Methane Production Pathways in a California Rice Paddy: Isotopic Evidence for Substantial CO2 Reduction as Cause for Isotopically Light Emitted CH4 Carbon

NASA Astrophysics Data System (ADS)

Tyler, S. C.; McMillan, A. M.; Bearden, K.; Chidthaisong, A.; Macalady, J.

2003-12-01

We report measurements of δ 13C of emitted CH4 and sediment CH4 and CO2 during the 1999 rice-growing season near Maxwell, CA. Two treatments, one with rice straw incorporated from the previous season and one without rice straw were studied. The δ 13C value of emitted CH4 was consistently lighter isotopically (-67‰ to -83‰ throughout the season) in both straw incorporated and straw removed (burned) plots than in fields we have studied in Texas, Kenya, and Japan. Measured isotopic values of the production zone CH4 were compared to a two-point mixing curve representative of isotopic CH4 produced from either pure methyl-group fermentation or CO2 reduction pathways to partition the production pathways and to track seasonal changes in the production processes. Our sediment CH4 and CO2 isotope data indicate that fermentation was rarely the dominant methanogenic pathway - on the contrary CO2 reduction with H2 was more prevalent than fermentation methanogenesis throughout most of the season. The relatively isotopically light CH4 emitted by the paddy fields is also a product of oxidation and stem-transport processes which have isotopic effects of their own. These effects are discussed in context with the methanogenic isotope effects to provide a complete picture of the paddy field CH4 carbon isotope system.

Carbon kinetic isotope effects in the gas-phase reactions of aromatic hydrocarbons with the OH radical at 296 +/- 4 K

NASA Astrophysics Data System (ADS)

Anderson, Rebecca S.; Iannone, Richard; Thompson, Alexandra E.; Rudolph, Jochen; Huang, Lin

2004-08-01

The carbon kinetic isotope effects (KIEs) of the room temperature reactions of benzene and several light alkyl benzenes with OH radicals were studied in a reaction chamber at ambient pressure using gas chromatography coupled with online combustion and isotope ratio mass spectrometry (GCC-IRMS). The KIEs are reported in per mil according to $\\varepsilon$ (‰) = (KIE - 1) × 1000, where KIE = k12/k13. The following average KIEs were obtained, (all in ‰): benzene 7.53 +/- 0.50; toluene 5.95 +/- 0.28; ethylbenzene 4.34 +/- 0.28; o-xylene 4.27 +/- 0.05, p-xylene 4.83 +/- 0.81; o-ethyltoluene 4.71 +/- 0.12 and 1,2,4-trimethylbenzene 3.18 +/- 0.09. Our KIE value for benzene + OH agrees with the only reported value known to us [Rudolph et al., 2000]. It is shown that measurements of the stable carbon isotope ratios of light aromatic compounds should be extremely useful to study atmospheric processing by the OH radical.

Carbon isotope fractionation between Fe-carbide and diamond; a light C isotope reservoir in the deep Earth and Core?

NASA Astrophysics Data System (ADS)

Mikhail, S.; Jones, A. P.; Hunt, S. A.; Guillermier, C.; Dobson, D. P.; Tomlinson, E.; Dan, H.; Milledge, H.; Franchi, I.; Wood, I.; Beard, A.; Verchovsky, S.

2010-12-01

The largest accessible reservoir for terrestrial carbon is the mantle; however the core may yield even more. Carbon is commonly proposed as the light element (or one of) to make up the observed density deficit in the earth’s metallic core (NAKAJIMA et al., 2009). The potential isotopic effects of carbon incorporation into the core have not yet been investigated. In-situ ion probe (nanoSIMS) mapping and imaging of carbon isotope variations across rare sub-mm-scale Fe-rich carbide inclusions in mantle diamond (from Jagersfontein, South Africa) show the carbide to be significantly depleted in 13C relative to their diamond host. Distinctive textures suggest metallic liquid precipitates similar in geometry to (giant) nitrogen platelets, controlled by the octahedral symmetry of diamond, which we interpret as syngenic formation. The difference in δ13C values between the two natural phases for diamond-Fe carbide, gives an isotopic fractionation factor (ΔC) which agrees well with HPHT multi-anvil experiments (5-9 GPa and >1400°C). Our measured ΔC between Fe-carbide and diamond may only have local significance, but the measured isotopic values represent characterization of the highest PT carbide known (i.e. > minimum depth of the diamond stability field ≈ 150 km). The direction and magnitude of ΔC agrees with observations of the ΔC between cohenite-graphite in iron meteorites (DEINES and WICKMAN, 1975) and both agree with HPHT experiments, thus suggesting that carbon in the deep Earth, and particularly in the core, may be similarly fractionated (i.e. depleted in the 13C). Since metallic liquid drained from the silicate mantle to form the core during the early Earth, we can use our values as a proxy to constrain evolution of deep carbon reservoirs such as the core and bulk silicate Earth. For example, we can test the suggestion of Grady et al (2004) that the upper mantle value of δ13C ≈ -5 ‰ may not be representative of the bulk Earth, since solar system meteorites (from Mars, Vesta and the Moon) suggest a preferred value of δ13C ≈ -20 +/- 4 ‰. If we adopt this particular model, not only could we explain fractionation between a bulk silicate Earth δ13C value of -5 ‰ from an initial δ13C value of -20 ‰, but we can constrain the relative proportion of carbon in the core/mantle by using simple isotopic mass balance. Such fractionation of carbon isotopes between HPT carbides (and/or metallic iron) within the lower mantle and core would be expected immediately from the time of core formation. Therefore, isotopically light carbon reservoirs may have been present deep in the Earth throughout its history, offering an alternative explanation for light carbon (eg in diamonds) which was not formed by, and/or predated subduction of oceanic crust and organic carbon. Deines, P. and Wickman, F. E., 1975. GCA; Grady, M. M. et al. 2004. Int Journal of Astrobiology; Nakajima, Y. et al. K.-i., 2009. Physics of the Earth and Planetary Interiors.

Determining and quantifying specific sources of light alkane

NASA Astrophysics Data System (ADS)

Bill, M.; Conrad, M. E.

2015-12-01

Determining and quantifying specific sources of emission of methane (an important greenhouse gas) and light alkanes from abandoned gas and oil wells, hydraulic fracturing or associated with CO2 sequestration are a challenge in determining their contribution to the atmospheric greenhouse gas budget or to identify source of groundwater contamination. Here, we review organic biogeochemistry proprieties and isotopic fingerprinting of C1-C5 alkanes to address this problem. For instance, the concentration ratios of CH4 to C2-C5 alkanes can be used to distinguish between thermogenic and microbial generated CH4. Together C and H isotopes of CH4 are used to differentiate bacterial generated sources and thermogenic CH4 and may also identify processes such as alteration and source mixing. Carbon isotope ratios pattern of C1-C5 alkanes highlight sources and oxidation processes in the gas reservoirs. Stable carbon isotope measurements are a viable tool for monitoring the degradation progress of methane and light hydrocarbons. The carbon isotope ratios of the reactants and products are independent of the concentration and only depend on the relative progress of the particular reaction. Oxidation/degradation of light alkanes are typically associated with increasing ð13C values. Isotopic mass balances offer the possibility to independently determine the fractions coming from microbial versus thermogenic and would also permit differentiation of the isotope fractionations associated with degradation. Unlike conventional concentration measurements, this approach is constrained by the different isotopic signatures of various sources and sinks.

Can Biomass Burning Explain Isotopically Light Fe in Marine Aerosols?

NASA Astrophysics Data System (ADS)

Sherry, A. M.; Anbar, A. D.; Herckes, P.; Romaniello, S. J.

2016-02-01

Iron (Fe) is an important micronutrient that limits primary productivity in large parts of the ocean. In these regions, atmospheric aerosol deposition is an important source of Fe to the surface ocean and thus has a critical impact on ocean biogeochemistry. Fe-bearing aerosols originate from many sources with potentially distinct Fe isotopic compositions. Consequently, Fe isotopes may provide a new tool to trace the sources of aerosol Fe to the oceans. Mead et al. (2013) first discovered that Fe in the fine fraction of Bermuda aerosols is often isotopically lighter than Fe from known anthropogenic and crustal sources. 1 These authors suggested that this light isotopic signature was likely the result of biomass burning, since Fe in plants is the only known source of isotopically light Fe. More recently, Conway et al. found that Fe in the soluble fraction of aerosols collected during 2010-2011 North Atlantic GEOTRACES cruises also showed light isotope values, which they likewise attributed to biomass burning.2 These studies are further supported by new modeling work which suggests that biomass burning aerosols should contribute significant amounts of soluble Fe to tropical and southern oceans.3To test if biomass burning releases aerosols with a light Fe isotope composition, we are conducting lab-scale biomass burning experiments using natural samples of vegetation and leaf litter. Burn aerosols were collected on cellulose filters, then digested and analyzed for trace metal concentrations using inductively-coupled mass spectrometry (ICP-MS). Fe isotopes were determined by using multiple collector ICP-MS following separation and purification of Fe using anion exchange chromatography. We will discuss metal concentration and isotope data from these experiments with implications for the interpretation of Fe isotope signals in aerosol samples. 1Mead, C et al. GRL, 2013, 40, 5722-5727. 2 Conway, T et al. Goldschmidt Abs 2015 593. 3Ito, A. ES&T Lett, 2015, 2, 70-75.

Copper isotope signatures in modern marine sediments

NASA Astrophysics Data System (ADS)

Little, Susan H.; Vance, Derek; McManus, James; Severmann, Silke; Lyons, Timothy W.

