of K. All samples lie on a single mass fractionation line. There is a total range of 0.4 \\permil variation in \\delta44Ca with values from 0.63 \\permil - 0.21 \\permil relative to the SRM915a standard. This is comparable to that already reported with \\delta44/40Ca for small catchments and global rivers. Small first order catchments from each of the main lithotectonic units of the Himalaya have been analysed to examine the effect of lithology on dissolved Ca isotopic composition. In agreement with previous studies elsewhere there is little correlation between source rock and dissolved composition for small rivers spanning a range of source rock from limestone to various silicates and covering a vegetation range from temperate semi-desert to jungle. \\delta44Ca is not correlated with 87Sr/86Sr or Na/Ca ratios confirming that source rock composition is not the dominant control on the observed range in \\delta44Ca. A time-series has been examined for the Marsyandi River, central Nepal. In spite of significant systematic variations in major element chemistry including Ca concentration and 87Sr/86Sr the variations in \\delta44Ca are

  3. Osmium Isotope Compositions of Komatiite Sources Through Time

    NASA Astrophysics Data System (ADS)

    Walker, R. J.

    2001-12-01

    Extending Os isotopic measurements to ancient plume sources may help to constrain how and when the well-documented isotopic heterogeneities in modern systems were created. Komatiites and picrites associated with plume-related volcanism are valuable tracers of the Os isotopic composition of plumes because of their typically high Os concentrations and relatively low Re/Os. Re-Os data are now available for a variety of Phanerozoic, Proterozoic and Archean komatiites and picrites. As with modern plumes, the sources of Archean and Proterozoic komatiites exhibit a large range of initial 187Os/188Os ratios. Most komatiites are dominated by sources with chondritic Os isotopic compositions (e.g. Song La; Norseman-Wiluna; Pyke Hill; Alexo), though some (e.g. Gorgona) derive from heterogeneous sources. Of note, however, two ca. 2.7 Ga systems, Kostomuksha (Russia) and Belingwe (Zimbabwe), have initial ratios enriched by 2-3% relative to the contemporary convecting upper mantle. These results suggest that if the 187Os enrichment was due to the incorporation of minor amounts of recycled crust into the mantle source of the rocks, the crust formed very early in Earth history. Thus, the Os results could reflect derivation of melt from hybrid mantle whose composition was modified by the addition of mafic crustal material that would most likely have formed between 4.2 and 4.5 Ga. Alternately, the mantle sources of these komatiites may have derived a portion of their Os from the putative 187Os - and 186Os -enriched outer core. For this hypothesis to be applicable to Archean rocks, an inner core of sufficient mass would have to have crystallized sufficiently early in Earth history to generate an outer core with 187Os enriched by at least 3% relative to the chondritic average. Using the Pt-Re-Os partition coefficients espoused by our earlier work, and assuming linear growth of the inner core started at 4.5 Ga and continued to present, would yield an outer core at 2.7 Ga with a gamma Os

  4. Improved luminescence intensity and stability of thermal annealed ZnO incorporated Alq3 composite films.

    PubMed

    Cuba, M; Muralidharan, G

    2015-11-01

    The 30 wt% of ZnO (weight percentage of ZnO has been optimised) incorporated tris- (8-hydroxyquinoline)aluminum (Alq3) has been synthesised and coated on to glass substrates using dip coating method. The structural and optical properties of the Alq3/ZnO composite film after thermal annealing from 50 to 300 °C insteps 50° has been studied and reported. XRD pattern reveals the presence of crystalline ZnO in all the annealed films. The films annealed above 150 °C reveal the presence of crystalline Alq3 along with crystalline ZnO. The FTIR spectra confirm the presence of hydroxyquinoline and ZnO vibration in all the annealed composite films. The composite films annealed above 150 °C show a partial sublimation and degradation of hydroxyquinoline compounds. The ZnO incorporated composite films (Alq3/ZnO) exhibit two emission peaks, one corresponding to ZnO at 487 nm and another at 513 nm due to Alq3. The films annealed at 200 °C exhibit maximum photoluminescence (PL) intensity than pristine film at 513 nm when excited at 390 nm.

  5. Zn and Cu isotopes as tracers of anthropogenic contamination in a sediment core from an urban lake

    USGS Publications Warehouse

    Thapalia, Anita; Borrok, David M.; Van Metre, Peter C.; Musgrove, MaryLynn; Landa, Edward R.

    2010-01-01

    In this work, we use stable Zn and Cu isotopes to identify the sources and timing of the deposition of these metals in a sediment core from Lake Ballinger near Seattle, Washington, USA. The base of the Lake Ballinger core predates settlement in the region, while the upper sections record the effects of atmospheric emissions from a nearby smelter and rapid urbanization of the watershed. δ66Zn and δ65Cu varied by 0.50‰ and 0.29‰, respectively, over the 500 year core record. Isotopic changes were correlated with the presmelter period (∼1450 to 1900 with δ66Zn = +0.39‰ ± 0.09‰ and δ65Cu = +0.77‰ ± 0.06‰), period of smelter operation (1900 to 1985 with δ66Zn = +0.14 ± 0.06‰ and δ65Cu = +0.94 ± 0.10‰), and postsmelting/stable urban land use period (post 1985 with δ66Zn = 0.00 ± 0.10‰ and δ65Cu = +0.82‰ ± 0.12‰). Rapid early urbanization during the post World War II era increased metal loading to the lake but did not significantly alter the δ66Zn and δ65Cu, suggesting that increased metal loads during this time were derived mainly from mobilization of historically contaminated soils. Urban sources of Cu and Zn were dominant since the smelter closed in the 1980s, and the δ66Zn measured in tire samples suggests tire wear is a likely source of Zn.

  6. Effect of Wood Aging on Wine Mineral Composition and 87Sr/86Sr Isotopic Ratio.

    PubMed

    Kaya, Ayse D; Bruno de Sousa, Raúl; Curvelo-Garcia, António S; Ricardo-da-Silva, Jorge M; Catarino, Sofia

    2017-06-14

    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.

  7. Isospin degree of freedom in even-even 68-76Ge and 62-70Zn isotopes

    NASA Astrophysics Data System (ADS)

    Jalili Majarshin, A.

    2018-01-01

    The introduction of isotopic spin is significant in light nuclei as Ge and Zn isotopes in order to take into account isospin effects on energy spectra. Dynamical symmetries in spherical, γ-soft limits and transition in the interacting boson model IBM-3 are analyzed. Analytic expressions and exact eigenenergies, electromagnetic transitions probabilities are obtained for the transition between spherical and γ-soft shapes by using the Bethe ansatz within an infinite-dimensional Lie algebra in light mass nuclei. The corresponding algebraic structure and reduction chain are studied in IBM-3. For examples, the nuclear structure of the 68-76Ge and 62-70Zn isotopes is calculated in IBM-3 and compared with experimental results.

  8. Lead-isotopic, sulphur-isotopic, and trace-element studies of galena from the Silesian-Cracow Zn-Pb ores, polymetallic veins from the Gory Swietokrzyskie MTS, and the Myszkow porphyry copper deposit, Poland

    USGS Publications Warehouse

    Church, S.E.; Vaughn, R.B.; Gent, C.A.; Hopkins, R.T.

    1996-01-01

    as indicated by the geologic evidence, the source rocks probably contained elevated concentrations of Zn and Pb (75-100 ppm), and relatively low concentrations of U and Th (2 and 8 ppm or less, respectively). The Carboniferous coal-bearing molasse rocks of the Upper Silesian Coal Basin are a prime candidate for such a source region. The presence of ammonia and acetate in the fluid inclusions (Viets et al., 1996a) also indicate that the Carboniferous coal-bearing molasse sequence in the Upper Silesian Coal Basin may have been a suitable pathway for the MVT ore fluids. The lead-isotopic homogeneity, when coupled with the sulfur-isotopic heterogeneity of the ores suggests that mixing of a single metal-bearing fluid with waters from separate aquifers containing variable sulfur-isotopic compositions in karsts in the Muschelkalk Formation of Middle Triassic age may have been responsible for the precipitation of the ores of the Silesian-Cracow district.

  9. Modeling the carbon isotope composition of bivalve shells (Invited)

    NASA Astrophysics Data System (ADS)

    Romanek, C.

    2010-12-01

    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., <10%) in shells from aquatic 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

  10. Mass-independent sulfur isotopic compositions in stratospheric volcanic eruptions.

    PubMed

    Baroni, Mélanie; Thiemens, Mark H; Delmas, Robert J; Savarino, Joël

    2007-01-05

    The observed mass-independent sulfur isotopic composition (Delta33S) of volcanic sulfate from the Agung (March 1963) and Pinatubo (June 1991) eruptions recorded in the Antarctic snow provides a mechanism for documenting stratospheric events. The sign of Delta33S changes over time from an initial positive component to a negative value. Delta33S is created during photochemical oxidation of sulfur dioxide to sulfuric acid on a monthly time scale, which indicates a fast process. The reproducibility of the results reveals that Delta33S is a reliable tracer to chemically identify atmospheric processes involved during stratospheric volcanism.

  11. Sulfur Isotopic Composition of Sulfides in Skarn and Vein Mineralization of the Dal'negorsk Ore Region (Primorye)

    NASA Astrophysics Data System (ADS)

    Rogulina, L. I.; Moiseenko, V. G.; Odarichenko, E. G.; Voropayeva, E. N.

    2018-03-01

    The S isotopic composition in the ore-forming minerals galena and sphalerite was studied in different Ag-Pb-Zn deposits of the region. It was pointed out that the δ34S modal values range from-1.2 to +6.7‰ in the minerals with a positive value for the skarn mineralization. In the flyschoid formation, the vein-type mineralization is characterized by negative and positive values. The narrow range of δ34S values indicates the marginal-continental type of the mineralization and the multiple origins of its sources.

  12. Ni-P/Zn-Ni compositionally modulated multilayer coatings - Part 1: Electrodeposition and growth mechanism, composition, morphology, roughness and structure

    NASA Astrophysics Data System (ADS)

    Bahadormanesh, Behrouz; Ghorbani, Mohammad

    2018-06-01

    The Ni-P/Zn-Ni compositionally modulated multilayer coatings CMMCs were electrodeposited from a single bath by switching the cathodic current density. The composition, surface morphology, roughness, layers growth pattern as well as the phase structure of deposits were extensively studied via SEM, EDS, AFM and XRD analysis. Effects of bath ingredients on the electrodeposition behavior were analyzed through cathodic linear sweep voltammetry. Although the concentration of Zn2+ in bath was 13 times higher than Ni2+, the Zn-Ni deposition potential was much nearer to Ni deposition potential rather than that of Zn. Addition of NaH2PO2 to the Ni deposition bath considerably raised the current density and shifted the crystallization potential of Ni to more nobble values. Codeposition of P with Zn-Ni alloy lead to crack formation in the monolayer that was deposited in 60 mA/cm2. However, the cracks were not observed in the Zn-Ni layers of multilayers. Zn-Ni layers in CMMCs exhibited a three-dimensional pattern of growth while that of Ni-P layers was two-dimensional. Also, the Ni-P deposits tends to fill the discontinuities in Zn-Ni layers and performed leveling properties and lowered the surface roughness of Zn-Ni layers and CMMCs. Structural analysis demonstrated that Ni-P layers were amorphous and the Zn-Ni layers exhibited crystallite phase of Zn11Ni2. Thus, the Ni-P/Zn-Ni CMMCs comprised of alternate layers of amorphous Ni-P and nanocrystalline Zn Ni.

  13. Origin and tectonic implications of the Zhaxikang Pb-Zn-Sb-Ag deposit in northern Himalaya: evidence from structures, Re-Os-Pb-S isotopes, and fluid inclusions

    NASA Astrophysics Data System (ADS)

    Zhou, Qing; Li, Wenchang; Qing, Chengshi; Lai, Yang; Li, Yingxu; Liao, Zhenwen; Wu, Jianyang; Wang, Shengwei; Dong, Lei; Tian, Enyuan

    2018-04-01

    The Zhaxikang Pb-Zn-Sb-Ag-(Au) deposits, located in the eastern part of northern Himalaya, totally contain more than 1.146 million tonnes (Mt) of Pb, 1.407 Mt of Zn, 0.345 Mt of Sb, and 3 kilotonnes (kt) of Ag. Our field observations suggest that these deposits are controlled by N-S trending and west- and steep-dipping normal faults, suggesting a hydrothermal rather than a syngenetic sedimentary origin. The Pb-Zn-Sb-Ag-(Cu-Au) mineralization formed in the Eocene as indicated by a Re-Os isochron age of 43.1 ± 2.5 Ma. Sulfide minerals have varying initial Pb isotopic compositions, with (206Pb/204Pb)i of 19.04-19.68, (207Pb/204Pb)i of 15.75-15.88, and (208Pb/204Pb)i of 39.66-40.31. Sulfur isotopic values display a narrow δ34S interval of +7.8-+12.2‰. These Pb-S isotopic data suggest that the Zhaxikang sources of Pb and S should be mainly from the coeval felsic magmas and partly from the surrounding Mesozoic strata including metasedimentary rocks and layered felsic volcanic rocks. Fluid inclusion studies indicate that the hydrothermal fluids have medium temperatures (200-336 °C) but varying salinities (1.40-18.25 wt.% NaCl equiv.) with densities of 0.75-0.95 g/cm3, possibly suggesting an evolution mixing between a high salinity fluid, perhaps of magmatic origin, with meteoric water.

  14. Mercury emissions and stable isotopic compositions at Vulcano Island (Italy)

    NASA Astrophysics Data System (ADS)

    Zambardi, T.; Sonke, J. E.; Toutain, J. P.; Sortino, F.; Shinohara, H.

    2009-01-01

    Sampling and analyses methods for determining the stable isotopic compositions of Hg in an active volcanic system were tested and optimized at the volcanic complex of Vulcano (Aeolian Islands, Italy). Condensed gaseous fumarole Hg (fum)T, plume gaseous elemental Hg (g)0 and plume particulate Hg (p)II were obtained at fumaroles F0, F5, F11, and FA. The average total Hg emissions, based on Hg T/SO 2 in condensed fumarolic gases and plumes, range from 2.5 to 10.1 kg y - 1 , in agreement with published values [Ferrara, R., Mazzolai, B., Lanzillotta, E., Nucaro, E., Pirrone, N., 2000. Volcanoes as emission sources of atmospheric mercury in the Mediterranean Basin. Sci. Total Environ. 259(1-3), 115-121; Aiuppa, A., Bagnato, E., Witt, M.L.I., Mather, T.A., Parello, F., Pyle, D.M., Martin, R.S., 2007. Real-time simultaneous detection of volcanic Hg and SO 2 at La Fossa Crater, Vulcano (Aeolian Islands, Sicily). Geophys. Res. Lett. 34(L21307).]. Plume Hg (p)II increases with distance from the fumarole vent, at the expense of Hg (g)0 and indicates significant in-plume oxidation and condensation of fumarole Hg (fum)T. Relative to the NIST SRM 3133 Hg standard, the stable isotopic compositions of Hg are δ 202Hg (fum)T = - 0.74‰ ± 0.18 (2SD, n = 4) for condensed gaseous fumarole Hg (fum)T, δ 202Hg (g)0 = - 1.74‰ ± 0.36 (2SD, n = 1) for plume gaseous elemental Hg (g)0 at the F0 fumarole, and δ 202Hg (p)II = - 0.11‰ ± 0.18 (2SD, n = 4) for plume particulate Hg (p)II. The enrichment of Hg (p)II in the heavy isotopes and Hg (g)0 in the light isotopes relative to the total condensed fumarolic Hg (fum)T gas complements the speciation data and demonstrates a gas-particle fractionation occurring after the gas expulsion in ambient T° atmosphere. A first order Rayleigh equilibrium condensation isotope fractionation model yields a fractionation factor α cond-gas of 1.00135 ± 0.00058.

  15. Cellular proliferation, cellular viability, and biocompatibility of HA-ZnO composites.

    PubMed

    Saha, Naresh; Dubey, Ashutosh K; Basu, Bikramjit

    2012-01-01

    One of the important issues in the development of hydroxyapatite (HA)-based biomaterials is the prosthetic infection, which limits wider use of monolithic HA despite superior cellular response. Recently, we reported that ZnO addition to HA can induce bactericidal property. It is therefore important to assess how ZnO addition influences the cytotoxicity property and cell adhesion/proliferation on HA-ZnO composite surfaces in vitro. In the above perspective, the objective of this study is to investigate the cell type and material composition dependent cellular proliferation and viability of pressureless sintered HA-ZnO composites. The combination of cell viability data as well as morphological observations of cultured human osteoblast-like SaOS2 cells and mouse fibroblast L929 cells suggests that HA-ZnO composites containing 10 Wt % or lower ZnO exhibit the ability to support cell adhesion and proliferation. Both SaOS2 and L929 cells exhibit extensive multidirectional network of actin cytoskeleton and cell flattening on the lower ZnO containing (≤10 Wt %) HA-ZnO composites. The in vitro results illustrate how variation in ZnO content can influence significantly the cell vitality, as evaluated using MTT biochemical assay. Also, the critical statistical analysis reveals that ZnO addition needs to be carefully tailored to ensure good in vitro cytocompatibility. The underlying reasons for difference in biological properties are analyzed. It is suggested that surface wettability as well as dissolution of ZnO, both contribute to the observed differences in cellular viability and proliferation. Copyright © 2011 Wiley Periodicals, Inc.

  16. Research on the Dielectric Properties of Nano-ZnO/Silicone Rubber Composites

    NASA Astrophysics Data System (ADS)

    Wang, Fei-feng; Yan, Dan-dan; Su, Yi; Lu, Yu-feng; Xia, Xiao-fei; Huang, Hui-min

    2017-09-01

    The samples of 1%, 2%, 3% and 4% Zinc Oxide (ZnO) nano-composite silicone rubber were prepared by mechanical method. The dielectric properties of each sample were measured by dielectric spectroscopy. The experimental results showed that the dielectric constant of the silicone rubber composite increases with the increase of the content of nano-ZnO. The breakdown test results showed that with the increase of the content of nano-ZnO, the breakdown strength of silicone rubber composites increased first and then decreased. The breakdown test results indicate that the nano-ZnO can reduce the breakdown strength of silicone rubber. The hydrophobic test results showed that nano-ZnO will reduce the hydrophobic of silicone rubber.

  17. V isotope composition in modern marine hydrothermal sediments

    NASA Astrophysics Data System (ADS)

    Wu, F.; Owens, J. D.; Nielsen, S.; German, C. R.; Rachel, M.

    2017-12-01

    Vanadium is multivalence transition metal with two isotopes (51V and 50V). Recent work has shown that large V isotope variations occur with oxygen variations in modern sediments (Wu et al., 2016 and 2017 Goldschmidt Abstracts), providing its potential as a promising proxy for determining low oxygen conditions. However, the development of V isotopes as a proxy to probe past redox conditions requires a comprehensive understanding of the modern oceanic isotopic mass balance. Therein, the scavenging of V from the hydrous iron oxides in hydrothermal fluid has been shown to be an important removal process from seawater (Rudnicki and Elderfield, 1993 GCA) but remains unquantified. In this study, we analyzed V isotopic compositions of metalliferous sediments around the active TAG hydrothermal mound from the mid-Atlantic Ridge (26° degrees North) and the Eastern Pacific Zonal Transect (GEOTRACES EPZT cruise GP16). The TAG sediments deposited as Fe oxyhydroxides from plume fall-out, and have δ51V values between -0.3 to 0‰. The good correlation between Fe and V for these metalliferous sediments indicate that the accumulation of V in these samples is directly related to the deposition of Fe oxyhydroxides, which also control their V isotope signature. The EPZT samples cover 8,000 km in the South Pacific Ocean with sedimentary areas that underlie the Peru upwelling region and the well-oxygenated deep South Pacific Ocean influenced by hydtorthermal plume material from southern East Pacific Rise (EPR). The sediments collected at the east of the EPR have δ51V values between -1.2 to -0.7‰, similar to previous δ51V of oxic sediments. In contrast, the sediments from the west of the EPR have δ51V values (-0.4 to 0‰) similar to hydrothermal sediments from the mid-Atlantic Ridge, indicating the long transportation (more than 4,000 km, Fitzsimmons et al., 2017 NG) of Fe and Mn from hydrothermal plume and their incorporation into sediments have a major impact on the cycle of V

  18. Zinc isotopic fractionation in Phragmites australis in response to toxic levels of zinc

    PubMed Central

    Caldelas, Cristina; Dong, Shuofei; Araus, José Luis; Jakob Weiss, Dominik

    2011-01-01

    Stable isotope signatures of Zn have shown great promise in elucidating changes in uptake and translocation mechanisms of this metal in plants during environmental changes. Here this potential was tested by investigating the effect of high Zn concentrations on the isotopic fractionation patterns of Phragmites australis (Cav.) Trin. ex Steud. Plants were grown for 40 d in a nutritive solution containing 3.2 μM (sufficient) or 2 mM (toxic) Zn. The Zn isotopic composition of roots, rhizomes, shoots, and leaves was analysed. Stems and leaves were sampled at different heights to evaluate the effect of long-distance transport on Zn fractionation. During Zn sufficiency, roots, rhizomes, and shoots were isotopically heavy (δ66ZnJMC Lyon=0.2‰) while the youngest leaves were isotopically light (–0.5‰). During Zn excess, roots were still isotopically heavier (δ66Zn=0.5‰) and the rest of the plant was isotopically light (up to –0.5‰). The enrichment of heavy isotopes at the roots was attributed to Zn uptake mediated by transporter proteins under Zn-sufficient conditions and to chelation and compartmentation in Zn excess. The isotopically lighter Zn in shoots and leaves is consistent with long-distance root to shoot transport. The tolerance response of P. australis increased the range of Zn fractionation within the plant and with respect to the environment. PMID:21193582

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

    NASA Technical Reports Server (NTRS)

    Blum, J. D.; Klaue, Bjorn

    2005-01-01

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

  20. ISOTOPIC COMPOSITION OF THE COMMON LEAD OF JAPAN

    SciTech Connect

    Sakai, H.; Sato, K.

    1958-11-01

    Lead tetramethyl was synthesized from lead iodide isolated from 14 galenas, 2 anglesites, and 6 pyromorphites of Japan. The mass spectrometric analysis was carried out for the peaks of lead and lead hydride ions. The isotopic compositions of leads from these minerais lie wiyhn a narrow range. The average values for gnlanas are 18.51 O 0.05 for Pb/sup 238//Pb/sup 204/ 15.60 plus or minus 0.05 for Pb/sup 207//Pb/sup 204/8.76 plus or minus 0.15 forPb/ sup 208//Pb/sup 204/ For lead of secondary minerals they are 18.52 plus or minus 0.05, 15.62 plus or minus 0.05, and 38.78 plus or minus 0.15,more » respectively. No detectabla difference was observed between the isotopic compositions of primary and secondary lead ores. The ratios, U/sub 238/Pb/sup 204, and Th/sup 232/ U/sup 238/, in the source magma are estimated from the lead abundances. They are« less

  1. Stable-carbon isotopic composition of maple sap and foliage.

    PubMed

    Leavitt, S W; Long, A

    1985-06-01

    The (13)C/(12)C ratios of Acer grandidentatum sap sugar collected during the dormant period are compared to those of buds, leaves, and wood developed over the following growing season. As the primary carbon source for cellulose manufacture at initiation of annual growth in deciduous trees, sap sucrose would be expected to have an isotopic composition similar to first-formed cellulose. Although constancy in concentration and (13)C/(12)C ratios of the maple sap sugar suggests any gains or losses (e.g. to maintenance metabolism) do not appreciably alter composition, the (13)C/(12)C ratios of cellulose of the enlarging buds in the spring are quite distinct from those of the sap sugar, seemingly precluding a simple direct biochemical pathway of sap sucrose-->glucose-->cellulose in favor of a more complex pathway with greater likelihood of isotopic fractionation. The (13)C/(12)C ratios of the leaves and in the growth ring were initially similar to the sap sugar but decreased steadily over the growing season.

  2. Cu, Fe, and Zn Isotope Variations Within a High-Temperature Mid-Ocean Ridge Sulfide Structure

    NASA Astrophysics Data System (ADS)

    Ewing, S. M.; Nelson, B. K.; Kelley, D. S.; Nielsen, D. C.

    2006-12-01

    Hydrothermal processes at mid-ocean ridges play an important role in controlling the transition metal budget of seawater and the crust through which it circulates. Preliminary work has shown stable metal isotope variations accompany these processes. We report Cu, Zn, and Fe isotope analyses of transects through a high temperature sulfide structure ("Fin") collected during the 1998 Edifice Rex Sulfide Recovery Project. We analyzed two horizontal transects through the sulfide edifice, from inner conduit to outer surface. Transects A and F are 9 and 6 cm in length, respectively. Each displays radially zoned mineralogy progressing from a chalcopyrite (ccp) zone through zones of zinc sulfide, pyrite-anhydrite (pyr-anh) matrix, zinc sulfide-anhydrite (zns-anh) matrix, to an outer well-cemented silica (Si) zone. Additional ccp and pyr-anh zones appear in transect A resulting from a smaller breakout conduit. In transect A, Cu displays the most isotopic variation, with little variation in Fe and Zn isotopes. From the inner ccp zone outward, the Cu isotope profile shows a 0.4‰ (±0.05‰ 2σ) increase in the first pyr-anh zone over the coarse-grained ccp zone. The δ65Cu drops by 0.6‰ in the secondary ccp zone and recovers to values of the innermost wall in the following zone where it is constant until the outermost portion of the Si rich zone, which shows a 1.3‰ increase over inner zone values. The Zn isotope profile has a total variation of 0.27‰ (±0.05‰ 2σ), with a 0.2‰ increase in the first pyr- anh zone followed by a .27‰ decrease in the adjacent zone, and recovering to its heaviest values in the second pyr-anh zone. The Zn profile lacks any significant increase of the δ^{64}Zn in the outermost zones. The Fe isotope profile shows very little variation across the chimney wall, but does have a sharp 0.7‰ (±0.1‰ 2σ) increase in the δ56Fe in the well-cemented Si rich zone. In transect F, the Cu isotope profile again shows the most variation, but

  3. Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

    NASA Astrophysics Data System (ADS)

    Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

    2018-04-01

    Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy

  4. The initial Hf isotopic composition of the Earth

    NASA Astrophysics Data System (ADS)

    Bouvier, A.; Boyet, M. M.; Vervoort, J. D.; Patchett, P. J.

    2011-12-01

    One area of considerable activity in trying to understand the formation and evolution of Earth's crust is the isotopic analysis of Hf in parallel with Sm-Nd and U-Pb zircon studies, either to constrain early crustal growth and evolution [1], or as a complement to detrital zircon studies [2]. The 176Lu decay constant deduced from early planetary and Earth materials have different values. It has been suggested that a period of irradiation in the early Solar System affected the 176Hf production rate in meteoritic and planetary materials [3,4]. In this scenario, the initial Hf isotopic composition of the Solar System and the Earth would be ~4 ∈Hf units lower, affecting tremendously the interpretation of the differentiation history of the early Earth. We investigated Lu-Hf compositions of calcium-aluminum-rich inclusions, the oldest known objects of the Solar System dated at 4568 Ma [5], to assess the possibility of neutrino irradiation in the solar nebula. Here we report high-precision 176Lu-176Hf systematics of leached and unleached, and spiked and unspiked, bulk fractions and mineral separates of 6 individual CAIs from 2 CV3 chondrites. Isotopic analyses were carried out by Neptune MC-ICPMS at ASU. Analytical details are in [6,7]. The unspiked Hf fractions reveal stable isotope anomalies of μ178Hf= 20 ± 6 and μ180Hf= 31 ± 9 (2SD) for the CAI B4 fractions (n=3) and μ178Hf= -4 ± 10 and μ180Hf= 2 ± 10 (n=2) for BCR-2 relative to the JMC 475 Hf standard. Further high-precision analysis of unspiked Sm and Nd fractions of the samples will be made to correct from nucleosynthetic or neutron capture anomalies [8]. Such Hf stable isotopic anomalies predict no more than 50ppm correction on 176Hf/177Hf. At this stage, we have thus regressed together the spiked and unspiked Hf compositions of CAI fractions (n=13) for isochron calculations. The slope of the Lu-Hf isochron is 0.0882 ± 0.0026 (2SD) which corresponds to a 176Lu decay constant value of 1.852 (± 0.052) ×10

  5. Spectroscopic metrology for isotope composition measurements and transfer standards

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

    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

  6. Seasonality of Leaf Carbon Isotopic Composition and Leaf Water Isotopic Enrichment in a Mixed Evergreen Forest in Southern California

    NASA Astrophysics Data System (ADS)

    Santiago, L. S.; Sickman, J. O.; Goulden, M.; DeVan, C.; Pasquini, S. C.; Pivovaroff, A. L.

    2011-12-01

    Leaf carbon isotopic composition and leaf water isotopic enrichment reflect physiological processes and are important for linking local and regional scale processes to global patterns. We investigated how seasonality affects the isotopic composition of bulk leaf carbon, leaf sugar carbon, and leaf water hydrogen under a Mediterranean climate. Leaf and stem samples were collected monthly from four tree species (Calocedrus decurrens, Pinus lambertiana, Pinus ponderosa, and Quercus chrysolepis) at the James San Jacinto Mountain Reserve in southern California. Mean monthly bulk leaf carbon isotopic composition varied from -34.5 % in P. ponderosa to -24.7 % in P. lambertiana and became more depleted in 13C from the spring to the summer. Mean monthly leaf sugar varied from -29.3 % in P. ponderosa to -21.8 % in P. lambertiana and was enriched in 13C during the winter, spring and autumn, but depleted during the mid-summer. Leaf water hydrogen isotopic composition was 28.4 to 68.8 % more enriched in deuterium than source water and this enrichment was greater as seasonal drought progressed. These data indicate that leaf carbon and leaf water hydrogen isotopic composition provide sensitive measures that connect plant physiological processes to short-term climatic variability.

  7. Zinc isotope anomalies. [in Allende meteorite

    NASA Technical Reports Server (NTRS)

    Volkening, J.; Papanastassiou, D. A.

    1990-01-01

    The Zn isotope composition in refractory-element-rich inclusions of the Allende meteorite are determined. Typical inclusions contain normal Zn. A unique inclusion of the Allende meteorite shows an excess for Zn-66 of 16.7 + or - 3.7 eu (1 eu = 0.01 percent) and a deficit for Zn-70 of 21 + or - 13 eu. These results indicate the preservation of exotic components even for volatile elements in this inclusion. The observed excess Zn-66 correlates with excesses for the neutron-rich isotopes of Ca-48, Ti-50, Cr-54, and Fe-58 in the same inclusion.

  8. ZnO/graphite composites and its antibacterial activity at different conditions.

    PubMed

    Dědková, Kateřina; Janíková, Barbora; Matějová, Kateřina; Čabanová, Kristina; Váňa, Rostislav; Kalup, Aleš; Hundáková, Marianna; Kukutschová, Jana

    2015-10-01

    The paper reports laboratory preparation, characterization and in vitro evaluation of antibacterial activity of ZnO/graphite nanocomposites. Zinc chloride and sodium carbonate served as precursors for synthesis of zinc oxide, while micromilled and natural graphite were used as the matrix for ZnO nanoparticles anchoring. During the reaction of ZnCl2 with saturated aqueous solution of Na2CO3a new compound is created. During the calcination at the temperature of 500 °C this new precursors decomposes and ZnO nanoparticles are formed. Composites ZnO/graphite with 50 wt.% of ZnO particles were prepared. X-ray powder diffraction and Raman microspectroscopy served as phase-analytical methods. Scanning electron microscopy technique was used for morphology characterization of the prepared samples and EDS mapping for visualization of elemental distribution. A developed modification of the standard microdilution test was used for in vitro evaluation of daylight induced antibacterial activity and antibacterial activity at dark conditions. Common human pathogens served as microorganism for antibacterial assay. Antibacterial activity of ZnO/graphite composites could be based on photocatalytic reaction; however there is a role of Zn(2+) ions on the resulting antibacterial activity which proved the experiments in dark condition. There is synergistic effect between Zn(2+) caused and reactive oxygen species caused antibacterial activity. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Origin of the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Evidence from regional Pb and Sr isotope sources

    USGS Publications Warehouse

    Ayuso, R.A.; Kelley, K.D.; Leach, D.L.; Young, L.E.; Slack, J.F.; Wandless, G.; Lyon, A.M.; Dillingham, J.L.

    2004-01-01

    Pb and Sr isotope data were obtained on the shale-hosted Zn-Pb-Ag Red Dog deposits (Qanaiyaq, Main, Aqqaluk, and Paalaaq), other shale-hosted deposits near Red Dog, and Zn-Pb-Ag sulfide and barite deposits in the western and central Brooks Range. The Red Dog deposits and other shale-hosted Zn-Pb-Ag deposits near Red Dog are hosted in the Mississippian Kuna Formation, which is underlain by a sequence of marine-deltaic clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. Ag-Pb-Zn vein-breccias are found in the Endicott Group. Galena formed during the main mineralization stages in the Red Dog deposits and from the Anarraaq and Wulik deposits have overlapping Pb isotope compositions in the range 206Pb/204Pb = 18.364 to 18.428, 207Pb/204Pb = 15.553 to 15.621, and 208Pb/204Pb = 38.083 to 38.323. Galena and sphalerite formed during the main ore-forming stages in the Red Dog deposits define a narrow field on standard uranogenic and thorogenic Pb isotope diagrams. Lead in sulfides of the Red Dog district is less radiogenic (238U/204Pb: ?? = 9.51-9.77) than is indicated by the average crustal lead evolution model (?? = 9.74), a difference consistent with a long history of evolution at low ratios of ?? before the Carboniferous. The homogeneous regional isotopic reservoir of Pb may indicate large-scale transport and leaching of minerals with various ?? ratios and Th/Pb ratios. Younger and genetically unrelated fluids did not significantly disturb the isotopic compositions of galena and sphalerite after the main mineralization event in the Red Dog district. Some pyrite shows evidence of minor Pb remobilization. The overall lead isotope homogeneity in the shale-hosted massive sulfide deposits is consistent with three types of control: a homogeneous regional source, mixing of lead during leaching of a thick sedimentary section and fluid transport, or mixing at the site of deposition. Isotopic variability of the hydrothermal fluids, as represented by galena

  10. Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

    NASA Astrophysics Data System (ADS)

    Juillot, Farid; Maréchal, Chloe; Morin, Guillaume; Jouvin, Delphine; Cacaly, Sylvain; Telouk, Philipe; Benedetti, Marc F.; Ildefonse, Philippe; Sutton, Steve; Guyot, François; Brown, Gordon E., Jr.

    2011-05-01

    Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ 66Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2 σ) to +0.34 ± 0.17‰ (2 σ) at the lowest horizons and from +0.38 ± 0.45‰ (2 σ) to +0.76 ± 0.14‰ (2 σ) near the surface. The δ 66Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ 66Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe 2O 4)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ 66Zn values of +0.81 ± 0.20‰ (2 σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ 66Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ 66Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.

  11. Study of white light emission from ZnS/PS composite system

    NASA Astrophysics Data System (ADS)

    Wang, Caifeng; Li, Qingshan; Lu, Lei; Zhang, Lichun; Qi, Hongxia

    2007-09-01

    ZnS films were deposited by pulsed laser deposition (PLD) on porous silicon (PS) substrates formed by electrochemical anodization of p-type (100) silicon wafer. The photoluminescence (PL) spectra of ZnS/PS composites were measured at room temperature. Under different excitation wavelengths, the relative integrated intensities of the red light emission from PS layers and the blue-green emission from ZnS films had different values. After samples were annealed in vacuum at different temperatures (200, 300, and 400 Celsius degree) for 30 min respectively, a new green emission located at around 550 nm appeared in the PL spectra of all ZnS/PS samples, and all of the ZnS/PS composites had a broad PL band (450-700 nm) in the visible region, exhibiting intensively white light emission.

  12. A vanadium-doped ZnO nanosheets-polymer composite for flexible piezoelectric nanogenerators.

    PubMed

    Shin, Sung-Ho; Kwon, Yang Hyeog; Lee, Min Hyung; Jung, Joo-Yun; Seol, Jae Hun; Nah, Junghyo

    2016-01-21

    We report high performance flexible piezoelectric nanogenerators (PENGs) by employing vanadium (V)-doped ZnO nanosheets (NSs) and the polydimethylsiloxane (PDMS) composite structure. The V-doped ZnO NSs were synthesized to overcome the inherently low piezoelectric properties of intrinsic ZnO. Ferroelectric phase transition induced in the V-doped ZnO NSs contributed to significantly improve the performance of the PENGs after the poling process. Consequently, the PENGs exhibited high output voltage and current up to ∼32 V and ∼6.2 μA, respectively, under the applied strain, which are sufficient to directly turn on a number of light emitting diodes (LEDs). The composite approach for PENG fabrication is scalable, robust, and reproducible during periodic bending/releasing over extended cycles. The approach introduced here extends the performance limits of ZnO-based PENGs and demonstrates their potential as energy harvesting devices.