2017-09-01

The development of metal stable isotopes as tools in paleoceanography requires a thorough understanding of their modern marine cycling. To date, no Cu isotope data has been published for modern sediments deposited under low oxygen conditions. We present data encompassing a broad spectrum of hydrographic and redox regimes, including continental margin and euxinic (sulphide-containing) settings. Taken together with previously published data from oxic settings, these data indicate that the modern oceanic sink for Cu has a surprisingly homogeneous isotopic composition of about +0.3‰ (δ65Cu, relative to NIST SRM976). We suggest that this signature reflects one of two specific water-column processes: (1) an equilibrium isotope fractionation between soluble, isotopically heavy, Cu complexed to strong organic ligands and an isotopically light pool sorbed to particles that deliver Cu to the sediment, or (2) an equilibrium isotope fractionation between the same isotopically heavy ligand-bound pool and the particle reactive free Cu2+ species, with the latter being scavenged by particulates and thereby delivered to the sediment. An output flux of about +0.3‰ into sediments is isotopically light relative to the known inputs to the ocean (at around +0.6‰) and the seawater value of +0.6 to +0.9‰, suggesting the presence of an as yet unidentified isotopically light source of Cu to the oceans. We hypothesize that this source may be hydrothermal, or may result from the partial dissolution of continentally derived particles.

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

NASA Astrophysics Data System (ADS)

Gaschnig, Richard M.; Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Asael, Dan; Chauvel, Catherine

2017-12-01

Molybdenum isotopes are fractionated by Earth-surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ˜7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ˜7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo-enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB-like end-member and different sedimentary compositions identified in the DSDP cores. The lavas older than ˜7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ˜7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age-equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Fe (hydro) oxide controls Mo isotope fractionation during the weathering of granite

NASA Astrophysics Data System (ADS)

Wang, Zhibing; Ma, Jinlong; Li, Jie; Wei, Gangjian; Zeng, Ti; Li, Lei; Zhang, Le; Deng, Wenfeng; Xie, Luhua; Liu, Zhifeng

2018-04-01

Understanding the fractionation mechanisms of Mo isotopes and seeking the main hosts of light δ98/95Mo during chemical weathering of continental rocks is a prerequisite for constraining heavy δ98/95Mo input into rivers. This study investigates the Mo concentrations and δ98/95Mo values of bulk samples, chemical extractions, and clay fractions of weathering products in a granite weathering profile in Guangdong province, South China, as well as in surrounding stream water. Results from bulk samples show that the τ MoTiO2 values systematically decrease from 59.1% to -77.0%, and δ98/95Mo values systematically increase from -1.46‰ to -0.17‰, upwards in the profile (from 30 to 0 m depth). Atmospheric input has a limited effect on δ98/95Mo variations in the weathering profile. Adsorption and desorption processes of Fe (hydro) oxide are the dominant factors controlling the variations in δ98/95Mo, with light Mo isotopes preferentially adsorbed by Fe (hydro) oxide, and released during desorption process, whereas the incongruent dissolution of primary minerals has little effect. Organic materials and the clay fraction are not the main hosts of light δ98/95Mo, as indicated by the results of chemical extractions, which show that a large proportion (41.5-86.2%) of total Mo with light δ98/95Mo (-1.57‰ to -0.59‰) is associated with Fe (hydro) oxide. Moreover, a significant positive correlation exists between Mo concentrations and δ98/95Mo in the Fe (hydro) oxide extractions from bulk samples. Finally, δ98/95Mo in stream water indicates the release of heavier δ98/95Mo into river water during the chemical weathering of granite rock. The results advance our understanding the mechanisms of Mo isotope fractionation during chemical weathering and its isotopic mass balance in Earth's surface system.

Molybdenum isotope systematics in subduction zones

NASA Astrophysics Data System (ADS)

König, Stephan; Wille, Martin; Voegelin, Andrea; Schoenberg, Ronny

2016-08-01

This study presents Mo isotope data for arc lavas from different subduction zones that range between δ 98 / 95 Mo = - 0.72 and + 0.07 ‰. Heaviest isotope values are observed for the most slab fluid dominated samples. Isotopically lighter signatures are related to increasing relevance of terrigenous sediment subduction and sediment melt components. Our observation complements previous conclusions that an isotopically heavy Mo fluid flux likely mirrors selective incorporation of isotopically light Mo in secondary minerals within the subducting slab. Analogue to this interpretation, low δ 98 / 95 Mo flux that coincides with terrigenous sediment subduction and sediment melting cannot be simply related to a recycled input signature. Instead, breakdown of the controlling secondary minerals during sediment melting may release the light component and lead to decreasing δ 98 / 95 Mo influx into subarc mantle sources. The natural range between slab dehydration and hydrous sediment melting may thus cause a large spread of δ 98 / 95 Mo in global subduction zone magmas.

The Chlorine Isotope Composition of the Solar Nebula & Implications to the Sources of Volatiles to the Terrestrial Planets

NASA Astrophysics Data System (ADS)

Gargano, A. M.; Sharp, Z. D.

2017-12-01

It was originally proposed by Sharp et al., 2016 that the solar nebula was isotopically light based on limited sampling of the Ol-phyric shergottites and two ordinary chondrites (Parnallee LL3.00, and NWA 8276 L3.00). Iron meteorites are remnants of early planetesimals which segregated cores <1Ma after CAI's and have δ37Cl values as low as -7‰, consistent with a light nebular source. Chondrules are relatively younger than iron meteorite parent bodies (2-3Ma after CAI's) and exhibit evidence for mixing with & recycling numerous isotopically distinct precursors as observed by Cl rich chondrules in Semarkona, and Qingzhen. The average δ37Cl values of chondrites are around 0‰, independent of petrologic type or [Cl], suggesting that chondrule forming regions have similar chlorine isotope sources. The average δ37Cl values of chondrites are consistent with a +3 to +6‰ isotopic fractionation of HCl clathrate from HCl gas, which occurred beyond the snow-line at 150K. The recycling of chondritic precursors mixed with HCl clathrate can account for pristine type 3.00 chondrites with δ37Cl values at approximately 0‰ independent of [Cl], or petrologic type. The source of volatiles to the terrestrial planets is commonly assumed to be chondritic in origin. These preliminary chlorine isotope data suggest that early planetesimals and planetary embryos had a solar Cl component at -7‰ or less, and secondary processes has since increased the δ37Cl values of Earth, Mars, and most chondrites. The chlorine isotope system therefore provides a new constraint regarding the sources of volatiles to the terrestrial planets. The δ37Cl value of the bulk Earth is around 0‰, inconsistent with a nebular source as measured in the Martian mantle but similar to that of chondrites with HCl clathrate precursors. The prolonged accretion of heavy chondritic material to Earth can account for the chlorine isotope discrepancy between the Earth and Mars, but is unconstrained by HSE abundances before complete core-mantle differentiation. Here, we examine the amount of chondritic chlorine and water that can added to the Earth allowable by HSE abundances and explore other potential sources of volatiles to the terrestrial planets to account for isotopic and elemental discrepancies.

Intra-seasonal dynamics in metabolic processes of 13C/12C and 18O/16O in components of Scots pine twigs from southern Siberia interpreted with a conceptual framework based on the Carbon Metabolism Oscillatory Model.

PubMed

Voronin, Victor; Ivlev, Alexander A; Oskolkov, Vladimir; Boettger, Tatjana

2012-05-30

Carbon isotope data from conifer trees play an important role in research on the boreal forest carbon reservoir in the global carbon cycle. Carbon isotopes are routinely used to study interactions between the environment and tree growth. Moreover, carbon isotopes became an essential tool for the evaluation of carbon assimilation and transport from needles into reserve pools, as well as the allocation of stored assimilates within a tree. The successful application and interpretation of carbon isotopes rely on the coherence of isotopic fractionation modeling. This study employs a new Carbon Metabolism Oscillatory Model (CMOM) to interpret the experimental data sets on metabolic seasonal dynamics of 13C/12 C and 18O/16O ratios measured in twig components of Scots pine growing in southern Siberia (Russia). The dynamics of carbon isotopic variables were studied in components of Pinus sylvestris L. in light and in dark chambers during the vegetation period from 14 June to 28 July 2006. At the beginning of this period water-soluble organic matter, mostly labile sugars (including sucrose as the main component) and newly formed bulk needle material, displayed relatively "light" δ13C values (depletion in 13 C). Then, 13 C content increased again with noticeable "depletion" events in the middle of the growth period. A gradual 13 C accumulation took place in the second half of the vegetation period. Similar effects were observed both in the light and in the dark with some temporal shifts. Environmental factors did not influence the δ13C values. A gradual 12C-depletion effect was noticed in needles of the previous year. The δ13C values of sucrose and proteins from needle biomass altered independently from each other in the light chamber. A distinct negative correlation between δ13C and δ18O values was revealed for all studied variables. The abrupt 13C depletion recorded by all tested trees for the period from June to July provides clear evidence of the transition from the dominant role of reserve carbohydrate pool (RCP) during the first half of the growth season to the preferable current year carbohydrate pool (CCP) consumption by new needles during its second half. The investigation of the isotopic signatures of Pinus sylvestris L. emphasizes the pivotal role of the intra-seasonal dynamics in carbon metabolism through the transport of assimilates from autotrophic (needles) to heterotrophic (twigs) organs of the studied trees. This provides an explanation for changes of carbon isotopic values observed within the growth season. The CMOM-based results support the hypothesis of the integration of three carbohydrate pools by photosynthesizing cells. The fluctuations of the carbon isotope ratios in different carbohydrate pools underlie various physiological processes in the tree metabolism. The possible mechanisms and pathways of formation of these carbohydrate pools are further discussed. Hence, CMOM provides a reasonable explanation for the absence of the impact of environmental conditions on the needle isotopic variables, the 12C-depletion effects and the use of RCP in needles. The model explains the negative connections between δ13C and δ18O values in all studied variables.

A guide for the laboratory information management system (LIMS) for light stable isotopes--Versions 7 and 8

USGS Publications Warehouse

Coplen, Tyler B.

2000-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program, the Laboratory Information Management System (LIMS) for Light Stable Isotopes, is presented herein. Major benefits of this system include (i) a dramatic improvement in quality assurance, (ii) an increase in laboratory efficiency, (iii) a reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) a decrease in errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for laboratories. LIMS for Light Stable Isotopes is available for both Microsoft Office 97 Professional and Microsoft Office 2000 Professional as versions 7 and 8, respectively. Both source code (mdb file) and precompiled executable files (mde) are available. Numerous improvements have been made for continuous flow isotopic analysis in this version (specifically 7.13 for Microsoft Access 97 and 8.13 for Microsoft Access 2000). It is much easier to import isotopic results from Finnigan ISODAT worksheets, even worksheets on which corrections for amount of sample (linearity corrections) have been added. The capability to determine blank corrections using isotope mass balance from analyses of elemental analyzer samples has been added. It is now possible to calculate and apply drift corrections to isotopic data based on the time of day of analysis. Whereas Finnigan ISODAT software is confined to using only a single peak for calculating delta values, LIMS now enables one to use the mean of two or more reference injections during a continuous flow analysis to calculate delta values. This is useful with Finnigan?s GasBench II online sample preparation system. Concentrations of carbon, nitrogen, and sulfur can be calculated based one or more isotopic reference materials analyzed with a group of samples. Both sample data and isotopic analysis data can now be exported to Excel files. A calculator for determining the amount of sample needed for isotopic analysis based on a previous amount of sample and continuous flow area is now an integral part of LIMS for Light Stable Isotopes. LIMS for Light Stable Isotopes can now assign an error code to Finnigan elemental analyzer analyses in which one of the electrometers has saturated due to analysis of too much sample material, giving rise to incorrect isotopic abundances. Information on downloading this report and downloading code and databases is provided at the Internet addresses: http://water.usgs.gov/software/geochemical.html or http://www.geogr.uni-jena.de/software/geochemical.html in the Eastern Hemisphere.

Isotope and chemical compositions of meteoric and thermal waters and snow from the greater Yellowstone National Park region

USGS Publications Warehouse

Kharaka, Yousif K.; Thordsen, James J.; White, Lloyd D.

2002-01-01

An intensive hydrogeologic investigation, mandated by U.S. Congress and centered on the Norris-Mammoth corridor was conducted by USGS and other scientists during 1988-90 to determine the effects of using thermal water from a private well located in the Corwin Springs Known Geothermal Resources Area, Montana, on the thermal springs of Yellowstone National Park (YNP), especially Mammoth Hot Springs. As part of this investigation, we carried out a detailed study of the isotopic and chemical compositions of meteoric water from cold springs and wells, of thermal water, especially from the Norris-Mammoth corridor and of snow. Additional sampling of meteoric and thermal waters from YNP and surrounding region in northwest Wyoming, southwest Montana and southeast Idaho was carried out in 1991-92 to characterize the distribution of water isotopes in this mountainous region and to determine the origin and possible recharge locations of thermal waters in and adjacent to the Park. The D and 18O values for 40 snow samples range from ?88 to ?178? and ?12.5 to ?23.9?, respectively, and define a well constrained line given by D = 8.2 18O + 14.7 (r2 = 0.99) that is nearly identical to the Global Meteoric Water Line. The D and 18O values of 173 cold water samples range from ?115 to ?153? and ?15.2 to ?20.2?, respectively, and exhibit a similar relationship although with more scatter and with some shift to heavier isotopes, most likely due to evaporation effects. The spatial distribution of cold-water isotopes shows a roughly circular pattern with isotopically lightest waters centered on the mountains and high plateau in the northwest corner of Yellowstone National Park and becoming heavier in all directions. The temperature effect due to altitude is the dominant control on stable water isotopes throughout the region; however, this effect is obscured in narrow 'canyons' and areas of high topographic relief. The effects due to distance (i.e. 'continental') and latitude on water isotopes probably are relatively minor and difficult to resolve from the major controls. The data indicate that the groundwater are derived predominantly from cold, isotopically light winter precipitation, and that the isotope values of groundwater from elevations above about 2.5-3.0 km in the Gallatin and northern Absaroka Ranges are light enough (The D ?149?) to be the presumed recharge water for the hydrothermal system in the Park. However, estimation of the present-day volume of this recharged, isotopically light water indicates that it is not adequate to supply the high (3-4 m3/s) thermal water discharges from YNP, and cooler temperatures at the time of recharge would be required. The volume of meteoric water with D values lighter than ?145? may be adequate for recharging the hydrothermal system, and this may be a more plausible value than the ?149? originally calculated from data that are subject to moderate uncertainties.

Discovering the Importance of Bi-directional Water Fluxes in Leaves

NASA Astrophysics Data System (ADS)

Kayler, Z. E.; Saurer, M.; Siegwolf, R.

2007-12-01

The stable isotope ratio 18O/16O is used for constraining climate change models, partitioning ecosystem water fluxes and for studies of plant ecophysiology. Leaf water enrichment is an essential starting point for each of these applications. In order to obtain a complete picture of the role leaf water plays, not only the 18O values from leaf water but also the signature of transpired water must be accurately predicted for plants under varying environmental conditions. We used a novel chamber approach using highly depleted water (-330 ‰) as a vapor source to leaves of the velvet bean (Mucuna pruriens). We used a Walz gas exchange system consisting of a chamber that is controlled for humidity, light, and temperature. Water and carbon dioxide fluxes were measured by an infrared gas analyzer and chamber vapor was collected in cold traps chilled to - 60°C. Three leaves were collected after 2 hours to insure isotopic steady-state followed by leaf water extraction and isotope analysis. From this experiment we were able to measure the outward flux of soil source water and the inward flux of ambient vapor over a range of environments that varied in relative humidity (80%, 45%, 20%), light (50, 1000 μmolm-2s-1) and CO2 (50, 800 ppm). Leaf water isotopic values were below the source water values reflecting the influx of the labeled vapor. The degree to which leaf water values were depleted was strongly related to the relative humidity. The Craig-Gordon model overestimated depletion of leaf water under high relative humidity and predictions were improved with the Péclet correction. However, our initial analysis indicates that these models may not fully account for stomatal conductance in predicting leaf water isotopic values.

Geochemical and iron isotopic insights into hydrothermal iron oxyhydroxide deposit formation at Loihi Seamount

NASA Astrophysics Data System (ADS)

Rouxel, Olivier; Toner, Brandy; Germain, Yoan; Glazer, Brian

2018-01-01

Low-temperature hydrothermal vents, such as those encountered at Loihi Seamount, harbor abundant microbial communities and provide ideal systems to test hypotheses on biotic versus abiotic formation of hydrous ferric oxide (FeOx) deposits at the seafloor. Hydrothermal activity at Loihi Seamount produces abundant microbial mats associated with rust-colored FeOx deposits and variably encrusted with Mn-oxyhydroxides. Here, we applied Fe isotope systematics together with major and trace element geochemistry to study the formation mechanisms and preservation of such mineralized microbial mats. Iron isotope composition of warm (<60 °C), Fe-rich and H2S-depleted hydrothermal fluids yielded δ56Fe values near +0.1‰, indistinguishable from basalt values. Suspended particles in the vent fluids and FeOx deposits recovered nearby active vents yielded systematically positive δ56Fe values. The enrichment in heavy Fe isotopes between +1.05‰ and +1.43‰ relative to Fe(II) in vent fluids suggest partial oxidation of Fe(II) during mixing of the hydrothermal fluid with seawater. By comparing the results with experimentally determined Fe isotope fractionation factors, we determined that less than 20% of Fe(II) is oxidized within active microbial mats, although this number may reach 80% in aged or less active deposits. These results are consistent with Fe(II) oxidation mediated by microbial processes considering the expected slow kinetics of abiotic Fe oxidation in low oxygen bottom water at Loihi Seamount. In contrast, FeOx deposits recovered at extinct sites have distinctly negative Fe-isotope values down to -1.77‰ together with significant enrichment in Mn and occurrence of negative Ce anomalies. These results are best explained by the near-complete oxidation of an isotopically light Fe(II) source produced during the waning stage of hydrothermal activity under more oxidizing conditions. Light Fe isotope values of FeOx are therefore generated by subsurface precipitation of isotopically heavy Fe-oxides rather than by the activity of dissimilatory Fe reduction in the subsurface. Overall, Fe-isotope compositions of microbial mats at Loihi Seamount display a remarkable range between -1.2‰ and +1.6‰ which indicate that Fe isotope compositions of hydrothermal Fe-oxide precipitates are particularly sensitive to local environmental conditions where they form, and are less sensitive to abiotic versus biotic origins. It follows that FeOx deposits at Loihi Seamount provides important modern analogues for ancient seafloor Fe-rich deposits allowing for testing hypotheses about the biogeochemical cycling of Fe isotopes on early Earth.

USGS48 Puerto Rico precipitation - A new isotopic reference material for δ2H and δ18O measurements of water

USGS Publications Warehouse

Qi, Haiping; Coplen, Tyler B.; Tarbox, Lauren V.; Lorenz, Jennifer M.; Scholl, Martha A.

2014-01-01

A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two isotopic reference waters for daily normalisation of stable hydrogen (δ2H) and stable oxygen (δ18O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The δ2H and δ18O values of this reference water are−2.0±0.4 and−2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ2H and δ18O values of Standard Light Antarctic Precipitation reference water are−428 and−55.5 ‰, respectively. Each uncertainty is an estimated expanded uncertainty (U=2uc) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.

Isotopic fractionation of oxygen and carbon in decomposed lower-mantle inclusions in diamond

DOE PAGES

Kaminsky, Felix; Matzel, Jennifer; Jacobsen, Ben; ...