  13. Highly selective room temperature NO2 gas sensor based on rGO-ZnO composite

    NASA Astrophysics Data System (ADS)

    Jyoti, Kanaujiya, Neha; Varma, G. D.

    2018-05-01

    Blending metal oxide nanoparticles with graphene or its derivatives can greatly enhance gas sensing characteristics. In the present work, ZnO nanoparticles have been synthesized via reflux method. Thin films of reduced graphene oxide (rGO) and composite of rGO-ZnO have been fabricated by drop casting method for gas sensing application. The samples have been characterized by X-ray diffraction (XRD) and Field-emission scanning electron microscope (FESEM) for the structural and morphological studies respectively. Sensing measurements have been carried out for the composite film of rGO-ZnO for different concentrations of NO2 ranging from 4 to 100 ppm. Effect of increasing temperature on the sensing performance has also been studied and the rGO-ZnO composite sensor shows maximum percentage response at room temperature. The limit of detection (LOD) for rGO-ZnO composite sensor is 4ppm and it exhibits a high response of 48.4% for 40 ppm NO2 at room temperature. To check the selectivity of the composite sensor, sensor film has been exposed to 40 ppm different gases like CO, NH3, H2S and Cl2 at room temperature and the sensor respond negligibly to these gases. The present work suggests that rGO-ZnO composite material can be a better candidate for fabrication of highly selective room temperature NO2 gas sensor.

  14. Mineralogical, textural, sulfur and lead isotope constraints on the origin of Ag-Pb-Zn mineralization at Bianjiadayuan, Inner Mongolia, NE China

    NASA Astrophysics Data System (ADS)

    Zhai, Degao; Liu, Jiajun; Cook, Nigel J.; Wang, Xilong; Yang, Yongqiang; Zhang, Anli; Jiao, Yingchun

    2018-04-01

    The Bianjiadayuan Ag-Pb-Zn deposit (4.81 Mt. @157.4 g/t Ag and 3.94% Pb + Zn) is located in the Great Hinggan Range Pb-Zn-Ag-Cu-Mo-Sn-Fe polymetallic metallogenic belt, NE China. Vein type Pb-Zn-Ag ore bodies are primarily hosted by slate, adjacent to a Sn ± Cu ± Mo mineralized porphyry intrusion. The deposit is characterized by silver-rich ores with Ag grades up to 3000 g/t. Four primary paragenetic sequences are recognized: (I) arsenopyrite + pyrite + quartz, (II) main sulfide + quartz, (III) silver-bearing sulfosalt + quartz, and (IV) boulangerite + calcite. A subsequent supergene oxidation stage has also been identified. Hydrothermal alteration consists of an early episode of silicification, two intermediate episodes (propylitic and phyllic), and a late argillic episode. Silver mineralization primarily belongs to the late paragenetic sequence III. Freibergite is the dominant and most important Ag-mineral in the deposit. Detailed ore mineralogy of Bianjiadayuan freibergite reveals evidence of chemical heterogeneity down to the microscale. Silver-rich sulfosalts in the late paragenetic sequence III are largely derived from a series of retrograde and solid-state reactions that redistribute Ag via decomposition and exsolution during cooling, illustrating that documentation of post-mineralization processes is essential for understanding silver ore formation. Sulfur and lead isotope compositions of sulfides, and comparison with those of local various geological units, indicate that the ore-forming fluids, lead, and other metals have a magmatic origin, suggesting a close genetic association between the studied Ag-Pb-Zn veins and the local granitic intrusion. Fluid cooling coupled with decreases in fO2 and fS2 are the factors inferred to have led to a decrease of silver solubility in the hydrothermal fluid, and successively promoted extensive Ag deposition.

  15. Coordinated Petrography and Oxygen Isotopic Compositions of Al-Rich Chondrules from CV3 Chondrites

    NASA Astrophysics Data System (ADS)

    Zhang, M. M.; Lin, Y. T.; Tang, G. Q.; Li, X. H.

    2017-07-01

    In this study, we coordinated the petrology, bulk compositions and oxygen isotope compositions of 12 ARCs from Allende and Leoville and Ningqiang chondrites in order to elucidate any potential genetic relationships between ARCs, CAIs and FMCs.

  16. Variations in Urine Calcium Isotope: Composition Reflect Changes in Bone Mineral Balance in Humans

    NASA Technical Reports Server (NTRS)

    Skulan, Joseph; Anbar, Ariel; Bullen, Thomas; Puzas, J. Edward; Shackelford, Linda; Smith, Scott M.

    2004-01-01

    Changes in bone mineral balance cause rapid and systematic changes in the calcium isotope composition of human urine. Urine from subjects in a 17 week bed rest study was analyzed for calcium isotopic composition. Comparison of isotopic data with measurements of bone mineral density and metabolic markers of bone metabolism indicates the calcium isotope composition of urine reflects changes in bone mineral balance. Urine calcium isotope composition probably is affected by both bone metabolism and renal processes. Calcium isotope. analysis of urine and other tissues may provide information on bone mineral balance that is in important respects better than that available from other techniques, and illustrates the usefulness of applying geochemical techniques to biomedical problems.

  17. Osmium Isotopic Composition of the Sumbar Cretaceous- Tertiary Boundary, Turkmenia

    NASA Astrophysics Data System (ADS)

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

    1992-07-01

    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

  18. Ni-P/Zn-Ni compositionally modulated multilayer coatings - Part 2: Corrosion and protection mechanisms

    NASA Astrophysics Data System (ADS)

    Bahadormanesh, Behrouz; Ghorbani, Mohammad

    2018-06-01

    The Ni-P/Zn-Ni compositionally modulated multilayer coatings CMMCs were electrodeposited from a single bath by switching the deposition current density. The corrosion resistance of the deposits was studied and compared with that of monolayers of Ni-P and Zn-Ni alloys via Tafel polarization, EIS and salt spray tests. Characterization of corrosion products by means of EDS and XRD revealed more details from the corrosion mechanism of the monolayers and multilayers. The corrosion current density of Ni-P/Zn-Ni CMMCs were around one tenth of Zn-Ni monolayer. The CMMC with incomplete layers performed lower polarization resistance and higher corrosion current density compared to the CMMC with complete layers. The electrical circuit that was proposed for modeling the corrosion process based on the EIS spectrum, proved that layering reduces the porosity and consequently improves the barrier properties. Although, layering of Zn-Ni layers with Ni-P deposits increased the time to red rust in salt spray test, the time for white rust formation decreased. The corrosion mechanism of both Zn-Ni and Ni-P (containing small amount of Zn) was preferential dissolution of Zn and the corrosion products were comprised of mainly Zn hydroxychloride and Zn hydroxycarbonate. Also, Ni and P did not take part in the corrosion products. Based on the electrochemical character of the layers and the morphology of the corroded surface, the corrosion mechanism of multilayers was discussed.

  19. A vanadium-doped ZnO nanosheets-polymer composite for flexible piezoelectric nanogenerators

    NASA Astrophysics Data System (ADS)

    Shin, Sung-Ho; Kwon, Yang Hyeog; Lee, Min Hyung; Jung, Joo-Yun; Seol, Jae Hun; Nah, Junghyo

    2016-01-01

    We report high performance flexible piezoelectric nanogenerators (PENGs) by employing vanadium (V)-doped ZnO nanosheets (NSs) and the polydimethylsiloxane (PDMS) composite structure. The V-doped ZnO NSs were synthesized to overcome the inherently low piezoelectric properties of intrinsic ZnO. Ferroelectric phase transition induced in the V-doped ZnO NSs contributed to significantly improve the performance of the PENGs after the poling process. Consequently, the PENGs exhibited high output voltage and current up to ~32 V and ~6.2 μA, respectively, under the applied strain, which are sufficient to directly turn on a number of light emitting diodes (LEDs). The composite approach for PENG fabrication is scalable, robust, and reproducible during periodic bending/releasing over extended cycles. The approach introduced here extends the performance limits of ZnO-based PENGs and demonstrates their potential as energy harvesting devices.We report high performance flexible piezoelectric nanogenerators (PENGs) by employing vanadium (V)-doped ZnO nanosheets (NSs) and the polydimethylsiloxane (PDMS) composite structure. The V-doped ZnO NSs were synthesized to overcome the inherently low piezoelectric properties of intrinsic ZnO. Ferroelectric phase transition induced in the V-doped ZnO NSs contributed to significantly improve the performance of the PENGs after the poling process. Consequently, the PENGs exhibited high output voltage and current up to ~32 V and ~6.2 μA, respectively, under the applied strain, which are sufficient to directly turn on a number of light emitting diodes (LEDs). The composite approach for PENG fabrication is scalable, robust, and reproducible during periodic bending/releasing over extended cycles. The approach introduced here extends the performance limits of ZnO-based PENGs and demonstrates their potential as energy harvesting devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07185b

  20. Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    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

  1. Stable Cl isotope composition of the Changjiang River water

    NASA Astrophysics Data System (ADS)

    Lang, Y.; Liu, C. Q.; LI, S. L.; Aravena, R.; Ding, H.; WANG, B.; Benjamin, C.

    2017-12-01

    To understand chemical wreathing, nutrient cycling, and the impact of human activities on eco-environments of the Changjiang River (Yangtze River) Basin, we carried out a geochemical study on water chemistry and multiple isotopes (C, N, S, Sr…...) of Changjiang River water in the summer season. Some of the research results about the water chemistry, boron isotope geochemistry and suspended matter have been published (Chetelat et al., 2008; Li et al., 2010). Ten samples were selected for the measurement of δ37Cl values, among which 7 samples were collected from main stream and 3 samples from tributaries. The range of δ37Cl values varies between 0.02‰ and 0.33‰ in the main stream and between 0.16‰ and 0.71‰ in the tributary waters. The δ37Cl values in general are negatively correlated with Cl- concentrations for both main stream and tributary waters. δ37Cl value of Wujiang, which is one of the large tributaries in the upper reach of Changjiang and dominated by carbonate rocks in lithology of the watershed, has the maximum value but minimum value of Cl- concentration in this study. The lowest δ37Cl value was measured for the water collected from the estuary of Changjiang River. The variation of δ37Cl values in the waters would be attributed to mixing of different sources of chlorine, which most likely include rain water, ground water, seawater, and pollutants. Systematic characterization of different Cl sources in terms of their chlorine isotope composition is imperative for better understanding of sources and processes of chlorine cycling. Acknowledgements: This work was financially supported by NSFC through project 41073099. (Omit references)

  2. Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

    Treesearch

    Scott T. Allen; Richard F. Keim; Jeffrey J. McDonnell

    2015-01-01

    Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability...

  3. Argon isotopic composition of Archaean atmosphere probes early Earth geodynamics.

    PubMed

    Pujol, Magali; Marty, Bernard; Burgess, Ray; Turner, Grenville; Philippot, Pascal

    2013-06-06

    Understanding the growth rate of the continental crust through time is a fundamental issue in Earth sciences. The isotopic signatures of noble gases in the silicate Earth (mantle, crust) and in the atmosphere afford exceptional insight into the evolution through time of these geochemical reservoirs. However, no data for the compositions of these reservoirs exists for the distant past, and temporal exchange rates between Earth's interior and its surface are severely under-constrained owing to a lack of samples preserving the original signature of the atmosphere at the time of their formation. Here, we report the analysis of argon in Archaean (3.5-billion-year-old) hydrothermal quartz. Noble gases are hosted in primary fluid inclusions containing a mixture of Archaean freshwater and hydrothermal fluid. Our analysis reveals Archaean atmospheric argon with a (40)Ar/(36)Ar value of 143 ± 24, lower than the present-day value of 298.6 (for which (40)Ar has been produced by the radioactive decay of the potassium isotope (40)K, with a half-life of 1.25 billion years; (36)Ar is primordial in origin). This ratio is consistent with an early development of the felsic crust, which might have had an important role in climate variability during the first half of Earth's history.

  4. Changes in stable isotope composition in Lake Michigan trout ...

    EPA Pesticide Factsheets

    Researchers have frequently sought to use environmental archives of sediment, peat and glacial ice to try and assess historical trends in atmospheric mercury (Hg) deposition to aquatic ecosystems. While this information is valuable in the context of identifying temporal source trends, these types of assessments cannot account for likely changes in bioavailability of Hg sources that are tied to the formation of methylmercury (MeHg) and accumulation in fish tissues. For this study we propose the use of long-term fish archives and Hg stable isotope determination as an improved means to relate temporal changes in fish Hg levels to varying Hg sources in the Great Lakes. For this study we acquired 180 archived fish composites from Lake Michigan over a 40-year time period (1975 to 2014) from the Great Lakes Fish Monitoring and Surveillance Program, which were analyzed for their total Hg content and Hg isotope abundances. The results reveal that Hg sources to Lake Michigan trout (Salvelinus namaycush) have encountered considerable changes as well as a large shift in the food web trophic position as a result of the introduction of several invasive species, especially the recent invasion of dreissenid mussels. Total Hg concentrations span a large range (1,600 to 150 ng g-1) and exhibit large variations from 1975 to 1985. Ä199Hg signatures similarly exhibit large variation (3.2 to 6.9‰) until 1985, followed by less variation through the end of the data record in 2014.

  5. Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

    NASA Technical Reports Server (NTRS)

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

    2017-01-01

    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.

  6. Spatial evolution of Zn-Fe-Pb isotopes of sphalerite within a single ore body: A case study from the Dongshengmiao ore deposit, Inner Mongolia, China

    NASA Astrophysics Data System (ADS)

    Gao, Zhaofu; Zhu, Xiangkun; Sun, Jian; Luo, Zhaohua; Bao, Chuang; Tang, Chao; Ma, Jianxiong

    2018-01-01

    Analyses of sphalerite minerals from the characteristic brecciated Zn-Pb ores of the main ore body in the giant Dongshengmiao deposit have revealed variations in δ66Zn from 0.17 to 0.40‰ and in δ56Fe from -1.78 to -0.35‰. Further, the investigated pyrrhotite samples have iron that is isotopically similar to that of associated sphalerite minerals. The most distinctive pattern revealed by the zinc and iron isotope data is the lateral trend of increasing δ66Zn and δ56Fe values from southwest to northeast within the main ore body. The lead isotopic homogeneity of ore sulfides from the main ore body suggests that there is only one significant source for metal, thus precluding the mixing of multiple metal sources as the key factor controlling spatial variations of zinc and iron isotopes. The most likely control on spatial variations is Rayleigh fractionation during hydrothermal fluid flow, with lighter Zn and Fe isotopes preferentially incorporated into the earliest sulfides to precipitate from fluids. Precipitations of sphalerite and pyrrhotite have played vital roles in the Zn and Fe isotopic variations, respectively, of the ore-forming system. Accordingly, the larger isotopic variability for Fe than Zn within the same hydrothermal system perhaps resulted from a larger proportion of precipitation for pyrrhotite than for sphalerite. The lateral trend pattern revealed by the zinc and iron isotope data is consistent with the occurrence of a cystic-shaped breccia zone, which is characterized by marked elevation in Cu. The results further confirm that Zn and Fe isotopes can be used as a vectoring tool for mineral prospecting.

  7. Chemical composition of HAL, an isotopically-unusual Allende inclusion

    NASA Astrophysics Data System (ADS)

    Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

    1982-09-01

    Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

  8. Chemical composition of HAL, an isotopically-unusual Allende inclusion

    NASA Technical Reports Server (NTRS)

    Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

    1982-01-01

    Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

  9. Isotopic composition of a sample enriched in 93Zr

    DOE PAGES

    Fujii, Toshiyuki; Hori, Jun-ichi; Du, Miting; ...

    2015-10-22

    A project to determine the neutron-capture cross section of long lived fission products and minor actinides has been started by using a beam-line at Japan Proton Accelerator Research Complex (J-PARC). We prepared one of the target nuclides is Zr-93, which in Oak Ridge National Laboratory. Qualitative and quantitative analyses on the sample were performed at Kyoto University. The isotopic composition of (m) Zr (m 90, 91, 92, 93, 94, and 96) was precisely determined by multi-collector thermal ionization mass spectrometry with < 0.1 % of 2 sigma uncertainty. We determined that the atomic abundance of Zr-93 in the sample tomore » be 18.86 ± A 0.05 %.« less

  10. Low cost fabrication of polymer composite (h-ZnO + PDMS) material for piezoelectric device application

    NASA Astrophysics Data System (ADS)

    Singh, Akanksha; Das, Sonatan; Bharathkumar, Mareddi; Revanth, D.; Karthik, ARB; Sudhakara Sastry, Bala; Ramgopal Rao, V.

    2016-07-01

    Flexible piezoelectric composites offer alternative and/or additional solutions to sensor, actuator and transducer applications. Here in this work, we have successfully fabricated highly flexible piezoelectric composites with poly dimethyl siloxane (PDMS) using herbal zinc oxide (h-ZnO) as filler having weight fractions up to 50 wt.% by solution casting of dispersions of h-ZnO in PDMS. Excellent piezo properties (Resonant frequency 935 Hz, d*33 29.76 pm V-1), physiochemical properties (Wurtzite structure ZnO, 380 nm absorbance) and mechanical properties (Young modulus 16.9 MPa) have been optimized with theoretical simulations and observed experimentally for h-ZnO + PDMS. As such, the demonstrated piezoelectric PDMS membranes combined with the excellent properties of these composites open new ways to ‘soft touch’ applications and could serve as a variety of soft and sensitive electromechanical transducers, which are desired for a variety of sensor and energy harvesting applications.

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

    NASA Astrophysics Data System (ADS)

    Chen, Guo; Schnyder, Hans; Auerswald, Karl

    2017-04-01

    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 (p<0.05) to the isotope composition in meteoric water 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.

  12. Two-step fabrication of ZnO-PVP composites with tunable visible emissions

    NASA Astrophysics Data System (ADS)

    Agulto, Verdad C.; Empizo, Melvin John F.; Kawano, Keisuke; Minami, Yuki; Yamanoi, Kohei; Sarukura, Nobuhiko; Yago, Allan Christopher C.; Sarmago, Roland V.

    2018-02-01

    We report a two-step fabrication of zinc oxide-polyvinylpyrrolidone (ZnO-PVP) composites for potential phosphor-based applications. The composites are fabricated by initially preparing ZnO microrods using hydrothermal growth method and then dip-coating the microrods into aqueous PVP solutions with varying molar concentrations. The as-prepared ZnO microrods exhibit smooth surfaces and broad visible emissions, while the ZnO-PVP composites have pitted surfaces with shifted and reduced visible emissions. These changes in the structural and optical properties, which are found to depend on the PVP concentration, are attributed to the adsorption of PVP on the microrod surface. Although the surface morphology and visible emission are modified by PVP, the composites still maintain a hexagonal wurtzite crystal structure and near-band-edge ultraviolet (UV) emission similar with the as-prepared microrods. Our results therefore suggest that the ZnO-PVP composites can be used as phosphors that offer not only properties found in both ZnO and PVP but also tunable visible emissions which can be controlled during material fabrication.

  13. Baseline shifts in coral skeletal oxygen isotopic composition: a signature of symbiont shuffling?

    NASA Astrophysics Data System (ADS)

    Carilli, J. E.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

    2013-06-01

    Decades-long records of the stable isotopic composition of coral skeletal cores were analyzed from four sites on the Mesoamerican Reef. Two of the sites exhibited baseline shifts in oxygen isotopic composition after known coral bleaching events. Changes in pH at the calcification site caused by a change in the associated symbiont community are invoked to explain the observed shift in the isotopic composition. To test the hypothesis that changes in symbiont clade could affect skeletal chemistry, additional coral samples were collected from Belize for paired Symbiodinium identification and skeletal stable isotopic analysis. We found some evidence that skeletal stable isotopic composition may be affected by symbiont clade and suggest this is an important topic for future investigation. If different Symbiodinium clades leave consistent signatures in skeletal geochemical composition, the signature will provide a method to quantify past symbiont shuffling events, important for understanding how corals are likely to respond to climate change.

  14. The isotopic composition of CO in vehicle exhaust

    NASA Astrophysics Data System (ADS)

    Naus, S.; Röckmann, T.; Popa, M. E.

    2018-03-01

    We investigated the isotopic composition of CO in the exhaust of individual vehicles. Additionally, the CO2 isotopes, and the CO:CO2, CH4:CO2 and H2:CO gas ratios were measured. This was done under idling and revving conditions, and for three vehicles in a full driving cycle on a testbench. The spread in the results, even for a single vehicle, was large: for δ13 C in CO ∼ -60 to 0‰, for δ18 O in CO ∼ +10 to +35‰, and for all gas ratios several orders of magnitude. The results show an increase in the spread of isotopic values for CO compared to previous studies, suggesting that increasing complexity of emission control in vehicles might be reflected in the isotopic composition. When including all samples, we find a weighted mean for the δ13 C and δ18 O in CO of -28.7 ± 0.5‰ and +24.8 ± 0.3‰ respectively. This result is dominated by cold petrol vehicles. Diesel vehicles behaved as a distinct group, with CO enriched in 13C and depleted in 18O, compared to petrol vehicles. For the H2:CO ratio of all vehicles, we found a value of 0.71 ± 0.31 ppb:ppb. The CO:CO2 ratio, with a mean of 19.4 ± 6.8 ppb:ppm, and the CH4:CO2 ratio, with a mean of 0.26 ± 0.05 ppb:ppm, are both higher than recent literature indicates. This is likely because our sampling distribution was biased towards cold vehicles, and therefore towards higher emission situations. The CH4:CO2 ratio was found to behave similarly to the CO:CO2 ratio, suggesting that the processes affecting CO and CH4 are similar. The δ13 C values in CO2 were close to the expected δ13 C in fuel, with no significant difference between petrol and diesel vehicles. The δ18 O values in CO2 for petrol vehicles covered a range of 20-35‰, similar to the δ18 O of CO. The δ18 O values in CO2 for diesel vehicles were close to the δ18 O in atmospheric oxygen. A set of polluted atmospheric samples, taken near a highway and inside parking garages, showed an isotopic signature of CO and a H2:CO ratio that were

  15. Iron and nickel isotope compositions of presolar silicon carbide grains from supernovae

    NASA Astrophysics Data System (ADS)

    Kodolányi, János; Stephan, Thomas; Trappitsch, Reto; Hoppe, Peter; Pignatari, Marco; Davis, Andrew M.; Pellin, Michael J.

    2018-01-01

    We report the carbon, silicon, iron, and nickel isotope compositions of twenty-five presolar SiC grains of mostly supernova (SN) origin. The iron and nickel isotope compositions were measured with the new Chicago Instrument for Laser Ionization, CHILI, which allows the analysis of all iron and nickel isotopes without the isobaric interferences that plagued previous measurements with the NanoSIMS. Despite terrestrial iron and nickel contamination, significant isotopic anomalies in 54Fe/56Fe, 57Fe/56Fe, 60Ni/58Ni, 61Ni/58Ni, 62Ni/58Ni, and 64Ni/58Ni were detected in nine SN grains (of type X). Combined multi-isotope data of three grains with the largest nickel isotope anomalies (>100‰ or <-100‰ in at least one isotope ratio, when expressed as deviation from the solar value) are compared with the predictions of two SN models, one with and one without hydrogen ingestion in the He shell prior to SN explosion. One grain's carbon-silicon-iron-nickel isotope composition is consistent with the prediction of the model without hydrogen ingestion, whereas the other two grains' isotope anomalies could not be reproduced using either SN models. The discrepancies between the measured isotope compositions and model predictions may indicate element fractionation in the SN ejecta prior to or during grain condensation, and reiterate the need for three-dimensional SN models.

  16. Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico

    NASA Astrophysics Data System (ADS)

    Jimenez, A.

    2012-04-01

    Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico Abigail Jimenez-Franco1*, Pura Alfonso Abella2, Carles Canet3, Eduardo González-Partida4 1 Posgrado en Ciencias de la Tierra, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 2 Departament d'Enginyeria Minera i Recursos Naturals, Universitat Politècnica de Catalunya, Av de Les Bases de Manresa 61-73, 08242 Manresa. 3Instituto de Geofísica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 4Centro de Geociencias, Universidad Nacional Autónoma de México, Campus Juriquilla, Boulevard Juriquilla 3001, 76230 Santiago de Querétaro, Qro., Mexico The Velardeña mining district is located in north-eastern part of the state of Durango, in northern of Mexico. The ore deposit is a lead-zinc, garnet-rich skarn developed at the contact between granite porphyry dikes (Eocene) and well-laminated limestones with interbedded chert (Albian-Cenomanian). A study of sulfur isotopes has been carried out in various sulfide minerals of the ores of Velardeña, in order to: (a) constrain the possible sources of sulfur and, therefore, better understand the sulfide mineralizing processes, and (b) to estimate the temperature of the ore-forming stage of the skarn. Sulfur isotope analyses were performed in 21 pure fractions of sulfide minerals of the ore mineralization (pyrite, chalcopyrite, sphalerite and galena). The mineral separation was performed using a series of sieves, and the purity of the samples was verified under a binocular microscope. Isotopic analyses were done on a Finnigan MAT Delta C flow elemental analyzer coupled to a TC-EA, according with the method of Giesemann et al. (1974). The δ34S values of the analyzed sulfides range mostly between -0.6 and +2.6 ‰ (relative to the CDT standard). These values are indicative of a magmatic source of sulfur. A single analysis falls

  17. Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels.

    PubMed

    Borrok, David M; Gieré, Reto; Ren, Minghua; Landa, Edward R

    2010-12-01

    Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.

  18. Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels

    USGS Publications Warehouse

    Borrok, D.M.; Gieré, R.; Ren, M.; Landa, E.R.

    2010-01-01

    Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.

  19. Tooth enamel maturation reequilibrates oxygen isotope compositions and supports simple sampling methods

    NASA Astrophysics Data System (ADS)

    Trayler, Robin B.; Kohn, Matthew J.

    2017-02-01

    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.

  20. Enhanced wound healing activity of Ag-ZnO composite NPs in Wistar Albino rats.

    PubMed

    Kantipudi, Sravani; Sunkara, Jhansi Rani; Rallabhandi, Muralikrishna; Thonangi, Chandi Vishala; Cholla, Raga Deepthi; Kollu, Pratap; Parvathaneni, Madhu Kiran; Pammi, Sri Venkata Narayana

    2018-06-01

    In the present study, silver (Ag) and Ag-zinc oxide (ZnO) composite nanoparticles (NPs) were synthesised and studied their wound-healing efficacy on rat model. Ultraviolet-visible spectroscopy of AgNPs displayed an intense surface plasmon (SP) resonance absorption at 450 nm. After the addition of aqueous Zn acetate solution, SP resonance band has shown at 413.2 nm indicating a distinct blue shift of about 37 nm. X-ray diffraction analysis Ag-ZnO composite NPs displayed existence of two mixed sets of diffraction peaks, i.e. both Ag and ZnO, whereas AgNPs exhibited face-centred cubic structures of metallic Ag. Scanning electron microscope (EM) and transmission EM analyses of Ag-ZnO composite NPs revealed the morphology to be monodispersed hexagonal and quasi-hexagonal NPs with distribution of particle size of 20-40 nm. Furthermore, the authors investigated the wound-healing properties of Ag-ZnO composite NPs in an animal model and found that rapid healing within 10 days when compared with pure AgNPs and standard drug dermazin.

  1. Fabrication of Well-Aligned ZnO Nanorods Using a Composite Seed Layer of ZnO Nanoparticles and Chitosan Polymer.

    PubMed

    Khun, Kimleang; Ibupoto, Zafar Hussain; AlSalhi, Mohamad S; Atif, Muhammad; Ansari, Anees A; Willander, Magnus

    2013-09-30

    In this study, by taking the advantage of both inorganic ZnO nanoparticles and the organic material chitosan as a composite seed layer, we have fabricated well-aligned ZnO nanorods on a gold-coated glass substrate using the hydrothermal growth method. The ZnO nanoparticles were characterized by the Raman spectroscopic techniques, which showed the nanocrystalline phase of the ZnO nanoparticles. Different composites of ZnO nanoparticles and chitosan were prepared and used as a seed layer for the fabrication of well-aligned ZnO nanorods. Field emission scanning electron microscopy, energy dispersive X-ray, high-resolution transmission electron microscopy, X-ray diffraction, and infrared reflection absorption spectroscopic techniques were utilized for the structural characterization of the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods on a gold-coated glass substrate. This study has shown that the ZnO nanorods are well-aligned, uniform, and dense, exhibit the wurtzite hexagonal structure, and are perpendicularly oriented to the substrate. Moreover, the ZnO nanorods are only composed of Zn and O atoms. An optical study was also carried out for the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods, and the obtained results have shown that the fabricated ZnO nanorods exhibit good crystal quality. This study has provided a cheap fabrication method for the controlled morphology and good alignment of ZnO nanorods, which is of high demand for enhancing the working performance of optoelectronic devices.

  2. Fabrication of Well-Aligned ZnO Nanorods Using a Composite Seed Layer of ZnO Nanoparticles and Chitosan Polymer

    PubMed Central

    Khun, Kimleang; Ibupoto, Zafar Hussain; AlSalhi, Mohamad S.; Atif, Muhammad; Ansari, Anees A.; Willander, Magnus

    2013-01-01

    In this study, by taking the advantage of both inorganic ZnO nanoparticles and the organic material chitosan as a composite seed layer, we have fabricated well-aligned ZnO nanorods on a gold-coated glass substrate using the hydrothermal growth method. The ZnO nanoparticles were characterized by the Raman spectroscopic techniques, which showed the nanocrystalline phase of the ZnO nanoparticles. Different composites of ZnO nanoparticles and chitosan were prepared and used as a seed layer for the fabrication of well-aligned ZnO nanorods. Field emission scanning electron microscopy, energy dispersive X-ray, high-resolution transmission electron microscopy, X-ray diffraction, and infrared reflection absorption spectroscopic techniques were utilized for the structural characterization of the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods on a gold-coated glass substrate. This study has shown that the ZnO nanorods are well-aligned, uniform, and dense, exhibit the wurtzite hexagonal structure, and are perpendicularly oriented to the substrate. Moreover, the ZnO nanorods are only composed of Zn and O atoms. An optical study was also carried out for the ZnO nanoparticles/chitosan seed layer-coated ZnO nanorods, and the obtained results have shown that the fabricated ZnO nanorods exhibit good crystal quality. This study has provided a cheap fabrication method for the controlled morphology and good alignment of ZnO nanorods, which is of high demand for enhancing the working performance of optoelectronic devices. PMID:28788336

  3. Reassessing the stable isotope composition assigned to methane flux from natural wetlands in isotope-constrained budgets

    NASA Astrophysics Data System (ADS)

    Hornibrook, Edward; Maxfield, Peter; Gauci, Vincent; Stott, Andrew

    2013-04-01

    Stable isotope ratios in CH4 preserve information about its origin and history, and are commonly used to constrain global CH4 budgets. Wetlands are key contributors to the atmospheric burden of CH4 and typically are assigned a stable carbon isotope composition of ~-60 permil in isotope-weighted stable isotope models despite the considerable range of δ13C(CH4) values (~ -100 to -40 permil) known to occur in these diverse ecosystems. Kinetic isotope effects (KIEs) associated with the metabolism of CH4-producing microorganisms generate much of the natural variation but highly negative and positive δ13C(CH4) values generally result from secondary processes (e.g., diffusive transport or oxidation by soil methanotrophs). Despite these complexities, consistent patterns exist in the isotope composition of wetland CH4 that can be linked conclusively to trophic status and consequently, natural succession or human perturbations that impact nutrient levels. Another challenge for accurate representation of wetlands in carbon cycle models is parameterisation of sporadic CH4 emission events. Abrupt release of large volumes of CH4-rich bubbles in short periods of time can account for a significant proportion of the annual CH4 flux from a wetland but such events are difficult to detect using conventional methods. New infrared spectroscopy techniques capable of high temporal resolution measurements of CH4 concentration and stable isotope composition can readily quantify short-lived CH4 pulses. Moreover, the isotope data can be used conclusively to determine shifts in the mode of CH4 transport and provide the potential to link initiation of abrupt emission events to forcing by internal or external factors.

  4. Advanced thermopower wave in novel ZnO nanostructures/fuel composite.

    PubMed

    Lee, Kang Yeol; Hwang, Hayoung; Choi, Wonjoon

    2014-09-10

    Thermopower wave is a new concept of energy conversion from chemical to thermal to electrical energy, produced from the chemical reaction in well-designed hybrid structures between nanomaterials and combustible fuels. The enhancement and optimization of energy generation is essential to make it useful for future applications. In this study, we demonstrate that simple solution-based synthesized zinc oxide (ZnO) nanostructures, such as nanorods and nanoparticles are capable of generating high output voltage from thermopower waves. In particular, an astonishing improvement in the output voltage (up to 3 V; average 2.3 V) was achieved in a ZnO nanorods-based composite film with a solid fuel (collodion, 5% nitrocellulose), which generated an exothermic chemical reaction. Detailed analyses of thermopower waves in ZnO nanorods- and cube-like nanoparticles-based hybrid composites have been reported in which nanostructures, output voltage profile, wave propagation velocities, and surface temperature have been characterized. The average combustion velocities for a ZnO nanorods/fuel and a ZnO cube-like nanoparticles/fuel composites were 40.3 and 30.0 mm/s, while the average output voltages for these composites were 2.3 and 1.73 V. The high output voltage was attributed to the amplified temperature in intermixed composite of ZnO nanostructures and fuel due to the confined diffusive heat transfer in nanostructures. Moreover, the extended interfacial areas between ZnO nanorods and fuel induced large amplification in the dynamic change of the chemical potential, and it resulted in the enhanced output voltage. The differences of reaction velocity and the output voltage between ZnO nanorods- and ZnO cube-like nanoparticles-based composites were attributed to variations in electron mobility and grain boundary, as well as thermal conductivities of ZnO nanorods and particles. Understanding this astonishing increase and the variation of the output voltage and reaction velocity, precise

  5. Solution processable RGO-CdZnS composite for solar light responsive photocatalytic degradation of 4-Nitrophenol

    NASA Astrophysics Data System (ADS)

    Ibrahim, Sk; Chakraborty, Koushik; Pal, Tanusri; Ghosh, Surajit

    2017-05-01

    We report the one pot single step synthesis and characterization of solution processable reduced graphene oxide (RGO) - cadmium zinc sulfide (CdZnS) nanocomposite materials. The composite was characterized structurally and morphologically by XRD and TEM studies. The reduction of GO in RGO-CdZnS composite, was confirmed by XPS and Raman spectroscopy. The photocatalytic activity of the RGO-CdZnS composite was investigated towards the degradation of 4-Nitrophenol. A notable increase of photocatalytic efficiency of RGO-CdZnS compare to controlled CdZnS was observed. Here RGO plays a crucial role to efficient photo induced charge separation from the CdZnS, and decreases the electron-hole recombination probability and subsequently enhanced the photocatalytic activity of the RGO-CdZnS composite material under simulated solar light irradiation. This work highlights the potential application of RGO-based materials in the field of photocatalytic degradation of organic water pollutant.

  6. Optical, thermal and morphological study of ZnS doped PVA polymer nano composites

    NASA Astrophysics Data System (ADS)

    Guruswamy, B.; Ravindrachary, V.; Shruthi, C.; Sagar, Rohan N.; Hegde, Shreedatta

    2018-05-01

    The effect of ZnS nano particle doping on optical, thermal properties and morphological study of the PVA polymer has been investigated using FTIR, UV-Visible and TGA, FESEM techniques. Nano sized ZnS particles were synthesized by a simple wet chemical route. Pure and ZnS/PVA nano composites were prepared using solution casting technique. The FTIR study confirms that the ZnS nano particles interacts with the OH group of PVA polymer and forms the complex. The formation of these complexes affects the optical and thermal properties of the composite. The changes in optical properties were studied using UV-Vis absorption method. The variation in thermal property was analysed using TGA results. The modified surface morphology analysis was carried out using FESEM.

  7. Effect of composition on SILAR deposited CdxZn1-xS thin films

    NASA Astrophysics Data System (ADS)

    Ashith V., K.; Gowrish Rao, K.

    2018-04-01

    In the group of II-VI compound semiconductor, cadmium zinc sulphide (CdxZn1-xS) thin films have broad application in photovoltaic, optoelectronic devices etc. For heterojunction aspects, CdxZn1-xS thin film can be used as heterojunction partner for CdTe as the absorber layer. In this work, CdZnS thin films prepared on glass substrates by Successive Ion Layer Adsorption and Reaction (SILAR) method by varying the composition. The XRD patterns of deposited films showed polycrystalline with the hexagonal phase. The crystallite size of the films was estimated from W-H plot. The bond length of the film varied w.r.to the composition of the CdxZn1-xS films. The urbach energy of the films was calcualted from absorbance data.

  8. Measurement of total Zn and Zn isotope ratios by quadrupole ICP-MS for evaluation of Zn uptake in gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss)

    USGS Publications Warehouse

    Wolf, R.E.; Todd, A.S.; Brinkman, S.; Lamothe, P.J.; Smith, K.S.; Ranville, J.F.