2015-07-25

Two carbonatitic mineral assemblages, calcite + wollastonite and calcite + monticellite, which are encapsulated in two diamond grains from the Rio Soriso basin in the Juina area, Mato Grosso State, Brazil, were studied utilizing the NanoSIMS technique. The assemblages were formed as the result of the decomposition of the lower-mantle assemblage calcite + CaSi-perovskite + volatile during the course of the diamond ascent under pressure conditions from 15 to less than 0.8 GPa. The oxygen and carbon isotopic compositions of the studied minerals are inhomogeneous. They fractionated during the process of the decomposition of primary minerals to very varying values:more » δ 18O from –3.3 to +15.4 ‰ SMOW and δ 13C from –2.8 to +9.3 ‰ VPDB. As a result, these values significantly extend the mantle values for these elements in both isotopically-light and isotopically-heavy areas.« less

Subducted slab-plume interaction traced by magnesium isotopes in the northern margin of the Tarim Large Igneous Province

NASA Astrophysics Data System (ADS)

Cheng, Zhiguo; Zhang, Zhaochong; Xie, Qiuhong; Hou, Tong; Ke, Shan

2018-05-01

Incorporation of subducted slabs may account for the geochemical and isotopic variations of large igneous provinces (LIPs). However, the mechanism and process by which subducted slabs are involved into magmas is still highly debated. Here, we report a set of high resolution Mg isotopes for a suite of alkaline and Fe-rich rocks (including basalts, mafic-ultramafic layered intrusions, diabase dykes and mantle xenoliths in the kimberlitic rocks) from Tarim Large Igneous Province (TLIP). We observed that δ26 Mg values of basalts range from -0.29 to - 0.45 ‰, -0.31 to - 0.42 ‰ for mafic-ultramafic layered intrusions, -0.28 to - 0.31 ‰ for diabase dykes and -0.29 to - 0.44 ‰ for pyroxenite xenoliths from the kimberlitic rocks, typically lighter than the normal mantle source (- 0.25 ‰ ± 0.04, 2 SD). After carefully precluding other possibilities, we propose that the light Mg isotopic compositions and high FeO contents should be ascribed to the involvement of recycled sedimentary carbonate rocks and pyroxenite/eclogite. Moreover, from basalts, through layered intrusions to diabase dykes, (87Sr/86Sr)i values and δ18OV-SMOW declined, whereas ε (Nd) t and δ26 Mg values increased with progressive partial melting of mantle, indicating that components of carbonate rock and pyroxenite/eclogite in the mantle sources were waning over time. In combination with the previous reported Mg isotopes for carbonatite, nephelinite and kimberlitic rocks in TLIP, two distinct mantle domains are recognized for this province: 1) a lithospheric mantle source for basalts and mafic-ultramafic layered intrusions which were modified by calcite/dolomite and eclogite-derived high-Si melts, as evidenced by enriched Sr-Nd-O and light Mg isotopic compositions; 2) a plume source for carbonatite, nephelinite and kimberlitic rocks which were related to magnesite or periclase/perovskite involvement as reflected by depleted Sr-Nd-O and extremely light Mg isotopes. Ultimately, our study suggests that subducted slabs could make important contributions to LIP generation, and establishes a potential linkage between plate tectonics and mantle plume.

IUPAC Periodic Table of Isotopes for the Educational Community

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holden N. E.; Holden,N.E.; Coplen,T.B.

2012-07-15

John Dalton first proposed the concept of atomic weights of the elements in the first decade of the nineteenth century. These atomic weights of the chemical elements were thought of as constants of nature, similar to the speed of light. Dmitri Mendeleev arranged the atomic weights of the elements in ascending order of value and used the systematic variation of their chemical properties to produce his Periodic Table of the Elements in 1869. Measurement of atomic weight values became an important chemical activity for a century and a half. Theodore Richards received a Noble Prize for his work in thismore » area. In 1913, Fredrick Soddy found a species of radium, which had an atomic weight value of 228, compared to the familiar radium gas value of 226. Soddy coined the term 'isotope' (Greek for 'in the same place') to account for this second atomic weight value in the radium position of the Periodic Table. Both of these isotopes of radium are radioactive. Radioactive isotopes are energetically unstable and will decay (disintegrate) over time. The time it takes for one half of a sample of a given radioactive isotope to decay is the half-life of that isotope. In addition to having different atomic weight values, radium-226 and radium-228 also have different half-life values. Around the same time as Soddy's work, J.J. Thomson (discoverer of the electron) identified two stable (non-radioactive) isotopes of the same element, neon. Over the next 40 years, the majority of the known chemical elements were found to have two or more stable (or long-lived radioactive isotopes that contribute significantly to the determination of the atomic weights of the elements).« less

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.

Forward Modeling of Carbonate Proxy Data from Planktonic Foraminifera using Oxygen Isotope Tracers in a Global Ocean Model

NASA Technical Reports Server (NTRS)

Schmidt, Gavin A.

1999-01-01

The distribution and variation of oxygen isotopes in seawater are calculated using the Goddard Institute for Space Studies global ocean model. Simple ecological models are used to estimate the planktonic foraminiferal abundance as a function of depth, column temperature, season, light intensity, and density stratification. These models are combined to forward model isotopic signals recorded in calcareous ocean sediment. The sensitivity of the results to the changes in foraminiferal ecology, secondary calcification, and dissolution are also examined. Simulated present-day isotopic values for ecology relevant for multiple species compare well with core-top data. Hindcasts of sea surface temperature and salinity are made from time series of the modeled carbonate isotope values as the model climate changes. Paleoclimatic inferences from these carbonate isotope records are strongly affected by erroneous assumptions concerning the covariations of temperature, salinity, and delta (sup 18)O(sub w). Habitat-imposed biases are less important, although errors due to temperature-dependent abundances can be significant.

Geochemical evidence for groundwater behavior in an unconfined aquifer, south Florida

NASA Astrophysics Data System (ADS)

Meyers, Jayson B.; Swart, Peter K.; Meyers', Janet L.

1993-07-01

Five well sites have been investigated along an east-west transect across the surfical aquifer system (SAS) of south Florida. Differences between rainfall during wet seasons (June-October) and evaporation during dry seasons (November-May) give surface waters of this region isotopically light ( δ 18O -22‰ and δ D -7.6‰ ) and heavy ( δ 18O +4.2‰ ) compositions, respectively. Surface waters and shallow groundwaters are enriched in 18O and D to the west, which is consistent with westward decrease in equal excess of rainfall. In the shallow portion of the SAS (less than 20 m, Biscayne sub-aquifer) heterogeneous stable isotopic compositions occur over short spans of time (less than 90 days), reflecting seasonal changes in the isotopic composition of recharge and rapid flushing. Homogeneous stable isotopic compositions occur below the Biscayne sub-aquifer, marking the zone of delayed circulation. Surface evaporation calculated from a stable isotope evaporation model agrees with previously published estimates of 75-95% by physical evaporation measurements and water budget calculations. This model contains many parameters that are assumed to be mean values, but short-term variability in some of these parameters may make this model unsuitable for the application of yearly mean values. For the Everglades, changes in the isotopic composition of atmospheric vapor during the dry season may cause the model to yield anomalous results when annual mean values are used. Chloride-enriched waters (more than 280 mg 1 -1) form a plume emanating from the bottom central portion of the transect. Elevated chloride concentration and light stable isotopic composition ( δ 18O ≈ -2‰ , δ D ≈ -8‰ ) suggest this plume is probably caused not by salinity of residual seawater in the aquifer, but by leakage from the minor artesian water-bearing zone of the Floridan aquifer system. Stable isotope values from Floridan aquifer groundwater plot close to the meteoric water line, in the same area as Everglades rainfall. These Floridan waters are interpreted to have originated in central Florida some 25 000-132 000 years ago, indicating that meteoric conditions in the Florida peninsula have changed little since late Pleistocene time.

Mg isotope fractionation during microbe-mineral interactions

NASA Astrophysics Data System (ADS)

Kim, Insu; Ryu, Jong-sik; Lee, Kwang-sik; Lee, Dongho

2014-05-01

Magnesium is involved in various biogeochemical processes important to the global climate change over geological time-scale. Mg isotopes allow us to directly trace the Mg cycle in the Earth's surface but the factors controlling Mg isotopic compositions have not fully understood yet. Here, we conducted a batch experiment using two bacterial species (Shewanella putrefaciens and Burkholderia fungorum) and three major Mg-bearing minerals (biotite, dolomite and hornblende). All elemental concentrations increased by 336 h and then reached to steady-state values, of which Mg concentrations varied depending on minerals and bacterial species. This result indicates that the mineral dissolution is affect by the presence of microbes, which either provide organic acids or attach onto mineral surface. The Mg isotopic compositions of initial minerals biotite, dolomite and hornblende are -0.35o of biotite, -0.99o of dolomite, and -0.24o of hornblende, in δ26Mg. Similarly, δ26Mg values increased by 336 h and reached to steady-state values, which also varied with minerals and microbes. During dissolution of three minerals, the light isotope of Mg is preferentially incorporated into the dissolved phases and then the dissolved δ26Mg values become consistent with those of minerals with the time.

U-Th-Pb, Rb-Sr, and Sm-Nd isotopic systematics of lunar troctolitic cumulate 76535 - Implications on the age and origin of this early lunar, deep-seated cumulate

NASA Technical Reports Server (NTRS)

Premo, Wayne R.; Tatsumoto, M.

1992-01-01

The U-Th-Pb, Rb-Sr, and Sm-Nd isotopic systematics of four lightly leached residues of pristine, high-Mg, troctolitic cumulate 76535 were analyzed in order to determine their ages and magma sources. The data indicate that the cumulate was in isotopic equilibrium with a fluid or magma characterized by a high U-238/Pb-204 (mu) value of 600 at 4.236 Ga. Two and three stage Pb evolution calculations define even greater source mu values of about 1000, assuming low lunar initial mu values between 5 and 40 prior to about 4.43 Ga. These results are similar to mu values for KREEP sources and are also consistent with values from 78235, suggesting that at least some high-Mg suite rocks were derived from magma sources with high-mu values similar to KREEP, and support that idea that these rocks postdate primary lunar differentiation and formation of ferroan anorthosites.

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits, Cantabria, Spain

NASA Astrophysics Data System (ADS)

Pašava, Jan; Tornos, Fernando; Chrastný, Vladislav

2014-10-01

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ66Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from -0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ34S = +6.6 and stage 2 has δ34S = -0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light 66Zn-depleted signatures with δ66Zn values from -0.80 to -0.01 per mil (mostly between -0.80 and -0.24 per mil) and δ34S values from +10.7 to +15.7 per mil without any relationship between the δ66Zn and δ34S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250-320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH2S > mZn2+ as a result of change in pH, T, and Zn predominant species. The light δ66Zn accompanied by heavy δ34S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ66Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.

Light stable isotope analysis of meteorites by ion microprobe

NASA Technical Reports Server (NTRS)

Mcsween, Harry Y., Jr.

1994-01-01

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

Pleistocene Variations in Delivery and Deposition of Organic Matter Under the Benguela Current Upwelling System - Biomarker Isotopic Evidence From Sediment Light-Dark Color Cycles

NASA Astrophysics Data System (ADS)

Meyers, P. A.; Bouloubassi, I.; Pancost, R. D.; Robinson, R. S.

2007-12-01

The light-dark color cycles that are distinctive features of sediment beneath the Benguela Current Upwelling System imply repetitive alternations in organic matter delivery and deposition. Organic geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in two sediment sequences from ODP Site 1084 corresponding to 0.7 and 1.1 Mya. Concentrations of total organic carbon (TOC) vary between 3.5 and 17.1 wt percent, and those of calcium carbonate fluctuate inversely between 68 and 1 percent, suggesting that carbonate dissolution is involved with the light-dark cycles. Bulk organic del 13C and del 15N values that remain constant across the two light-dark sediment intervals indicate that the extent of nutrient utilization did not change in each cycle. Biomarker compositions in both sequences reflect a range of organic matter sources. Abundant n-alkanes and n-alkanols with odd-over-even and even-over-odd distributions, respectively, record land-plant inputs. Other terrestrial biomakers (e.g triterpenoid acids and alcohols) are present but in very low abundances, suggesting that the n- alkyl components derive predominantly from eolian inputs. Carbon isotopic values of n-alkanes range from -25 to -28 permil, suggesting a mixture of C3 and C4 sources. In contrast, n-alkanol isotopic compositions range from -28 to -34 permil, suggesting that they derive solely from C3 plants. Algal biomarkers are abundant and diverse, represented by 1,15-C30 diols (eustigmatophytes), 4-desmethyl and -methylsterols (diatoms, dinoflagellates), and alkenones (haptophytes). These compounds all have del 13C values ranging from ca. -22 to -24 permil, consistent with a marine origin. Systematic differences in isotopic values imply that marine productivity at 1.1 Mya was higher than at 0.7 Mya, but alkenone-based sea-surface temperatures are higher at 1.1 Mya (21 deg) than at 0.7 Mya (15 deg), which indicates that changes in water-mass properties were also involved.

Fluid sources and metallogenesis in the Blackbird Co-Cu-Au-Bi-Y-REE district, Idaho, U.S.A.: Insights from major-element and boron isotopic compositions of tourmaline

USGS Publications Warehouse

Trumbull, Robert B.; Slack, John F.; Krienitz, M.-S.; Belkin, Harvey E.; Wiedenbeck, M.

2011-01-01

Tourmaline is a widespread mineral in the Mesoproterozoic Blackbird Co–Cu–Au–Bi–Y–REE district, Idaho, where it occurs in both mineralized zones and wallrocks. We report here major-element and B-isotope compositions of tourmaline from stratabound sulfide deposits and their metasedimentary wallrocks, from mineralized and barren pipes of tourmaline breccia, from late barren quartz veins, and from Mesoproterozoic granite. The tourmalines are aluminous, intermediate in the schorl–dravite series, with Fe/(Fe + Mg) values of 0.30 to 0.85, and 10 to 50% X-site vacancies. Compositional zoning is prominent only in tourmaline from breccias and quartz veins; crystal rims are enriched in Mg, Ca and Ti, and depleted in Fe and Al relative to cores. The chemical composition of tourmaline does not correlate with the presence or absence of mineralization. The δ11B values fall into two groups. Isotopically light tourmaline (−21.7 to −7.6‰) occurs in unmineralized samples from wallrocks, late quartz veins and Mesoproterozoic granite, whereas heavy tourmaline (−6.9 to +3.2‰) is spatially associated with mineralization (stratabound and breccia-hosted), and is also found in barren breccia. At an inferred temperature of 300°C, boron in the hydrothermal fluid associated with mineralization had δ11B values of −3 to +7‰. The high end of this range indicates a marine source of the boron. A likely scenario involves leaching of boron principally from marine carbonate beds or B-bearing evaporites in Mesoproterozoic strata of the region. The δ11B values of the isotopically light tourmaline in the sulfide deposits are attributed to recrystallization during Cretaceous metamorphism, superimposed on a light boron component derived from footwall siliciclastic sediments (e.g., marine clays) during Mesoproterozoic mineralization, and possibly a minor component of light boron from a magmatic–hydrothermal fluid. The metal association of Bi–Be–Y–REE in the Blackbird ores suggests some magmatic input, but involvement of granite-derived fluids cannot be conclusively established from the present database.

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.

A multi-proxy isotope study (δ41K, δ26Mg, 87Sr/86Sr) of low-temperature oceanic crust alteration: the Troodos Ophiolite and Ocean Drilling Program Hole 801C

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2017-12-01

Low-temperature alteration of oceanic crust plays an important role in a number of geochemical cycles, thus modulating the chemical composition of the oceans. In particular, it has been established that low-temperature (<150oC) alteration of basalt is a major sink of seawater potassium. However, little is known about the effects of this process on the potassium isotope composition of seawater, which is 0.5‰ enriched relative to bulk silicate Earth (δ41KBSE=-0.54‰). Here we measure a number of isotope systems (δ41K, δ26Mg, 87Sr/86Sr) in both host rock and vein material from the upper volcanic section of Cretaceous (Troodos Ophiolite) and Jurassic (ODP 801C) oceanic crust using a MC-ICP-MS. The goal is to estimate the K isotopic fractionation associated with basalt alteration in low-temperature conditions, and how it might affect the K isotope enrichment of seawater relative to BSE. We find that marine hydrothermal samples from Troodos and ODP site 801C are enriched in potassium relative to the unaltered glass compositions and have δ41K values both higher and lower than BSE, ranging from -0.45‰ to -0.69‰ (n = 9) and -0.32‰ to -0.71‰ (n = 5), respectively. The low measured δ41K values could represent 1) fractionation (α<1) of K isotopes during uptake from seawater (δ41KSW 0‰), or 2) remobilized mantle-sourced K (δ41KBSE=-0.54‰) from deeper within the ophiolite sequence. Measurements of δ26Mg (n=15) and 87Sr/86Sr (n=12) in these samples yield enriched values relative to bulk silicate Earth, suggesting that alteration of oceanic crust likely happened under high water-to-rock ratios in both Troodos and ODP 801C, and that the added potassium is seawater-sourced. We thus suggest that the isotopically light δ41K values measured in both sites are associated with the formation of secondary clays enriched in the 39K isotope. This light isotope enrichment could be intensified if seawater K sourcing is a diffusion-limited process, as aqueous potassium diffusion has been associated with K isotope fractionations between 0.9967 and 0.9984. Our results indicate that the uptake of potassium in altered oceanic crust could be responsible, in part, for the observed K isotope enrichment of seawater relative to bulk silicate Earth.

Segregation of Calcium Isotopes in the Atmospheres of CP Stars as a Consequence of Light-Induced Drift

NASA Astrophysics Data System (ADS)

Parkhomenko, A. I.; Shalagin, A. M.

2018-06-01

A mechanism for the segregation of calcium isotopes in the atmospheres of chemically peculiar (CP) stars due to light-induced drift (LID) of singly charged 48Ca+ ions is discussed. One peculiarity of Ca+ is that an adequate description of the effect of LID requires taking into account several energy levels of Ca+, and thus several pairs of relative differences ( ν i - ν k )/ ν i for the transport frequencies for collisions of levels i and k with neutral atoms (hydrogen, helium). The known real (calculated ab initio) interaction potentials are used to numerically calculate the factors ( ν i - ν k )/ ν i for several states of Ca+ for collisions with H and He atoms. These computations show that, at the temperatures characteristic of the atmospheres of CP stars, T = 6600-12 000 K, fairly high values are obtained for Ca+ ions, ( ν i - ν k )/ ν i ≈ 0.4-0.6. Simple, transparent computations demonstrate that the LID rates of Ca+ ions in the atmospheres of cool CP stars ( T eff = 6600 K) exceed the drift rate due to light pressure by two orders of magnitude. The LID is directed upward in the stellar atmosphere, and the heavy isotope 48Ca is pushed into upper layers of the atmosphere. This can explain the observed predominance of the heavy isotope 48Ca in the upper atmospheric layers of CP stars; according to the radiative-diffusion theory, the action of light pressure alone (in the absence of LID) would lead to sinking of the isotope 48Ca deeper into stellar atmosphere, following the lighter main isotope 40Ca. The 48Ca+ LIDrate decreases and its drift rate due to light pressure increases with growth of the effective temperatures in the atmospheres of CP stars. The manifestations of LID and light pressure are roughly comparable in the atmospheres of CP stars with effective temperatures near T eff = 9500 K.

Nickel distribution and isotopic fractionation in a Brazilian lateritic regolith: Coupling Ni isotopes and Ni K-edge XANES

NASA Astrophysics Data System (ADS)

Ratié, G.; Garnier, J.; Calmels, D.; Vantelon, D.; Guimarães, E.; Monvoisin, G.; Nouet, J.; Ponzevera, E.; Quantin, C.