    2009-01-01

    This study evaluates the potential use of stable zinc isotopes in toxicity studies measuring zinc uptake by the gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss). The use of stable isotopes in such studies has several advantages over the use of radioisotopes, including cost, ease of handling, elimination of permit requirements, and waste disposal. A pilot study using brown trout was performed to evaluate sample preparation methods and the ability of a quadrupole inductively coupled plasma mass spectrometer (ICP-MS) system to successfully measure changes in the 67Zn/66Zn ratios for planned exposure levels and duration. After completion of the pilot study, a full-scale zinc exposure study using rainbow trout was performed. The results of these studies indicate that there are several factors that affect the precision of the measured 67Zn/66Zn ratios in the sample digests, including variations in sample size, endogenous zinc levels, and zinc uptake rates by individual fish. However, since these factors were incorporated in the calculation of the total zinc accumulated by the gills during the exposures, the data obtained were adequate for their intended use in calculating zinc binding and evaluating the influences of differences in water quality parameters.

  9. Modelling and intepreting the isotopic composition of water vapour in convective updrafts

    NASA Astrophysics Data System (ADS)

    Bolot, M.; Legras, B.; Moyer, E. J.

    2012-08-01

    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, droplet 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.

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

    NASA Astrophysics Data System (ADS)

    Bolot, M.; Legras, B.; Moyer, E. J.

    2013-08-01

    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.

  11. Enhanced photocatalytic activity and synthesis of ZnO nanorods/MoS2 composites

    NASA Astrophysics Data System (ADS)

    Li, Hui; Shen, Hao; Duan, Libing; Liu, Ruidi; Li, Qiang; Zhang, Qian; Zhao, Xiaoru

    2018-05-01

    A stable and recyclable organic degradation catalyst based on MoS2 functionalized ZnO nanorods was introduced. ZnO nanorods were synthesized on the glass substrates (2 cm*2 cm) by sol-gel method and hydrothermal method and functionalized with MoS2 via an argon flow annealing method. The structure and morphology of the as-prepared samples were characterized by XRD, SEM and TEM. Results showed that a small amount of MoS2 was successfully wrapped on the surfaces of ZnO nanorods. XPS analyses showed the existence of Zn-S between ZnO and MoS2, indicating that the MoS2 was combined with ZnO through chemical bonds and formed the ZnO/MoS2 heterostructure. PL results revealed that ZnO/MoS2 had lower fluorescence spectra indicating an electron transport channel between ZnO and MoS2 which separated electrons and holes. Photocatalytic experiment showed that ZnO/MoS2 composites showed a better photodegradation performance of Rhodamine B (RhB) after functionalized with MoS2 under the UV light irradiation which could be attributed to the separation and transfer of photogenerated electrons and holes between ZnO and MoS2. Meanwhile, the high active adsorption sites on the edges of MoS2 also accelerated the degradation process. Furthermore, the scavengers were used to investigate the major active species and results indicated that h+ was the major reactive species for the degradation.

  12. Incorporation of ZnO and their composite nanostructured material into a cotton fabric platform for wearable device applications.

    PubMed

    Veluswamy, Pandiyarasan; Sathiyamoorthy, Suhasini; Khan, Faizan; Ghosh, Aranya; Abhijit, Majumdar; Hayakawa, Yasuhiro; Ikeda, Hiroya

    2017-02-10

    The central idea of this paper is to innovate a new approach for the development of wearable device materials through the coating of cotton fabric with ZnO and Sb-/Ag-/ZnO composites. The study was designed in order to have a clear understanding of the role of ZnO as well as the modified composite thereof under investigation. Cotton fabric with uniform ZnO/ZnO-composite layers on the surface was successfully synthesized via a solvothermal method. The growth behaviors were investigated by comparing ZnO and ZnO-composites. The structural, morphological, chemical states, optical, electrical and thermopower properties of these fabrics were studied. Nanostructured ZnO-composite fabric had enhanced UV shielding with a value of 83.96. It is found that the ZnO-composite fabrics have increased electrical conductivity. The thermopower value of the ZnO-composite fabric could reach 471.9μVK -1 . Such materials are anticipated to be worthwhile as wearable electronic devices and as protective textiles. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. ZnS/diamond composite coatings for infrared transmission applications formed by the aerosol deposition method

    NASA Astrophysics Data System (ADS)

    Johnson, Scooter D.; Kub, Fritz J.; Eddy, Charles R.

    2013-06-01

    The deposition of nano-crystalline ZnS/diamond composite protective coatings on silicon, sapphire, and ZnS substrates, as a preliminary step to coating infrared transparent ZnS substrates from powder mixtures by the aerosol deposition method is presented. Advantages of the aerosol deposition method include the ability to form dense, nanocrystalline lms up to hundreds of microns thick at room temperature and at a high deposition rate on a variety of substrates. Deposition is achieved by creating a pressure gradient that accelerates micrometer- scale particles in an aerosol to high velocity. Upon impact with the target substrate the particles fracture and embed. Continued deposition forms the thick compacted lm. Deposition from an aerosolized mixture of ZnS and diamond powders onto all targets results in linear trend from apparent sputter erosion of the substrate at 100% diamond to formation of a lm with increasing fractions of ZnS. The crossover from abrasion to lm formation on sapphire occurs above about 50% ZnS and a mixture of 90% ZnS and 10% diamond forms a well-adhered lm of about 0.7 μm thickness at a rate of 0.14 μm/min. Resulting lms are characterized by scanning electron microscopy, pro lometry, infrared transmission spectroscopy, and x-ray photoemission spectroscopy. These initial lms mark progress toward the future goal of coating ZnS substrates for abrasion resistance.

  14. Composites of ZnO nanoparticles and biomass based activated carbon: adsorption, photocatalytic and antibacterial capacities.

    PubMed

    Cruz, G J F; Gómez, M M; Solis, J L; Rimaycuna, J; Solis, R L; Cruz, J F; Rathnayake, B; Keiski, R L

    2018-05-01

    Composite material (AC-ZnO) was prepared by growing ZnO nanoparticles during the production of biomass based-activated carbon (AC) via the incorporation of zinc acetate in the process. Comprehensive analyses confirmed the presence of ZnO nanoparticles over the AC surface and described the particular nature of the composite adsorbent. Methylene blue (MB) equilibrium data fitted the Dubinin-Radushkevich model. The MB adsorption capacity was higher for the bare activated carbons (197.9-188.7 mg/g) than the activated carbons with ZnO nanoparticles (137.6-149.7 mg/g). The adsorption of the MB on the adsorbents is physical because the mean adsorption energy (E) is between 1.76 and 2.00 kJ/mol. Experiments that combine adsorption and photocatalysis were carried out with different loads of adsorbents and with and without UV-light exposure. Photocatalytic activity was identified mostly at the first stage of the adsorption process and, in the case of experiments with less load of the composite AC-ZnO, because the light obstruction effect of the activated carbon is more for higher loads. The ZnO grown over AC improves the adsorption of cations such as Pb, Al and Fe in aqueous phase (polluted river water) and provides antibacterial capacity against Escherichia coli and Salmonella typhimurium.

  15. Amplified spontaneous emission from ZnO in n-ZnO/ZnO nanodots-SiO(2) composite/p-AlGaN heterojunction light-emitting diodes.

    PubMed

    Shih, Ying Tsang; Wu, Mong Kai; Li, Wei Chih; Kuan, Hon; Yang, Jer Ren; Shiojiri, Makoto; Chen, Miin Jang

    2009-04-22

    This study demonstrates amplified spontaneous emission (ASE) of the ultraviolet (UV) electroluminescence (EL) from ZnO at lambda~380 nm in the n-ZnO/ZnO nanodots-SiO(2) composite/p- Al(0.12)Ga(0.88)N heterojunction light-emitting diode. A SiO(2) layer embedded with ZnO nanodots was prepared on the p-type Al(0.12)Ga(0.88)N using spin-on coating of SiO(2) nanoparticles followed by atomic layer deposition (ALD) of ZnO. An n-type Al-doped ZnO layer was deposited upon the ZnO nanodots-SiO(2) composite layer also by the ALD technique. High-resolution transmission electron microscopy (HRTEM) reveals that the ZnO nanodots embedded in the SiO(2) matrix have diameters of 3-8 nm and the wurtzite crystal structure, which allows the transport of carriers through the thick ZnO nanodots-SiO(2) composite layer. The high quality of the n-ZnO layer was manifested by the well crystallized lattice image in the HRTEM picture and the low-threshold optically pumped stimulated emission. The low refractive index of the ZnO nanodots-SiO(2) composite layer results in the increase in the light extraction efficiency from n-ZnO and the internal optical feedback of UV EL into n-ZnO layer. Consequently, significant enhancement of the UV EL intensity and super-linear increase in the EL intensity, as well as the spectral narrowing, with injection current were observed owing to ASE in the n-ZnO layer.

  16. Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition

    NASA Astrophysics Data System (ADS)

    Nielson, Kristine E.; Bowen, Gabriel J.

    2010-03-01

    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 composition effect on the thermal and optical properties across CdZnTe crystals

    NASA Astrophysics Data System (ADS)

    Strzałkowski, K.

    2016-11-01

    Cd1-x Zn x Te mixed crystals investigated in this work were grown from the melt using the vertical Bridgman-Stockbarger method in the whole range of composition 0  <  x  <  1 that is from one binary crystal (CdTe) to another (ZnTe). The real composition of grown crystals was measured with the SEM/EDS method along the growth axis. The segregation coefficient of Zn in a CdTe matrix has been evaluated as being close to unity. The energy gap as a function of the composition was determined from transmission spectroscopy. Thanks to that, the bowing parameter of this ternary alloy was found to be 0.458. In this work the systematical study of thermal properties of Cd1-x Zn x Te alloys from one binary crystal (CdTe) to another (ZnTe) grown by the vertical Bridgman technique were undertaken for the first time. The thermal diffusivity and effusivity of the investigated crystals were derived from the experimental data and allowed the thermal conductivity to be calculated. Diagrams of the thermal conductivity versus composition were analyzed applying the model for mixed semiconducting crystals given by Sadao Adachi. Thanks to that, the contribution of the thermal resistivity arising from the lattice disorder to the total resistivity of the crystal has been determined.

  18. Lead-Free KNbO3:xZnO Composite Ceramics.

    PubMed

    Lv, Xiang; Li, Zhuoyun; Wu, Jiagang; Xiao, Dingquan; Zhu, Jianguo

    2016-11-09

    It is a tough issue to develop dense and water resistant KNbO 3 ceramics due to high evaporation and hygroscopicity of K 2 O. Here, KNbO 3 :xZnO composite ceramics were used to successfully solve this problem, where ZnO particles were randomly distributed into a KNbO 3 matrix. The addition of ZnO hardly affects the phase structure of KNbO 3 , and moreover, the enhancement of electrical properties, thermal stability, and aging characteristics was observed in KNbO 3 :xZnO composite ceramics. The composites possessed the maximum d 33 of 120 ± 5 pC/N, which is superior to that of pure KNbO 3 (d 33 = 80 pC/N). More importantly, a strong water resistance and an aging-free characteristic were observed in KNbO 3 :0.4ZnO. This is the first time for KNbO 3 ceramics to simultaneously improve electrical properties and resolve the water-absorbing properties. We believe that these composite ceramics are promising for practical applications.

  19. Synthesis of Carbon-Coated ZnO Composite and Varistor Properties Study

    NASA Astrophysics Data System (ADS)

    Sun, Wei-Jie; Liu, Jin-Ran; Yao, Da-Chuan; Chen, Yong; Wang, Mao-Hua

    2017-03-01

    In this article, monodisperse ZnO composite nanoparticles were successfully prepared by sol-gel mixed precursor method. Subsequently, carbon as the shell was homogeneously coated on the surface of the ZnO composite nanoparticles via a simple adsorption and calcination process. Microstructural studies of the as-obtained powders were carried out using the techniques of the x-ray powder diffraction, scanning electron microscopy, field emission scanning electron microscopy, transmission electron microscopy with energy dispersive x-ray spectroscopy, and Fourier transform infrared spectroscopy. The results show that the pink ZnO composite powders were fully coated by carbon. Based on the results, the effect of glucose content on the microstructure of the synthesized composites and the electrical properties of the ZnO varistors sintered in air at 1150°C for 2 h were also fully studied. As the amount of glucose increased, the thickness of carbon can be increased from 2.5 nm to 5 nm. In particular, the ZnO varistor fabricated with the appropriate thickness of the carbon coating (5 nm) leads to the superior electrical performance, with present high breakdown voltage ( V b = 420 V/mm) and excellent nonlinear coefficient ( α = 61.7), compared with the varistors obtained without carbon coating.

  20. Oxygen isotopic composition and U-Pb discordance in zircon

    USGS Publications Warehouse

    Booth, A.L.; Kolodny, Y.; Chamberlain, C.P.; McWilliams, M.; Schmitt, A.K.; Wooden, J.

    2005-01-01

    We have investigated U-Pb discordance and oxygen isotopic composition of zircon using high-spatial resolution ??18O measurement by ion microprobe. ??18O in both concordant and discordant zircon grains provides an indication of the relationship between fluid interaction and discordance. Our results suggest that three characteristics of zircon are interrelated: (1) U-Pb systematics and concomitant age discordance, (2) ??18O and the water-rock interactions implied therein, and (3) zircon texture, as revealed by cathodoluminescence and BSE imaging. A key observation is that U-Pb-disturbed zircons are often also variably depleted in 18O, but the relationship between discordance and ??18O is not systematic. ??18O values of discordant zircons are generally lighter but irregular in their distribution. Textural differences between zircon grains can be correlated with both U-Pb discordance and ??18O. Discordant grains exhibit either a recrystallized, fractured, or strongly zoned CL texture, and are characteristic of 18O depletion. We interpret this to be a result of metamictization, leading to destruction of the zircon lattice and an increased susceptibility to lead loss. Conversely, grains that are concordant have less-expressed zoning and a smoother CL texture and are enriched in 18O. From this it is apparent that various stages of water-rock interaction, as evidenced by systematic variations in ??18O, leave their imprint on both the texture and U-Pb systematics of zircon. Copyright ?? 2005 Elsevier Ltd.

  1. Zinc isotope anomalies in Allende meteorite inclusions

    NASA Technical Reports Server (NTRS)

    Loss, R. D.; Lugmair, G. W.

    1990-01-01

    The isotopic compositions of Zn, Cr, Ti, and Ca have been measured in a number of CAIs from the Allende meteorite. The aim was to test astrophysical models which predict large excesses of Zn-66 to accompany excesses in the neutron-rich isotopes of Ca, Ti, Cr, and Ni. Some of the CAIs show clearly resolved but small excesses for Zn-66 which are at least an order of magnitude smaller than predicted. This result may simply reflect the volatility and chemical behavior of Zn as compared to the other (more refractory) anomalous elements found in these samples. Alternatively, revision of parameters and assumptions used for the model calculations may be required.

  2. Cooperative cytotoxic activity of Zn and Cu in bovine serum albumin-conjugated ZnS/CuS nano-composites in PC12 cancer cells

    NASA Astrophysics Data System (ADS)

    Wang, Hua-Jie; Yu, Xue-Hong; Wang, Cai-Feng; Cao, Ying

    2013-11-01

    Series of self-assembled and mono-dispersed bovine serum albumin (BSA)-conjugated ZnS/CuS nano-composites with different Zn/Cu ratios had been successfully synthesized by a combination method of the biomimetic synthesis and ion-exchange strategy under the gentle conditions. High-resolution transmission electron microscopy observation, Fourier transform infrared spectra and zeta potential analysis demonstrated that BSA-conjugated ZnS/CuS nano-composites with well dispersity had the hierarchical structure and BSA was a key factor to control the morphology and surface electro-negativity of final products. The real-time monitoring by atomic absorption spectroscopy and powder X-ray diffraction revealed that the Zn/Cu ratio of nano-composites could be controlled by adjusting the ion-exchange time. In addition, the metabolic and morphological assays indicated that the metabolic proliferation and spread of rat pheochromocytoma (PC12) cells could be inhibited by nano-composites, with the high anti-cancer activity at a low concentration (4 ppm). What were more important, Zn and Cu in nano-composites exhibited a positive cooperativity at inhibiting cancer cell functions. The microscope observation and biochemical marker analysis clearly revealed that the nano-composites-included lipid peroxidation and disintegration of membrane led to the death of PC12 cells. Summarily, the present study substantiated the potential of BSA-conjugated ZnS/CuS nano-composites as anti-cancer drug.

  3. Effects of climatic seasonality on the isotopic composition of evaporating soil waters

    NASA Astrophysics Data System (ADS)

    Benettin, Paolo; Volkmann, Till H. M.; von Freyberg, Jana; Frentress, Jay; Penna, Daniele; Dawson, Todd E.; Kirchner, James W.

    2018-05-01

    Stable water isotopes are widely used in ecohydrology to trace the transport, storage, and mixing of water on its journey through landscapes and ecosystems. Evaporation leaves a characteristic signature on the isotopic composition of the water that is left behind, such that in dual-isotope space, evaporated waters plot below the local meteoric water line (LMWL) that characterizes precipitation. Soil and xylem water samples can often plot below the LMWL as well, suggesting that they have also been influenced by evaporation. These soil and xylem water samples frequently plot along linear trends in dual-isotope space. These trend lines are often termed "evaporation lines" and their intersection with the LMWL is often interpreted as the isotopic composition of the precipitation source water. Here we use numerical experiments based on established isotope fractionation theory to show that these trend lines are often by-products of the seasonality in evaporative fractionation and in the isotopic composition of precipitation. Thus, they are often not true evaporation lines, and, if interpreted as such, can yield highly biased estimates of the isotopic composition of the source water.

  4. Soil drying effects on the carbon isotope composition of soil respiration

    EPA Science Inventory

    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 opp...

  5. On the equilibrium isotopic composition of the thorium-uranium-plutonium fuel cycle

    NASA Astrophysics Data System (ADS)

    Marshalkin, V. Ye.; Povyshev, V. M.

    2016-12-01

    The equilibrium isotopic compositions and the times to equilibrium in the process of thorium-uranium-plutonium oxide fuel recycling in VVER-type reactors using heavy water mixed with light water are estimated. It is demonstrated thEhfat such reactors have a capacity to operate with self-reproduction of active isotopes in the equilibrium mode.

  6. On the equilibrium isotopic composition of the thorium–uranium–plutonium fuel cycle

    SciTech Connect

    Marshalkin, V. Ye., E-mail: marshalkin@vniief.ru; Povyshev, V. M.

    2016-12-15

    The equilibrium isotopic compositions and the times to equilibrium in the process of thorium–uranium–plutonium oxide fuel recycling in VVER-type reactors using heavy water mixed with light water are estimated. It is demonstrated thEhfat such reactors have a capacity to operate with self-reproduction of active isotopes in the equilibrium mode.

  7. ZrO{sub 2}-ZnO composite thin films for humidity sensing

    SciTech Connect

    Velumani, M., E-mail: velumanimohan@gmail.com; Sivacoumar, R.; Alex, Z. C.

    2016-05-23

    ZrO{sub 2}-ZnO composite thin films were grown by reactive DC magnetron sputtering. X-ray diffraction studies reveal the composite nature of the films with separate ZnO and ZrO{sub 2} phase. Scanning electron microscopy studies confirm the nanocrystalline structure of the films. The films were studied for their impedometric relative humidity (RH) sensing characteristics. The complex impedance plot was fitted with a standard equivalent circuit consisting of an inter-granular resistance and a capacitance in parallel. The DC resistance was found to be decreasing with increase in RH.

  8. Zinc Isotopic Signatures of the Upper Continental Crust

    NASA Astrophysics Data System (ADS)

    Xia, Y.; Zhang, X.; Zhang, H.; Huang, F.

    2016-12-01

    To examine the Zn isotope systematics within the Upper Continental Crust (UCC), and isotope fractionation during chemical weathering in large spatial and temporal scales, we analyzed Zn isotopic compositions of loess, glacial diamictites, river sediments, and igneous rocks (samples in total 77). The Zn isotopic compositions (δ66Zn relative to JMC-Lyon) of loess display a limited variation (0.17‰ to 0.29‰), which is negatively correlated with Zn content and proxies for chemical weathering (e.g. CIA values), reflect the impact of chemical weathering. Glacial diamictites have more variable δ66Zn (0.09‰ to 0.48‰), but the average δ66Zn (0.29±0.03‰, 2SD) is similar to loess. δ66Zn of glacial diamictites correlate roughly negatively with CIA values, but have no correlation with Zn content, implying source heterogeneity and effect from chemical weathering. δ66Zn of A-type (0.39‰ to 0.45‰) and S-type (0.28‰ to 0.35‰) granites are both homogeneous, but the latter have systematically lighter δ66Zn. This may reflect no Zn isotopic fractionation during magmatic processes and involvement of isotopically light meta-sedimentary into the sources of S-type granites. Furthermore, δ66Zn in riverine sediments display a small variation from 0.23‰ to 0.37‰, while δ66Zn of the the shales vary from 0.14‰ to 0.53‰, which could result from a combination of processes, such as biological cycling and chemical weathering. Overall, our data suggest that incipient chemical weathering can fractionate Zn isotopes significantly, meanwhile, during this process, heavy Zn are released preferentially. The UCC is estimated to have an average δ66Zn of 0.30 ±0.03‰ (2SD) with data collected in this study, which is similar to the estimated value of Bulk Silicate Earth (0.28±0.05‰)[1] and mean dissolved riverine flux (0.33‰)[2], but distinctly lighter than the bulk composition of dissolved Zn in the ocean (0.51‰)[2]. [1] Chen et al., Zinc isotope fractionation

  9. Titanium and Oxygen Isotope Compositions of Individual Chondrules from Ordinary Chondrites

    NASA Astrophysics Data System (ADS)

    Bauer, K. K.; Schönbächler, M.; Fehr, M. A.; Vennemann, T.; Chaumard, N.; Zanda, B.

    2016-08-01

    We measured Ti and triple-O isotope compositions of individual chondrules (characterized by CT scanning) from ordinary chondrites. We will discuss correlations between Ti and ∆17O and their implication for the origin of nucleosynthetic anomalies.

  10. High Precision Iron Isotope Compositions in Components From the Allende CV3 Meteorite by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Mullane, E.; Russell, S. S.; Weiss, D.; Mason, T. F.; Gounelle, M.

    2001-12-01

    Four chondrules and one matrix sample of Allende were examined for Fe-isotope frac-tionation, using multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Iron is the most volatile major constituent of chondrules and a recent study [1] suggested that solar system Fe was initially isotopically homogeneous. Thus, any isotopic variation is likely due to mass fractionation during nebular process-ing. The chondrule samples were split. One portion was subject to a standard acid dis-solution whilst the other was polished, ena-bling textural and compositional characteri-zation. Fe, Cu and Zn are separated from the remaining matrix elements [2], removing potential interfering ions from the solution. 100 % elemental recovery (within error) is achieved, ensuring that chromatographic fractionation does not occur [2]. Hydrogen is bled into the collision cell, minimising Ar polyatomic species interferences. Typical precisions of 0.1‰ (2σ ) for 54Fe/56Fe ratios are achieved for 75 replicates. Instrumental mass bias is assessed using (1) sample-standard brack-eting and (2) doping with Cu. A variation of 0.8‰ /amu is observed, which is approximately 18 times the analyti-cal uncertainty at the 2σ level. Our high precision data show that: (1) Allende chondrules and matrix exhibit clear isotopic variation in iron. (2) δ 54Fe val-ues appear to be correlated to the bulk FeO content, with the more iron rich samples enriched in the lighter 54Fe isotope. (3) δ 54Fe values appear to be unre-lated to texture, and consequently to the temperature of chondrule formation. Bulk Fe-content may be a proxy for the amount of volatilisation experienced, and volatilisation of Fe in chondrule precursor material has resulted in a residue of the heavier Fe isotopes. Chondrules are known to have often experienced several heating events, and their texture primarily reflects the nature of the last event. Thus, the lack of correlation between the δ 54Fe value and chondrule texture

  11. Composition dependent band offsets of ZnO and its ternary alloys

    NASA Astrophysics Data System (ADS)

    Yin, Haitao; Chen, Junli; Wang, Yin; Wang, Jian; Guo, Hong

    2017-01-01

    We report the calculated fundamental band gaps of wurtzite ternary alloys Zn1-xMxO (M = Mg, Cd) and the band offsets of the ZnO/Zn1-xMxO heterojunctions, these II-VI materials are important for electronics and optoelectronics. Our calculation is based on density functional theory within the linear muffin-tin orbital (LMTO) approach where the modified Becke-Johnson (MBJ) semi-local exchange is used to accurately produce the band gaps, and the coherent potential approximation (CPA) is applied to deal with configurational average for the ternary alloys. The combined LMTO-MBJ-CPA approach allows one to simultaneously determine both the conduction band and valence band offsets of the heterojunctions. The calculated band gap data of the ZnO alloys scale as Eg = 3.35 + 2.33x and Eg = 3.36 - 2.33x + 1.77x2 for Zn1-xMgxO and Zn1-xCdxO, respectively, where x being the impurity concentration. These scaling as well as the composition dependent band offsets are quantitatively compared to the available experimental data. The capability of predicting the band parameters and band alignments of ZnO and its ternary alloys with the LMTO-CPA-MBJ approach indicate the promising application of this method in the design of emerging electronics and optoelectronics.

  12. Improved sensitivity of polychlorinated-biphenyl-orientated porous-ZnO surface photovoltage sensors from chemisorption-formed ZnO-CuPc composites

    PubMed Central

    Li, Mingtao; Meng, Guowen; Huang, Qing; Zhang, Shile

    2014-01-01

    We report a new mechanism for the enhancement of porous-ZnO surface photovoltage (SPV) response to polychlorinated biphenyls (PCBs, a notorious class of persistent organic pollutants as global environmental hazard) based on copper phthalocyanine (CuPc) chemisorptive bonding on porous-ZnO. A new ZnO-CuPc composite is formed on the porous-ZnO surface due to the interaction between the surface ZnO and CuPc, with its valence band (VB) energy level being higher than that of the pristine porous-ZnO. So that the efficiency of the photogenerated-electron transfer from the composite VB to the adjacent ZnO's surface states is drastically increased due to the reduced energy gap between the transition states. As a result, the sensitivity of the PCB-orientated SPV sensor is much improved by showing amplified variation of the SPV-signals perturbed by PCBs adsorbed on the ZnO-CuPc@porous-ZnO sensitive material. PMID:24594662

  13. Cu Isotopic Composition in Surface Environments and in Biological Systems: A Critical Review

    PubMed Central

    Wang, Zhuhong; Chen, Jiubin; Zhang, Ting

    2017-01-01

    Copper (Cu) is a transition metal and an essential micronutrient for organisms, but also one of the most widespread toxic inorganic contaminants at very high content. The research on Cu isotopes has grown rapidly in the last decade. Hitherto, a large number of studies have been published on the theoretical fractionation mechanisms, experimental data and natural variations of Cu isotopes in variable environments and ecosystems. These studies reported a large variation of δ65Cu (−16.49 to +20.04‰) in terrestrial samples and showed that Cu isotopes could be fractionated by various biogeochemical processes to different extent. Several papers have previously reviewed the coupling of Cu and Zn isotope systematics, and we give here a tentative review of the recent publications only on Cu isotopesin variable surface repositories, animals and human beings, with a goal to attract much attention to research on Cu (and other metals) behaviors in the environment and biological systems. PMID:28524094

  14. Characteristics of Heavy Metals and Pb Isotopic Composition in Sediments Collected from the Tributaries in Three Gorges Reservoir, China

    PubMed Central

    Gao, Bo; Zhou, Huaidong; Huang, Yong; Wang, Yuchun; Gao, Jijun; Liu, Xiaobo

    2014-01-01

    The concentrations, distribution, accumulation, and potential ecological risk of heavy metals (Cr, Cu, Zn, Ni, As, Pb, Cd, and Hg) in sediments from the Three Gorges Reservoir (TGR) tributaries were determined and studied. Pb isotopic compositions in sediments were also measured to effectively identify the potential Pb sources. The results showed that the average concentrations of heavy metals in sediment of TGR tributaries were higher than the local background values of soils and sediments in China. The assessment by Geoaccumulation Index indicated that Cu, Ni, and Hg were at the “slightly polluted” level and Cd was ranked as the “moderately polluted” level in tributary sediments of TGR. The assessment by Potential Ecological Risk Index showed that Hg and Cd were the predominant elements in tributary sediments in TGR. The Pb isotopic ratios in sediments varied from 1.171 to 1.202 for 206Pb/207Pb and from 2.459 to 2.482 for 208Pb/207Pb in TGR. All Pb isotopic ratios in sediments were similar to those from coal combustion, lead ores (the mining activities and smelting process), and cement material, indicating that these anthropogenic inputs may be the main sources for Pb pollution in sediments of TGR tributaries. PMID:24624045

  15. Isotopic composition of Pb and Th in interplinian volcanics from Somma-Vesuvius volcano, Italy

    USGS Publications Warehouse

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

    2004-01-01

    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

  16. Spacecraft measurements of the elemental and isotopic composition of solar energetic particles

    NASA Technical Reports Server (NTRS)

    Mewaldt, R. A.

    1980-01-01

    Within the past few years, instruments flown on satellites and space probes have made significant progress in measuring the elemental and isotopic composition of energetic heavy nuclei accelerated in solar flares. These new observations are discussed, focusing on: (1) the energy dependence of the elemental composition at energies not greater than 1 MeV/nucleon; (2) flare to flare variations in the composition; and (3) comparisons of the average solar particle abundances (Z not less than 2 and not greater than 28) with other measures of the solar composition, including photospheric, coronal, and solar wind observations. These comparisons have led to the suggestion that solar flares sample the composition of the corona. Isotopic measurements of heavy solar flare nuclei have recently added a new dimension to these studies. In particular, the isotopic composition of solar flare neon has been found to be significantly different from that measured in the solar wind, but consistent with the meteoritic component neon-A.

  17. Reversible superhydrophobic-superhydrophilic transition of ZnO nanorod/epoxy composite films.

    PubMed

    Liu, Yan; Lin, Ziyin; Lin, Wei; Moon, Kyoung Sik; Wong, C P

    2012-08-01

    Tuning the surface wettability is of great interest for both scientific research and practical applications. We demonstrated reversible transition between superhydrophobicity and superhydrophilicity on a ZnO nanorod/epoxy composite film. The epoxy resin serves as an adhesion and stress relief layer. The ZnO nanorods were exposed after oxygen reactive ion etching of the epoxy matrix. A subsequent chemcial treatment with fluoroalkyl and alkyl silanes resulted in a superhydrophobic surface with a water contact angle up to 158.4° and a hysteresis as low as 1.3°. Under UV irradiation, the water contact angle decreased gradually, and the surface eventually became superhydrophilic because of UV induced decomposition of alkyl silanes and hydroxyl absorption on ZnO surfaces. A reversible transition of surface wettability was realized by alternation of UV illumination and surface treatment. Such ZnO nanocomposite surface also showed improved mechanical robustness.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    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

  19. Microstructure and dielectric properties of cellulose acetate-ZnO/ITO composite films based on water hyacinth

    NASA Astrophysics Data System (ADS)

    Diantoro, M.; Mustikasari, A. A.; Wijayanti, N.; Yogihati, C.; Taufiq, A.

    2017-05-01

    The electrical properties of Cellulose Acetate (CA), especially extracted from water hyacinth, is rarely informed. CA is generally more stable compared to its cellulose. It has a good potential for electronic application with specific modifications such as inducing metal oxide. A combination of intrinsic properties of Zinc Oxide (ZnO) and CA is expected as a great potential for electrical and optical applications. CA-ZnO/ITO composite film was investigated in relation with its structure, dielectric constant, and the effect of light intensity on their dielectric constant. CA-ZnO composite films were prepared with different mass of ZnO i.e. 0; 0,02; 0,04; 0,06 and 0,08 grams. CA-ZnO solution was synthesized via the mixing method with PEG:DMF solvents by using a magnetic hotplate stirrer with the rotation rate of 1500 rpm at 80°C. The CA-ZnO solution was then deposited onto ITO/glass substrate by using spin coating technique. The CA-ZnO/ITO films were annealed at 160°C to remove the remaining solvents. The effects of ZnO composition on the structure (crystallinity and morphology) and dielectric constant properties were investigated by using X-Ray Diffractometer, Scanning Electron Microscopy, Fourier Transform Infrared Spectroscopy, and LCR meter. It was shown that cellulose can be isolated from water hyacinth with the yield of 67,72 % by Chesson method and can further be transformed into CA. The X-ray diffraction pattern showed that there are 2 phases formed i.e. CA and ZnO. Furthermore, greater ZnO amount increased the crystallinity of composite films. The CA-ZnO films exhibit porous films with ZnO distributed on the CA surface films. Therefore, ZnO increases the dielectric constant of CA-ZnO composite films.

  20. New Insights from Zinc and Copper Isotopic Compositions into the Sources of Atmospheric Particulate Matter from Two Major European Cities.

    PubMed

    Gonzalez, R Ochoa; Strekopytov, S; Amato, F; Querol, X; Reche, C; Weiss, D

    2016-09-20

    This study reports spatial and temporal variability of Zn and Cu isotopes in atmospheric particulate matter (PM) collected in two major European cities with contrasting atmospheric pollution, Barcelona and London. We demonstrate that nontraditional stable isotopes identify source contributions of Zn and Cu and can play a major role in future air quality studies. In Barcelona, samples of fine PM were collected at street level at sites with variable traffic density. The isotopic signatures ranged between -0.13 ± 0.09 and -0.51 ± 0.05‰ for δ(66)ZnIRMM and between +0.04 ± 0.20 and +0.33 ± 0.15‰ for δ(65)CuAE633. Copper isotope signatures similar to those of Cu sulfides and Cu/Sb ratios within the range typically found in brake wear suggest that nonexhaust emissions from vehicles are dominant. Negative Zn isotopic signatures characteristic for gaseous emissions from smelting and combustion and large enrichments of Zn and Cd suggest contribution from metallurgical industries. In London, samples of coarse PM collected on the top of a building over 18 months display isotope signatures ranging between +0.03 ± 0.04 and +0.49 ± 0.02‰ for δ(66)ZnIRMM and between +0.37 ± 0.17 and +0.97 ± 0.21‰ for δ(65)CuAE633. Heavy Cu isotope signatures (up to +0.97 ± 0.21‰) and higher enrichments and Cu/Sb ratios during winter time indicate important contribution from fossil fuel combustion. The positive δ(66)ZnIRMM signatures are in good agreement with signatures characteristic for ore concentrates used for the production of tires and galvanized materials, suggesting nonexhaust emissions from vehicles as the main source of Zn pollution.

  1. Long-term data set analysis of stable isotopic composition in German rivers

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

    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

  2. Elemental and iron isotopic composition of aerosols collected in a parking structure.

    PubMed

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

    2009-09-01

    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 in diameter (the fine fraction) and 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 PM<2.5 microm and PM>2.5 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.

  3. Model resin composites incorporating ZnO-NP: activity against S. mutans and physicochemical properties characterization

    PubMed Central

    Brandão, Natasha Lamego; Portela, Maristela Barbosa; Maia, Luciane Cople; Antônio, Andréa; Silva, Vanessa Loureiro Moreira e

    2018-01-01

    Abstract Although resin composites are widely used in the clinical practice, the development of recurrent caries at composite-tooth interface still remains as one of the principal shortcomings to be overcome in this field. Objectives To evaluate the activity against S. mutans biofilm of model resin composites incorporating different concentrations of ZnO-nanoparticles (ZnO-NP) and characterize their physicochemical properties. Materials and Methods Different concentrations of ZnO-NP (wt.%): E1=0, E2=0.5, E3=1, E4=2, E5=5 and E6=10 were incorporated into a model resin composite consisting of Bis-GMA-TEGDMA and barium borosilicate particles. The activity against S. mutans biofilm was evaluated by metabolic activity and lactic acid production. The following physicochemical properties were characterized: degree of conversion (DC%), flexural strength (FS), elastic modulus (EM), hardness (KHN), water sorption (Wsp), water solubility (Wsl) and translucency (TP). Results E3, E4, E5 and E6 decreased the biofilm metabolic activity and E5 and E6 decreased the lactic acid production (p<0.05). E6 presented the lowest DC% (p<0.05). No significant difference in FS and EM was found for all resin composites (p>0.05). E5 and E6 presented the lowest values of KHN (p<0.05). E6 presented a higher Wsp than E1 (p<0.05) and the highest Wsl (p<0.05). The translucency significantly decreased as the ZnO- NP concentration increased (p<0.05). Conclusions The incorporation of 2 – 5 wt.% of ZnO-NP could endow antibacterial activity to resin composites, without jeopardizing their physicochemical properties. PMID:29742262

  4. Model resin composites incorporating ZnO-NP: activity against S. mutans and physicochemical properties characterization.