2018-06-01

Ultramafic (UM) rocks are known to be nickel (Ni) rich and to weather quickly, which makes them a good candidate to look at the Ni isotope systematics during weathering processes at the Earth's surface. The present study aims at identifying the Ni solid speciation and discussing the weathering processes that produce Ni isotope fractionation in two deep laterite profiles under tropical conditions (Barro Alto, Goiás State, Brazil). While phyllosilicates and to a lower extent goethite are the main Ni-bearing phases in the saprolitic part of the profile, iron (Fe) oxides dominate the Ni budget in the lateritic unit. Nickel isotopic composition (δ60Ni values) has been measured in each unit of the regolith, i.e., rock, saprock, saprolite and laterite (n = 52). δ60Ni varies widely within the two laterite profiles, from -0.10 ± 0.05‰ to 1.43 ± 0.05‰, showing that significant Ni isotope fractionation occurs during the weathering of UM rocks. Overall, our results show that during weathering, the solid phase is depleted in heavy Ni isotopes due to the preferential sorption and incorporation of light Ni isotopes into Fe oxides; the same mechanisms likely apply to the incorporation of Ni into phyllosilicates (type 2:1). However, an isotopically heavy Ni pool is observed in the solid phase at the bottom of the saprolitic unit. This feature can be explained by two hypotheses that are not mutually exclusive: (i) a depletion in light Ni isotopes during the first stage of weathering due to the preferential dissolution of light Ni-containing minerals, and (ii) the sorption or incorporation of isotopically heavy Ni carried by percolating waters (groundwater samples have δ60Ni of 2.20 and 2.27‰), that were enriched in heavy Ni isotopes due to successive weathering processes in the overlying soil and laterite units.

Astronaut Bones: Stable Calcium Isotopes in Urine as a Biomarker of Bone Mineral Balance

NASA Astrophysics Data System (ADS)

Skulan, J.; Gordon, G. W.; Romaniello, S. J.; Anbar, A. D.; Smith, S. M.; Zwart, S.

2016-12-01

Bone loss is a common health concern, in conditions ranging from osteoporosis to cancer. Bone loss due to unloading is also an important health issue for astronauts. We demonstrate stable calcium isotopes, a tool developed in geochemistry, are capable of detecting real-time quantitative changes in net bone mineral balance (BMB) using serum and urine [1]. We validated this technique by comparing with DEXA and biomarker data in subjects during bed rest, a ground-based analog of space flight effects [2-4]. We now apply this tool to assess changes in astronauts' BMB before, during and after 4-6 month space missions. There is stable isotope fractionation asymmetry between bone formation and resorption. During bone formation there is a mass-dependent preference for "lighter" calcium isotopes to be removed from serum and incorporated into bone mineral. During bone resorption, there is no measurable isotopic discrimination between serum and bone. Hence, when bone formation rates exceed that of resorption, serum and urine become isotopically "heavy" due to the sequestration of "light" calcium in bone. Conversely, when bone resorption exceeds bone formation, serum and urine become isotopically "light" due to the release of the sequestered light calcium from bone. We measured Ca isotopes in urine of thirty International Space Station astronauts. Average Ca isotope values in astronauts' urine shift isotopically lighter during microgravity, consistent with negative net BMB. Within a month of return to Earth, astronauts returned to within error of their δ44Ca value prior to departure. Urine samples from astronauts testing bone loss countermeasures showed bisphosphonates provide a viable pharmacological countermeasure. Some, but not all, individuals appear able to resist bone loss through diet and intensive resistive exercise alone. This is a promising new technique for monitoring BMB in astronauts, and hopefully someday on the way to/from Mars, this also has important clinical applications for human health and terrestrial medicine [5]. REFERENCES [1] Morgan, J.L. et al (2011) Anal Chem 83, 6956-6962. [2] Skulan, J.L. et al. (2007) Clin Chem 53, 1155-1158. [3] Morgan, J.L. et al (2012) PNAS 109, 9989-9994. [4] Channon, M.B. et al (2015) Bone 77, 69-74. [5] Gordon, G.W. et al (2014) Leukemia 28, 2112-2115.

Titanium Isotopes Link the High 3He/4He Reservoir to Continent Formation

NASA Astrophysics Data System (ADS)

Millet, M. A.; Jackson, M. G.; Dauphas, N.; Burton, K. W.; Williams, H. M.; Kurz, M. D.; Doucelance, R.; Smithies, H.; Champion, D. C.; Nowell, G. M.

2016-12-01

Elevated 3He/4He ratios found in ocean island basalts (OIB) argue for the survival of an early-formed reservoir (>4.5 Ga) in the Earth's mantle [1]. However, its nature remains debated. A characteristic of high 3He/4He OIBs is their anomalous enrichment in Ti abundance relative to elements of similar incompatibility (Sm and Tb). Here we use a new geochemical tool, the stable isotopes of Titanium, to investigate the origin of Ti enrichment of high 3He/4He OIBs. Recent work [2] has shown that Ti isotopes are a powerful tracer of oxide-melt equilibrium in magmatic systems. Results show that primitive OIB samples from localities associated with low 3He/4He ratios (≤15 R/Ra) have δ49Ti values within error of the mantle (δ49Ti=0.005±0.005 [2]) and chondrite values (+0.004±0.010 [3]) regardless of their Ti anomaly (0.93He/4He ratios (>25R/Ra) display δ49Ti values ranging from mantle-like to enriched in light isotopes (up to -0.065‰±0.005) that are negatively correlated with their Ti/Ti* and uncorrelated to indices of magma differentiation. This indicates that i) elevated Ti/Ti* in high 3He/4He OIBs is a mantle source signature and ii) that the high 3He/4He reservoir is enriched in light isotopes of Ti relative to the BSE. This enrichment in light isotopes is balanced by the heavy δ49Ti values and negative Ti/Ti* of Archean Tonalite-Throndhjemite-Granodiorite samples (TTG) from the Pilbara and Yilgarn Craton (+0.20<δ49Ti<+0.40), a proxy for early-formed, juvenile continental crust. Given the chondritic composition of the Earth's mantle and the inability of the typical mantle lithologies to fractionate Ti isotopes, this implies that the Ti enrichment of the high 3He/4He mantle reservoir is linked to the recycling of residues of partial melting events in the presence of rutile (TiO2), a process that drove continent formation in the Archean and possibly earlier. In addition, since these residues cannot display elevated 3He/4He ratios, it requires the Ti-He signature of the high 3He/4He reservoir is due to recycling of entire slab packages. [1] Rizo et al., Science, 2016 [2] Millet et al., EPSL, 2016 [3] Greber et al., LPSC, 2016

Investigating the behaviour of Mg isotopes during the formation of clay minerals

NASA Astrophysics Data System (ADS)

Wimpenny, Joshua; Colla, Christopher A.; Yin, Qing-Zhu; Rustad, James R.; Casey, William H.

2014-03-01

We present elemental and isotopic data detailing how the Mg isotope system behaves in natural and experimentally synthesized clay minerals. We show that the bulk Mg isotopic composition (δ26Mg) of a set of natural illite, montmorillonite and kaolinite spans a 2‰ range, and that their isotopic composition depends strongly on a balance between the relative proportions of structural and exchangeable Mg. After acid leaching, these natural clays become relatively enriched in isotopically heavy Mg by between 0.2‰ and 1.6‰. Results of exchange experiments indicate that the Mg that has adsorbed to interlayer spaces and surface charged sites is relatively enriched in isotopically light Mg compared to the residual clay. The isotopic composition of this exchangeable Mg (-1.49‰ to -2.03‰) is characteristic of the isotopic composition of Mg found in many natural waters. Further experiments with an isotopically characterized MgCl2 solution shows that the clay minerals adsorb this exchangeable Mg with little or no isotopic fractionation, although we cannot discount the possibility that the uptake of exchangeable Mg does so with a slight preference for 24Mg. To characterize the behaviour of Mg isotopes during clay mineral formation we synthesized brucite (Mg(OH)2), which we consider to be a good analogue for the incorporation of Mg into the octahedral sheet of Mg-rich clay minerals or into the brucitic layer of clays such as chlorite. In our experiment the brucite mineral becomes enriched in the heavy isotopes of Mg while the corresponding solution is always relatively enriched in isotopically light Mg. The system reaches a steady state after 10 days with a final fractionation factor (αsolid-solution) of 1.0005 at near-neutral pH. This result is consistent with the general consensus that secondary clay minerals preferentially take up isotopically heavy Mg during their formation. However our results also show that exchangeable Mg is an important component within bulk clay minerals and can have an important influence over the bulk clay δ26Mg value. Modeling shows that in certain soils or sediments where the percentage of exchangeable Mg is >30% and the isotopic composition of the exchangeable Mg is around -2‰, the generation of bulk δ26Mg values of <-0.5‰ is likely. On a broader scale, Mg-rich minerals such as smectite and illite are likely to impart a stronger control over the Mg budget in clay rich sediments, and their high structural Mg component is likely to result in bulk sediment δ26Mg values that are closer in composition to the UCC. Despite this, results of modeling, together with experimental observation suggests that the uptake of exchangeable Mg into these clay rich sediments could cause a decrease in the bulk δ26Mg value by up to ˜0.3-0.4‰. This should be accounted for when assessing the δ26Mg value of sediments on a crustal scale.

Intra-seasonal dynamics in metabolic processes of 13C/12C and 18O/16O in components of Scots pine twigs from southern Siberia interpreted with a conceptual framework based on the Carbon Metabolism Oscillatory Model

PubMed Central

2012-01-01

Background Carbon isotope data from conifer trees play an important role in research on the boreal forest carbon reservoir in the global carbon cycle. Carbon isotopes are routinely used to study interactions between the environment and tree growth. Moreover, carbon isotopes became an essential tool for the evaluation of carbon assimilation and transport from needles into reserve pools, as well as the allocation of stored assimilates within a tree. The successful application and interpretation of carbon isotopes rely on the coherence of isotopic fractionation modeling. This study employs a new Carbon Metabolism Oscillatory Model (CMOM) to interpret the experimental data sets on metabolic seasonal dynamics of 13C/12 C and 18O/16O ratios measured in twig components of Scots pine growing in southern Siberia (Russia). Results The dynamics of carbon isotopic variables were studied in components of Pinus sylvestris L. in light and in dark chambers during the vegetation period from 14 June to 28 July 2006. At the beginning of this period water-soluble organic matter, mostly labile sugars (including sucrose as the main component) and newly formed bulk needle material, displayed relatively “light” δ13C values (depletion in 13 C). Then, 13 C content increased again with noticeable “depletion” events in the middle of the growth period. A gradual 13 C accumulation took place in the second half of the vegetation period. Similar effects were observed both in the light and in the dark with some temporal shifts. Environmental factors did not influence the δ13C values. A gradual 12C-depletion effect was noticed in needles of the previous year. The δ13C values of sucrose and proteins from needle biomass altered independently from each other in the light chamber. A distinct negative correlation between δ13C and δ18O values was revealed for all studied variables. Conclusions The abrupt 13C depletion recorded by all tested trees for the period from June to July provides clear evidence of the transition from the dominant role of reserve carbohydrate pool (RCP) during the first half of the growth season to the preferable current year carbohydrate pool (CCP) consumption by new needles during its second half. The investigation of the isotopic signatures of Pinus sylvestris L. emphasizes the pivotal role of the intra-seasonal dynamics in carbon metabolism through the transport of assimilates from autotrophic (needles) to heterotrophic (twigs) organs of the studied trees. This provides an explanation for changes of carbon isotopic values observed within the growth season. The CMOM-based results support the hypothesis of the integration of three carbohydrate pools by photosynthesizing cells. The fluctuations of the carbon isotope ratios in different carbohydrate pools underlie various physiological processes in the tree metabolism. The possible mechanisms and pathways of formation of these carbohydrate pools are further discussed. Hence, CMOM provides a reasonable explanation for the absence of the impact of environmental conditions on the needle isotopic variables, the 12C-depletion effects and the use of RCP in needles. The model explains the negative connections between δ13C and δ18O values in all studied variables. PMID:22646756

Cr isotope stratigraphy of Ediacaran cap dolostones, Doushantuo Formation, South China

NASA Astrophysics Data System (ADS)

Rodler, Alexandra; Hohl, Simon V.; Guo, Qingjun; Frei, Robert

2016-04-01

The Yangtze Platform in South China is considered a key site for studying Neoproterozoic ocean oxygenation. The chromium isotope composition (δ53Cr) of marine carbonates has shown to be a sensitive tracer of changing (paleo)redox conditions and was previously linked to photosynthetic activity (1). We applied this emerging proxy to cap dolostones of a deep water and a shallow marine carbonate section pertaining to the Doushantuo Formation that have previously been used to constrain the redox evolution of Ediacaran seawater (2,3). Postglacial detrital contamination and diagenetic alteration appear to have influenced the δ53Cr values of Doushantuo cap dolostones as evidenced by systematic changes in δ53Cr and Cr concentrations coupled with several geochemical tracers. We use Al concentrations as indicator of detrital contamination and to calculate the authigenic Cr isotope composition. Further, we hypothesis that post-depositional remobilization of Cr might have resulted in the loss of heavy Cr isotopes and the retention of light Cr isotopes during precipitation of secondary carbonates. This scenario is supported by a decrease in δ53Cr values that is correlated with a loss of Sr and increasingly light δ18Ocarb signals, which would indicate meteoric fluid/rock interaction and diagenetic alteration by continental basin fluids. However, some cap dolostones may still show pristine Ediacaran seawater signals with positively fractionated δ53Cr (relative to bulk silicate Earth; 4), 87Sr/86Sr close to Ediacaran seawater values and a pronounced negative Ce anomaly. These tracers reveal light pulses of enhanced postglacial oxidative weathering during cap dolostone deposition. The Cr isotope composition of Ediacaran cap dolostones pertaining to the Doushantuo Formation trace changes in past redox conditions, where fine-scale δ53Cr fluctuations are perhaps a result of detrital contamination and diagenetic alteration balanced against a signal of oxidative weathering. Although, a careful assessment of detrital contamination and diagenetic alteration is necessary, we propose that using the stable Cr isotope system can provide valuable information and further enhance our understanding of Neoproterozoic ocean oxygenation, past weathering regimes as well as past climate and environmental changes. References: (1) Frei et al. (2011) EPSL 312, 114-125. (2) Guo et al. (2007) Palaeogeogr. Palaeoclimatol. Palaeoecol. 254, 140-157. (3) Hohl et al. (2015) GCA 163, 262-278. (4) Schoenberg et al. (2008) Chem. Geology 249, 294-306.

Sea surface salinity of the Eocene Arctic Azolla event using innovative isotope modeling

NASA Astrophysics Data System (ADS)

Speelman, E. N.; Sewall, J. O.; Noone, D.; Huber, M.; Sinninghe Damste, J. S.; Reichart, G. J.

2009-04-01

With the realization that the Eocene Arctic Ocean was covered with enormous quantities of the free floating freshwater fern Azolla, new questions regarding Eocene conditions facilitating these blooms arose. Our present research focuses on constraining the actual salinity of, and water sources for, the Eocene Arctic basin through the application of stable water isotope tracers. Precipitation pathways potentially strongly affect the final isotopic composition of water entering the Arctic Basin. Therefore we use the Community Atmosphere Model (CAM3), developed by NCAR, combined with a recently developed integrated isotope tracer code to reconstruct the isotopic composition of global Eocene precipitation and run-off patterns. We further addressed the sensitivity of the modeled hydrological cycle to changes in boundary conditions, such as pCO2, sea surface temperatures (SSTs) and sea ice formation. In this way it is possible to assess the effect of uncertainties in proxy estimates of these parameters. Overall, results of all runs with Eocene boundary conditions, including Eocene topography, bathymetry, vegetation patterns, TEX86 derived SSTs and pCO2 estimates, show the presence of an intensified hydrological cycle with precipitation exceeding evaporation in the Arctic region. Enriched, precipitation weighted, isotopic values of around -120‰ are reported for the Arctic region. Combining new results obtained from compound specific isotope analyses (δD) on terrestrially derived n-alkanes extracted from Eocene sediments, and model outcomes make it possible to verify climate reconstructions for the middle Eocene Arctic. Furthermore, recently, characteristic long-chain mid-chain ω20 hydroxy wax constituents of Azolla were found in ACEX sediments. δD values of these C32 - C36 diols provide insight into the isotopic composition of the Eocene Arctic surface water. As the isotopic signature of the runoff entering the Arctic is modelled, and the final isotopic composition of the surface waters can be deduced from the isotopic composition of the diols, we can calculate the degree of mixing between freshwater (isotopically light) and seawater (isotopically heavy) in the surface waters. This way we quantify Eocene Arctic surface water salinity, which in turn will shed light on the degree of (seasonal) mixing and stratification.

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.

Depletion of 13C in Cretaceous marine organic matter: Source, diagenetic, or environmental sigal?

USGS Publications Warehouse

Dean, W.E.; Arthur, M.A.; Claypool, G.E.

1986-01-01

Geochemical studies of Cretaceous strata rich in organic carbon (OC) from Deep Sea Drilling Project (DSDP) sites and several land sections reveal several consistent relationships among amount of OC, hydrocarbon generating potential of kerogen (measured by pyrolysis as the hydrogen index, HI), and the isotopic composition of the OC. First, there is a positive correlation between HI and OC in strata that contain more than about 1% OC. Second, percent OC and HI often are negatively correlated with carbon isotopic composition (?? 13C) of kerogen. The relationship between HI and OC indicates that as the amount of organic matter increases, this organic matter tends to be more lipid rich reflecting the marine source of the organic matter. Cretaceous samples that contain predominantly marine organic matter tend to be isotopically lighter than those that contain predominantly terrestrial organic matter. Average ?? 13C values for organic matter from most Cretaceous sites are between -26 and -28???, and values heavier than about -25??? occur at very few sites. Most of the ?? 13C values of Miocene to Holocene OC-rich strata and modern marine plankton are between -16 to -23???. Values of ??13C of modern terrestrial organic matter are mostly between -23 and -33???. The depletion of terrestial OC in 13C relative to marine planktonic OC is the basis for numerous statements in the literature that isotopically light Cretaceous organic matter is of terrestrial origin, even though other organic geochemical and(or) optical indicators show that the organic matter is mainly of marine origin. A difference of about 5??? in ?? 13C between modern and Cretaceous OC-rich marine strata suggests either that Cretaceous marine planktonic organic matter had the same isotopic signature as modern marine plankton and that signature has been changed by diagenesis, or that OC derived from Cretaceous marine plankton was isotopically lighter by about 5??? relative to modern plankton OC. Diagenesis does not produce a significant shift in ?? 13C in Miocene to Holocene sediments, and therefore probably did not produce the isotopically light Cretaceous OC. This means that Cretaceous marine plankton must have had ?? 13C values that were about 5??? lighter than modern marine plankton, and at least several per mil lighter than Cretaceous terrestrial vegetation. The reason for these lighter values, however, is not obvious. It has been proposed that concentrations of CO2 were higher during the middle Cretaceous, and this more available CO2 may be responsible for the lighter ?? 13C values of Cretaceous marine organic matter. ?? 1986.

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--preliminary study on TATP and PETN.

PubMed

Benson, Sarah J; Lennard, Christopher J; Maynard, Philip; Hill, David M; Andrew, Anita S; Roux, Claude

2009-06-01

The application of isotopic techniques to investigations requiring the provision of evidence to a Court is limited. The objective of this research was to investigate the application of light stable isotopes and isotope ratio mass spectrometry (IRMS) to solve complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. Due to the current threat of organic peroxide explosives, such as triacetone triperoxide (TATP), research was undertaken to determine the potential of IRMS to differentiate samples of TATP that had been manufactured utilising different starting materials and/or manufacturing processes. In addition, due to the prevalence of pentaerythritoltetranitrate (PETN) in detonators, detonating cord, and boosters, the potential of the IRMS technique to differentiate PETN samples from different sources was also investigated. Carbon isotope values were measured in fourteen TATP samples, with three definite groups appearing in the initial sample set based on the carbon data alone. Four additional TATP samples (in a second set of samples) were distinguishable utilising the carbon and hydrogen isotopic compositions individually, and also in combination with the oxygen isotope values. The 3D plot of the carbon, oxygen and hydrogen data demonstrated the clear discrimination of the four samples of TATP. The carbon and nitrogen isotope values measured from fifteen PETN samples, allowed samples from different sources to be readily discriminated. This paper demonstrates the successful application of IRMS to the analysis of explosives of forensic interest to assist in discriminating samples from different sources. This research represents a preliminary evaluation of the IRMS technique for the measurement of stable isotope values in TATP and PETN samples, and supports the dedication of resources for a full evaluation of this application in order to achieve Court reportable IRMS results.