    PubMed

    Brandão, Natasha Lamego; Portela, Maristela Barbosa; Maia, Luciane Cople; Antônio, Andréa; Silva, Vanessa Loureiro Moreira E; Silva, Eduardo Moreira da

    2018-01-01

    Although resin composites are widely used in the clinical practice, the development of recurrent caries at composite-tooth interface still remains as one of the principal shortcomings to be overcome in this field. Objectives To evaluate the activity against S. mutans biofilm of model resin composites incorporating different concentrations of ZnO-nanoparticles (ZnO-NP) and characterize their physicochemical properties. Materials and Methods Different concentrations of ZnO-NP (wt.%): E1=0, E2=0.5, E3=1, E4=2, E5=5 and E6=10 were incorporated into a model resin composite consisting of Bis-GMA-TEGDMA and barium borosilicate particles. The activity against S. mutans biofilm was evaluated by metabolic activity and lactic acid production. The following physicochemical properties were characterized: degree of conversion (DC%), flexural strength (FS), elastic modulus (EM), hardness (KHN), water sorption (Wsp), water solubility (Wsl) and translucency (TP). Results E3, E4, E5 and E6 decreased the biofilm metabolic activity and E5 and E6 decreased the lactic acid production (p<0.05). E6 presented the lowest DC% (p<0.05). No significant difference in FS and EM was found for all resin composites (p>0.05). E5 and E6 presented the lowest values of KHN (p<0.05). E6 presented a higher Wsp than E1 (p<0.05) and the highest Wsl (p<0.05). The translucency significantly decreased as the ZnO- NP concentration increased (p<0.05). Conclusions The incorporation of 2 - 5 wt.% of ZnO-NP could endow antibacterial activity to resin composites, without jeopardizing their physicochemical properties.

  5. A facile solvothermal method to produce graphene-ZnS composites for superior photoelectric applications

    NASA Astrophysics Data System (ADS)

    Lei, Yun; Chen, Feifei; Li, Rong; Xu, Jun

    2014-07-01

    In this experiment, flake graphite (<30 μm) was prepared as raw materials. Graphite oxide is prepared with Hummers method by low temperature, middle temperature and high temperature, and further treated with super-sonic oscillation to get graphene oxide. Graphene-zinc sulfide composites were synthesized through a simple solvothermal method using thiourea or sodium sulfide as sulfur source in the ethylene glycol or ethylenediamine, respectively. The products were characterized by X-ray and SEM, and analyzed by the transient photocurrent response and electrochemical impedance spectra. The results indicate that the properties of graphene-zinc sulfide composites prepared with thiourea in ethylene glycol are superior to those of blank-ZnS and composites prepared with sodium sulfide and ethylenediamine, which is attributed to electron capture and transfer ability of graphene resulting in a more efficient separation of the photoexcited charge carriers from ZnS-graphene composites.

  6. Microstructure and Mechanical Properties of Zn-Ni-Al₂O₃ Composite Coatings.

    PubMed

    Bai, Yang; Wang, Zhenhua; Li, Xiangbo; Huang, Guosheng; Li, Caixia; Li, Yan

    2018-05-21

    Zn-Ni-Al₂O₃ composite coatings with different Ni contents were fabricated by low-pressure cold spray (LPCS) technology. The effects of the Ni content on the microstructural and mechanical properties of the coatings were investigated. According to X-ray diffraction patterns, the composite coatings were primarily composed of metallic-phase Zn and Ni and ceramic-phase Al₂O₃. The energy-dispersive spectroscopy results show that the Al₂O₃ content of the composite coatings gradually decreased with increasing of Ni content. The cross-sectional morphology revealed thick, dense coatings with a wave-like stacking structure. The process of depositing Zn and Ni particles and Al₂O₃ particles by the LPCS method was examined, and the deposition mechanism was demonstrated to be mechanical interlocking. The bond strength, micro hardness and friction coefficient of the coatings did not obviously change when the Ni content varied. The presence of Al₂O₃ and Ni increased the wear resistance of the composite coatings, which was higher than that of pure Zn coatings, and the wear mechanism was abrasive and adhesive wear.

  7. Microstructure and Mechanical Properties of Zn-Ni-Al2O3 Composite Coatings

    PubMed Central

    Bai, Yang; Wang, Zhenhua; Li, Xiangbo; Huang, Guosheng; Li, Caixia

    2018-01-01

    Zn-Ni-Al2O3 composite coatings with different Ni contents were fabricated by low-pressure cold spray (LPCS) technology. The effects of the Ni content on the microstructural and mechanical properties of the coatings were investigated. According to X-ray diffraction patterns, the composite coatings were primarily composed of metallic-phase Zn and Ni and ceramic-phase Al2O3. The energy-dispersive spectroscopy results show that the Al2O3 content of the composite coatings gradually decreased with increasing of Ni content. The cross-sectional morphology revealed thick, dense coatings with a wave-like stacking structure. The process of depositing Zn and Ni particles and Al2O3 particles by the LPCS method was examined, and the deposition mechanism was demonstrated to be mechanical interlocking. The bond strength, micro hardness and friction coefficient of the coatings did not obviously change when the Ni content varied. The presence of Al2O3 and Ni increased the wear resistance of the composite coatings, which was higher than that of pure Zn coatings, and the wear mechanism was abrasive and adhesive wear. PMID:29883391

  8. Power generation from base excitation of a Kevlar composite beam with ZnO nanowires

    NASA Astrophysics Data System (ADS)

    Malakooti, Mohammad H.; Hwang, Hyun-Sik; Sodano, Henry A.

    2015-04-01

    One-dimensional nanostructures such as nanowires, nanorods, and nanotubes with piezoelectric properties have gained interest in the fabrication of small scale power harvesting systems. However, the practical applications of the nanoscale materials in structures with true mechanical strengths have not yet been demonstrated. In this paper, piezoelectric ZnO nanowires are integrated into the fiber reinforced polymer composites serving as an active phase to convert the induced strain energy from ambient vibration into electrical energy. Arrays of ZnO nanowires are grown vertically aligned on aramid fibers through a low-cost hydrothermal process. The modified fabrics with ZnO nanowires whiskers are then placed between two carbon fabrics as the top and the bottom electrodes. Finally, vacuum resin transfer molding technique is utilized to fabricate these multiscale composites. The fabricated composites are subjected to a base excitation using a shaker to generate charge due to the direct piezoelectric effect of ZnO nanowires. Measuring the generated potential difference between the two electrodes showed the energy harvesting application of these multiscale composites in addition to their superior mechanical properties. These results propose a new generation of power harvesting systems with enhanced mechanical properties.

  9. A paired apatite and calcite clumped isotope thermometry approach to estimating Cambro-Ordovician seawater temperatures and isotopic composition

    NASA Astrophysics Data System (ADS)

    Bergmann, Kristin D.; Finnegan, Seth; Creel, Roger; Eiler, John M.; Hughes, Nigel C.; Popov, Leonid E.; Fischer, Woodward W.

    2018-03-01

    The secular increase in δ18O values of both calcitic and phosphatic marine fossils through early Phanerozoic time suggests either that (1) early Paleozoic surface temperatures were high, in excess of 40 °C (tropical MAT), (2) the δ18O value of seawater has increased by 7-8‰ VSMOW through Paleozoic time, or (3) diagenesis has altered secular trends in early Paleozoic samples. Carbonate clumped isotope analysis, in combination with petrographic and elemental analysis, can deconvolve fluid composition from temperature effects and therefore determine which of these hypotheses best explain the secular δ18O increase. Clumped isotope measurements of a suite of calcitic and phosphatic marine fossils from late Cambrian- to Middle-late Ordovician-aged strata-the first paired fossil study of its kind-document tropical sea surface temperatures near modern temperatures (26-38 °C) and seawater oxygen isotope ratios similar to today's ratios.

  10. A history of violence: Insights into post-accretionary heating in carbonaceous chondrites from volatile element abundances, Zn isotopes and water contents

    NASA Astrophysics Data System (ADS)

    Mahan, Brandon; Moynier, Frédéric; Beck, Pierre; Pringle, Emily A.; Siebert, Julien

    2018-01-01

    Carbonaceous chondrites (CCs) may have been the carriers of water, volatile and moderately volatile elements to Earth. Investigating the abundances of these elements, their relative volatility, and isotopes of state-change tracer elements such as Zn, and linking these observations to water contents, provide vital information on the processes that govern the abundances and isotopic signatures of these species in CCs and other planetary bodies. Here we report Zn isotopic data for 28 CCs (20 CM, 6 CR, 1 C2-ung, and 1 CV3), as well as trace element data for Zn, In, Sn, Tl, Pb, and Bi in 16 samples (8 CM, 6 CR, 1 C2-ung, and 1 CV3), that display a range of elemental abundances from case-normative to intensely depleted. We use these data, water content data from literature and Zn isotopes to investigate volatile depletions and to discern between closed and open system heating. Trace element data have been used to construct relative volatility scales among the elements for the CM and CR chondrites. From least volatile to most, the scale in CM chondrites is Pb-Sn-Bi-In-Zn-Tl, and for CR chondrites it is Tl-Zn-Sn-Pb-Bi-In. These observations suggest that heated CM and CR chondrites underwent volatile loss under different conditions to one another and to that of the solar nebula, e.g. differing oxygen fugacities. Furthermore, the most water and volatile depleted samples are highly enriched in the heavy isotopes of Zn. Taken together, these lines of evidence strongly indicate that heated CM and CR chondrites incurred open system heating, stripping them of water and volatiles concomitantly, during post-accretionary shock impact(s).

  11. Iron isotopic composition of blood serum in anemia of chronic kidney disease.

    PubMed

    Anoshkina, Yulia; Costas-Rodríguez, Marta; Speeckaert, Marijn; Van Biesen, Wim; Delanghe, Joris; Vanhaecke, Frank

    2017-05-24

    Chronic kidney disease (CKD) is a general term for disorders that affect the structure and function of the kidneys. Iron deficiency (ID) and anemia occur in the vast majority of CKD patients, most of whom are elderly. However, establishing the cause of anemia in CKD, and therefore making an informed decision concerning the corresponding therapeutic treatment, is still a challenge. High-precision Fe isotopic analysis of blood serum samples of CKD patients with and without ID/anemia was performed via multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) for such a purpose. Patients with CKD and/or iron disorders showed a heavier serum Fe isotopic composition than controls. Many clinical parameters used for the diagnosis and follow-up of anemia correlated significantly with the serum Fe isotopic composition. In contrast, no relation was observed between the serum Fe isotopic composition and the estimated glomerular filtration rate as a measure of kidney function. Among the CKD patients, the serum Fe isotopic composition was substantially heavier in the occurrence of ID anemia, while erythropoietin-related anemia did not exert this effect. The Fe isotopic composition can thus be useful for distinguishing these different types of anemias in CKD patients, i.e. ID anemia vs. erythropoietin-related anemia.

  12. Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

    NASA Astrophysics Data System (ADS)

    Allen, Scott T.; Keim, Richard F.; McDonnell, Jeffrey J.

    2015-03-01

    Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability in event-scale samples, (2) to determine if there are persistent controls over the variability and how these affect variability of seasonally accumulated throughfall, and (3) to analyze the distribution of measured throughfall isotopic composition associated with varying sampling regimes. We measured throughfall over two, three-month periods in western Oregon, USA under a Douglas-fir canopy. The mean spatial range of δ18O for each event was 1.6‰ and 1.2‰ through Fall 2009 (11 events) and Spring 2010 (7 events), respectively. However, the spatial pattern of isotopic composition was not temporally stable causing season-total throughfall to be less variable than event throughfall (1.0‰; range of cumulative δ18O for Fall 2009). Isotopic composition was not spatially autocorrelated and not explained by location relative to tree stems. Sampling error analysis for both field measurements and Monte-Carlo simulated datasets representing different sampling schemes revealed the standard deviation of differences from the true mean as high as 0.45‰ (δ18O) and 1.29‰ (d-excess). The magnitude of this isotopic variation suggests that small sample sizes are a source of substantial experimental error.

  13. Calcium and Oxygen Isotopic Composition of Calcium Carbonates

    NASA Astrophysics Data System (ADS)

    Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

    2016-04-01

    Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40

  14. Intracellular Cadmium Isotope Fractionation

    NASA Astrophysics Data System (ADS)

    Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

    2011-12-01

    Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

  15. The isotopic composition of cosmic-ray calcium

    NASA Technical Reports Server (NTRS)

    Wiedenbeck, M. E.; George, J. S.; Binns, W. R.; Christian, E. R.; Cummings, A. C.; Davis, A. J.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A.; Stone, E. C.; hide

    2001-01-01

    We find that the relative abundance of cosmic ray calcium isotopes in the cosmic-ray source are very similar to those found in solar-system material, in spite of the fact that different types of stars are thought to be responsible for producing these two isotopes. This observation is consistent with the view that cosmic rays are derived from a mixed sample of interstellar matter.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  17. Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data.

    PubMed

    Estrada, Nubia Luz; Böhlke, J K; 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

    2017-10-01

    Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth

  18. Stable isotopic composition of perchlorate and nitrate accumulated in plants: Hydroponic experiments and field data

    USGS Publications Warehouse

    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

    2017-01-01

    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

  19. The isotope composition of selenium in chondrites constrains the depletion mechanism of volatile elements in solar system materials

    NASA Astrophysics Data System (ADS)

    Vollstaedt, Hauke; Mezger, Klaus; Leya, Ingo

    2016-09-01

    Solar nebula processes led to a depletion of volatile elements in different chondrite groups when compared to the bulk chemical composition of the solar system deduced from the Sun's photosphere. For moderately-volatile elements, this depletion primarily correlates with the element condensation temperature and is possibly caused by incomplete condensation from a hot solar nebula, evaporative loss from the precursor dust, and/or inherited from the interstellar medium. Element concentrations and interelement ratios of volatile elements do not provide a clear picture about responsible mechanisms. Here, the abundance and stable isotope composition of the moderately- to highly-volatile element Se are investigated in carbonaceous, ordinary, and enstatite chondrites to constrain the mechanism responsible for the depletion of volatile elements in planetary bodies of the inner solar system and to define a δ 82 / 78 Se value for the bulk solar system. The δ 82 / 78 Se of the studied chondrite falls are identical within their measurement uncertainties with a mean of - 0.20 ± 0.26 ‰ (2 s.d., n = 14, relative to NIST SRM 3149) despite Se abundance depletions of up to a factor of 2.5 with respect to the CI group. The absence of resolvable Se isotope fractionation rules out a kinetic Rayleigh-type incomplete condensation of Se from the hot solar nebula or partial kinetic evaporative loss on the precursor material and/or the parent bodies. The Se depletion, if acquired during partial condensation or evaporative loss, therefore must have occurred under near equilibrium conditions to prevent measurable isotope fractionation. Alternatively, the depletion and cooling of the nebula could have occurred simultaneously due to the continuous removal of gas and fine particles by the solar wind accompanied by the quantitative condensation of elements from the pre-depleted gas. In this scenario the condensation of elements does not require equilibrium conditions to avoid isotope

  20. Shell Layer Thickness-Dependent Photocatalytic Activity of Sputtering Synthesized Hexagonally Structured ZnO-ZnS Composite Nanorods

    PubMed Central

    Liang, Yuan-Chang; Lo, Ya-Ru; Wang, Chein-Chung; Xu, Nian-Cih

    2018-01-01

    ZnO-ZnS core-shell nanorods are synthesized by combining the hydrothermal method and vacuum sputtering. The core-shell nanorods with variable ZnS shell thickness (7–46 nm) are synthesized by varying ZnS sputtering duration. Structural analyses demonstrated that the as-grown ZnS shell layers are well crystallized with preferring growth direction of ZnS (002). The sputtering-assisted synthesized ZnO-ZnS core-shell nanorods are in a wurtzite structure. Moreover, photoluminance spectral analysis indicated that the introduction of a ZnS shell layer improved the photoexcited electron and hole separation efficiency of the ZnO nanorods. A strong correlation between effective charge separation and the shell thickness aids the photocatalytic behavior of the nanorods and improves their photoresponsive nature. The results of comparative degradation efficiency toward methylene blue showed that the ZnO-ZnS nanorods with the shell thickness of approximately 17 nm have the highest photocatalytic performance than the ZnO-ZnS nanorods with other shell layer thicknesses. The highly reusable catalytic efficiency and superior photocatalytic performance of the ZnO-ZnS nanorods with 17 nm-thick ZnS shell layer supports their potential for environmental applications. PMID:29316671

  1. Synthesis of ZnO Nanocrystal-Graphene Composite by Mechanical Milling and Sonication-Assisted Exfoliation

    NASA Astrophysics Data System (ADS)

    Arora, Sweety; Srivastava, Chandan

    2017-02-01

    A ZnO nanocrystal-graphene composite was synthesized by a two-step method involving mechanical milling and sonication-assisted exfoliation. Zn metal powder was first ball-milled with graphite powder for 30 h in water medium. This ball-milled mixture was then subjected to exfoliation by sonication in the presence of sodium lauryl sulfate surfactant to produce graphene decorated with spherical agglomerates of ultrafine nanocrystalline ZnO. The presence of a few layers of graphene was confirmed by Raman spectroscopy and atomic force microscopy measurements. The size, phase identity and composition of the ZnO nanocrystals was determined by transmission electron microscopy measurements.

  2. Behaviour of Structural Carbonate Stable Carbon and Oxygen Isotope Compositions in Bioapatite During Burning of Bone

    NASA Astrophysics Data System (ADS)

    Munro, L. E.; Longstaffe, F. J.; White, C. D.

    2003-12-01

    Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by

  3. Synthesis and Photocatalytic Property of ZnO/TiO2 Inverse Opals Films with Controllable Composition and Topology

    NASA Astrophysics Data System (ADS)

    Xu, Jiao; Yang, Bei-fang; Fu, Zheng-ping; Wen, Mei-wang; Zhao, Yong-xun

    2012-04-01

    A novel method to fabricate composition- and topology-controlled ZnO/TiO2 inverse opals (IO) films using a positive sacrificial ZnO IO template has been developed. This method includes a two-step process, preparation of ZnO IO by a simple electrochemical deposition using a self-assembly polystyrene colloidal crystal template and preparation of ZnO/TiO2 IO by a liquid phase deposition (LPD) process at room temperature. The composition and topology of ZnO/TiO2 IO can be easily controlled by changing the duration of the LPD. After 20 min LPD process, a ZnO/TiO2 composite IO with non-close-packed face-centered cubic air sphere array was obtained. Prolonging the duration to 60 min, a pure TiO2 IO (TIO-LPD60) with obviously thickened walls was formed. The formation mechanism for the compositional and topological variation was discussed. A preliminary study on UV photocatalytic property of the samples for degradation of methylene blue reveals that the composition and topology significantly influenced the photocatalytic activity of the IO film. The ZnO/TiO2 composite IO demonstrates a higher degree of activity than both pure ZnO and pure TiO2 IO, although they have a similar IO wall thickness. Moreover, with increasing IO wall thickness from ~52 nm to ~90 nm, TIO-LPD60 exhibits the highest level of photocatalytic performance.

  4. Enhanced electrochemical performance of a ZnO-MnO composite as an anode material for lithium ion batteries.

    PubMed

    Song, Min Seob; Nahm, Sahn; Cho, Won Il; Lee, Chongmok

    2015-09-28

    A ZnO-MnO composite was synthesized using a simple solvothermal method combined with a high-temperature treatment. To observe the phase change during the heating process, in situ high-temperature XRD analysis was performed under vacuum conditions. The results indicated that ZnMn2O4 transformed into the ZnO-MnO composite phase starting from 500 °C and that this composite structure was retained until 700 °C. The electrochemical performances of the ZnO-MnO composite electrode were evaluated through galvanostatic discharge-charge tests and cyclic voltammetry analysis. Its initial coulombic efficiency was significantly improved to 68.3% compared to that of ZnMn2O4 at 54.7%. Furthermore, the ZnO-MnO composite exhibited improved cycling performance and enhanced rate capability compared with untreated ZnMn2O4. To clarify the discharge-charge mechanism of the ZnO-MnO composite electrode, the structural changes during the charge and discharge processes were also investigated using ex situ XRD and TEM.

  5. The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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

  6. Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

    NASA Astrophysics Data System (ADS)

    Du, De-Hong; Wang, Xiao-Lei; Yang, Tao; Chen, Xin; Li, Jun-Yong; Li, Weiqiang

    2017-12-01

    The origin of heavy Fe isotope compositions in high-silica (>70 wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05 ± 0.05‰ to 0.55 ± 0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.

  7. Trihalomethanes formed from natural organic matter isolates: Using isotopic and compositional data to help understand sources

    USGS Publications Warehouse

    Bergamaschi, Brian A.; Fram, Miranda S.; Fujii, Roger; Aiken, George R.; Kendall, Carol; Silva, Steven R.

    2000-01-01

    Over 20 million people drink water from the Sacramento-San Joaquin Delta despite problematic levels of natural organic matter (NOM) and bromide in Delta water, which can form trihalomethanes (THMs) during the treatment process. It is widely believed that NOM released from Delta peat islands is a substantial contributor to the pool of THM precursors present in Delta waters. Dissolved NOM was isolated from samples collected at five channel sites within the Sacramento-San Joaquin Rivers and Delta, California, USA, and from a peat island agricultural drain. To help understand the sources of THM precursors, samples were analyzed to determine their chemical and isotopic composition, their propensity to form THMs, and the isotopic composition of the THMs.The chemical composition of the isolates was quite variable, as indicated by significant differences in carbon-13 nuclear magnetic resonance spectra and carbon-to-nitrogen concentration ratios. The lowest propensity to form THMs per unit of dissolved organic carbon was observed in the peat island agricultural drain isolate, even though it possessed the highest fraction of aromatic material and the highest specific ultraviolet absorbance. Changes in the chemical and isotopic composition of the isolates and the isotopic composition of the THMs suggest that the source of the THMs precursors was different between samples and between isolates. The pattern of variability in compositional and isotopic data for these samples was not consistent with simple mixing of river- and peat-derived organic material.

  8. The effect of annealing on structural, optical and electrical properties of ZnS/porous silicon composites

    NASA Astrophysics Data System (ADS)

    Wang, Cai-Feng; Li, Qing-Shan; Hu, Bo; Li, Wei-Bing

    2009-06-01

    ZnS films were prepared by pulsed laser deposition (PLD) on porous silicon (PS) substrates. This paper investigates the effect of annealing temperature on the structural, morphological, optical and electrical properties of ZnS/PS composites by x-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) and I-V characteristics. It is found that the ZnS films deposited on PS substrates were grown in preferred orientation along β-ZnS (111) direction, and the intensity of diffraction peak increases with increasing annealing temperature, which is attributed to the grain growth and the enhancement of crystallinity of ZnS films. The smooth and uniform surface of the as-prepared ZnS/PS composite becomes rougher through annealing treatment, which is related to grain growth at the higher annealing temperature. With the increase of annealing temperature, the intensity of self-activated luminescence of ZnS increases, while the luminescence intensity of PS decreases, and a new green emission located around 550 nm appeared in the PL spectra of ZnS/PS composites which is ascribed to the defect-center luminescence of ZnS. The I-V characteristics of ZnS/PS heterojunctions exhibited rectifying behavior, and the forward current increases with increasing annealing temperature.

  9. Tracing dust transport from Middle-East over Delhi in March 2012 using metal and lead isotope composition

    NASA Astrophysics Data System (ADS)

    Kumar, S.; Aggarwal, S. G.; Malherbe, J.; Barre, J. P. G.; Berail, S.; Gupta, P. K.; Donard, O. F. X.

    2016-05-01

    A severe dust-storm which was originated in Middle-East crossed over Delhi during March 20-22, 2012. We have collected these dust-storm (DS) aerosol samples, and analyzed them for selected metals (As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, Se, Sn, Sr, V and Zn) together with after dust-storm (ADS) and winter (WS) samples. High aerosol mass loadings were observed in DS samples (1097-1965 μg/m3). On the contrary, metals derived prominently from the anthropogenic sources were found lower in concentration compared to that of ADS and WS aerosols. We observed significantly high concentrations of Ni and V (which are abundantly found in crude oils of Middle-East origin) in the DS samples than that of ADS and WS samples. Also enrichment factor (EF) of these metals with respect to Fe shows no significant enrichment (<10). Fe (and Sr) concentrations were also 3-5 fold higher in DS samples compared to ADS and WS. These results suggest that Ni and V can be used as tracers for dust aerosols transported from Middle-East region. Lead isotope signatures can tell about the variation in the sources of urban aerosols. Therefore Pb isotope analyses of these samples were performed using MC-ICP-MS. The isotope ratios, 208Pb/206Pb is determined to be (mean ± sd) 2.1315 ± 0.0018, 2.1370 ± 0.0022 and 2.1389 ± 0.0016, whereas 206Pb/207Pb is 1.1311 ± 0.0022, 1.1244 ± 0.0017 and 1.1233 ± 0.0016 in DS, ADS and WS aerosols, respectively. There is a clear distinction in Pb isotope composition between DS and urban (ADS and WS) aerosols. Further, these results suggest that in urban aerosols, Pb is less radiogenic in nature compared to that of in transported dust aerosols collected in New Delhi.

  10. Fabrication of Porous ZnO/Co₃O₄ Composites for Improving Cycling Stability of Supercapacitors.

    PubMed

    Su, Dongqing; Zhang, Longmei; Tang, Zehua; Yu, Tingting; Liu, Huili; Zhang, Junhao; Liu, Yuanjun; Yuan, Aihua; Kong, Qinghong

    2018-07-01

    To tackle the issue of poor cycling stability for metal oxide nanoparticles as supercapacitor electrode, porous ZnO/Co3O4 composites were fabricated via solid-state thermolysis of [CoZn(BTC)(NO3)](2H2O)(0.5DMF) under air atmosphere. The results demonstrate that the products are mesoporous polyhedron structure with the diameter of about 10 μm, which are constructed by many interconnected nanocrystals with the sizes of around 20 nm. ZnO/Co3O4 composites as supercapacitor electrode exhibited excellent cyclic stability capacity, showing a maximum specific capacitance of 106.7 F g-1 and a capacity retention of 102.7 F · g-1 after 1000 cycles at 0.5 A · g-1. The superior electrochemical performance was contributed to ZnO/Co3O4 composites with porous structures and small size, which shortened the route of electronic transmission as well as ions insertion and desertion processes. Additionally, the synergetic effect of bimetallic oxides improved the electrochemical stability.

  11. Highly Sensitive Flexible Human Motion Sensor Based on ZnSnO3/PVDF Composite

    NASA Astrophysics Data System (ADS)

    Yang, Young Jin; Aziz, Shahid; Mehdi, Syed Murtuza; Sajid, Memoon; Jagadeesan, Srikanth; Choi, Kyung Hyun

    2017-07-01

    A highly sensitive body motion sensor has been fabricated based on a composite active layer of zinc stannate (ZnSnO3) nano-cubes and poly(vinylidene fluoride) (PVDF) polymer. The thin film-based active layer was deposited on polyethylene terephthalate flexible substrate through D-bar coating technique. Electrical and morphological characterizations of the films and sensors were carried out to discover the physical characteristics and the output response of the devices. The synergistic effect between piezoelectric ZnSnO3 nanocubes and β phase PVDF provides the composite with a desirable electrical conductivity, remarkable bend sensitivity, and excellent stability, ideal for the fabrication of a motion sensor. The recorded resistance of the sensor towards the bending angles of -150° to 0° to 150° changed from 20 MΩ to 55 MΩ to 100 MΩ, respectively, showing the composite to be a very good candidate for motion sensing applications.

  12. Uniformity in sulfur isotope composition in the orogenic gold deposits from the Dharwar Craton, southern India

    NASA Astrophysics Data System (ADS)

    Sakthi Saravanan, C.; Mishra, B.

    2009-07-01

    The sulfur isotope composition of sulfides (mainly pyrite and arsenopyrite) from gold deposits/prospects of the Dharwar Craton such as Hutti, Hira-Buddini, Uti, Kolar (Chigargunta), Ajjanahalli, and Jonnagiri has a narrow range (δ34S = +1.1 to +7.1‰). Such craton-scale uniformity of the above gold camps is noteworthy, in spite of the wide diversity in host rock compositions and their metamorphic conditions, and suggests a magmatic or average crustal source of sulfur for all deposits studied. In addition, our study points towards gold precipitation from reduced ore fluids, with near-homogeneous sulfur isotope compositions.

  13. Measurement of natural carbon isotopic composition of acetone in human urine.

    PubMed

    Yamada, Keita; Ohishi, Kazuki; Gilbert, Alexis; Akasaka, Mai; Yoshida, Naohiro; Yoshimura, Ryoko

    2016-02-01

    The natural carbon isotopic composition of acetone in urine was measured in healthy subjects using gas chromatography-combustion-isotope ratio mass spectrometry combined with headspace solid-phase microextraction (HS-SPME-GC-C-IRMS). Before applying the technique to a urine sample, we optimized the measurement conditions of HS-SPME-GC-C-IRMS using aqueous solutions of commercial acetone reagents. The optimization enabled us to determine the carbon isotopic compositions within ±0.2 ‰ of precision and ±0.3‰ of error using 0.05 or 0.2 mL of aqueous solutions with acetone concentrations of 0.3-121 mg/L. For several days, we monitored the carbon isotopic compositions and concentrations of acetone in urine from three subjects who lived a daily life with no restrictions. We also monitored one subject for 3 days including a fasting period of 24 h. These results suggest that changes in the availability of glucose in the liver are reflected in changes in the carbon isotopic compositions of urine acetone. Results demonstrate that carbon isotopic measurement of metabolites in human biological samples at natural abundance levels has great potential as a tool for detecting metabolic changes caused by changes in physiological states and disease.

  14. The influence of kinetics on the oxygen isotope composition of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

    2013-08-01

    Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

  15. Assessment of shock effects on amphibole water contents and hydrogen isotope compositions: 1. Amphibolite experiments

    NASA Astrophysics Data System (ADS)

    Minitti, Michelle E.; Rutherford, Malcolm J.; Taylor, Bruce E.; Dyar, M. Darby; Schultz, Peter H.

    2008-02-01

    Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10

  16. Kinetics and equilibrium models for the sorption of tributyltin to nZnO, activated carbon and nZnO/activated carbon composite in artificial seawater.

    PubMed

    Ayanda, Olushola S; Fatoki, Olalekan S; Adekola, Folahan A; Ximba, Bhekumusa J

    2013-07-15

    The removal of tributyltin (TBT) from artificial seawater using nZnO, activated carbon and nZnO/activated carbon composite was systematically studied. The equilibrium and kinetics of adsorption were investigated in a batch adsorption system. Equilibrium adsorption data were analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) isotherm models. Pseudo first- and second-order, Elovich, fractional power and intraparticle diffusion models were applied to test the kinetic data. Thermodynamic parameters such as ΔG°, ΔS° and ΔH° were also calculated to understand the mechanisms of adsorption. Optimal conditions for the adsorption of TBT from artificial seawater were then applied to TBT removal from natural seawater. A higher removal efficiency of TBT (>99%) was obtained for the nZnO/activated carbon composite material and for activated carbon but not for nZnO. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. First Measurement of the Radionuclide Purity of the Therapeutic Isotope 67Cu Produced by 68Zn(n,x) Reaction Using natC(d,n) Neutrons

    NASA Astrophysics Data System (ADS)

    Sato, Nozomi; Tsukada, Kazuaki; Watanabe, Satoshi; Ishioka, Noriko S.; Kawabata, Masako; Saeki, Hideya; Nagai, Yasuki; Kin, Tadahiro; Minato, Futoshi; Iwamoto, Nobuyuki; Iwamoto, Osamu

    2014-07-01

    We have for the first time studied the radionuclide purity of the therapeutic isotope 67Cu produced by the 68Zn(n,x)67Cu reaction. The neutrons were obtained by the natC(d,n) reaction using 40 MeV deuterons. We measured the γ-ray spectra of the reaction products produced by bombarding an enriched 68ZnO sample with the neutrons with a high-purity Ge detector. We found that the relative production yields of the impurity radionuclides 64Cu, 65Zn, and 69mZn to 67Cu are extremely low. The result indicates that the 68Zn(n,x)67Cu reaction is the most promising among those proposed routes until now for producing high-quality 67Cu, and could solve a longstanding problem of establishing an appropriate production method for 67Cu.

  18. Natural variations in the rhenium isotopic composition of meteorites

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    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.

  19. The photocatalytic properties of hollow (GaN)1-x(ZnO)x composite nanofibers synthesized by electrospinning

    NASA Astrophysics Data System (ADS)

    Wang, Ding; Zhang, Minglu; Zhuang, Huaijuan; Chen, Xu; Wang, Xianying; Zheng, Xuejun; Yang, Junhe

    2017-02-01

    (GaN)1-x(ZnO)x composite nanofibers with hollow structure were prepared by initial electrospinning, and the subsequent calcination and nitridation. The structure and morphology characteristics of samples were investigated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The characterization results showed the phase transition from ZnGa2O4 to (GaN)1-x(ZnO)x solid-solution under ammonia atmosphere. The preparation conditions were explored and the optimum nitridation temperature and holding time are 750 °C and 2 h, respectively. The photocatalytic properties of (GaN)1-x(ZnO)x with different Ga:Zn atomic ratios were investigated by degrading Rhodamine B under the visible light irradiation. The photocatalytic activity sequence is (GaN)1-x(ZnO)x (Ga:Zn = 1:2) > (GaN)1-x(ZnO)x (Ga:Zn = 1:3) > ZnO nanofibers > (GaN)1-x(ZnO)x (Ga:Zn = 1:4) > (GaN)1-x(ZnO)x (Ga:Zn = 1:1). The photocatalytic mechanism of the (GaN)1-x(ZnO)x hollow nanofibers was further studied by UV-vis diffuse reflectance spectra. The excellent photocatalytic performance of (GaN)1-x(ZnO)x hollow nanofibers was attributed to the narrow band gap and high surface area of porous nanofibers with hollow structure.

  20. Ca-,Al-rich inclusions in the unique chondrite ALH85085 - Petrology, chemistry, and isotopic compositions

    NASA Technical Reports Server (NTRS)

    Kimura, Makoto; El-Goresy, Ahmed; Palme, Herbert; Zinner, Ernst

    1993-01-01

    A comprehensive study is performed for the Ca-,Al-rich inclusions (CAIs) in the unique chondrite ALH85085. The ALH85085 inclusions are smaller (5-80 microns) and more refractory than their counterparts in carbonaceous chondrites. The study includes 42 inclusions for petrography and mineralogy, 15 for bulk major and minor element chemical composition, six for Mg-Al isotopic systematics, 10 for Ca isotopes, nine for Ti isotopes, and six for trace element abundances. In addition, oxygen-isotopic compositions were determined in minerals from a single inclusion. No correlation is found between mineralogy, major element chemistry, and trace element abundances. It is further shown that the high-temperature geochemical behavior of ultrarefractory trace elements is decoupled from that of the major elements Ca and Ti (Ti is correlated with the relatively volatile elements Nb and Yb) implying that perovskite is of only minor importance as carrier of ultrarefractories.

  1. Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

    NASA Astrophysics Data System (ADS)

    Marzouk, E. R.; Chenery, S. R.; Young, S. D.

    2013-12-01

    The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (<0.22 μm) colloidal particles (SCP-metal). For most soils, the presence of non-labile SCP-metal caused only minor over-estimation of E-values (<2%) but the effect was greater for soils with particularly large humus or carbonate contents. Approximately 80%, 53% and 66% of the variability in Zn, Cd and Pb %E-values (respectively) could be explained by pH, loss on ignition and total metal content. E-values were affected by the presence of ore minerals at high metal contents leading to an inconsistent trend in the relationship between %E-value and soil metal concentration. Metal solubility, in the soil suspensions used to measure E-values, was predicted using the WHAM geochemical speciation model (versions VI and VII). The use of total and isotopically exchangeable metal as alternative input variables was compared; the latter provided significantly better predictions of solubility, especially in the case of Zn. Lead solubility was less well predicted by either version of WHAM, with over-prediction at low pH and under-prediction at high soil pH values. Quantify the isotopically exchangeable fractions of Zn, Cd and Pb (E-values), and assess their local and regional variability, using multi-element stable isotope dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop

  2. Osmium Stable Isotope Composition of Chondrites and Iron Meteorites: Implications for Planetary Core Formation

    NASA Astrophysics Data System (ADS)

    Nanne, J. A. M.; Millet, M. A.; Burton, K. W.; Dale, C. W.; Nowell, G. M.; Williams, H. M.

    2016-12-01

    Mass-dependent Os stable isotope fractionation is expected to occur during metal-silicate segregation as well as during crystallization of metal alloys due to the different bonding environment between silicate and metals. As such, Os stable isotopes have the potential to resolve questions pertaining to planetary accretion and differentiation. Here, we present stable Os isotope data for a set of chondrites and iron meteorites to examine the processes associated with core solidification. Carbonaceous, ordinary, and enstatite chondrites show no detectable stable isotope variation with a δ190Os weighted average of +0.12±0.04 (n=37). The uniform composition observed for chondrites implies Os stable isotope homogeneity of the bulk solar nebula. Contrary to chondrites, iron meteorites display a large range in Os stable isotope compositions from δ190Os of +0.05 up to +0.49‰. Variation is only observed in the IIAB and IIIAB irons. Type IVB irons display values similar to chondrites (+0.107±0.047 [n=3]) and IVA compositions are slightly different +0.187±0.004 (n=2). The type IIAB and IIIAB groups show values both within the chondritic range and up to heavier values extending up to +0.49‰. Since core formation in small planetary bodies is expected to quantitatively sequester Os in metal phases, bulk planetary cores are expected to display chondritic δ190Os values. Conversely, samples of the IIAB and IIIAB group display significant variation, possibly indicating that stable isotope fractionation occurred during solidification of the parent-body core. However, no covariation is observed between δ190Os and either Os abundance or radiogenic Os isotope ratios. Instead, liquid immiscibility during core crystallization, where the liquid metal splits into separate S- and P-rich liquids, may be a source of Os stable isotope fractionation.

  3. Clumped Isotope Composition of Cold-Water Corals: A Role for Vital Effects?

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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 < 1,000 yrs) with associated temperature data. They include a total of 11 solitary corals and 1 colonial coral from the Atlantic, and 8 solitary corals from the Southern Ocean. The data indicate that coral clumped isotope systematics may be more complicated than previously thought. For example, for the genus Caryophyllia we observe significant variations in clumped isotope compositions for corals which grew at the same temperature with an apparent negative correlation between Δ47 and δ18O, different to patterns previously observed in Desmophyllum. These results indicate that existing isotope models of 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.

  4. Variation in the terrestrial isotopic composition and atomic weight of argon

    USGS Publications Warehouse

    Böhlke, John Karl

    2014-01-01

    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.

  5. The GENESIS Mission: Solar Wind Isotopic and Elemental Compositions and Their Implications

    NASA Astrophysics Data System (ADS)

    Wiens, R. C.; Burnett, D. S.; McKeegan, K. D.; Kallio, A. P.; Mao, P. H.; Heber, V. S.; Wieler, R.; Meshik, A.; Hohenberg, C. M.; Mabry, J. C.; Gilmour, J.; Crowther, S. A.; Reisenfeld, D. B.; Jurewicz, A.; Marty, B.; Pepin, R. O.; Barraclough, B. L.; Nordholt, J. E.; Olinger, C. T.; Steinberg, J. T.

    2008-12-01

    The GENESIS mission was a novel NASA experiment to collect solar wind at the Earth's L1 point for two years and return it for analysis. The capsule crashed upon re-entry in 2004, but many of the solar-wind collectors were recovered, including separate samples of coronal hole, interstream, and CME material. Laboratory analyses of these materials have allowed higher isotopic precision than possible with current in-situ detectors. To date GENESIS results have been obtained on isotopes of O, He, Ne, Ar, Kr, and Xe on the order of 1% accuracy and precision, with poorer uncertainty on Xe isotopes and significantly better uncertainties on the lighter noble gases. Elemental abundances are available for the above elements as well as Mg, Si, and Fe. When elemental abundances are compared with other in situ solar wind measurements, agreement is generally quite good. One exception is the Ne elemental abundance, which agrees with Ulysses and Apollo SWC results, but not with ACE. Neon is of particular interest because of the uncertainty in the solar Ne abundance, which has significant implications for the standard solar model. Helium isotopic results of material from the different solar wind regimes collected by GENESIS is consistent with isotopic fractionation predictions of the Coulomb drag model, suggesting that isotopic fractionation corrections need to be applied to heavier elements as well when extrapolating solar wind to solar compositions. Noble gas isotopic compositions from GENESIS are consistent with those obtained for solar wind trapped in lunar grains, but have for the first time yielded a very precise Ar isotopic result. Most interesting for cosmochemistry is a preliminary oxygen isotopic result from GENESIS which indicates a solar enrichment of ~4% in 16O relative to the planets, consistent with a photolytic self-shielding phenomenon during solar system formation. Analyses of solar wind N and C isotopes may further elucidate this phenomenon. Preliminary results

  6. Clumped isotope composition of cold-water corals: A role for vital effects?

    NASA Astrophysics Data System (ADS)

    Spooner, Peter T.; Guo, Weifu; Robinson, Laura F.; Thiagarajan, Nivedita; Hendry, Katharine R.; Rosenheim, Brad E.; Leng, Melanie J.

    2016-04-01

    The carbonate clumped isotope thermometer is a promising tool for determining past ocean temperatures. It is based on the temperature dependence of rare isotopes 'clumping' into the same carbonate ion group in the carbonate mineral lattice. The extent of this clumping effect is independent of the isotope composition of the water from which carbonate precipitates, providing unique advantages over many other paleotemperature proxies. Existing calibrations of this thermometer in cold-water and warm-water corals suggest clumped isotope 'vital effects' are negligible in cold-water corals but may be significant in warm-water corals. Here, we test the calibration of the carbonate clumped isotope thermometer in cold-water corals with a recently collected and well characterised sample set spanning a range of coral genera (Balanophyllia, Caryophyllia, Dasmosmilia, Desmophyllum, Enallopsammia and Javania). The clumped isotope compositions (Δ47) of these corals exhibit systematic dependences on their growth temperatures, confirming the basis of the carbonate clumped isotope thermometer. However, some cold-water coral genera show Δ47 values that are higher than the expected equilibrium values by up to 0.05‰ (equivalent to underestimating temperature by ∼9 °C) similar to previous findings for some warm-water corals. This finding suggests that the vital effects affecting corals Δ47 are common to both warm- and cold-water corals. By comparison with models of the coral calcification process we suggest that the clumped isotope offsets in these genera are related to the kinetic isotope effects associated with CO2 hydration/hydroxylation reactions in the corals' calcifying fluid. Our findings complicate the use of the carbonate clumped isotope thermometer in corals, but suggest that species- or genus-specific calibrations could be useful for the future application of this paleotemperature proxy.

  7. MAST - A mass spectrometer telescope for studies of the isotopic composition of solar, anomalous, and galactic cosmic ray nuclei

    NASA Technical Reports Server (NTRS)

    Cook, Walter R.; Cummings, Alan C.; Cummings, Jay R.; Garrard, Thomas L.; Kecman, Branislav; Mewaldt, Richard A.; Selesnick, Richard S.; Stone, Edward C.; Von Rosenvinge, T. T.

    1993-01-01

    The Mass Spectrometer Telescope (MAST) on SAMPEX is designed to provide high resolution measurements of the isotopic composition of energetic nuclei from He to Ni (Z = 2 to 28) over the energy range from about 10 to several hundred MeV/nuc. During large solar flares MAST will measure the isotopic abundances of solar energetic particles to determine directly the composition of the solar corona, while during solar quiet times MAST will study the isotopic composition of galactic cosmic rays. In addition, MAST will measure the isotopic composition of both interplanetary and trapped fluxes of anomalous cosmic rays, believed to be a sample of the nearby interstellar medium.

  8. The relation between isotopic composition of argon and carbon in natural gases

    NASA Technical Reports Server (NTRS)

    Gavrilov, Y. Y.; Zhurov, Y. A.; Teplinskiy, G. I.

    1977-01-01

    The methods and results of determination of the argon and carbon isotope compositions of hydrocarbon gases of Mezozoic complexes of Western Siberia are presented. Based on the Ar-36, Ar-40, C-12, C-13 content of the various deposits and on the presumed mechanisms of entry of these isotopes into the deposits, it is concluded that formation of natural gas in some deposits included vertical migration from a lower complex.

  9. Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

    NASA Technical Reports Server (NTRS)

    Alperin, M. J.; Blair, Neal E.; Albert, D. B.; Hoehler, T. M.; Martens, C. S.

    1993-01-01

    The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane

  10. Potassium Isotopic Compositions of NIST Potassium Standards and 40Ar/39Ar Mineral Standards

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

    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.

  11. Nd and Sm isotopic composition of spent nuclear fuels from three material test reactors

    DOE PAGES

    Sharp, Nicholas; Ticknor, Brian W.; Bronikowski, Michael; ...

    2016-11-17

    Rare earth elements such as neodymium and samarium are ideal for probing the neutron environment that spent nuclear fuels are exposed to in nuclear reactors. The large number of stable isotopes can provide distinct isotopic signatures for differentiating the source material for nuclear forensic investigations. The rare-earth elements were isolated from the high activity fuel matrix via ion exchange chromatography in a shielded cell. The individual elements were then separated using cation exchange chromatography. In conclusion, the neodymium and samarium aliquots were analyzed via MC–ICP–MS, resulting in isotopic compositions with a precision of 0.01–0.3%.

  12. Isotopic composition of high-activity particles released in the Chernobyl accident.

    PubMed

    Osuch, S; Dabrowska, M; Jaracz, P; Kaczanowski, J; Le Van Khoi; Mirowski, S; Piasecki, E; Szeflińska, G; Szefliński, Z; Tropiło, J

    1989-11-01

    Gamma spectra were measured and activities of the detected isotopes were analyzed for 206 high-activity particles (hot particles, HPs) found in northeastern Poland after the Chernobyl accident. The isotopic composition of HPs observed in gamma-activity is compared with that of the general fallout and core inventory calculations. Particle formation and a process of depletion in Ru and Cs isotopes are discussed. On the basis of a search performed a year later, some comments on the behavior of HPs in the soil are made.

  13. Nd and Sm isotopic composition of spent nuclear fuels from three material test reactors

    SciTech Connect

    Sharp, Nicholas; Ticknor, Brian W.; Bronikowski, Michael

    Rare earth elements such as neodymium and samarium are ideal for probing the neutron environment that spent nuclear fuels are exposed to in nuclear reactors. The large number of stable isotopes can provide distinct isotopic signatures for differentiating the source material for nuclear forensic investigations. The rare-earth elements were isolated from the high activity fuel matrix via ion exchange chromatography in a shielded cell. The individual elements were then separated using cation exchange chromatography. In conclusion, the neodymium and samarium aliquots were analyzed via MC–ICP–MS, resulting in isotopic compositions with a precision of 0.01–0.3%.

  14. Compositional tuning of atomic layer deposited MgZnO for thin film transistors

    NASA Astrophysics Data System (ADS)

    Wrench, J. S.; Brunell, I. F.; Chalker, P. R.; Jin, J. D.; Shaw, A.; Mitrovic, I. Z.; Hall, S.

    2014-11-01

    Thin film transistors (TFTs) have been fabricated using magnesium zinc oxide (MgZnO) layers deposited by atomic layer deposition at 200 °C. The composition of the MgZnO is systematically modified by varying the ratio of MgO and ZnO deposition cycles. A blue-shift of the near band-edge photoluminescence after post-deposition annealing at 300 °C indicates significant activation of the Mg dopant. A 7:1 ratio of ZnO:MgO deposition cycles was used to fabricate a device with a TFT channel width of 2000 μm and a channel length of 60 μm. This transistor yielded an effective saturation mobility of 4 cm2/V s and a threshold voltage of 7.1 V, respectively. The on/off ratio was 1.6 × 10 6 and the maximum interface state density at the ZnO/SiO2 interface is ˜ 6.5 × 10 12 cm-2.

  15. Magnetic properties and loss separation in iron-silicone-MnZn ferrite soft magnetic composites

    SciTech Connect

    Wu, Shen; Sun, Aizhi; Xu, Wenhuan

    This paper investigates the magnetic and structural properties of iron-based soft magnetic composites coated with silicone-MnZn ferrite hybrid. The organic silicone resin was added to improve the flexibility of the insulated iron powder and causes better adhesion between particles to increase the mechanical properties. Scanning electron microscopy and distribution maps show that the iron particle surface is covered with a thin layer of silicone-MnZn ferrite. Silicone-MnZn ferrite coated samples have higher permeability when compared with the non-magnetic silicone resin coated compacts. The real part of permeability increases by 34.18% when compared with the silicone resin coated samples at 20 kHz.more » In this work, a formula for calculating the total loss component by loss separation method is presented and finally the different parts of total losses are calculated. The results show that the eddy current loss coefficient is close to each other for the silicone-MnZn ferrite, silicone resin and MnZn ferrite coated samples (0.0078« less

  16. ZnO thin film piezoelectric micromachined microphone with symmetric composite vibrating diaphragm

    NASA Astrophysics Data System (ADS)

    Li, Junhong; Wang, Chenghao; Ren, Wei; Ma, Jun

    2017-05-01

    Residual stress is an important factor affecting the sensitivity of piezoelectric micromachined microphone. A symmetric composite vibrating diaphragm was adopted in the micro electro mechanical systems piezoelectric microphone to decrease the residual stress and improve the sensitivity of microphone in this paper. The ZnO film was selected as piezoelectric materials of microphone for its higher piezoelectric coefficient d 31 and lower relative dielectric constant. The thickness optimization of piezoelectric film on square diaphragm is difficult to be fulfilled by analytic method. To optimize the thickness of ZnO films, the stress distribution in ZnO film was analyzed by finite element method and the average stress in different thickness of ZnO films was given. The ZnO films deposited using dc magnetron sputtering exhibits a densely packed structure with columnar crystallites preferentially oriented along (002) plane. The diaphragm of microphone fabricated by micromachining techniques is flat and no wrinkling at corners, and the sensitivity of microphone is higher than 1 mV Pa-1. These results indicate the diaphragm has lower residual stress.

  17. Determining the oxygen isotope composition of evapotranspiration with eddy covariance

    USDA-ARS?s Scientific Manuscript database

    The oxygen isotope componsition of evapotranspiration (dF) represents an important tracer in the study of biosphere-atmosphere interactions, hydrology, paleoclimate, and carbon cycling. Here we demonstrate direct measurement of dF based on eddy covariance (EC) and tunable diode laser (EC-TDL) techni...

  18. Zirconium isotope constraints on the composition of Theia and current Moon-forming theories

    NASA Astrophysics Data System (ADS)

    Akram, W.; Schönbächler, M.

    2016-09-01

    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

  19. Xenon isotopic composition of the Mid Ocean Ridge Basalt (MORB) source

    NASA Astrophysics Data System (ADS)

    Peto, M. K.; Mukhopadhyay, S.

    2012-12-01

    Although convection models do not preclude preservation of smaller mantle regions with more pristine composition throughout Earth's history, it has been widely assumed that the moon forming giant impact likely homogenizes the whole mantle following a magma ocean that extended all the way to the bottom of the mantle. Recent findings of tungsten and xenon heterogeneities in the mantle [1,2,3,4], however, imply that i) the moon forming giant impact may not have homogenized the whole mantle and ii) plate tectonics was inefficient in erasing early formed compositional differences, particularly for the xenon isotopes. Therefore, the xenon isotope composition in the present day mantle still preserves a memory of early Earth processes. However, determination of the xenon isotopic composition of the mantle source is still scarce, since the mantle composition is overprinted by post-eruptive atmospheric contamination in basalts erupted at ocean islands and mid ocean ridges. The xenon composition of the depleted upper mantle has been defined by the gas rich sample, 2πD43 (also known as "popping rock"), from the North Atlantic (13° 469`N). However, the composition of a single sample is not likely to define the composition of the upper mantle, especially since popping rock has an "enriched" trace element composition. We will present Ne, Ar and Xe isotope data on MORB glass samples with "normal" helium isotope composition (8±1 Ra) from the Southeast Indian Ridge, the South Atlantic Ridge, the Sojourn Ridge, the Juan de Fuca, the East Pacific Rise, and the Gakkel Ridge. Following the approach of [1], we correct for syn- and post-eruptive atmosphere contamination, and determine the variation of Ar and Xe isotope composition of the "normal" MORB source. We investigate the effect of atmospheric recycling in the variation of MORB mantle 40Ar/36Ar and 129Xe/130Xe ratios, and attempt to constrain the average upper mantle argon and xenon isotopic compositions. [1] Mukhopadhyay, Nature

  20. Electrophoretic Deposition of Chitosan/45S5 Bioactive Glass Composite Coatings Doped with Zn and Sr

    PubMed Central

    Miola, Marta; Verné, Enrica; Ciraldo, Francesca Elisa; Cordero-Arias, Luis; Boccaccini, Aldo R.

    2015-01-01

    In this research work, the original 45S5 bioactive glass was modified by introducing zinc and/or strontium oxide (6 mol%) in place of calcium oxide. Sr was added for its ability to stimulate bone formation and Zn for its role in bone metabolism, antibacterial properties, and anti-inflammatory effect. The glasses were produced by means of melting and quenching process. SEM and XRD analyses evidenced that Zr and Sr introduction did not modify the glass structure and morphology while compositional analysis (EDS) demonstrated the effective incorporation of these elements in the glass network. Bioactivity test in simulated body fluid (SBF) up to 1 month evidenced a reduced bioactivity kinetics for Zn-doped glasses. Doped glasses were combined with chitosan to produce organic/inorganic composite coatings on stainless steel AISI 316L by electrophoretic deposition (EPD). Two EPD processes were considered for coating development, namely direct current EPD (DC-EPD) and alternating current EPD (AC-EPD). The stability of the suspension was analyzed and the deposition parameters were optimized. Tape and bending tests demonstrated a good coating-substrate adhesion for coatings containing 45S5-Sr and 45S5-ZnSr glasses, whereas the adhesion to the substrate decreased by using 45S5-Zn glass. FTIR analyses demonstrated the composite nature of coatings and SEM observations indicated that glass particles were well integrated in the polymeric matrix, the coatings were fairly homogeneous and free of cracks; moreover, the AC-EPD technique provided better results than DC-EPD in terms of coating quality. SEM, XRD analyses, and Raman spectroscopy, performed after bioactivity test in SBF solution, confirmed the bioactive behavior of 45S5-Sr-containing coating while coatings containing Zn exhibited no hydroxyapatite formation. PMID:26539431

  1. Luminescence study of ZnSe/PVA (polyvinyl alcohol) composite film

    SciTech Connect

    Lahariya, Vikas

    The ZnSe nanocrystals have been prepared into poly vinyl alcohol(PVA) polymer matrix on glass using ZnCl2 and Na2SeSO3 as zinc and selenium source respectively. Poly vinyl Alcohol (PVA) used as polymer matrix cum capping agent due to their high viscosity and water solubility. It is transparent for visible region and prevents Se- ions to photo oxidation. The ZnSe/PVA composite film was deposited on glass substrate. The film was characterized by X Ray Diffraction (XRD) and UV-Visible absorption Spectroscopy and Photoluminescence. The X Ray Diffraction (XRD) study confirms the nanometer size (10 nm) particle formation within PVA matrix with cubic zinc blendmore » crystal structure. The UV-Visible Absorption spectrum of ZnSe/PVA composite film shown blue shift in absorption edge indicating increased band gap due to quantum confinement. The calculated energy band gap from the absorption edge using Tauc relation is 3.4 eV. From the Photoluminescence study a broad peak at 435 nm has been observed in violet blue region due to recombination of surface states.« less

  2. Elemental composition, isotopes, electrons and positrons in cosmic rays

    NASA Technical Reports Server (NTRS)

    Balasubrahmanyan, V. K.

    1979-01-01

    Papers presented at the 16th International Cosmic Ray Conference, Kyoto, Japan, dealing with the composition of cosmic rays are reviewed. Particular interest is given to data having bearing on nucleosynthesis sites, supernovae, gamma-process, comparison with solar system composition, multiplicity of sources, and the energy dependence of composition.

  3. Field-assisted sintering and phase transition of ZnS-CaLa 2S 4 composite ceramics

    DOE PAGES

    Li, Yiyu; Zhang, Lihua; Kisslinger, Kim; ...

    2017-07-17

    In the present study, zinc sulfide (ZnS) and calcium lanthanum sulfide (CaLa 2S 4, CLS) composite ceramics were consolidated via field-assisted sintering of 0.5ZnS-0.5CLS (volume ratio) composite powders at 800–1050 °C. Through sintering curve analyses and microstructural observations, it was determined that between 800 and 1000 °C, grain boundary diffusion was the main mechanism controlling grain growth for both the ZnS and CLS phases within the composite ceramics. The consolidated composite ceramics were determined to be composed of sphalerite ZnS, wurtzite ZnS and thorium phosphate CLS. The sphalerite-wurtzite phase transition of ZnS was further demonstrated to be accompanied by themore » formation of stacking faults and twins in the ceramics. Furthermore, it was also found that the addition of the CLS phase improved the indentation hardness of the ceramics relative to pure ZnS by homogeneous dispersion of ZnS and CLS small grains.« less

  4. Field-assisted sintering and phase transition of ZnS-CaLa 2S 4 composite ceramics

    SciTech Connect

    Li, Yiyu; Zhang, Lihua; Kisslinger, Kim

    In the present study, zinc sulfide (ZnS) and calcium lanthanum sulfide (CaLa 2S 4, CLS) composite ceramics were consolidated via field-assisted sintering of 0.5ZnS-0.5CLS (volume ratio) composite powders at 800–1050 °C. Through sintering curve analyses and microstructural observations, it was determined that between 800 and 1000 °C, grain boundary diffusion was the main mechanism controlling grain growth for both the ZnS and CLS phases within the composite ceramics. The consolidated composite ceramics were determined to be composed of sphalerite ZnS, wurtzite ZnS and thorium phosphate CLS. The sphalerite-wurtzite phase transition of ZnS was further demonstrated to be accompanied by themore » formation of stacking faults and twins in the ceramics. Furthermore, it was also found that the addition of the CLS phase improved the indentation hardness of the ceramics relative to pure ZnS by homogeneous dispersion of ZnS and CLS small grains.« less

  5. Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

    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

  6. SIMSISH Technique Does Not Alter the Apparent Isotopic Composition of Bacterial Cells

    PubMed Central

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

    2013-01-01

    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. PMID:24204855

  7. The uranium-isotopic composition of Saharan dust collected over the central Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Aciego, Sarah M.; Aarons, Sarah M.; Sims, Kenneth W. W.

    2015-06-01

    Uranium isotopic compositions, (234U/238U)activity , are utilized by earth surface disciplines as chronometers and source tracers, including in soil science where aeolian dust is a significant source to the total nutrient pool. However, the (234U/238U)activity composition of dust is under characterized due to material and analytical constraints. Here we present new uranium isotope data measured by high precision MC-ICP-MS on ten airborne dust samples collected on the M55 trans-Atlantic cruise in 2002. Two pairs of samples are presented with different size fractions, coarse (1-30 μm) and fine (<1 μm), and all samples were processed to separate the water soluble component in order to assess the controls on the (234U/238U)activity of mineral aerosols transported from the Sahara across the Atlantic. Our results indicate (234U/238U)activity above one for both the water soluble (1.13-1.17) and the residual solid (1.06-1.18) fractions of the dust; no significant correlation is found between isotopic composition and travel distance. Residual solids indicate a slight dependance of (234U/238U)activity on particle size. Future modeling work that incorporates dust isotopic compositions into mixing or isotopic fractionation models will need to account for the wide variability in dust (234U/238U)activity .

  8. Linking Barbados Mineral Dust Aerosols to North African Sources Using Elemental Composition and Radiogenic Sr, Nd, and Pb Isotope Signatures

    NASA Astrophysics Data System (ADS)

    Bozlaker, Ayse; Prospero, Joseph M.; Price, Jim; Chellam, Shankararaman

    2018-01-01

    Large quantities of African dust are carried across the Atlantic to the Caribbean Basin and southern United States where it plays an important role in the biogeochemistry of soils and waters and in air quality. Dusts' elemental and isotopic composition was comprehensively characterized in Barbados during the summers of 2013 and 2014, the season of maximum dust transport. Although total suspended insoluble particulate matter (TSIP) mass concentrations varied significantly daily and between the two summers, the abundances (μg element/g TSIP) of 50 elements during "high-dust days" (HDD) were similar. Aerosols were regularly enriched in Na, Cu, Zn, As, Se, Mo, Cd, Sn, Sb, and W relative to the upper continental crust. Enrichment of these elements, many of which are anthropogenically emitted, was significantly reduced during HDD, attributed to mixing and dilution with desert dust over source regions. Generally, Ti/Al, Si/Al, Ca/Al, Ti/Fe, Si/Fe, and Ca/Fe ratios during HDD differed from their respective values in hypothesized North African source regions. Nd isotope composition was relatively invariant for "low-dust days" (LDD) and HDD. In contrast, HDD-aerosols were more radiogenic exhibiting higher 87Sr/86Sr, 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios compared to LDD. Generally, Barbados aerosols' composition ranged within narrow limits and was much more homogeneous than that of hypothesized African source soils. Our results suggest that summertime Barbados aerosols are dominated by a mixture of particles originating from sources in the Sahara-Sahel regions. The Bodélé Depression, long suspected as a major source, appears to be an insignificant contributor of summertime western Atlantic dust.

  9. Evaluating climate model performance in the tropics with retrievals of water isotopic composition from Aura TES

    NASA Astrophysics Data System (ADS)

    Field, Robert; Kim, Daehyun; Kelley, Max; LeGrande, Allegra; Worden, John; Schmidt, Gavin

    2014-05-01

    Observational and theoretical arguments suggest that satellite retrievals of the stable isotope composition of water vapor could be useful for climate model evaluation. The isotopic composition of water vapor is controlled by the same processes that control water vapor amount, but the observed distribution of isotopic composition is distinct from amount itself . This is due to the fractionation that occurs between the abundant H216O isotopes (isotopologues) and the rare and heavy H218O and HDO isotopes during evaporation and condensation. The fractionation physics are much simpler than the underlying moist physics; discrepancies between observed and modeled isotopic fields are more likely due to problems in the latter. Isotopic measurements therefore have the potential for identifying problems that might not be apparent from more conventional measurements. Isotopic tracers have existed in climate models since the 1980s but it is only since the mid 2000s that there have been enough data for meaningful model evaluation in this sense, in the troposphere at least. We have evaluated the NASA GISS ModelE2 general circulation model over the tropics against water isotope (HDO/H2O) retrievals from the Aura Tropospheric Emission Spectrometer (TES), alongside more conventional measurements. A small ensemble of experiments was performed with physics perturbations to the cumulus and planetary boundary layer schemes, done in the context of the normal model development process. We examined the degree to which model-data agreement could be used to constrain a select group of internal processes in the model, namely condensate evaporation, entrainment strength, and moist convective air mass flux. All are difficult to parameterize, but exert strong influence over model performance. We found that the water isotope composition was significantly more sensitive to physics changes than precipitation, temperature or relative humidity through the depth of the tropical troposphere. Among the

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

    PubMed Central

    2009-01-01

    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. PMID:19930701

  11. Reduced graphene oxide-ZnO composites based gas sensors: A review

    NASA Astrophysics Data System (ADS)

    Thakare, N. B.; Raghuwanshi, F. C.; Kalyamwar, V. S.; Tamgadge, Y. S.

    2018-05-01

    The need to monitor and control life threatening gases has led to research and development of a wide variety of sensors using different materials and technologies. Recently rGO (reduced graphene oxide)-MOS (Metal Oxide Semiconductor) architectures have been studied for efficient and cost effective gas sensors that will operate at low temperature. In this review paper, we review latest findings and progress in rGO-ZnO composites as sensors to detect volatile and toxic gases.

  12. Vanadium isotopic composition of the sea squirt (Ciona savignyi).

    PubMed

    Nomura, Masao; Nakamura, Mana; Soeda, Ryosuke; Kikawada, Yoshikazu; Fukushima, Michiko; Oi, Takao

    2012-09-01

    Vanadium (V) in the sea squirt (Ciona savignyi) from Onagawa Bay, Miyagi, Japan, was isolated and purified through adsorption on a diamine resin and anion and cation exchanges after the dissolution of sea squirt samples with nitric acid and hydrogen peroxide. The (50)V/(51)V isotope ratio of V thus obtained was mass-spectrometrically determined to be from 2.51×10(-3) to 2.55×10(-3) with the average of 2.53×10(-3) by the thermal ionisation technique. This value agreed with those of vanadyl chloride and vanadyl nitrate both prepared from vanadyl sulphate (Wako Pure Chemical Industries, Ltd., Japan) and of V in coastal seawater (Shimokita Peninsula, Aomori, Japan) within experimental uncertainties (standard deviation of±0.04), which suggested that no appreciable V isotope fractionation occurs accompanying V uptake by the sea squirt from sea water.

  13. Investigating nuclear shell structure in the vicinity of 78Ni: Low-lying excited states in the neutron-rich isotopes Zn,8280

    NASA Astrophysics Data System (ADS)

    Shiga, Y.; Yoneda, K.; Steppenbeck, D.; Aoi, N.; Doornenbal, P.; Lee, J.; Liu, H.; Matsushita, M.; Takeuchi, S.; Wang, H.; Baba, H.; Bednarczyk, P.; Dombradi, Zs.; Fulop, Zs.; Go, S.; Hashimoto, T.; Honma, M.; Ideguchi, E.; Ieki, K.; Kobayashi, K.; Kondo, Y.; Minakata, R.; Motobayashi, T.; Nishimura, D.; Otsuka, T.; Otsu, H.; Sakurai, H.; Shimizu, N.; Sohler, D.; Sun, Y.; Tamii, A.; Tanaka, R.; Tian, Z.; Tsunoda, Y.; Vajta, Zs.; Yamamoto, T.; Yang, X.; Yang, Z.; Ye, Y.; Yokoyama, R.; Zenihiro, J.

    2016-02-01

    The low-lying level structures of nuclei in the vicinity of 78Ni were investigated using in-beam γ -ray spectroscopy to clarify the nature of the nuclear magic numbers Z =28 and N =50 in systems close to the neutron drip line. Nucleon knockout reactions were employed to populate excited states in 80Zn and 82Zn. A candidate for the 41+ level in 80Zn was identified at 1979(30) keV, and the lifetime of this state was estimated to be 136-67+92 ps from a line-shape analysis. Moreover, the energy of the 21+ state in 82Zn is reported to lie at 621(11) keV. The large drop in the 21+ energy at 82Zn indicates the presence of a significant peak in the E (21+) systematics at N =50 . Furthermore, the E (41+) /E (21+) and B (E 2 ;41+→21+) /B (E 2 ;21+→0g.s . +) ratios in 80Zn were deduced to be 1.32 (3 ) and 1 .12-60+80 , respectively. These results imply that 80Zn can be described in terms of two-proton configurations with a 78Ni core and are consistent with a robust N =50 magic number along the Zn isotopic chain. These observations, therefore, indicate a persistent N =50 shell closure in nuclei far from the line of β stability, which in turn suggests a doubly magic structure for 78Ni.

  14. Oxygen isotope effect in disordered underdoped and overdoped La 2-xSr xCu 1-yZn yO 4 superconductors

    NASA Astrophysics Data System (ADS)

    Naqib, S. H.; Islam, R. S.

    2011-04-01

    The effect of oxygen isotopic substitution on the superconducting transition temperature has been studied for heavily underdoped and overdoped La 2-xSr xCu 1-yZn yO 4 compounds with different Zn contents in the CuO 2 plane. The effect of Zn on the isotope coefficient, α, was significantly more pronounced in the case of the underdoped ( x = 0.09) compounds compared to the overdoped ( x = 0.22) ones. The variation of α with disorder content can be described quite well within a model based solely on Cooper pair-breaking in the case of the underdoped compounds. This model fails to describe the behavior of α( y) for the overdoped samples, even though Zn still suppresses T c very effectively at this hole (Sr) content, indicating that the Zn induced pair-breaking is still very much at play. We discuss the implications of these findings in details by considering the Zn induced magnetism, stripe correlations, and possible changes in the superconducting order parameter as hole content in the CuO 2 plane, p (≡ x), is varied.

  15. Nickel and zinc isotope fractionation in hyperaccumulating and nonaccumulating plants.

    PubMed

    Deng, Teng-Hao-Bo; Cloquet, Christophe; Tang, Ye-Tao; Sterckeman, Thibault; Echevarria, Guillaume; Estrade, Nicolas; Morel, Jean-Louis; Qiu, Rong-Liang

    2014-10-21

    Until now, there has been little data on the isotope fractionation of nickel (Ni) in higher plants and how this can be affected by plant Ni and zinc (Zn) homeostasis. A hydroponic cultivation was conducted to investigate the isotope fractionation of Ni and Zn during plant uptake and translocation processes. The nonaccumulator Thlaspi arvense, the Ni hyperaccumulator Alyssum murale and the Ni and Zn hyperaccumulator Noccaea caerulescens were grown in low (2 μM) and high (50 μM) Ni and Zn solutions. Results showed that plants were inclined to absorb light Ni isotopes, presumably due to the functioning of low-affinity transport systems across root cell membrane. The Ni isotope fractionation between plant and solution was greater in the hyperaccumulators grown in low Zn treatments (Δ(60)Ni(plant-solution) = -0.90 to -0.63‰) than that in the nonaccumulator T. arvense (Δ(60)Ni(plant-solution) = -0.21‰), thus indicating a greater permeability of the low-affinity transport system in hyperaccumulators. Light isotope enrichment of Zn was observed in most of the plants (Δ(66)Zn(plant-solution) = -0.23 to -0.10‰), but to a lesser extent than for Ni. The rapid uptake of Zn on the root surfaces caused concentration gradients, which induced ion diffusion in the rhizosphere and could result in light Zn isotope enrichment in the hyperaccumulator N. caerulescens. In high Zn treatment, Zn could compete with Ni during the uptake process, which reduced Ni concentration in plants and decreased the extent of Ni isotope fractionation (Δ(60)Ni(plant-solution) = -0.11 to -0.07‰), indicating that plants might take up Ni through a low-affinity transport system of Zn. We propose that isotope composition analysis for transition elements could become an empirical tool to study plant physiological processes.

  16. Using isotopic dilution to assess chemical extraction of labile Ni, Cu, Zn, Cd and Pb in soils.

    PubMed

    Garforth, J M; Bailey, E H; Tye, A M; Young, S D; Lofts, S

    2016-07-01

    Chemical extractants used to measure labile soil metal must ideally select for and solubilise the labile fraction, with minimal solubilisation of non-labile metal. We assessed four extractants (0.43 M HNO3, 0.43 M CH3COOH, 0.05 M Na2H2EDTA and 1 M CaCl2) against these requirements. For soils contaminated by contrasting sources, we compared isotopically exchangeable Ni, Cu, Zn, Cd and Pb (EValue, mg kg(-1)), with the concentrations of metal solubilised by the chemical extractants (MExt, mg kg(-1)). Crucially, we also determined isotopically exchangeable metal in the soil-extractant systems (EExt, mg kg(-1)). Thus 'EExt - EValue' quantifies the concentration of mobilised non-labile metal, while 'EExt - MExt' represents adsorbed labile metal in the presence of the extractant. Extraction with CaCl2 consistently underestimated EValue for Ni, Cu, Zn and Pb, while providing a reasonable estimate of EValue for Cd. In contrast, extraction with HNO3 both consistently mobilised non-labile metal and overestimated the EValue. Extraction with CH3COOH appeared to provide a good estimate of EValue for Cd; however, this was the net outcome of incomplete solubilisation of labile metal, and concurrent mobilisation of non-labile metal by the extractant (MExtEValue). The Na2H2EDTA extractant mobilised some non-labile metal in three of the four soils, but consistently solubilised the entire labile fraction for all soil-metal combinations (MExt ≈ EExt). Comparison of EValue, MExt and EExt provides a rigorous means of assessing the underlying action of soil chemical extraction methods and could be used to refine long-standing soil extraction methodologies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Preparation and characterization of PVP-PVA–ZnO blend polymer nano composite films

    SciTech Connect

    Divya, S., E-mail: divi.fysics@gmail.com; Saipriya, G.; Hemalatha, J., E-mail: hemalatha@nitt.edu

    Flexible self-standing films of PVP-PVA blend composites are prepared by using ZnO as a nano filler at different concentrations. The structural, compositional, morphological and optical studies made with the help of X-ray diffraction (XRD), Fourier Transform Infra-Red spectroscopy (FTIR), Scanning electron microscope (SEM), Atomic Force Microscopy (AFM), Ultraviolet-visible spectroscopy (UV-vis) and Photoluminescence (PL) spectra are presented in this paper. The results of XRD indicate that ZnO nanoparticles are formed with hexagonal phase in the polymeric matrix. SEM images show the dispersion of ZnO nano filler in the polymer matrix. UV–vis spectra reveal that the absorption peak is centered around 235more » nm and 370 nm for the nano composite films. The blue shift is observed with decrease in the concentration of the nano filler. PL spectra shows the excitation wavelength is given at 320 nm.The emission peaks were observed at 383 nm ascribing to the electronic transitions between valence band and conduction band and the peak at 430 nm.« less

  18. Tracing of ca 800 yr old mining activity in peat bog using Pb elemental concentrations and isotope compositions.

    NASA Astrophysics Data System (ADS)

    Baron, S.; Carignan, J.; Ploquin, A.

    2003-04-01

    Sixty sites of slags have been documented on the Mont-Lozère in southern France. The petrographic analysis shows that slags are metallurgical wastes (800 to 850 yr BP) which certainly result from smelting activity for lead and silver extraction (Ploquin et al., 2001). The aims of this study are: 1) to trace the source of Pb ores which supplied the smelting sites, by using the Pb isotopic composition of several surrounding Pb deposits, 2) to evaluate the actual pollution caused by these slags, by using elemental and isotopic compositions of soils, water and vegetation, and 3) to document the pollution history of the region, by using elemental and isotopic compositions of peat bog cores collected in the neighbourhood of the historical smelting sites. The lead isotopic composition of galena collected in most surrounding ores is very similar to that of different slag samples. On the other hand, the high precision of the results allowed us to select the mineralised areas which were probably the ore sources. The Pb isotopic composition of slags is even more homogeneous: 208/206 Pb: 2.092±0.002; 206/207 Pb: 1.179±0.001; 208/204 Pb: 38.663±0.025; 207/204 Pb: 15.665±0.006; 206/204 Pb: 18.476±0.023, and will allow source tracing in the environment. The "Narses Mortes" peat bog, around which two smelting sites have been reported, is strongly minerotrophic and contains 8 to 60% ash. A 1.40 m core have been retrieved and divided into 58 individual samples. Minerotrophic peat bog records both atmospheric deposition, soils leaching and the grounwater influence. The measured metal concentrations are normalised to Al contents of peat bog samples and the metal/Al ratios are compared to that of the Mont-Lozère granite: relative excess in metal concentrations are found in peat bog samples. An increasing excess of most metals (Pb, Zn, Cd...) was measured for surface samples, from 55 cm depth to the top of the core (23 cm depth). This profil might be attributed to atmospheric

  19. Manipulation of ZnO composition affecting electrical properties of MEH-PPV: ZnO nanocomposite thin film via spin coating for OLEDs application

    NASA Astrophysics Data System (ADS)

    Azhar, N. E. A.; Shariffudin, S. S.; Alrokayan, Salman A. H.; Khan, Haseeb A.; Rusop, M.

    2018-05-01

    Recent investigations of the promising materials for optoelectronic have been demonstrated by introducing n-type inorganic material into conjugated polymer. Morphology, optical and electrical of nanocomposites thin films based on poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and zinc oxide (ZnO) nanotetrapods with various ZnO composition (0 wt% to 0.4 wt%) have been investigated. The MEH-PPV: ZnO nanocomposite thin film was deposited using spin-coating method. Surface morphology was characterized using field emission scanning electron microscopy and shows the uniform dispersion of MEH-PPV and ZnO phases for sample deposited at 0.2 wt%. The photoluminescence (PL) spectra shows the visible emission intensities increased when the ZnO composition increased. The current-voltage (I-V) measurement shows the highest conductivity of nanocomposite thin film deposited at 0.2 wt% of ZnO is 7.40 × 10-1 S. cm-1. This study will provide better performance and suitable for optoelectronic device especially OLEDs application.

  20. Isotopic composition of Pb in ore deposits of the Betic Cordillera, Spain; origin and relationship to other European deposits

    USGS Publications Warehouse

    Arribas , Antonio; Tosdal, Richard M.

    1994-01-01

    The Betic Cordillera in southern Spain is a complex Alpine fold belt that resulted from the Cretaceous through Cenozoic collision of Africa with Europe. The region is illustrative of one of the characteristics of the Alpine-Mediterranean orogen: the occurrence over a limited area of mineral deposits with a wide variety of host rocks, mineralization ages, and styles. The metamorphic basement in the Betic zone is characterized by a nappe structure of superimposed tectonostratigraphic units and consists of lower Paleozoic to Lower Triassic clastic metasedimentary rocks. This is overlain by Middle to Upper Triassic platform carbonate rocks with abundant strata-bound F-Pb-Zn-(Ba) deposits (e.g., Sierra de Gador, Sierra Alhamilla). Cretaceous to Paleogene subduction-related compression in southeastern Spain was followed by Miocene postcollisional extension and resulted in the formation of the Almeria-Cartagena volcanic belt and widespread hydrothermal activity and associated polymetallic mineralization. Typical Miocene hydrothermal deposits include volcanic-hosted Au (e.g., Rodalquilar) and Ag-rich base metal (e.g., Cabo de Gata, Mazarron) deposits as well as complex polymetallic veins, mantos, and irregular replacement bodies which are hosted by Paleozoic and Mesozoic metamorphic rocks and Neogene sedimentary and volcanic rocks (e.g., Cartagena, Sierra Almagrera, Sierra del Aguilon, Loma de Bas).Lead isotope compositions were measured on sulfide samples from nine ore districts and from representative fresh samples of volcanic and basement rock types of the region. The results have been used to evaluate ore-forming processes in southeastern Spain with emphasis on the sources of metals. During a Late Triassic mineralizing event, Pb was leached from Paleozoic clastic metasedimentary rocks and incorporated in galena in strata-bound F-Pb-Zn-(Ba) deposits ( 206 Pb/ 204 Pb = 18.332 + or - 12, 207Pb/ 204 Pb = 15.672 + or - 12, 208 Pb/ 204 Pb = 38.523 + or - 46). The second

  1. Plutonium isotopes in the atmosphere of Central Europe: Isotopic composition and time evolution vs. circulation factors.

    PubMed

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

    2016-11-01

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

    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.

  3. Molybdenum Isotopic Composition of the Archean Mantle As Inferred from Studies of Komatiites

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    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.

  4. Facile preparation of well-combined lignin-based carbon/ZnO hybrid composite with excellent photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Wang, Huan; Qiu, Xueqing; Liu, Weifeng; Yang, Dongjie

    2017-12-01

    In this work, a novel lignin-based carbon/ZnO (LC/ZnO) hybrid composite with excellent photocatalytic performance was prepared through a convenient and environment friendly method using alkali lignin (AL) as carbon source. The morphological, microstructure and optical properties of the as-prepared LC/ZnO hybrid composite was characterized with scanning electron microscope (SEM), X-ray diffraction (XRD), Raman and UV-vis. The resulting LC/ZnO hybrid is composed of highly dispersed ZnO nanoparticles embedded on a lignin-based carbon nanosheet, showing excellent photogenerated electrons and holes separation and migration efficiency. The photocatalytic activity of LC/ZnO was much higher than the pure ZnO. The LC/ZnO hybrid composite showed different photocatalytic mechanism for degradation of negative methyl orange (MO) and positive Rhodamine B (RhB). It showed that h+ was the main photocatalytic active group during the degradation of MO, ·O2- and ·OH were the photocatalytic active groups during degradation of RhB. This reported photocatalyst with selective degradation of positive and negative organic dyes may have a great application prospect for photoelectric conversion and catalytic materials. Results of this work were of practical importance for high-valued utilization of lignin for carbon materials.

  5. Lead isotope studies of the Guerrero composite terrane, west-central Mexico: implications for ore genesis

    NASA Astrophysics Data System (ADS)

    Potra, Adriana; Macfarlane, Andrew W.

    2014-01-01

    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

  6. Efficient mixing of the solar nebula from uniform Mo isotopic composition of meteorites.

    PubMed

    Becker, Harry; Walker, Richard J

    2003-09-11

    The abundances of elements and their isotopes in our Galaxy show wide variations, reflecting different nucleosynthetic processes in stars and the effects of Galactic evolution. These variations contrast with the uniformity of stable isotope abundances for many elements in the Solar System, which implies that processes efficiently homogenized dust and gas from different stellar sources within the young solar nebula. However, isotopic heterogeneity has been recognized on the subcentimetre scale in primitive meteorites, indicating that these preserve a compositional memory of their stellar sources. Small differences in the abundance of stable molybdenum isotopes in bulk rocks of some primitive and differentiated meteorites, relative to terrestrial Mo, suggest large-scale Mo isotopic heterogeneity between some inner Solar System bodies, which implies physical conditions that did not permit efficient mixing of gas and dust. Here we report Mo isotopic data for bulk samples of primitive and differentiated meteorites that show no resolvable deviations from terrestrial Mo. This suggests efficient mixing of gas and dust in the solar nebula at least to 3 au from the Sun, possibly induced by magnetohydrodynamic instabilities. These mixing processes must have occurred before isotopic fractionation of gas-phase elements and volatility-controlled chemical fractionations were established.

  7. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O 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 17O 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(1D), 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 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

  8. Composition Dependence of the Hydrostatic Pressure Coefficients of the Bandgap of ZnSe(1-x)Te(x) Alloys

    NASA Technical Reports Server (NTRS)

    Wu, J.; Yu, K. M.; Walukiewicz, W.; Shan, W.; Ager, J. W., III; Haller, E. E.; Miotkowski, I.; Ramdas, A. K.; Su, Ching-Hua

    2003-01-01

    Optical absorption experiments have been performed using diamond anvil cells to measure the hydrostatic pressure dependence of the fundamental bandgap of ZnSe(sub 1-xTe(sub x) alloys over the entire composition range. The first and second-order pressure coefficients are obtained as a function of composition. Starting from the ZnSe side, the magnitude of both coefficients increases slowly until x approx. 0.7, where the ambient-pressure bandgap reaches a minimum. For larger values of x the coefficients rapidly approach the values of ZnTe. The large deviations of the pressure coefficients from the linear interpolation between ZnSe and ZnTe are explained in terms of the band anticrossing model.

  9. Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

    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.

  10. Local Structures Around Co Atoms in Wurtzite ZnO Nano-Composites Probed by Fluorescence XAFS

    SciTech Connect

    Shi Tongfei; National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029; Liu Wenhan

    2007-02-02

    The local structures around Co ions in the Zn1-xCoxO nano-composites prepared by the sol-gel method have been investigated by fluorescence X-ray absorption fine structure (XAFS) technique. The results indicate that for dilute Co-doped ZnO (x=0.02, 0.05), the Co2+ ions are incorporated into the ZnO lattice, and are located at the position of the substitutional Zn2+ ions. As the Co content increases to 0.10 or higher, only part of the Co ions enter the lattice of the wurtzite and the others exist in the form of a Co3O4 phase whose content increases with the doped Co concentration. In the substitutional Zn0.98Co0.02Omore » sample, the bond length of the first shell RCo-O and the second shell RCo-Zn is smaller than the second shell Zn-Zn distance in ZnO by about 0.01{approx}0.02 A. These results imply that only small local lattice deformation is induced by dilute Co2+ substituting into the Zn2+ sites.« less

  11. Magnesium isotope compositions of Solar System materials determined by double spiking

    NASA Astrophysics Data System (ADS)

    Hin, R.; Lai, Y. J.; Coath, C.; Elliott, T.

    2015-12-01

    As a major element, magnesium is of interest for investigating large scale processes governing the formation and evolution of rocky planetary bodies. Determining the Mg isotope composition of the Earth and other planetary bodies has hence been a topic of interest ever since mass-dependent fractionation of 'non-traditional' stable isotopes has been used to study high-temperature processes. Published results, however, suffer from disagreement on the Mg isotope compositions of the Earth and chondrites [1-5], which is attributed to residual matrix effects. Nonetheless, most recent studied have converged towards a homogeneous (chondritic) Mg isotope composition in the Solar System [2-5]. However, in several of the recent studies there is a hint of a systematic difference of about 0.02-0.06‰ in the 26Mg/24Mg isotope compositions of chondrites and Earth. Such difference, however, is only resolvable by taking standard errors, which assumes robust data for homogenous sample sets. The discrepancies between various studies unfortunately undermine the confidence in such robustness and homogeneity. The issues with matrix effects during isotopic analyses can be overcome by using a double spike approach. Such methodology generally requires three isotope ratios to solve for three unknowns, a requirement that cannot be met for Mg. However, using a newly developed approach, we present Mg isotope compositions obtained by critical mixture double spiking. This new approach should allow greater confidence in the robustness of the data and hence enable improvement of. Preliminary data indicate that chondrites have a resolvable ~0.04‰ lighter 26Mg/24Mg than (ultra)mafic rocks from Earth, Mars and the eucrite parent body, which appear indistinguishable from each other. It seems implausible that this difference is caused by magmatic process such as partial melting or crystallisation. More likely, Mg isotopes are fractionated by a non-magmatic process during the formation of planets, e

  12. [Changes of chlorine isotope composition characterize bacterial dehalogenation of dichloromethane].

    PubMed

    Ziakun, A M; Firsova, Iu E; Torgonskaia, M L; Doronina, N V; Trotsenko, Iu A

    2007-01-01

    Fractionation of dichloromethane (DCM) molecules with different chlorine isotopes by aerobic methylobacteria Methylobacterium dichloromethanicum DM4 and Albibacter nethylovorans DM10; cell-free extract of strain DM4; and transconjugant Methylobacterium evtorquens Al1/pME 8220, expressing the dcmA gene for DCM dehalogenase but unable to grow on DCM, was studied. Kinetic indices of DCM isotopomers for chlorine during bacterial dehalogenation and diffusion were compared. A two-step model is proposed, which suggests diffusional DCM transport to bacterial cells.

  13. Novel ZnO/MgO/Fe2O3 composite optomagnetic nanoparticles.

    PubMed

    Kamińska, I; Sikora, B; Fronc, K; Dziawa, P; Sobczak, K; Minikayev, R; Paszkowicz, W; Elbaum, D

    2013-05-15

    A facile sol-gel synthesis of novel ZnO/MgO/Fe2O3 nanoparticles (NPs) is reported and their performance is compared to that of ZnO/MgO. Powder x-ray diffraction (XRD) patterns reveal the crystal structure of the prepared samples. The average particle size of the sample was found to be 4.8 nm. The optical properties were determined by UV-vis absorption and fluorescence measurements. The NPs are stable in biologically relevant solutions (phosphate buffered saline (PBS), 20 mM, pH = 7.0) contrary to ZnO/MgO NPs which degrade in the presence of inorganic phosphate. Superparamagnetic properties were determined with a superconducting quantum interference device (SQUID). Biocompatible and stable in PBS ZnO/MgO/Fe2O3 core/shell composite nanocrystals show luminescent and magnetic properties confined to a single NP at room temperature (19-24 ° C), which may render the material to be potentially useful for biomedical applications.

  14. In situ observations of the isotopic composition of methane at the Cabauw tall tower site

    NASA Astrophysics Data System (ADS)

    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

    2016-08-01

    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.

  15. Lithium contents and isotopic compositions of ferromanganese deposits from the global ocean

    USGS Publications Warehouse

    Chan, L.-H.; Hein, J.R.

    2007-01-01

    To test the feasibility of using lithium isotopes in marine ferromanganese deposits as an indicator of paleoceanographic conditions and seawater composition, we analyzed samples from a variety of tectonic environments in the global ocean. Hydrogenetic, hydrothermal, mixed hydrogenetic–hydrothermal, and hydrogenetic–diagenetic samples were subjected to a two-step leaching and dissolution procedure to extract first the loosely bound Li and then the more tightly bound Li in the Mn oxide and Fe oxyhydroxide. Total leachable Li contents vary from 2 by coulombic force. Hence, the abundant Li in hydrothermal deposits is mainly associated with the dominant phase, MnO2. The surface of amorphous FeOOH holds a slightly positive charge and attracts little Li, as demonstrated by data for hydrothermal Fe oxyhydroxide. Loosely sorbed Li in both hydrogenetic crusts and hydrothermal deposits exhibit Li isotopic compositions that resemble that of modern seawater. We infer that the hydrothermally derived Li scavenged onto the surface of MnO2 freely exchanged with ambient seawater, thereby losing its original isotopic signature. Li in the tightly bound sites is always isotopically lighter than that in the loosely bound fraction, suggesting that the isotopic fractionation occurred during formation of chemical bonds in the oxide and oxyhydroxide structures. Sr isotopes also show evidence of re-equilibration with seawater after deposition. Because of their mobility, Li and Sr in the ferromanganese crusts do not faithfully record secular variations in the isotopic compositions of seawater. However, Li content can be a useful proxy for the hydrothermal history of ocean basins. Based on the Li concentrations of the globally distributed hydrogenetic and hydrothermal samples, we estimate a scavenging flux of Li that is insignificant compared to the hydrothermal flux and river input to the ocean.

  16. Silicon isotope fractionation by marine sponges and the reconstruction of the silicon isotope composition of ancient deep water

    NASA Astrophysics Data System (ADS)

    de La Rocha, Christina L.

    2003-05-01

    The silicon isotope composition (δ30Si) of biogenic opal provides a view of the silica cycle at times in the past. Reconstructions require the knowledge of silicon isotope fractionation during opal biomineralization. The δ30Si of specimens of hexactinellid sponges and demosponges growing in the modern ocean ranged from -1.2‰ to -3.7‰ (n = 6), corresponding to the production of opal that has a δ30Si value 3.8‰ ± 0.8‰ more negative than seawater silicic acid and a fractionation factor (α) of 0.9964. This is three times the fractionation observed during opal formation by marine diatoms and terrestrial plants and is the largest fractionation of silicon isotopes observed for any natural process on Earth. The δ30Si values of sponge spicules across the Eocene-Oligocene boundary at Ocean Drilling Program Site 689 on Maud Rise range from -1.1‰ to -3.0‰, overlapping the range observed for sponges growing in modern seawater.

  17. Isotopic composition analysis and age dating of uranium samples by high resolution gamma ray spectrometry

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  18. Controls on the distribution and isotopic composition of helium in deep ground-water flows

    USGS Publications Warehouse

    Zhao, X.; Fritzel, T.L.B.; Quinodoz, H.A.M.; Bethke, C.M.; Torgersen, T.

    1998-01-01

    The distribution and isotopic composition of helium in sedimentary basins can be used to interpret the ages of very old ground waters. The piston-flow model commonly used in such interpretation, how ever, does not account for several important factors and as such works well only in very simple flow regimes. In this study of helium transport in a hypothetical sedimentary basin, we develop a numerical model that accounts for the magnitude and distribution of the basal helium flux, hydrodynamic dispersion, and complexities in flow regimes such as subregional flow cells. The modeling shows that these factors exert strong controls on the helium distribution and isotopic composition. The simulations may provide a basis for more accurate interpretations of observed helium concentrations and isotopic ratios in sedimentary basins.

  19. Constraints on Galactic Cosmic-Ray Origins from Elemental and Isotopic Composition Measurements

    NASA Technical Reports Server (NTRS)

    Binns, W. R.; Christian, E. R.; Cummings, A. C.; deNolfo, G. A.; Israel, M. H.; Leske, R. A.; Mewaldt, R. A,; Stone, E. C.; vonRosevinge, T. T.; Wiedenbeck, M. E.

    2013-01-01

    The most recent measurements by the Cosmic Ray Isotope Spectrometer (CRIS) aboard the Advanced Composition Explorer (ACE) satellite of ultra-heavy cosmic ray isotopic and elemental abundances will be presented. A range of isotope and element ratios, most importantly Ne-22/Ne-20, Fe-58/Fe-56, and Ga-31/Ge -32 show that the composition is consistent with source material that is a mix of approx 80% ISM (with Solar System abundances) and 20% outflow/ejecta from massive stars. In addition, our data show that the ordering of refractory and volatile elements with atomic mass is greatly improved when compared to an approx 80%/20% mix rather than pure ISM, that the refractory and volatile elements have similar slopes, and that refractory elements are preferentially accelerated by a factor of approx 4. We conclude that these data are consistent with an OB association origin of GCRs.

  20. The isotopic composition of methane in polar ice cores

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

    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.

  1. Sulphur isotopic compositions of deep-sea hydrothermal vent animals

    NASA Technical Reports Server (NTRS)

    Fry, B.; Gest, H.; Hayes, J. M.

    1983-01-01

    The S-34/S-32 ratios of tissues from vestimentiferan worms, brachyuran crabs, and giant clams living around deep hydrothermal vents are reported. Clean tissues were dried, ground, suspended in 0.1 M LiCl, shaken twice at 37 C to remove seawater sulfates, dried at 60 C, combusted in O2 in a Parr bomb. Sulfur was recovered as BaSO4, and the isotopic abundances in SO2 generated by thermal decomposition of 5-30-mg samples were determined using an isotope-ratio mass spectrometer. The results are expressed as delta S-34 and compared with values measured in seawater sulfates and in normal marine fauna. The values ranged from -4.7 to 4.7 per thousand, comparable to vent sulfide minerals (1.3-4.1 per thousand) and distinct from seawater sulfates (20.1 per thousand) and normal marine fauna (about 13-20 per thousand). These results indicate that vent sulfur rather than seawater sulfur is utilized by these animals, a process probably mediated by chemoautotrophic bacteria which can use inorganic sulfur compounds as energy sources.

  2. Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

    NASA Astrophysics Data System (ADS)

    Henkes, Gregory A.; Passey, Benjamin H.; Grossman, Ethan L.; Shenton, Brock J.; Yancey, Thomas E.; Pérez-Huerta, Alberto

    2018-05-01

    Surface temperature is among the most important parameters describing planetary climate and habitability, and yet there remains considerable debate about the temperature evolution of the Earth's oceans during the Phanerozoic Eon (541 million years ago to present), the time during which complex metazoan life radiated on Earth. Here we critically assess the emerging record of Phanerozoic ocean temperatures based on carbonate clumped isotope thermometry of fossil brachiopod and mollusk shells, and we present new data that fill important gaps in the Late Paleozoic record. We evaluate and reject the hypothesis that solid-state reordering of 13C-18O bonds has destroyed the primary clumped isotope temperature signal of most fossils during sedimentary burial at elevated temperatures. The resulting Phanerozoic record, which shows a general coupling between tropical seawater temperatures and atmospheric carbon dioxide (CO2) levels since the Paleozoic, indicates that tropical temperatures during the icehouse climate of the Carboniferous period were broadly similar to present (∼25-30 °C), and suggests that benthic metazoans were able to thrive at temperatures of 35-40 °C during intervals of the early and possibly the latest Paleozoic when CO2 levels were likely 5-10× higher than present-day values. Equally important, there is no resolvable trend in seawater oxygen isotope ratios (δ18 O) over the past ∼500 million years, indicating that the average temperature of oxygen exchange between seawater and the oceanic crust has been high (∼270 °C) since at least the early Paleozoic, which points to mid-ocean ridges as the dominant locus of water-rock interaction over the past half-billion years.

  3. Effect of process conditions and chemical composition on the microstructure and properties of chemically vapor deposited SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x)

    NASA Technical Reports Server (NTRS)

    Pickering, Michael A.; Taylor, Raymond L.; Goela, Jitendra S.; Desai, Hemant D.

    1992-01-01

    Subatmospheric pressure CVD processes have been developed to produce theoretically dense, highly pure, void-free and large area bulk materials, SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x). These materials are used for optical elements, such as mirrors, lenses and windows, over a wide spectral range from the VUV to the IR. We discuss the effect of CVD process conditions on the microstructure and properties of these materials, with emphasis on optical performance. In addition, we discuss the effect of chemical composition on the properties of the composite material ZnS(x)Se(1-x). We first present a general overview of the bulk CVD process and the relationship between process conditions, such as temperature, pressure, reactant gas concentration and growth rate, and the microstructure, morphology and properties of CVD-grown materials. Then we discuss specific results for CVD-grown SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x).

  4. Chemical and stable-radiogenic isotope compositions of Polatlı-Haymana thermal waters (Ankara, Turkey)

    NASA Astrophysics Data System (ADS)

    Akilli, Hafize; Mutlu, Halim

    2016-04-01

    Complex tectono-magmatic evolution of the Anatolian land resulted in development of numerous geothermal areas through Turkey. The Ankara region in central Anatolia is surrounded by several basins which are filled with upper Cretaceous-Tertiary sediments. Overlying Miocene volcanics and step faulting along the margins of these basins played a significant role in formation of a number of low-enthalpy thermal waters. In this study, chemical and isotopic compositions of Polatlı and Haymana geothermal waters in the Ankara region are investigated. The Polatlı-Haymana waters with a temperature range of 24 to 43 °C are represented by Ca-(Na)-HCO3 composition implying derivation from carbonate type reservoir rocks. Oxygen-hydrogen isotope values of the waters are conformable with the Global Meteoric Water Line and point to a meteoric origin. The carbon isotopic composition in dissolved inorganic carbon (DIC) of the studied waters is between -21.8 and -1.34 permil (vs. VPDB). Marine carbonates and organic rocks are the main sources of carbon. There is a high correlation between oxygen (3.7 to 15.0 permil; VSMOW) and sulfur (-9.2 to 19.5 permil; VCDT) isotope compositions of sulfate in waters. The mixing of sulfate from dissolution of marine carbonates and terrestrial evaporite units is the chief process behind the observed sulfate isotope systematics of the samples. 87Sr/86Sr ratios of waters varying from 0.705883 to 0.707827 are consistent with those of reservoir rocks. The temperatures calculated by SO4-H2O isotope geothermometry are between 81 and 138 °C nearly doubling the estimates from chemical geothermometers.

  5. Stable water isotopic composition of the Antarctic subglacial Lake Vostok: implications for understanding the lake's hydrology.

    PubMed

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

    2016-01-01

    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.

  6. Effects of diagenesis on strontium, carbon, nitrogen and oxygen concentration and isotopic composition of bone

    NASA Astrophysics Data System (ADS)

    Nelson, Bruce K.; Deniro, Michael J.; Schoeninger, Margaret J.; De Paolo, Donald J.; Hare, P. E.

    1986-09-01

    Paleodietary analysis based on variations in the trace element and stable isotopic composition of inorganic and organic phases in fossil bone depends on the assumption that measured values reflect in vivo values. To test for postmortem alteration, we measured 87Sr /86Sr , 13C /12C , 18O /16O and 15N /14N ratios and Sr concentrations in modern and prehistoric (610 to 5470 yr old) bones of animals with marine or terrestrial diets from Greenland. Bones from modern terrestrial feeders have substantially lower Sr concentrations and more radiogenic 87Sr /86Sr ratios than those from modern marine feeders. This contrast was not preserved in the prehistoric samples, which showed almost complete overlap for both Sr concentration and isotopic composition in bones from the two types of animals. Leaching experiments, X-ray diffraction analysis and infrared spectroscopy indicate that alteration of the Sr concentration and isotopic composition in prehistoric bone probably results from nearly complete exchange with groundwater. Oxygen isotope ratios in fossil apatite carbonate also failed to preserve the original discrimination between modern terrestrial and marine feeders. The C isotope ratio of apatite carbonate did not discriminate between animals with marine or terrestrial diets in the modern samples. Even so, the ranges of apatite δ 13C values in prehistoric bone are more scattered than in modern samples for both groups, suggesting alteration had occurred. δ 13C and δ 15N values of collagen in modern bone are distinctly different for the two feeding types, and this distinction is preserved in most of the prehistoric samples. Our results suggest that postmortem alteration of dietary tracers in the inorganic phases of bone may be a problem at all archaeological sites and must be evaluated in each case. While collagen analyzed in this study was resistant to alteration, evaluation of the possibility of diagenetic alteration of its isotopic composition in bones from other

  7. Soil moisture effects on the carbon isotopic composition of soil respiration

    EPA Science Inventory

    The carbon isotopic composition ( 13C) 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 13C of soil respiration, which suggests indir...

  8. Habitat use and trophic position effects on contaminant bioaccumulation in fish indicated by stable isotope composition

    EPA Science Inventory

    The objective of our study was to determine the relationship between fish tissue stable isotope composition and total mercury or polychlorinated biphenyl (PCB) concentrations in a Great Lakes coastal food web. We sampled two resident fishes, Yellow Perch (Perca flavescens) and Bl...

  9. Soil moisture effects on the carbon isotope composition of soil respiration

    Treesearch

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

    2010-01-01

    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...

  10. Bulk Chemistry and Oxygen Isotopic Compositions of Lunar Meteorites Dhofar 025 and Dhofar 026

    NASA Astrophysics Data System (ADS)

    Taylor, L. A.; Nazarov, M. A.; Cohen, B. A.; Warren, P. H.; Barsukova, L. D.; Clayton, R. N.; Mayeda, T. K.

    2001-03-01

    The major- and trace-element composition of highlands meteorites Dh25 and Dh26 show that both are dominated by a FAN component. Incompatible element depletion and low Ti abundances suggest a farside origin. O-isotopes are typical for lunar meteorites.

  11. Development of Electrodeposited Zn/nano-TiO2 Composite Coatings with Enhanced Corrosion Performance

    NASA Astrophysics Data System (ADS)

    Benea, L.; Dănăilă, E.

    2017-06-01

    Pure zinc coatings have been found ineffective when are used in aggressive environments such as those which contain chlorides or industrial pollutants [1]. In this paper, Zn/nano-TiO2 composite coatings with various contents of TiO2 nanoparticles (diameter size of 10 nm) were prepared on low-carbon steel by electro-codeposition technique. The deposition was carried out at different cathodic potentials ranging from -1600 mV to -2100 mV for different deposition times between 5-15 min. Pure Zn coatings were also produced under the same experimental conditions for comparison. Present work aims to investigate the effects of selected electrodeposition parameters (cathodic potential, TiO2 nanoparticle concentration in the plating bath and electrodeposition time) on the corrosion behavior of electrodeposited Zn/nano-TiO2 composite obtained. The corrosion experiments were performed in natural seawater, using electrochemical methods such as open circuit potential, potentiodynamic polarization and linear polarization resistance. The results showed that the inclusion of TiO2 nanoparticles into zinc matrix lead to an improved corrosion resistance comparatively with pure zinc coatings obtained under similar conditions.

  12. Synthesis of SiO2-Coated Core-Shell ZnO Composites for Preparing High-Voltage Varistors

    NASA Astrophysics Data System (ADS)

    Qu, Xiao; Yao, Da-Chuan; Liu, Jin-Ran; Wang, Mao-Hua; Zhang, Han-Ping

    2018-01-01

    Monodispersed ZnO composite microspheres were successfully prepared by a facile ultrasound irradiation method. Then, the uniform core-shell structured composites were synthesized through the hydrolysis of tetraethyl orthosilicate on the surface of the ZnO composite microspheres. Microstructural studies of the as-obtained powders were carried out using the techniques of the x-ray powder diffraction, field emission scanning electron microscopy and transmission electron microscopy with energy dispersive x-ray spectroscopy. The results show that the pink ZnO composite powders as the core were spherical structures with the size of approximately 100 nm, and the SiO2 shell was fully coated on the surface of the core. On the basis of these results, the effect of SiO2 content on the thickness of the synthesized composites and microstructure, as well as the electrical properties of the ZnO varistors sintered in air at 1150°C for 2 h, were fully studied. In particular, the ZnO varistor prepared with the appropriate amount of the SiO2 coating (˜40 nm) leads to a superior electrical performance with the high breakdown voltage of 418 V mm-1 and an excellent nonlinear coefficient of 70.7, compared with the varistors obtained without the SiO2 coating. The high performance is attributed to the smaller and more homogeneous ZnO grains obtained via the SiO2 coating.

  13. Isotopic composition and neutronics of the Okelobondo natural reactor

    NASA Astrophysics Data System (ADS)

    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

  14. Variations in the isotopic composition of stable mercury isotopes in typical mangrove plants of the Jiulong estuary, SE China.

    PubMed

    Sun, Lumin; Lu, Bingyan; Yuan, Dongxing; Hao, Wenbo; Zheng, Ying

    2017-01-01

    Variations in the composition of stable isotopes of mercury contained in tissues (root, stem, leaf, and hypocotyl or flower) of three typical mangrove plants (Kandelia candel, Aegiceras corniculata, and Bruguiera gymnorhiza), collected from the mangrove wetland of Jiulong estuary, SE China, were used to investigate the sources and transformation of mercury in the mangrove plants. Tissue samples from the plants were digested and mercury in the solution was pre-concentrated with purge-trap method and then analyzed by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The results showed that the mass dependent fractionation (MDF) of mercury ranged from -2.67 to -0.87 ‰ for δ 202 Hg while the mass independent fractionation (MIF) of mercury isotopes ranged from -0.16 to 0.09 and -0.19 to 0.05 ‰ for Δ 199 Hg and Δ 201 Hg, respectively, relative to the standard NIST SRM 3133. The ratio of Δ 199 Hg/Δ 201 Hg was 0.991, indicating that the mercury had been photo-reduced before being accumulated in mangrove plants. Analyses of the data from MIF studies revealed that the major portion of the mercury measured in leaves (∼90 %) originated from the atmosphere while the source of over half of the mercury present in roots was the surficial sediment. This study, the first of its kind investigating the variations in isotopic composition of mercury in the tissues of mangrove plants, could be helpful to identify the source of mercury contamination in mangroves and understand the biogeochemical cycle of mercury in the estuarine mangrove wetlands.

  15. Visible light-driven photocatalytic H{sub 2}-generation activity of CuS/ZnS composite particles

    SciTech Connect

    Xiao, Liang; Chen, Hua; Huang, Jianhua, E-mail: jhhuang@zstu.edu.cn

    2015-04-15

    Highlights: • Preparation of CuS/ZnS composite photocatalyst by cation-exchange reaction. • Visible light photocatalytic activity for H{sub 2} evolution without cocatalyst. • The H{sub 2}-evolution rate from water splitting depends on the CuS content. • The highest rate of H{sub 2} evolution is obtained with CuS (0.5 mol%)/ZnS composite. - Abstract: CuS/ZnS composite particles with diameter of 200–400 nm were successfully prepared by a simple cation-exchange reaction using ZnS spheres as a precursor. CuS nanoparticles with a few nanometers in diameter were observed on the surface of composite particles. The synthesized CuS/ZnS composite particles showed photocatalytic property effective for H{submore » 2} evolution from an aqueous Na{sub 2}S and Na{sub 2}SO{sub 3} solution under visible light irradiation without any cocatalysts. The rate of H{sub 2} generation was found to be strongly dependent on the CuS content. The highest rate of H{sub 2} evolution reached 695.7 μmol h{sup −1} g{sup −1}, which was almost 7 times as high as that of the mechanical mixture of CuS and ZnS. The enhancement in the photocatalytic activity of CuS/ZnS composite particles is supposed to be due to the direct interfacial charge transfer of the CuS/ZnS heterojunction.« less

  16. The dielectric behavior of Zn1-xNixO/NiO two-phase composites

    NASA Astrophysics Data System (ADS)

    Joshi, D. C.; Thota, S.; Nayak, S.; Harish, D. D.; Mahesh, P.; Kumar, A.; Pamu, D.; Qureshi, Md

    2014-10-01

    The effect of nickel content on the dielectric permittivity ‘ɛr’ and the ac-electrical conductivity of Zn1-xNixO/NiO (0 ≤ x ≤ 0.55) two-phase composites were investigated. The antiferro to the paramagnetic Néel temperature TN (~ 523 K) of the NiO associated with the structural phase transition from the rhombohedral to the cubic phase has been exploited to realize a dielectric anomaly across 523-541 K in the Zn1-xNixO/NiO composite system. Also, a giant dielectric peak across 410 °C in pure NiO was observed together with an anomaly across TN. The formation of tiny polar clusters due to the compositional heterogeneity for the samples with x ≥ 0.16 drove the system to exhibit a weakly coupled relaxor-like behavior with a locally varying maximum temperature of T* (~ 530 K at 106 Hz), obeying the Vogel-Fulcher law and the Uchino-Nomura criteria. The values of the diffuseness-exponent ‘γ’ (1.91) and the shape-parameter ‘δ’ (88 °C) were determined by using the empirical scaling relation (ɛA/ɛr = 1 + 0.5 (T - TA)2/ δ2), which is often used to describe relaxor-like behavior. Our results provide strong evidence for the variable-range-hopping of charge carriers between the localized states. The effects of non-ohmic sample-electrode contact impedance and negative-capacitance on the global dielectric behavior of a Zn1-xNixO/NiO composite system are discussed.

  17. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

    2016-09-28

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous

  18. Anti-icing properties of superhydrophobic ZnO/PDMS composite coating

    NASA Astrophysics Data System (ADS)

    Yang, Chao; Wang, Fajun; Li, Wen; Ou, Junfei; Li, Changquan; Amirfazli, Alidad

    2016-01-01

    We present the excellent anti-icing performance for a superhydrophobic coating surface based on ZnO/polydimethylsiloxane (ZnO/PDMS) composite. The superhydrophobic ZnO/PDMS coating surface was prepared by a facile solution mixing, drop coating, room-temperature curing and surface abrading procedure. The superhydrophobic ZnO/PDMS composite coating possesses a water contact angle of 159.5° and a water sliding angle of 8.3° at room temperature (5 °C). The anti-icing properties of the superhydrophobic coating were investigated by continuously dropping cold-water droplets (about 0 °C) onto the pre-cooled surface using a home-made apparatus. The sample was placed at different tilting angle (0° and 10°) and pre-cooled to various temperatures (-5, -10 and -15 °C) prior to measure. The pure Al surface was also studied for comparison. It was found that icing accretion on the surface could be reduced apparently because the water droplets merged together and slid away from the superhydrophobic surface at all of the measuring temperatures when the surface is horizontally placed. In addition, water droplet slid away completely from the superhydrophobic surface at -5 and -10 °C when the surface is tilted at 10°, which demonstrates its excellent anti-icing properties at these temperatures. When the temperature decreased to -15 °C, though ice accretion on the tilted superhydrophobic coating surface could not be avoided absolutely, the amount of ice formed on the surface is very small, which indicated that the coating surface with superhydrophobicity could significantly reduce ice accumulation on the surface at very low temperature (-15 °C). Importantly, the sample is also stable against repeated icing/deicing cycles. More meaningfully, once the superhydrophobic surface is damaged, it can be repaired easily and rapidly.

  19. Variable Isotopic Compositions of Host Plant Populations Preclude Assessment of Aphid Overwintering Sites

    PubMed Central

    Voegtlin, David J.; Hamilton, Krista L.; Hogg, David B.

    2017-01-01

    Soybean aphid (Aphis glycines Matsumura) is a pest of soybean in the northern Midwest whose migratory patterns have been difficult to quantify. Improved knowledge of soybean aphid overwintering sites could facilitate the development of control efforts with exponential impacts on aphid densities on a regional scale. In this preliminary study, we explored the utility of variation in stable isotopes of carbon and nitrogen to distinguish soybean aphid overwintering origins. We compared variation in bulk 13C and 15N content in buckthorn (Rhamnus cathartica L.) and soybean aphids in Wisconsin, among known overwintering locations in the northern Midwest. Specifically, we looked for associations between buckthorn and environmental variables that could aid in identifying overwintering habitats. We detected significant evidence of correlation between the bulk 13C and 15N signals of soybean aphids and buckthorn, despite high variability in stable isotope composition within and among buckthorn plants. Further, the 15N signal in buckthorn varied predictably with soil composition. However, lack of sufficient differentiation of geographic areas along axes of isotopic and environmental variation appears to preclude the use of carbon and nitrogen isotopic signals as effective predictors of likely aphid overwintering sites. These preliminary data suggest the need for future work that can further account for variability in 13C and 15N within/among buckthorn plants, and that explores the utility of other stable isotopes in assessing likely aphid overwintering sites. PMID:29206134

  20. Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts.

    PubMed

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

    2015-01-01

    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.

  1. Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

    SciTech Connect

    Gao, Weidong; Cao, Di; Jin, Yunxue

    Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

  2. Microstructure and properties of Cu-Sn-Zn-TiO 2 nano-composite coatings on mild steel

    DOE PAGES

    Gao, Weidong; Cao, Di; Jin, Yunxue; ...

    2018-04-18

    Cu-Sn-Zn coatings have been widely used in industry for their unique properties, such as good conductivity, high corrosion resistance and excellent solderability. To further improve the mechanical performance of Cu-Sn-Zn coatings, powder-enhanced method was applied and Cu-Sn-Zn-TiO 2 nano-composite coatings with different TiO 2 concentration were fabricated. The microstructure of Cu-Sn-Zn-TiO 2 nano-composite coatings were investigated by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). The mechanical properties of coatings including microhardness and wear resistance were studied. The results indicate that the incorporation of TiO 2 nanoparticle can significantly influence the properties of Cu-Sn-Zn coatings. The microhardness of Cu-Sn-Zn coatingmore » was increased to 383 HV from 330 HV with 1 g/L TiO 2 addition. Also, the corrosion resistance of coating was enhanced. The effects of TiO 2 nanoparticle concentration on the microstructure, mechanical properties and corrosion resistance of Cu-Sn-Zn-TiO 2 nano-composite coatings were discussed.« less

  3. Stable bromine isotopic composition of methyl bromide released from plant matter

    NASA Astrophysics Data System (ADS)

    Horst, Axel; Holmstrand, Henry; Andersson, Per; Thornton, Brett F.; Wishkerman, Asher; Keppler, Frank; Gustafsson, Örjan

    2014-01-01

    Methyl bromide (CH3Br) emitted from plants constitutes a natural source of bromine to the atmosphere, and is a component in the currently unbalanced global CH3Br budget. In the stratosphere, CH3Br contributes to ozone loss processes. Studies of stable isotope composition may reduce uncertainties in the atmospheric CH3Br budget, but require well-constrained isotope fingerprints of the source end members. Here we report the first measurements of stable bromine isotopes (δ81Br) in CH3Br from abiotic plant emissions. Incubations of both KBr-fortified pectin, a ubiquitous cell-stabilizing macromolecule, and of a natural halophyte (Salicornia fruticosa), yielded an enrichment factor (ε) of -2.00 ± 0.23‰ (1σ, n = 8) for pectin and -1.82 ± 0.02‰ (1σ, n = 4) for Salicornia (the relative amount of the heavier 81Br was decreased in CH3Br compared to the substrate salt). For short incubations, and up to 10% consumption of the salt substrate, this isotope effect was similar for temperatures from 30 up to 300 °C. For longer incubations of up to 90 h at 180 °C the δ81Br values increased from -2‰ to 0‰ for pectin and to -1‰ for Salicornia. These δ81Br source signatures of CH3Br formation from plant matter combine with similar data for carbon isotopes to facilitate multidimensional isotope diagnostics of the CH3Br budget.

  4. Coordinated Oxygen Isotopic and Petrologic Studies of CAIS Record Varying Composition of Protosolar

    NASA Technical Reports Server (NTRS)

    Simon, Justin I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.

    2012-01-01

    Ca-, Al-rich inclusions (CAIs) record the O-isotope composition of Solar nebular gas from which they grew [1]. High spatial resolution O-isotope measurements afforded by ion microprobe analysis across the rims and margin of CAIs reveal systematic variations in (Delta)O-17 and suggest formation from a diversity of nebular environments [2-4]. This heterogeneity has been explained by isotopic mixing between the O-16-rich Solar reservoir [6] and a second O-16-poor reservoir (probably nebular gas) with a "planetary-like" isotopic composition [e.g., 1, 6-7], but the mechanism and location(s) where these events occur within the protoplanetary disk remain uncertain. The orientation of large and systematic variations in (Delta)O-17 reported by [3] for a compact Type A CAI from the Efremovka reduced CV3 chondrite differs dramatically from reports by [4] of a similar CAI, A37 from the Allende oxidized CV3 chondrite. Both studies conclude that CAIs were exposed to distinct, nebular O-isotope reservoirs, implying the transfer of CAIs among different settings within the protoplanetary disk [4]. To test this hypothesis further and the extent of intra-CAI O-isotopic variation, a pristine compact Type A CAI, Ef-1 from Efremovka, and a Type B2 CAI, TS4 from Allende were studied. Our new results are equally intriguing because, collectively, O-isotopic zoning patterns in the CAIs indicate a progressive and cyclic record. The results imply that CAIs were commonly exposed to multiple environments of distinct gas during their formation. Numerical models help constrain conditions and duration of these events.

  5. Fabrication of ZnAl mixed metal-oxides/RGO nanohybrid composites with enhanced photocatalytic activity under visible light

    NASA Astrophysics Data System (ADS)

    Ni, Jie; Xue, Jinjuan; Shen, Jing; He, Guangyu; Chen, Haiqun

    2018-05-01

    The ZnAl mixed metal-oxides (MMOs)/graphene nanocomposites were successfully fabricated by a facile hydrothermal method combined with a calcination process. The thermal treatment enables simultaneously the formation of ZnO/ZnAl2O4 heterogeneous structure, which are uniformly decorated on the surface of graphene, accompanying with the reduction of graphene oxide. The as-prepared heterostructure photocatalysts were well characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and UV-vis diffuse reflectance spectroscopy (DRS) to conduct investigations into the phase structures, microstructure and optical capability. The ZnAl MMO/RGO20 composite displayed favorable adsorption property and photo-degradation efficiency for Ciprofloxacin (CIP) aqueous solution under visible light. The photo-degradation efficiency of the as-prepared ZnAl MMO/RGO20 was 3.0 and even 4.6 times higher than that of ZnAl MMO and pure ZnAl LDH, respectively. The improvement of photocatalytic performance is ascribed to the synergistic effect of heterogeneous structure coupled with graphene, which realizes efficient charge separation efficiency, enlarged visible light adsorption range, and chemical stability of hybrid nanocomposite. The results of EIS, PL and photocurrent response also explained the best performance of ZnAl MMO/RGO20 nanocomposite. Besides, the mechanism of ZnAl MMO/RGO20 photocatalytic system was proposed and analyzed in detail.

  6. The distribution of lead concentrations and isotope compositions in the eastern Tropical Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Bridgestock, Luke; Rehkämper, Mark; van de Flierdt, Tina; Paul, Maxence; Milne, Angela; Lohan, Maeve C.; Achterberg, Eric P.

    2018-03-01

    Anthropogenic emissions have dominated marine Pb sources during the past century. Here we present Pb concentrations and isotope compositions for ocean depth profiles collected in the eastern Tropical Atlantic Ocean (GEOTRACES section GA06), to trace the transfer of anthropogenic Pb into the ocean interior. Variations in Pb concentration and isotope composition were associated with changes in hydrography. Water masses ventilated in the southern hemisphere generally featured lower 206Pb/207Pb and 208Pb/207Pb ratios than those ventilated in the northern hemisphere, in accordance with Pb isotope data of historic anthropogenic Pb emissions. The distributions of Pb concentrations and isotope compositions in northern sourced waters were consistent with differences in their ventilation timescales. For example, a Pb concentration maximum at intermediate depth (600-900 m, 35 pmol kg-1) in waters sourced from the Irminger/Labrador Seas, is associated with Pb isotope compositions (206Pb/207Pb = 1.1818-1.1824, 208Pb/207Pb = 2.4472-2.4483) indicative of northern hemispheric emissions during the 1950s and 1960s close to peak leaded petrol usage, and a transit time of ∼50-60 years. In contrast, North Atlantic Deep Water (2000-4000 m water depth) featured lower Pb concentrations and isotope compositions (206Pb/207Pb = 1.1762-1.184, 208Pb/207Pb = 2.4482-2.4545) indicative of northern hemispheric emissions during the 1910s and 1930s and a transit time of ∼80-100 years. This supports the notion that transient anthropogenic Pb inputs are predominantly transferred into the ocean interior by water mass transport. However, the interpretation of Pb concentration and isotope composition distributions in terms of ventilation timescales and pathways is complicated by (1) the chemical reactivity of Pb in the ocean, and (2) mixing of waters ventilated during different time periods. The complex effects of water mass mixing on Pb distributions is particularly apparent in seawater in the

  7. Calcium isotopic fractionation in mantle peridotites by melting and metasomatism and Ca isotope composition of the Bulk Silicate Earth

    NASA Astrophysics Data System (ADS)

    Kang, Jin-Ting; Ionov, Dmitri A.; Liu, Fang; Zhang, Chen-Lei; Golovin, Alexander V.; Qin, Li-Ping; Zhang, Zhao-Feng; Huang, Fang

    2017-09-01

    To better constrain the Ca isotopic composition of the Bulk Silicate Earth (BSE) and explore the Ca isotope fractionation in the mantle, we determined the Ca isotopic composition of 28 peridotite xenoliths from Mongolia, southern Siberia and the Siberian craton. The samples are divided in three chemical groups: (1) fertile, unmetasomatized lherzolites (3.7-4.7 wt.% Al2O3); (2) moderately melt-depleted peridotites (1.3-3.0 wt.% Al2O3) with no or very limited metasomatism (LREE-depleted cpx); (3) strongly metasomatized peridotites (LREE-enriched cpx and bulk rock) further divided in subgroups 3a (harzburgites, 0.1-1.0% Al2O3) and 3b (fertile lherzolites, 3.9-4.3% Al2O3). In Group 1, δ44/40Ca of fertile spinel and garnet peridotites, which experienced little or no melting and metasomatism, show a limited variation from 0.90 to 0.99‰ (relative to SRM 915a) and an average of 0.94 ± 0.05‰ (2SD, n = 14), which defines the Ca isotopic composition of the BSE. In Group 2, the δ44/40Ca is the highest for three rocks with the lowest Al2O3, i.e. the greatest melt extraction degrees (average 1.06 ± 0.04 ‰, i.e. ∼0.1‰ heavier than the BSE estimate). Simple modeling of modal melting shows that partial melting of the BSE with 103 ln ⁡αperidotite-melt ranging from 0.10 to 0.25 can explain the Group 2 data. By contrast, δ44/40Ca in eight out of nine metasomatized Group 3 peridotites are lower than the BSE estimate. The Group 3a harzburgites show the greatest δ44/40Ca variation range (0.25-0.96‰), with δ44/40Ca positively correlated with CaO and negatively correlated with Ce/Eu. Chemical evidence suggests that the residual, melt-depleted, low-Ca protoliths of the Group 3a harzburgites were metasomatized, likely by carbonate-rich melts/fluids. We argue that such fluids may have low (≤0.25‰) δ44/40Ca either because they contain recycled crustal components or because Ca isotopes, similar to trace elements and their ratios, may be fractionated by kinetic and

  8. Mg-Zn based composites reinforced with bioactive glass (45S5) fabricated via powder metallurgy

    NASA Astrophysics Data System (ADS)

    Ab llah, N.; Jamaludin, S. B.; Daud, Z. C.; Zaludin, M. A. F.

    2016-07-01

    Metallic implants are shifting from bio-inert to bioactive and biodegradable materials. These changes are made in order to improve the stress shielding effect and bio-compatibility and also avoid the second surgery procedure. Second surgery procedure is required if the patient experienced infection and implant loosening. An implant is predicted to be well for 15 to 20 years inside patient body. Currently, magnesium alloys are found to be the new biomaterials because of their properties close to the human bones and also able to degrade in the human body. In this work, magnesium-zinc based composites reinforced with different content (5, 15, 20 wt. %) of bioactive glass (45S5) were fabricated through powder metallurgy technique. The composites were sintered at 450˚C. Density and porosity of the composites were determined using the gas pycnometer. Microstructure of the composites was observed using an optical microscope. In-vitro bioactivity behavior was evaluated in the simulated body fluid (SBF) for 7 days. Fourier Transform Infrared (FTIR) was used to characterize the apatite forming on the samples surface. The microstructure of the composite showed that the pore segregated near the grain boundaries and bioglass clustering was observed with increasing content of bioglass. The true density of the composites increased with the increasing content of bioglass and the highest value of porosity was indicated by the Mg-Zn reinforced with 20 wt.% of bioglass. The addition of bio-glass to the Mg-Zn has also induced the formation of apatite layer after soaking in SBF solution.

  9. Synthesis of CdS/ZnO/graphene composite with high-efficiency photoelectrochemical activities under solar radiation

    NASA Astrophysics Data System (ADS)

    Han, Weijia; Ren, Long; Qi, Xiang; Liu, Yundan; Wei, Xiaolin; Huang, Zongyu; Zhong, Jianxin

    2014-04-01

    A novel ternary CdS/ZnO/graphene composite has been successfully prepared by loading ZnO and CdS nanoparticles in graphene nanosheets via a facile one-step hydrothermal method. The microstructures and properties have been examined by X-ray diffraction (XRD), scanning electron microscopy with an energy dispersive spectroscope (EDS), transmission electron microscopy, Raman and UV-vis diffuse reflectance spectra (DRS). The characterization results reveal that the crystalline of the composite is very well, the graphene sheets were tightly coated with ZnO and CdS nanoparticles, and the light-harvesting was effectively strengthened. Taking photoelectrochemical test, the ternary CdS/ZnO/graphene composite exhibits enhanced photocatalytic activity compared with its foundation matrix binary composites and pure ZnO and CdS. The improved photocatalytic performance can be attributed to the enhanced light absorption, the extremely efficient charge separation, as well as superior durability of the ternary composite. It is proposed that graphene-based composites by coupling graphene to suitable, multiple semiconductors can not only greatly improve the capacity for photocatalytic, but also expand the exploration and utilization of graphene-based nanocomposites for energy conversion.

  10. Regulation of Isotopic Composition of Water - way of Improvement of Cosmonauts Drinking Water Functional Properties

    NASA Astrophysics Data System (ADS)

    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.

  11. Isotopic composition of Mg and Fe in garnet peridotites from the Kaapvaal and Siberian cratons

    NASA Astrophysics Data System (ADS)

    An, Yajun; Huang, Jin-Xiang; Griffin, W. L.; Liu, Chuanzhou; Huang, Fang

    2017-03-01

    We present Mg and Fe isotopic data for whole rocks and separated minerals (olivine, clinopyroxene, orthopyroxene, garnet, and phlogopite) of garnet peridotites that equilibrated at depths of 134-186 km beneath the Kaapvaal and Siberian cratons. There is no clear difference in δ26Mg and δ56Fe of garnet peridotites from these two cratons. δ26Mg of whole rocks varies from -0.243‰ to -0.204‰ with an average of -0.225 ± 0.037‰ (2σ, n = 19), and δ56Fe from -0.038‰ to 0.060‰ with an average of -0.003 ± 0.068‰ (2σ, n = 19). Both values are indistinguishable from the fertile upper mantle, indicating that there is no significant Mg-Fe isotopic difference between the shallow and deep upper mantle. The garnet peridotites from ancient cratons show δ26Mg similar to komatiites and basalts, further suggesting that there is no obvious Mg isotopic fractionation during different degrees of partial melting of deep mantle peridotites and komatiite formation. The precision of the Mg and Fe isotope data (⩽±0.05‰ for δ26Mg and δ56Fe, 2σ) allows us to distinguish inter-mineral isotopic fractionations. Olivines are in equilibrium with opx in terms of Mg and Fe isotopes. Garnets have the lowest δ26Mg and δ56Fe among the coexisting mantle minerals, suggesting the dominant control of crystal structure on the Mg-Fe isotopic compositions of garnets. Elemental compositions and mineralogy suggest that clinopyroxene and garnet were produced by later metasomatic processes as they are not in chemical equilibrium with olivine or orthopyroxene. This is consistent with the isotopic disequilibrium of Mg and Fe isotopes between orthopyroxene/olivine and garnet/clinopyroxene. Combined with one sample showing slightly heavy δ26Mg and much lighter δ56Fe, these disequilibrium features in the garnet peridotites reveal kinetic isotopic fractionation due to Fe-Mg inter-diffusion during reaction between peridotites and percolating melts in the Kaapvaal craton.

  12. Sr isotopic composition of Afar volcanics and its implication for mantle evolution

    NASA Astrophysics Data System (ADS)

    Barberi, F.; Civetta, L.; Varet, J.

    1980-10-01

    Investigations of Rb-Sr systematics of basalts from the Afar depression (Ethiopia) indicate the presence of a heterogeneous mantle source region. The Sr isotopic compositions of the basalts from the Afar axial and transverse ranges identify source regions which are enriched in LIL elements and radiogenic Sr (axial ranges) and others which are relatively depleted (transverse ranges). Sr isotopic composition of basalts from the Red Sea, Gulf of Aden and Gulf of Tadjoura, which range from 0.70300 to 0.70340 are also reported and compared with the more radiogenic Afar region, which is characterized by 87Sr/ 86Sr ranging from 0.70328 to 0.70410. Available geochemical and isotopic data suggest that a relation exists between magma composition and the advancement of the rifting process through progressive lithosphere attenuation leading to continental break-up. However, the petrogenetic process is not simple and probably implies a vertically zoned mantle beneath the Afar region. Sr isotopic evidence suggests that the vertically zoned mantle is more radiogenic and enriched in LIL elements in its upper part.

  13. A non-terrestrial 16O-rich isotopic composition for the protosolar nebula.

    PubMed

    Hashizume, Ko; Chaussidon, Marc

    2005-03-31

    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.

  14. Boron Isotopic Composition of Metasomatized Mantle Xenoliths from the Western Rift, East Africa

    NASA Astrophysics Data System (ADS)

    Hudgins, T.; Nelson, W. R.

    2017-12-01

    The Western Branch of the East African Rift System is known to have a thick lithosphere and sparse, alkaline volcanism associated with a metasomatized mantle source. Recent work investigating the relationship between Western Branch metasomatized mantle xenoliths and associated lavas has suggested that these metasomes are a significant factor in the evolution of the rift. Hydrous/carbonated fluids or silicate melts are potent metasomatic agents, however gaining insight into the source of a metasomatic agent proves challenging. Here we investigate the potential metasomatic fluid sources using B isotope analysis of mineral separates from Western Branch xenoliths. Preliminary SIMS analyses of phlogopite from Katwe Kikorongo and Bufumbira have and average B isotopic composition of -28.2‰ ± 5.1 and -16.4‰ ± 3.6, respectively. These values are are dissimilar to MORB (-7.5‰ ± 0.7; Marschall and Monteleone, 2015), primitive mantle (-10‰ ± 2; Chaussidon and Marty, 1995), and bulk continental crust (-9.1‰ ± 2.4; Marschall et al., 2017) and display significant heterogeneity across a relatively short ( 150km) portion of the Western Branch. Though displaying large variability, these B isotopic compositions are indicative of a metasomatic agent with a more negative B isotopic composition than MORB, PM, or BCC. These results are consistent with fluids that released from a subducting slab and may be related to 700 Ma Pan-African subduction.

  15. Effect of calcination temperature on the photodegradation efficiency of Ni/ZnO composite in removal of organic dye

    NASA Astrophysics Data System (ADS)

    Thein, Myo Thuya; Pung, Swee-Yong; Aziz, Azizan; Lockman, Zainovia; Itoh, Mitsuru

    2017-07-01

    ZnO based composite is an attractive UV light driven semiconductor photocatalyst to degrade organic compounds attributed to its wide bandgap (3.37 eV). In this study, Ni/ZnO composites were synthesized via solution precipitation method. The composites were calcinated at various temperature, i.e. from 250 °C to 700 °C and subsequently annealed at 500°C in reductive environment (hydrogen atmosphere). The diffraction peaks of all samples could be indexed to the hexagonal wurtzite ZnO. No diffraction peaks from Ni could be observed in all samples, suggesting that the amount of Ni in the composites were below the detection limit of X-ray diffraction (XRD). The field emission scanning electron microscope (FESEM) images confirm that all samples were rod-like structure with hexagonal tips. In addition, small Ni particles were homogeneously deposited on the surface of ZnO rods. This observation is supported by energy dispersive X-ray spectroscopy (EDX) analysis, showing present of Zn, O and Ni elements. It is noted that ZnO rods coupled with Ni experienced quenching of visible emission and enhancing of UV emission in room temperature photoluminescence (RTPL) analysis. The photodegradation efficiency of Ni/ZnO rods was improved when a higher calcination temperature was used. The removal of RhB dye under UV light (352 nm) by these photocatalysts followed pseudo first-order kinetic reaction. The Ni/ZnO composites synthesized at calcination temperature of 500 °C demonstrated the highest photodegradation efficiency of 37 % and the largest rate constant of 0.0053 min-1 after 75 min UV irradiation.

  16. Preservation of Earth-forming events in the tungsten isotopic composition of modern flood basalts.

    PubMed

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

    2016-05-13

    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. Copyright © 2016, American Association for the Advancement of Science.

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

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

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

  18. Southern Greenland water vapour isotopic composition at the crossroads of Atlantic and Arctic moisture

    NASA Astrophysics Data System (ADS)

    Bonne, J. L.; Steen-Larsen, H. C.; Risi, C. M.; Werner, M.; Sodemann, H.; Lacour, J. L.; Fettweis, X.; Cesana, G.; Delmotte, M.; Cattani, O.; Clerbaux, C.; Sveinbjörnsdottir, A. E.; Masson-Delmotte, V.

    2014-12-01

    Since September 2011, a continuous water vapour isotopic composition monitoring instrument has been remotely operated in Ivittuut (61.21°N, 48.17°W), southern Greenland. Meteorological parameters are monitored and precipitation has been sampled and analysed for isotopic composition, suggesting equilibrium between surface vapour and precipitation. The data depict small summer diurnal variations. δ18O and deuterium excess (d-excess) are generally anti-correlated and show important seasonal variations (with respective amplitudes of 10 and 20 ‰), and large synoptic variations associated to low-pressure systems (typically +5‰ on δ18O and -15‰ on d-excess). The moisture sources, estimated based on Lagrangian back-trajectories, are primarily influenced by the western North Atlantic, and north-eastern American continent. Notable are important seasonal and synoptic shifts of the moisture sources, and sporadic influences of the Arctic or the eastern North Atlantic. Moisture sources variations can be related to changes in water vapour isotopic composition, and the isotopic fingerprints can be attributed to the areas of moisture origins. Isotopic enabled AGCMs nudged to meteorology (LMDZiso, ECHAM5-wiso), despite biases, correctly capture the δ18O changes, but underestimate the d-excess changes. They allow to identify a high correlation between the southern Greenland d-excess and the simulated relative humidity and d-excess in the moisture source region south of Greenland. An extreme high temperature event in July 2012 affecting all Greenland, similar to ice sheet melt events during the medieval periods and one event in 1889 documented by Greenland ice core records, has been analysed regarding water vapour isotopic composition, using remote sensing (IASI) and in situ observations from Bermuda to northern Greenland (NEEM station). Our southern Greenland observations allow to track the water vapour evolution during this event along the moisture transport path

  19. The boron and lithium isotopic composition of mid-ocean ridge basalts and the mantle

    NASA Astrophysics Data System (ADS)

    Marschall, Horst R.; Wanless, V. Dorsey; Shimizu, Nobumichi; Pogge von Strandmann, Philip A. E.; Elliott, Tim; Monteleone, Brian D.

    2017-06-01

    A global selection of 56 mid-ocean ridge basalt (MORB) glasses were analysed for Li and B abundances and isotopic compositions. Analytical accuracy and precision of analyses constitute an improvement over previously published MORB data and allow a more detailed discussion of the Li and B systematics of the crust-mantle system. Refined estimates for primitive mantle abundances ([ Li ] = 1.39 ± 0.10 μg/g and [ B ] = 0.19 ± 0.02 μg/g) and depleted mantle abundances ([ Li ] = 1.20 ± 0.10 μg/g and [ B ] = 0.077 ± 0.010 μg/g) are presented based on mass balance and on partial melting models that utilise observed element ratios in MORB. Assimilation of seawater (or brine) or seawater-altered material beneath the ridge, identified by high Cl / K , causes significant elevation of MORB δ11 B and variable elevation in δ7 Li . The B isotope ratio is, hence, identified as a reliable indicator of assimilation in MORB and values higher than -6‰ are strongly indicative of shallow contamination of the magma. The global set of samples investigated here were produced at various degrees of partial melting and include depleted and enriched MORB from slow and fast-spreading ridge segments with a range of radiogenic isotope signatures and trace element compositions. Uncontaminated (low- Cl / K) MORB show no significant boron isotope variation at the current level of analytical precision, and hence a homogenous B isotopic composition of δ11 B = - 7.1 ± 0.9 ‰ (mean of six ridge segments; 2SD). Boron isotope fractionation during mantle melting and basalt fractionation likely is small, and this δ11 B value reflects the B isotopic composition of the depleted mantle and the bulk silicate Earth, probably within ±0.4‰. Our sample set shows a mean δ7 Li = + 3.5 ± 1.0 ‰ (mean of five ridge segments; 2SD), excluding high- Cl / K samples. A significant variation of 1.0-1.5‰ exists among various ridge segments and among samples within individual ridge segments, but this

  20. Experimental constraints on reconstruction of Archean seawater Ni isotopic composition from banded iron formations

    NASA Astrophysics Data System (ADS)

    Wang, Shui-Jiong; Wasylenki, Laura E.

    2017-06-01

    The Ni isotopic systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater over Precambrian geological history. However, the utility of BIFs as proxies requires quantitative knowledge of how Ni isotopes fractionated as dissolved Ni was initially incorporated into iron-rich sediments and how diagenesis may have affected the Ni isotopic systematics. Here we report results of synthesis experiments to investigate the behavior of Ni isotopes during Ni coprecipitation with ferrihydrite and then transformation of ferrihydrite to hematite. Ferrihydrite coprecipitation experiments at neutral pH demonstrated that the dissolved Ni was variably heavier than coprecipitated Ni (likely a mixture of surface-adsorbed and structurally incorporated Ni), with the isotope fractionation becoming larger as the fraction of Ni associated with solid increased (Δ60/58Nisolution-solid = +0.08 to +0.50‰). Further experiments at lower pH (3.7-6.7), in which structurally incorporated Ni likely dominated in solids, documented a decrease in Δ60/58Nisolution-solid from +0.44‰ to -0.18‰ as the pH decreased. The negative value for Δ60/58Nisolution-solid at low pH indicates the enrichment of heavier isotopes in incorporated Ni relative to dissolved and adsorbed Ni, possibly as a result of the presence of a small amount of tetrahedral Ni2+ in addition to octahedral Ni2+ in the ferrihydrite structure. The results of the ferrihydrite experiments thus reflect equilibrium isotope fractionation between three pools of Ni, with δ60/58Ni values in the order of incorporated > dissolved > adsorbed. Hematite was synthesized by transformation of Ni-bearing ferrihydrite in aqueous solution at ∼100 °C. A significant amount of Ni (up to 60%) was released (desorbed) from solids into solutions as pH dropped from ∼7 to 4.5-5.5 upon phase transformation. Rinsing of the synthesized hematite in 2 M acetic acid released only very small amounts of Ni (<4

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

    USGS Publications Warehouse

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

    2002-01-01

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

  2. Boron isotope systematics of tourmaline formation in the Sullivan Pb-Zn-Ag deposit, British Columbia, Canada

    USGS Publications Warehouse

    Jiang, S.-Y.; Palmer, M.R.; Slack, J.F.; Shaw, D.R.

    1999-01-01

    We report here the results of 54 boron isotope analyses of tourmaline associated with the giant Sullivan Pb-Zn-Ag deposit in southeastern British Columbia, Canada. The ??11B values range from -11.1 to -2.9???, which is almost as great as the range found worldwide in tourmalines from 33 massive sulfide deposits and tourmalinites in dominantly clastic metasedimentary terranes. The major control on the overall ??11B values of the Sullivan tourmalinites is the boron source. Potential controls over the large range of the data also include: (1) differences in formation temperatures of the tourmalinites, (2) different stages of tourmaline formation, (3) variations in the proportions of dissolved boron incorporated into the tourmaline (Rayleigh fractionation), (4) seawater entrainment, and (5) post-depositional metamorphism. The boron isotope data at Sullivan are consistent with boron derivation from leaching of footwall clastic sediments. However, the great abundance of tourmaline in the Sullivan deposit suggests that the local clastic sediments were not the sole source of boron, and we argue that non-marine evaporites, buried deep below the orebody, are the most viable source of this additional boron. It is likely that some of the variation in tourmaline ??11B values reflect mixing of boron from these two sources. Comparison of the potential effects of these controls with geologic and other geochemical evidence suggests that major causes for the wide range of ??11B values measured at Sullivan are seawater entrainment and Rayleigh fractionation, although in places, post-depositional alteration and thermal metamorphism were important in determining ??11B values of some of the recrystallized tourmalinites.

  3. Synthesis of Zn-In-S Quantum Dots with Tunable Composition and Optical Properties.

    PubMed

    Wang, Xianliang; Damasco, Jossana; Shao, Wei; Ke, Yujie; Swihart, Mark T

    2016-03-03

    II-III-VI semiconductors are of interest due to their chemical stability and composition-tunable optical properties. Here, we report a methodology for the synthesis of monodisperse zinc-indium-sulfide (ZIS) alloy quantum dots (QDs, mean diameter from ∼2 to 3.5 nm) with an In content substantially below that of the stoichiometric ZnIn2 S4 compound. The effects of indium incorporation on the size, lattice constant, and optical properties of ZIS QDs are elucidated. In contrast to previous reports, we employ sulfur dissolved in oleic acid as the sulfur donor rather than thioacetamide (TAA). The size of the ZIS QDs and their crystal lattice constant increased with increasing In incorporation, but they maintained the cubic sphalerite phase of ZnS, rather than the hexagonal phase typical of ZnIn2 S4 . The QDs' absorbance onset at UV wavelengths red-shifts with increasing In content and the accompanying increase in NC size. The ZIS NCs and related materials, whose synthesis is enabled by the approach presented here, provide new opportunities to apply II-III-VI semiconductors in solution-processed UV optoelectronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Passive optical limiting studies of nanostructured Cu doped ZnO-PVA composite thin films

    NASA Astrophysics Data System (ADS)

    Tamgadge, Y. S.; Sunatkari, A. L.; Talwatkar, S. S.; Pahurkar, V. G.; Muley, G. G.

    2016-01-01

    We prepared undoped and Cu doped ZnO semiconducting nanoparticles (NPs) by chemical co-precipitation method and obtained Cu doped ZnO-polyvinyl alcohol (PVA) nanocomposite thin films by spin coating to investigate third order nonlinear optical and optical limiting properties under cw laser excitation. Powder samples of NPs were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy, transmission electron microscopy, ultraviolet-visible (UV-vis) and Fourier transform infrared spectroscopy. XRD pattern and FE-SEM micrograph revealed the presence of hexagonal wurtzite phase ZnO NPs having uniform morphology with average particle size of 20 nm. The presence of excitons and absorption peaks in the range 343-360 nm, revealed by UV-vis study, were attributed to excitons in n = 1 quantum state. Third order NLO properties of all composite thin films were investigated by He-Ne continuous wave (cw) laser of wavelength 632.8 nm using Z-scan technique. Thermally stimulated enhanced values of nonlinear refraction and absorption coefficients were obtained which may be attributed to self-defocusing effect, reverse saturable absorption, weak free carrier absorption and surface states properties originated from thermo optic effect. Optical limiting properties have been studied using cw diode laser of wavelength 808 nm and results are presented.

  5. Thallium isotope composition of the upper continental crust and rivers - An investigation of the continental sources of dissolved marine thallium

    USGS Publications Warehouse

    Nielsen, S.G.; Rehkamper, M.; Porcelli, D.; Andersson, P.; Halliday, A.N.; Swarzenski, P.W.; Latkoczy, C.; Gunther, D.

    2005-01-01

    The thallium (Tl) concentrations and isotope compositions of various river and estuarine waters, suspended riverine particulates and loess have been determined. These data are used to evaluate whether weathering reactions are associated with significant Tl isotope fractionation and to estimate the average Tl isotope composition of the upper continental crust as well as the mean Tl concentration and isotope composition of river water. Such parameters provide key constraints on the dissolved Tl fluxes to the oceans from rivers and mineral aerosols. The Tl isotope data for loess and suspended riverine detritus are relatively uniform with a mean of ??205Tl = -2.0 ?? 0.3 (??205Tl represents the deviation of the 205Tl/203Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 104). For waters from four major and eight smaller rivers, the majority were found to have Tl concentrations between 1 and 7 ng/kg. Most have Tl isotope compositions very similar (within ??1.5 ??205Tl) to that deduced for the upper continental crust, which indicates that no significant Tl isotope fractionation occurs during weathering. Based on these results, it is estimated that rivers have a mean natural Tl concentration and isotope composition of 6 ?? 4 ng/kg and ??205Tl = -2.5 ?? 1.0, respectively. In the Amazon estuary, both additions and losses of Tl were observed, and these correlate with variations in Fe and Mn contents. The changes in Tl concentrations have much lower amplitudes, however, and are not associated with significant Tl isotope effects. In the Kalix estuary, the Tl concentrations and isotope compositions can be explained by two-component mixing between river water and a high-salinity end member that is enriched in Tl relative to seawater. These results indicate that Tl can display variable behavior in estuarine systems but large additions and losses of Tl were not observed in the present study. Copyright ?? 2005 Elsevier Ltd.

  6. Nondestructive atomic compositional analysis of BeMgZnO quaternary alloys using ion beam analytical techniques

    NASA Astrophysics Data System (ADS)

    Zolnai, Z.; Toporkov, M.; Volk, J.; Demchenko, D. O.; Okur, S.; Szabó, Z.; Özgür, Ü.; Morkoç, H.; Avrutin, V.; Kótai, E.

    2015-02-01

    The atomic composition with less than 1-2 atom% uncertainty was measured in ternary BeZnO and quaternary BeMgZnO alloys using a combination of nondestructive Rutherford backscattering spectrometry with 1 MeV He+ analyzing ion beam and non-Rutherford elastic backscattering experiments with 2.53 MeV energy protons. An enhancement factor of 60 in the cross-section of Be for protons has been achieved to monitor Be atomic concentrations. Usually the quantitative analysis of BeZnO and BeMgZnO systems is challenging due to difficulties with appropriate experimental tools for the detection of the light Be element with satisfactory accuracy. As it is shown, our applied ion beam technique, supported with the detailed simulation of ion stopping, backscattering, and detection processes allows of quantitative depth profiling and compositional analysis of wurtzite BeZnO/ZnO/sapphire and BeMgZnO/ZnO/sapphire layer structures with low uncertainty for both Be and Mg. In addition, the excitonic bandgaps of the layers were deduced from optical transmittance measurements. To augment the measured compositions and bandgaps of BeO and MgO co-alloyed ZnO layers, hybrid density functional bandgap calculations were performed with varying the Be and Mg contents. The theoretical vs. experimental bandgaps show linear correlation in the entire bandgap range studied from 3.26 eV to 4.62 eV. The analytical method employed should help facilitate bandgap engineering for potential applications, such as solar blind UV photodetectors and heterostructures for UV emitters and intersubband devices.

  7. Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

    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.

  8. Stable isotope and chemical compositions of European and Australasian ciders as a guide to authenticity.

    PubMed

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

    2015-01-28

    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.

  9. The chlorine isotope composition of the moon and implications for an anhydrous mantle.

    PubMed

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

    2010-08-27

    Arguably, the most striking geochemical distinction between Earth and the Moon has been the virtual lack of water (hydrogen) in the latter. This conclusion was recently challenged on the basis of geochemical data from lunar materials that suggest that the Moon's water content might be far higher than previously believed. We measured the chlorine isotope composition of Apollo basalts and glasses and found that the range of isotopic values [from -1 to +24 per mil (per thousand) versus standard mean ocean chloride] is 25 times the range for Earth. The huge isotopic spread is explained by volatilization of metal halides during basalt eruption--a process that could only occur if the Moon had hydrogen concentrations lower than those of Earth by a factor of approximately 10(4) to 10(5), implying that the lunar interior is essentially anhydrous.

  10. Lead isotopic compositions of common arsenical pesticides used in New England

    USGS Publications Warehouse

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

    2004-01-01

    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

  11. The fabrication and photoelectrocatalytic study of composite ZnSe/Au/TiO2 nanotube films

    NASA Astrophysics Data System (ADS)

    Zhang, Guowei; Miao, Hui; Wang, Yongbo; Zhang, Dekai; Fan, Jun; Han, Tongxin; Mu, Jianglong; Hu, Xiaoyun

    2017-05-01

    In this paper, anatase TiO2 nanotube (NT) film photoelectrodes are successfully fabricated by a simple and effective hydrothermal method. Subsequently, an aqueous-phase processing technique is adopted to construct highly dispersed ZnSe quantum dots (QDs) on Au/TiO2 NT films prepared by microwave-assisted chemical reduction, which formed composite ZnSe/Au/TiO2 NT film systems (ZATs) with excellent performance in photoelectrocatalytic (PEC) applications. The morphology and performance of as-obtained ZATs were investigated based on various characterizations. The investigation revealed that as-obtained ZATs not only greatly extend spatial separation of charges and restrain the recombination rate of photogenerated electron-hole pairs, but also improve the efficiency to use visible light and display a wide and strong absorption in the visible light region ranging from 400 nm to 800 nm. Moreover, we observe a larger fluorescence quenching of ZATs compared with that of pure TiO2 NT films and binary composites. Experimental results indicate that the photocurrent densities of pure TiO2, 0.8 Au/TiO2, 60 min ZnSe/TiO2, and ZATs are 0.020 mA cm-2, 0.032 mA cm-2, 0.037 mA cm-2 and 0.070 mA cm-2, respectively, which is approximately 2-3.5 times higher than that of pure TiO2 NT films and binary compound photoelectrodes. Additionally, experimental results suggest that the as-prepared ZATs photoelectrode has exhibited considerable stability and significantly increased PEC activity for the degradation of methylene blue (MB) in distilled water under 100 mW cm-2 xenon lamp irradiation. The degradation efficiency on MB of 45 min ZnSe/0.8 Au/TiO2 NT films approaches 91%; however, the counterpart of TiO2 NT films is less than 10%. Eventually, the mechanism for the improvement of the PEC performance of ZATs is discussed to point out that ZATs display prominent charges transport performance, and a stepwise band alignment structure is built up in its photoelectrode, which indicates

  12. Enhanced photocatalytic degradation of phenol and photogenerated charges transfer property over BiOI-loaded ZnO composites.

    PubMed

    Jiang, Jingjing; Wang, Hongtao; Chen, Xiaodong; Li, Shuo; Xie, Tengfeng; Wang, Dejun; Lin, Yanhong

    2017-05-15

    In this paper, a series of BiOI/ZnO photocatalysts containing various BiOI contents were prepared by a facile two-step synthetic method. The structure and crystal phase, morphology, surface element analysis, optical property of as-prepared samples are measured by X-ray diffraction (XRD), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and UV-Vis diffuse reflectance spectrometry (DRS). BiOI/ZnO photocatalytic activities of the prepared photocatalysts were evaluated by photocatalytic degradation of phenol under simulated light irradiation. The phenol degradation rate reached 99.9% within 2h under simulated solar light irradiation. The probable photocatalytic mechanism of composites photocatalysts is discussed by active species trapping experiments, the surface photovoltage (SPV), the transient photovoltage (TPV) and photoluminescence (PL) measurements. The results manifest that the superior photocatalytic activity of BiOI/ZnO composites is derived from the strong internal electric field between BiOI and ZnO, which is beneficial for the effective separation and transfer of photogenerated charges in ZnO. Moreover, the loading of BiOI on the surface of ZnO inhibited the recombination of photogenerated charge carriers in ZnO, resulting in excellent photocatalytic activity. On the contrary, the effect of an extension of the light absorption range induced by the introduction of BiOI on the phenol degradation activity is not significant. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Neodymium Isotopic Compositions of the Titanite Reference Materials Used in U-Pb Geochronology

    NASA Astrophysics Data System (ADS)

    Ma, Q.; Yang, Y.; Zhao, Z.

    2017-12-01

    Titanite (CaTiSiO5) is a widespread mineral and preferentially incorporates considerable uranium and significant light rare earth elements (LREEs) in its structure. Geochronology based upon U-Pb and Pb-Pb analyses of titanite has proven to be useful for understanding the P-T-t evolution of many igneous, metamorphic and hydrothermally altered rock samples (Scott and St-Onge, 1995). In the meantime, Sm-Nd isotopic composition in single titanite can be used to obtain initial Nd isotope composition at the time of titanite crystallization when combined with its U-Pb age, making titanite the most versatile mineral for dating metamorphism and tracing hydrothermal source (Amelin et al., 2009). The widely utilized in situ analyses by SIMS and LA-(MC)-ICP-MS have emphasized the significance for uniform and homogeneous reference materials for external correction (Liu et al., 2012, Sun et al., 2012, Yang et al., 2014). Here, we present U-Pb ages and Sm-Nd isotope analyses of twelve natural titanite crystals (12YQ82, T004, Ontario, BLR-1, OLT1, Khan, Qinghu, TLS-36, NW-IOA, C253, Pakistan and MKED1) acquired by Agilent 7500a Q-ICP-MS and Neptune MC-ICP-MS, respectively, combined a 193 nm ArF excimer laser ablation system. For U-Pb dating, elemental fractionation and instrumental drift were externally corrected using MKED1 titanite standard, showing results of U-Pb analyses all within error of those recommended values. With respect to Sm-Nd isotopes, we employed the interference-free 147Sm/149Sm to deduct 144Sm isobaric interference on 144Nd, and the fractionation between 147Sm and 144Nd was calibrated using BLR-1 titanite, which is proved homogenous in Sm-Nd isotopic system. The obtained Sm-Nd isotopic compositions for natural titanite samples are all consistent with those values determined by isotope dilution (ID) MC-ICP-MS, demonstrating the precision and accuracy currently available for in situ Sm-Nd analyses. Our results demonstrate that BLR-1, OLT1 and Ontario titanites

  14. Experimental Constraints on Reconstruction of Archean Seawater Ni Isotopic Composition from Banded Iron Formations

    NASA Astrophysics Data System (ADS)

    Wang, S.; Wasylenki, L.

    2016-12-01

    Ni isotope systematics in banded iron formations (BIFs) potentially recorded the Ni isotopic composition of ancient seawater during the Precambrian Eon[1]. The use of BIFs as seawater proxies requires knowing how Ni isotopes fractionated during initial incorporation into iron-rich sediments and during early diagenesis. We conducted experiments to investigate Ni isotope behavior during coprecipitation with ferrihydrite and transformation of ferrihydrite to hematite. Ferrihydrite synthesis at neutral pH demonstrated that dissolved Ni was variably heavier than coprecipitated Ni (Δ60/58Ni = +0.08 to +0.50 ‰), in contrast to the constant offset observed earlier during adsorption to pre-existing ferrihydrite[2]. Experiments at lower pH (<7) yielded negative values of Δ60/58Ni ( -0.18 ‰), suggesting enrichment in heavier isotopes of structurally incorporated Ni relative to dissolved and adsorbed Ni, possibly due to the presence of a small amount of highly fractionated tetrahedral Ni2+ in the ferrihydrite structure. We model our results as equilibrium fractionation among three pools of Ni with systematically varied proportions. We synthesized hematite by transforming Ni-bearing ferrihydrite in aqueous solution at 100 °C and observed significant Ni release from solids (up to 60 %) as pH dropped from 7 to 4.5 - 5.5 during phase transformation. Rinsing hematite with acetic acid released very little Ni (presumably surface-adsorbed) compared to the amounts remaining in solid residues (presumably incorporated). We infer that Δ60/58Ni values (-0.04 to +0.77 ‰) observed in hematite experiments likely reflect Rayleigh fractionation between incorporated and dissolved Ni. The final hematite was slightly lighter than the ferrihydrite had been (by 0.08 ‰), indicating that this phase transformation results in very limited change in Ni isotopic composition, given current analytical uncertainty of ± 0.09 ‰. [1] Wasylenki and Wang (2016) Goldschmidt; [2] Wasylenki et al

  15. Detection of phosphohydrolytic enzyme activity through the oxygen isotope composition of dissolved phosphate

    NASA Astrophysics Data System (ADS)

    Colman, A. S.

    2016-02-01

    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.

  16. Natural calcium isotopic composition of urine as a marker of bone mineral balance.

    PubMed

    Skulan, Joseph; Bullen, Thomas; Anbar, Ariel D; Puzas, J Edward; Shackelford, Linda; LeBlanc, Adrian; Smith, Scott M

    2007-06-01

    We investigated whether changes in the natural isotopic composition of calcium in human urine track changes in net bone mineral balance, as predicted by a model of calcium isotopic behavior in vertebrates. If so, isotopic analysis of natural urine or blood calcium could be used to monitor short-term changes in bone mineral balance that cannot be detected with other techniques. Calcium isotopic compositions are expressed as delta(44)Ca, or the difference in parts per thousand between the (44)Ca/(40)Ca of a sample and the (44)Ca/(40)Ca of a standard reference material. delta(44)Ca was measured in urine samples from 10 persons who participated in a study of the effectiveness of countermeasures to bone loss in spaceflight, in which 17 weeks of bed rest was used to induce bone loss. Study participants were assigned to 1 of 3 treatment groups: controls received no treatment, one treatment group received alendronate, and another group performed resistive exercise. Measurements were made on urine samples collected before, at 2 or 3 points during, and after bed rest. Urine delta(44)Ca values during bed rest were lower in controls than in individuals treated with alendronate (P <0.05, ANOVA) or exercise (P <0.05), and lower than the control group baseline (P <0.05, t-test). Results were consistent with the model and with biochemical and bone mineral density data. Results confirm the predicted relationship between bone mineral balance and calcium isotopes, suggesting that calcium isotopic analysis of urine might be refined into a clinical and research tool.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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).

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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).

  19. Extreme Hf-Os Isotope Compositions in Hawaiian Peridotite Xenoliths: Evidence for an Ancient Recycled Lithosphere

    NASA Astrophysics Data System (ADS)

    Bizimis, M.; Lassiter, J. C.; Salters, V. J.; Sen, G.; Griselin, M.

    2004-12-01

    We report on the first combined Hf-Os isotope systematics of spinel peridotite xenoliths from the Salt Lake Crater (SLC), Pali and Kaau (PK) vents from the island of Oahu, Hawaii. These peridotites are thought to represent the Pacific oceanic lithosphere beneath Oahu, as residues of MORB-type melting at a paleo-ridge some 80-100Ma ago. Clinopyroxene mineral separates in these peridotites have very similar Nd and Sr isotope compositions with the post erosional Honolulu Volcanics (HV) lavas that bring these xenoliths to the surface. This and their relatively elevated Na and LREE contents suggest that these peridotites are not simple residues of MORB-type melting but have experience some metasomatic enrichment by the host HV lavas. However, the SLC and PK xenoliths show an extreme range in Hf isotope compositions towards highly radiogenic values (ɛ Hf= 7-80), at nearly constant Nd isotope compositions (ɛ Nd= 7-10), unlike any OIB or MORB basalt. Furthermore, these Oahu peridotites show a bimodal distribution in their bulk rock 187Os/186Os ratios: the PK peridotites have similar ratios to the abyssal peridotites (0.130-0.1238), while the SLC peridotites have highly subchondritic ratios (0.1237-0.1134) that yield 500Ma to 2Ga Re-depletion ages. Hf-Os isotopes show a broad negative correlation whereby the samples with the most radiogenic 176Hf/177Hf have the most unradiogenic 187Os/186Os ratios. Based on their combined Hf-Os-Nd isotope and major element compositions, the PK peridotites can be interpreted as fragments of the Hawaiian lithosphere, residue of MORB melting 80-100Ma ago, that have been variably metasomatized by the host HV lavas. In contrast, the extreme Hf-Os isotope compositions of the SLC peridotites suggest that they cannot be the source nor residue of any kind of Hawaiian lavas, and that Hf and Os isotopes survived the metasomatism or melt-rock reaction that has overprinted the Nd and Sr isotope compositions of these peridotites. The ancient (>1Ga

  20. Sulfur isotopes of host strata for Howards Pass (Yukon–Northwest Territories) Zn-Pb deposits implicate anaerobic oxidation of methane, not basin stagnation

    USGS Publications Warehouse

    Johnson, Craig A.; Slack, John F.; Dumoulin, Julie A.; Kelley, Karen Duttweiler; Falck, Hendrik

    2018-01-01

    A new sulfur isotope stratigraphic profile has been developed for Ordovician-Silurian mudstones that host the Howards Pass Zn-Pb deposits (Canada) in an attempt to reconcile the traditional model of a stagnant euxinic basin setting with new contradictory findings. Our analyses of pyrite confirm the up-section 34S enrichment reported previously, but additional observations show parallel depletion of carbonate 13C, an increase in organic carbon weight percent, and a change in pyrite morphology. Taken together, the data suggest that the 34S enrichment reflects a transition in the mechanism of pyrite formation during diagenesis, not isotopic evolution of a stagnant water mass. Low in the stratigraphic section, pyrite formed mainly in the sulfate reduction zone in association with organic matter–driven bacterial sulfate reduction. In contrast, starting just below the Zn-Pb mineralized horizon, pyrite formed increasingly within the sulfate-methane transition zone in association with anaerobic oxidation of methane. Our new insights on diagenesis have implications for (1) the setting of Zn-Pb ore formation, (2) the reliability of redox proxies involving metals, and (3) the source of ore sulfur for Howards Pass, and potentially for other stratiform Zn-Pb deposits contained in carbonaceous strata.

  1. The neodymium stable isotope composition of the silicate Earth and chondrites

    NASA Astrophysics Data System (ADS)

    McCoy-West, Alex J.; Millet, Marc-Alban; Burton, Kevin W.

    2017-12-01

    The non-chondritic neodymium (Nd) 142Nd/144Nd ratio of the silicate Earth potentially provides a key constraint on the accretion and early evolution of the Earth. Yet, it is debated whether this offset is due to the Earth being formed from material enriched in s-process Nd isotopes or results from an early differentiation process such as the segregation of a late sulfide matte during core formation, collisional erosion or a some combination of these processes. Neodymium stable isotopes are potentially sensitive to early sulfide segregation into Earth's core, a process that cannot be resolved using their radiogenic counterparts. This study presents the first comprehensive Nd stable isotope data for chondritic meteorites and terrestrial rocks. Stable Nd measurements were made using a double spike technique coupled with thermal ionisation mass spectrometry. All three of the major classes of chondritic meteorites, carbonaceous, enstatite and ordinary chondrites have broadly similar isotopic compositions allowing calculation of a chondritic mean of δ146/144Nd = -0.025 ± 0.025‰ (±2 s.d.; n = 39). Enstatite chondrites yield the most uniform stable isotope composition (Δ146/144Nd = 26 ppm), with considerably more variability observed within ordinary (Δ146/144Nd = 72 ppm) and carbonaceous meteorites (Δ146/144Nd = 143 ppm). Terrestrial weathering, nucleosynthetic variations and parent body thermal metamorphism appear to have little measurable effect on δ146/144Nd in chondrites. The small variations observed between ordinary chondrite groups most likely reflect inherited compositional differences between parent bodies, with the larger variations observed in carbonaceous chondrites being linked to varying modal proportions of calcium-aluminium rich inclusions. The terrestrial samples analysed here include rocks ranging from basaltic to rhyolitic in composition, MORB glasses and residual mantle lithologies. All of these terrestrial rocks possess a broadly similar Nd

  2. Hydrothermal synthesis and characterization of hybrid Al/ZnO-GO composite for significant photodegrdation of dyes

    SciTech Connect

    Lellala, Kashinath; Namratha, K.; Byrappa, K., E-mail: kashinathlellala@gmail.com, E-mail: kbyrappa@gmail.com

    In the present work, undoped and doped Aluminum/Zinc Oxide - graphene oxide (Al/ZnO-GO) nanocomposite have been successfully synthesized by hydrothermal method from zinc acetate and aluminum nitrate solutions without using of any surfactant/stabilizing agents. The results show that the composites of GO nanosheets are decorated densely by Al/ZnO nanoparticles, which displays a good morphology and blend between GO and Al/ZnO. Hybrid composites exhibit an enhanced photocatalytic performance in reduction of dyes under UV-Vis radiation better than bare ZnO-GO and GO for methylene blue dye. The hydrothermal method leads to particles with a higher crystalline due to ambient temperature of themore » reaction and autogenously pressure conditions, which alters the phases and crystallizations of the nanocomposite. The optical band gap is narrowed to lower energy values due to controlled addition of aluminum and GO in the composite. The improved optical property in Al-doped ZnO flower decorated on GO can be attributed to the decrease in oxygen deficiency after Al doping. XRD, FTIR, UV-Vis spectroscopy, Raman, and Field Emission Scanning Electron Microscopy characterized the effects of Al doping on the structural characteristics and optical properties on the ZnO-GO.« less

  3. Hydrothermal synthesis and characterization of hybrid Al/ZnO-GO composite for significant photodegrdation of dyes

    NASA Astrophysics Data System (ADS)

    Lellala, Kashinath; Namratha, K.; Sudhakar, K.; Byrappa, K.

    2016-05-01

    In the present work, undoped and doped Aluminum/Zinc Oxide - graphene oxide (Al/ZnO-GO) nanocomposite have been successfully synthesized by hydrothermal method from zinc acetate and aluminum nitrate solutions without using of any surfactant/stabilizing agents. The results show that the composites of GO nanosheets are decorated densely by Al/ZnO nanoparticles, which displays a good morphology and blend between GO and Al/ZnO. Hybrid composites exhibit an enhanced photocatalytic performance in reduction of dyes under UV-Vis radiation better than bare ZnO-GO and GO for methylene blue dye. The hydrothermal method leads to particles with a higher crystalline due to ambient temperature of the reaction and autogenously pressure conditions, which alters the phases and crystallizations of the nanocomposite. The optical band gap is narrowed to lower energy values due to controlled addition of aluminum and GO in the composite. The improved optical property in Al-doped ZnO flower decorated on GO can be attributed to the decrease in oxygen deficiency after Al doping. XRD, FTIR, UV-Vis spectroscopy, Raman, and Field Emission Scanning Electron Microscopy characterized the effects of Al doping on the structural characteristics and optical properties on the ZnO-GO.

  4. Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method

    USGS Publications Warehouse

    Casciotti, K.L.; Sigman, D.M.; Hastings, M. Galanter; Böhlke, J.K.; Hilkert, A.

    2002-01-01

    We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate.1Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO3-), lack of interference by other solutes, and ease of sample preparation.

  5. Spectroscopic analyses on sonocatalytic damage to bovine serum albumin (BSA) induced by ZnO/hydroxylapatite (ZnO/HA) composite under ultrasonic irradiation

    NASA Astrophysics Data System (ADS)

    Wang, Zhiqiu; Li, Ying; Wang, Jun; Zou, Mingming; Gao, Jingqun; Kong, Yumei; Li, Kai; Han, Guangxi

    ZnO/hydroxylapatite (ZnO/HA) composite with HA molar content of 6.0% was prepared by the method of precipitation and heat-treated at 500 °C for 40 min and was characterized by powder X-ray diffraction (XRD). The sonocatalytic activities of ZnO/HA composite was carried out through the damage of bovine serum albumin (BSA) in aqueous solution. Furthermore, the effects of several factors on the damage of BSA molecules were evaluated by means of UV-vis and fluorescence spectra. Experimental results indicated that the damage degree of BSA aggravated with the increase of ultrasonic irradiation time, irradiation power and ZnO/HA addition amount, but weakened with the increase of solution acidity and ionic strength. In addition, the damage site to BSA was also studied by synchronous fluorescence technology and the damage site was mainly at tryptophan (Trp) residue. This paper provides a valuable reference for driving sonocatalytic method to treat tumor in clinic application.

  6. Hydrogen isotope composition of leaf wax n-alkanes in Arabidopsis lines with different transpiration rates

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

    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

  7. Light Stable Isotopic Compositions of Enriched Mantle Sources: Resolving the Dehydration Paradox

    NASA Astrophysics Data System (ADS)

    Dixon, J. E.; Bindeman, I. N.; Kingsley, R. H.

    2017-12-01

    An outstanding puzzle in mantle geochemistry has been the origin and evolution of Earth's volatile components. The "dehydration paradox" refers to the following conundrum. Mantle compositions for some enriched mid-ocean ridge (MORB) and ocean island (OIB) basalts basalts require involvement of a mostly dehydrated slab component to explain the trace element ratios and radiogenic isotopic compositions, but a fully hydrated slab component to explain the stable isotopic compositions. Volatile and stable isotopic data on enriched MORB show a diversity of enriched components. Pacific PREMA-type basalts (H2O/Ce = 215 ± 30, δDSMOW = -45 ± 5 ‰) are similar to those in the north Atlantic (H2O/Ce = 220 ± 30; δDSMOW = -30 to -40 ‰). Basalts with EM-type signatures have regionally variable volatile compositions. North Atlantic EM-type basalts are wetter (H2O/Ce = 330 ± 30) and have isotopically heavier hydrogen (δDSMOW = -57 ± 5 ‰) than north Atlantic MORB. South Atlantic EM-type basalts are damp (H2O/Ce = 120 ± 10) with intermediate δDSMOW (-68 ± 2 ‰), similar to dDSMOW for Pacific MORB. North EPR EM-type basalts are dry (H2O/Ce = 110 ± 20) and isotopically light (δDSMOW = -94 ± 3 ‰). Boron and lithium isotopic ratios parallel the trends observed for dDSMOW. A multi-stage metasomatic and melting model accounts for the origin of the enriched components by extending the subduction factory concept down through the mantle transition zone, with slab temperature a key variable. The dehydration paradox is resolved by decoupling of volatiles from lithophile elements, reflecting primary dehydration of the slab followed by secondary rehydration and re-equilibration by fluids derived from subcrustal hydrous phases (e.g., antigorite) in cooler, deeper parts of the slab. The "expanded subduction factory" model includes melting at several key depths, including 1) 180 to 280 km, where EM-type mantle compositions are generated above slabs with average to hot thermal

  8. New ZnO@Cardanol Porphyrin Composite Nanomaterials with Enhanced Photocatalytic Capability under Solar Light Irradiation

    PubMed Central

    Ribeiro, Viviane Gomes Pereira; Marcelo, Ana Maria Pereira; da Silva, Kássia Teixeira; da Silva, Fernando Luiz Firmino; Mota, João Paulo Ferreira; do Nascimento, João Paulo Costa; Sombra, Antonio Sérgio Bezerra; Clemente, Claudenilson da Silva; Mazzetto, Selma Elaine

    2017-01-01

    This work describes the synthesis, characterization, and photocatalytic activity of new composite nanomaterials based on ZnO nanostructures impregnated by lipophlilic porphyrins derived from cashew nut shell liquid (CNSL). The obtained nanomaterials were characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and steady-state photoluminescence spectra (PL). The results confirm nanostructures showing average diameter of 55 nm and an improved absorption in the visible region. Further, the FTIR analysis proved the existence of non-covalent interactions between the porphyrin molecules and ZnO. The photocatalytic activity of prepared photocatalysts was investigated by degradation of rhodamine B (RhB) in aqueous solution under visible light irradiation and natural sunlight. It was demonstrated that the photocatalytic activity increases in the presence of the porphyrins and, also, depends on the irradiation source. The development of composite photocatalysts based on porphyrins derived from CNSL provides an alternative approach to eliminate efficiently toxic wastes from water under ambient conditions. PMID:28934117

  9. Stable isotope compositions of gases and vegetation near naturally burning coal

    USGS Publications Warehouse

    Gleason, J.D.; Kyser, T.K.

    1984-01-01

    Our measurements of stable isotope compositions of CO2 issuing from vents produced by naturally burning coal indicate that the coal is oxidized through a kinetic process in which groundwater is the oxidizing agent. The CO2 produced by the oxidation of the coal is extremely depleted in 13C relative to normal atmospheric CO2. The change in the ??13C value of atmospheric CO2 near the vents resulting from the burning coal was not recorded in tree rings from red cedars, but the ??13C values of some C3 and C4 type plants collected from within the area were greatly affected. Our results indicate that the ??13C values of some species of plants may be sensitive indicators of changes in the carbon isotopic composition of atmospheric CO2. ?? 1984 Nature Publishing Group.

  10. Isotopic compositions and probable origins of organic molecules in the Eocene Messel shale

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

    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. Isotopic composition of cosmic ray nitrogen at 1.5 GeV/amu

    NASA Technical Reports Server (NTRS)

    Dwyer, R.; Meyer, P.

    1975-01-01

    For any location, the earth's magnetic field acts as a filter for incoming cosmic rays, allowing only particles above a certain rigidity. The relative isotopic composition of abundant elements can be measured with a detector sensitive to the velocity of particles in the penumbra of the earth's magnetic field. In this paper, the nitrogen velocity spectrum is compared with that of carbon plus oxygen as a reference, since in this case Z-dependent effects are minimal. The form of the energy spectrum of carbon, nitrogen, and oxygen, needed for proper correction, was measured in the same experiment. The results were obtained using a scintillator-Cerenkov counter telescope with a geometric factor of 0.25 sq in sr, flown twice on high-altitude balloons from Palestine, Texas, obtaining an exposure factor of 20 sq m sr hr. Results are presented on the isotopic composition of nitrogen at about 1.5GeV/amu.

  12. In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael E.; Engrand, Cecile; Gounelle, Matthieu; Zolensky, Mike E.

    2001-01-01

    We have measured the oxygen isotopic composition of several components of Tagish Lake by ion microprobe. This meteorite constitutes the best preserved sample of C2 matter presently available for study. It presents two different lithologies (carbonate-poor and -rich) which have fairly comparable oxygen isotopic composition, with regard to both the primary or secondary minerals. For the olivine and pyroxene grains, their delta O-18 values range from - 10.5% to + 7.4% in the carbonate-poor lithology, with a mean Delta O-17 value of - 3.7 2.4%. In the carbonate-rich lithology, delta O-18 varies from - 7.9% to + 3.3%, and the mean Delta O-17 value is - 4.7 +/- 1.4%. Olivine inclusions (Fo(sub >99)) with extreme O-16-enrichment were found in both lithologies: delta O-18 = - 46.1 %, delta O-187= - 48.3% and delta O-18 = - 40.6%, delta O-17 = - 41.2% in the carbonate-rich lithology; delta O-18 = - 41.5%, delta O-17 = -43.4%0 in the carbonate-poor lithology. Anhydrous minerals in the carbonate-poor lithology are slightly more O-16-rich than in the carbonate-rich one. Four low-iron manganese-rich (LIME) olivine grains do not have an oxygen isotopic composition distinct from the other "normal" olivines. The phyllosilicate matrix presents the same range of oxygen isotopic compositions in both lithologies: delta O-18 from approximately 11 % to approximately 6%, with an average Delta. O-17 approximately 0%. Because the bulk Tagish Lake oxygen isotopic composition given by Brown et al. is on the high end of our matrix analyses, we assume that this "bulk Tagish Lake" composition probably only represents that of the carbonate-rich lithology. Calcium carbonates have delta O-18 values up to 35%, with Delta O-17 approximately 0.5%0. Magnetite grains present very high Delta O-17 values approximately + 3.4%0 +/- 1.2%. Given our analytical uncertainties and our limited carbonate data, the matrix and the carbonate seem to have formed in isotopic equilibrium. In that case, their large

  13. Isotopic composition of cosmic ray nuclei with Z greater than or equal to 10

    NASA Technical Reports Server (NTRS)

    Webber, W. R.; Lezniak, J. A.; Kish, J.

    1974-01-01

    Results of measurements of the isotopic composition of Z greater than or equal to 10 cosmic ray nuclei using a new technique employing a combination of Cerenkov and total energy counters. An effective mass resolution of about 0.4 AMU is obtained for particles with energies between 400 and 500 MeV/nuc and charges between 12 and 16. The preliminary mass distribution of nuclei with charges from 12 to 28 is presented and discussed.

  14. Assessment of oceanic productivity with the triple-isotope composition of dissolved oxygen.

    PubMed

    Luz, B; Barkan, E

    2000-06-16

    Plant production in the sea is a primary mechanism of global oxygen formation and carbon fixation. For this reason, and also because the ocean is a major sink for fossil fuel carbon dioxide, much attention has been given to estimating marine primary production. Here, we describe an approach for estimating production of photosynthetic oxygen, based on the isotopic composition of dissolved oxygen of seawater. This method allows the estimation of integrated oceanic productivity on a time scale of weeks.

  15. Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

    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.

  16. Microscale determination of the spectral characteristics and carbon-isotopic compositions of porphyrins

    NASA Technical Reports Server (NTRS)

    Popp, B. N.; Hayes, J. M.; Boreham, C. J.

    1993-01-01

    Molar extinction coefficients for band III of Ni porphyrins are calculated from results of spectrophotometric and manometric analyses of individual etioporphyrins, DPEP, cyclic, and diDPEP porphyrins known to initially be pure from mass spectrometry, 1H NMR, and analytical HPLC studies. A method for determining carbon-isotopic compositions and purity of micromolar quantities of individual porphyrins using combined spectrophotometric and manometric techniques is presented.

  17. The nitrogen isotopic composition in soils and plants: Its use in environmental studies (A Review)

    NASA Astrophysics Data System (ADS)

    Makarov, M. I.

    2009-12-01

    The results of studying the isotopic composition of the nitrogen in soils and plants and its use for characterizing the nitrogen cycle in ecosystems, the transformation of nitrogen compounds in soils, the sources of nitrogen nutrition for plants, and the assessment of the symbiotic nitrogen fixation’s contribution to the nitrogen budget of ecosystems were considered for a wide variety of natural and agricultural ecosystems.

  18. Synthesis of ZnFe2O4/SiO2 composites derived from a diatomite template.

    PubMed

    Liu, Zhaoting; Fan, Tongxiang; Zhou, Han; Zhang, Di; Gong, Xiaolu; Guo, Qixin; Ogawa, Hiroshi

    2007-03-01

    A novel porous ZnFe2O4/SiO2 composite product has been generated with a template-directed assembly method from porous diatomite under different synthesis conditions, such as precursor concentrations (metallic nitrates), calcination temperature and diatomite type. The phase composition and morphology of all the materials were examined by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The results indicated that an inherited hierarchical porous structure from the diatomite template can be obtained, and the synthesis conditions were found to have clear effects on the formation of the ZnFe2O4/SiO2 composite. The ideal composite of ZnFe2O4/SiO2 can be obtained through optimization of diatomite template type, precursor solution and calcination temperature. Furthermore, the adsorption abilities of two types of diatomites were analyzed in detail using FTIR spectra and nitrogen adsorption measurements etc, which proved that A-diatomite (Shengzhou-diatomite) is better than B-diatomite (Changbai-diatomite) on the aspect of adsorbing Zn and Fe ions, and of forming the ZnFe2O4.

  19. Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

    PubMed Central

    Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V.

    2017-01-01

    Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62−) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O) of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4), acid

  20. In-situ observations of the isotopic composition of methane at the Cabauw tall tower site

    NASA Astrophysics Data System (ADS)

    Röckmann, Thomas; Eyer, Simon; van der Veen, Carina; E Popa, Maria; 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

    2017-04-01

    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 +0.05 ± 0.03 ‰ for δ13C-CH4 and -3.6 ± 0.4 ‰ for δD-CH4. This was corrected for, yielding a combined dataset with more than 2500 measurements of both δ13C and δD. The high precision and temporal resolution dataset does not only reveal 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

  1. Tungsten isotopic compositions of iron meteorites: Chronological constraints vs. cosmogenic effects

    NASA Astrophysics Data System (ADS)

    Markowski, A.; Quitté, G.; Halliday, A. N.; Kleine, T.

    2006-02-01

    High-precision W isotopic compositions are presented for 35 iron meteorites from 7 magmatic groups (IC, IIAB, IID, IIIAB, IIIF, IVA, and IVB) and 3 non-magmatic groups (IAB, IIICD, and IIE). Small but resolvable isotopic variations are present both within and between iron meteorite groups. Variations in the 182W/ 184W ratio reflect either time intervals of metal-silicate differentiation, or result from the burnout of W isotopes caused by a prolonged exposure to galactic cosmic rays. Calculated apparent time spans for some groups of magmatic iron meteorites correspond to 8.5 ± 2.1 My (IID), 5.1 ± 2.3 My (IIAB), and 5.3 ± 1.3 My (IVB). These time intervals are significantly longer than those predicated from models of planetesimal accretion. It is shown that cosmogenic effects can account for a large part of the W isotopic variation. No simple relationship exists with exposure ages, compromising any reliable method of correction. After allowance for maximum possible cosmogenic effects, it is found that there is no evidence that any of the magmatic iron meteorites studied here have initial W isotopic compositions that differ from those of Allende CAIs [ ɛ182W = - 3.47 ± 0.20; [T. Kleine, K. Mezger, H. Palme, E. Scherer and C. Münker, Early core formation in asteroids and late accretion of chondrite parent bodies: evidence from 182Hf- 182W in CAIs, metal-rich chondrites and iron meteorites, Geochim. Cosmochim. Acta (in press)]. Cosmogenic corrections cannot yet be made with sufficient accuracy to obtain highly precise ages for iron meteorites. Some of the corrected ages nevertheless require extremely early metal-silicate segregation no later than 1 My after formation of CAIs. Therefore, magmatic iron meteorites appear to provide the best examples yet identified of material derived from the first planetesimals that grew by runaway growth, as modelled in dynamic simulations. Non-magmatic iron meteorites have a more radiogenic W isotopic composition than magmatic

  2. Mesozoic magmatism and timing of epigenetic Pb-Zn-Ag mineralization in the western Fortymile mining district, east-central Alaska: Zircon U-Pb geochronology, whole-rock geochemistry, and Pb isotopes

    USGS Publications Warehouse

    Dusel-Bacon, Cynthia; Aleinkoff, J.N.; Day, W.C.; Mortensen, J.K.

    2015-01-01

    Epigenetic Pb-Zn-Ag ± Cu prospects in the western Fortymile district are spatially associated with splays of the northeast-trending Kechumstuk sinistral-normal fault zone and with ca. 68-66 Ma felsic intrusions and dikes. The similarity between Pb isotope compositions of feldspars from the Late Cretaceous igneous bodies and sulfides from the epithermal prospects suggests a Late Cretaceous age for most of the mineralization. Fluid flow along the faults undoubtedly played a major role in mineralization. We interpret displacement on the northeast-trending faults to be a far-field effect of dextral translation along Late Cretaceous plate-scale boundaries and faults that were roughly parallel to the subsequently developed Denali and Tintina fault systems, which currently bound the region.

  3. Synthesis of TiO2 NRs - ZnO Composite for Dye Sensitized Solar Cell Photoanodes

    NASA Astrophysics Data System (ADS)

    Wahyuningsih, S.; Ramelan, A. H.; Hidayat, R.; Fadillah, G.; Munawaroh, H.; Saputri, L. N. M. Z.

    2017-07-01

    Composite of TiO2 NRs - ZnO were synthesized for DSSCs photoanode materials. TiO2 NRs was synthesized from TiO2 anatase by mechanochemical technique using ball milling process with agitation speed of 1000 rpm. While, the further hydrothermal refluxing process was conducted at 120°C under various concentration of NaOH in aqueous solution. The starting material of ZnO was prepared from ZnSO4.7H2O as a precursor. The hydrothermal treated TiO2 was added to the ZnO powder in a certain composition of 1:1, 1:2 and 2:1 (w/w), and the mixtures were then annealed at 400°C. The resulting material was characterized by X-ray diffraction (XRD), Surface area analyzer (SAA), Transmission electron microscopy (TEM), and Thermogravimetry/Differential thermal analysis (TG/DTA). The TiO2 revolution occurs from anatase phase into brookite phase. Rutile TiO2 phase was increasing when the NaOH was added at about 12 M. Nanograf of TEM showed the optimum condition for the formation of TiO2 NRs was obtained when 12 M NaOH was used. Structural transformation to 1D nanorods of TiO2 capable increase surface area up to 79 m2/g. TiO2 NRs-ZnO composite was prepared from TiO2 NRs and ZnO using comparation of TiO2 NRs: ZnO = 1:1, 1:2, dan 2:1. Anatase phase TiO2 as a single phase TiO2 was obtained in the TiO2-ZnO composite (1:1 w/w) upon heating the sample until 400°C. Difference TiO2 NRs-ZnO composite materials were investigated as good photovoltaic materials. Evaluation of the performance of DSSCs was conducted by I-V Keithley 2602A measurement indicate that photoanode built of TiO2 NRs - ZnO thin film has a higher solar cell efficiency than that of TiO2 thin film photoanode.