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 the known flux of micrometeorites to the lunar surface and a published estimate that micrometeorites generate 10 times their own mass of vapor, predicts heavy-isotope enrichments comparable to those observed in soils but only if the regolith gardening rate is set at about one twentieth of the generally accepted value of 1 cm/My. This discrepancy may reflect the difference in the time constants for micrometeorite milling and decimeter-scale gardening, or the importance of sputtering.

Precambrian tholeiitic-dacitic rock-suites and Cambrian ultramafic rocks in the Pennine nappe system of the Alps: Evidence from Sm-Nd isotopes and rare earth elements

USGS Publications Warehouse

Stille, P.; Tatsumoto, M.

1985-01-01

Major element, trace element and Sm-Nd isotope analyses were made of polymetamorphic hornblendefelses, plagioclase amphibolites and banded amphibolites from the Berisal complex in the Simplon area (Italy, Switzerland) to determine their age, origin and genetic relationships. In light of major and rare earth element data, the hornblendefelses are inferred to have originally been pyroxene-rich cumulates, the plagioclase amphibolites and the dark layers of the banded amphibolites to have been tholeiitic basalts and the light layers dacites. The Sm-Nd isotope data yield isochron ages of 475??81 Ma for the hornblendefelses, 1,018??59 Ma for the plagioclase amphibolites and 1,071??43 Ma for the banded amphibolites. The 1 Ga magmatic event is the oldest one ever found in the crystalline basement of the Pennine nappes. The Sm -Nd isotope data support the consanguinity of the tholeiitic dark layers and the dacitic light layers of the banded amphibolites with the tholeiitic plagioclase amphibolites and the ultramafic hornblendefelses. The initial e{open}Nd values indicate that all three rock types originated from sources depleted in light rare earth elements. We suggest that plagioclase and banded amphibolites were a Proterozoic tholeiite-dacite sequence that was strongly deformed and flattened during subsequent folding. The hornblendefelses are thought to be Cambrian intrusions of pyroxene-rich material. ?? 1985 Springer-Verlag.

Precambrian tholeiitic-dacitic rock-suites and Cambrian ultramafic rocks in the Pennine nappe system of the Alps: Evidence from Sm-Nd isotopes and rare earth elements

NASA Astrophysics Data System (ADS)

Stille, P.; Tatsumoto, M.

1985-04-01

Major element, trace element and Sm-Nd isotope analyses were made of polymetamorphic hornblendefelses, plagioclase amphibolites and banded amphibolites from the Berisal complex in the Simplon area (Italy, Switzerland) to determine their age, origin and genetic relationships. In light of major and rare earth element data, the hornblendefelses are inferred to have originally been pyroxene-rich cumulates, the plagioclase amphibolites and the dark layers of the banded amphibolites to have been tholeiitic basalts and the light layers dacites. The Sm-Nd isotope data yield isochron ages of 475±81 Ma for the hornblendefelses, 1,018±59 Ma for the plagioclase amphibolites and 1,071±43 Ma for the banded amphibolites. The 1 Ga magmatic event is the oldest one ever found in the crystalline basement of the Pennine nappes. The Sm -Nd isotope data support the consanguinity of the tholeiitic dark layers and the dacitic light layers of the banded amphibolites with the tholeiitic plagioclase amphibolites and the ultramafic hornblendefelses. The initial ɛ Nd values indicate that all three rock types originated from sources depleted in light rare earth elements. We suggest that plagioclase and banded amphibolites were a Proterozoic tholeiite-dacite sequence that was strongly deformed and flattened during subsequent folding. The hornblendefelses are thought to be Cambrian intrusions of pyroxene-rich material.

Fractionation of lithium isotopes in magmatic systems as a natural consequence of cooling

NASA Astrophysics Data System (ADS)

Gallagher, Kerry; Elliott, Tim

2009-02-01

High-temperature, diffusive fractionation has been invoked to account for striking Li isotopic variability recently observed within individual phenocrysts and xenolith minerals. It has been argued that chemical potential gradients required to drive such diffusion arise from changes in Li partitioning between coexisting phases during cooling. If so, Li isotopic zoning should be a common occurrence but the role of temperature-dependent partition coefficients in generating Li isotopic variability remains to be tested in a quantitative manner. Here we consider a basic scenario of a phenocryst in a cooling lava, using simple parameterisations of the temperature dependence of Li partitioning and diffusivity in clinopyroxene. Our model initially produces an asymmetric isotope profile across the crystal with a δ7Li minimum that remains close to the edge of a crystal. Such a distinctive shape mimics Li isotopic profiles documented in some olivine and clinopyroxene phenocrysts, which have isotopically normal cores but anomalously light rims. The temperature dependence of both the diffusivity and the partition coefficient of Li are key factors in generating this form of diffusion profile. Continued diffusion leads to an inversion in the sense of isotopic change between core and rim and results in the whole phenocryst attaining markedly light isotopic values. Our calculations show that significant Li isotopic zoning can occur as a natural consequence of cooling magmatic systems. Crystals that have experienced more complex thermal histories (e.g. re-entrained cumulates versus true phenocrysts) will therefore exhibit contrasting isotopic profiles and, as such, these data may be useful for tracing sub-volcanic processes.

Effect of cancellation in neutrinoless double beta decay

NASA Astrophysics Data System (ADS)

Mitra, Manimala; Pascoli, Silvia; Wong, Steven

2014-11-01

In light of recent experimental results, we carefully analyze the effects of interference in neutrinoless double beta decay, when more than one mechanism is operative. If a complete cancellation is at work, the half-life of the corresponding isotope is infinite, and any constraint on it will automatically be satisfied. We analyze this possibility in detail assuming a cancellation in Xe 136 , and find its implications on the half-life of other isotopes, such as Ge 76 . For definiteness, we consider the role of light and heavy sterile neutrinos. In this case, the effective Majorana mass parameter can be redefined to take into account all contributions, and its value gets suppressed. Hence, larger values of neutrino masses are required for the same half-life. The canonical light neutrino contribution cannot saturate the present limits of half-lives or the positive claim of observation of neutrinoless double beta decay, once the stringent bounds from cosmology are taken into account. For the case of cancellation, where all the sterile neutrinos are heavy, the tension between the results from neutrinoless double beta decay and cosmology becomes more severe. We show that the inclusion of light sterile neutrinos in this setup can resolve this issue. Using the recent results from GERDA, we derive upper limits on the active-sterile mixing angles and compare them with the case of no cancellation. The required values of the mixing angles become larger, if a cancellation is at work. A direct test of destructive interference in Xe 136 is provided by the observation of this process in other isotopes, and we study in detail the correlation between their half-lives. Finally, we discuss the model realizations which can accommodate light and heavy sterile neutrinos and the cancellation. We show that sterile neutrinos of few hundred MeV or GeV mass range, coming from an Extended seesaw framework or a further extension, can satisfy the required cancellation.

Microbial production of isotopically light iron(II) in a modern chemically precipitated sediment and implications for isotopic variations in ancient rocks

USGS Publications Warehouse

Tangalos, G.E.; Beard, B.L.; Johnson, C.M.; Alpers, Charles N.; Shelobolina, E.S.; Xu, H.; Konishi, H.; Roden, E.E.

2012-01-01

The inventories and Fe isotope composition of aqueous Fe(II) and solid-phase Fe compounds were quantified in neutral-pH, chemically precipitated sediments downstream of the Iron Mountain acid mine drainage site in northern California, USA. The sediments contain high concentrations of amorphous Fe(III) oxyhydroxides [Fe(III)am] that allow dissimilatory iron reduction (DIR) to predominate over Fe–S interactions in Fe redox transformation, as indicated by the very low abundance of Cr(II)-extractable reduced inorganic sulfur compared with dilute HCl-extractable Fe. δ56Fe values for bulk HCl- and HF-extractable Fe were ≈ 0. These near-zero bulk δ56Fe values, together with the very low abundance of dissolved Fe in the overlying water column, suggest that the pyrite Fe source had near-zero δ56Fe values, and that complete oxidation of Fe(II) took place prior to deposition of the Fe(III) oxide-rich sediment. Sediment core analyses and incubation experiments demonstrated the production of millimolar quantities of isotopically light (δ56Fe ≈ -1.5 to -0.5‰) aqueous Fe(II) coupled to partial reduction of Fe(III)am by DIR. Trends in the Fe isotope composition of solid-associated Fe(II) and residual Fe(III)am are consistent with experiments with synthetic Fe(III) oxides, and collectively suggest an equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)am of approximately -2‰. These Fe(III) oxide-rich sediments provide a model for early diagenetic processes that are likely to have taken place in Archean and Paleoproterozoic marine sediments that served as precursors for banded iron formations. Our results suggest pathways whereby DIR could have led to the formation of large quantities of low-δ56Fe minerals during BIF genesis.

Tracing alteration of mantle peridotite in the Samail ophiolite using Mg isotopes

NASA Astrophysics Data System (ADS)

de Obeso, J. C.; Kelemen, P. B.; Higgins, J. A.

2017-12-01

Magnesium is one of the main constituents of mantle peridotite ( 22.8 wt%), which has a homogeneous Mg isotopic composition (d26Mg = -0.25 ± 0.04 ‰ (2 sd) DSM3, Teng et al 2010 GCA). Mg isotopes are used as tracers of continental and oceanic weathering as they exhibit variable degrees of fractionation during alteration depending on the lithology. Here we report some of the first Mg isotopic compositions of the mantle section of the Samail ophiolite in Oman and its alteration products. The mantle section of the ophiolite is composed mainly of depleted harzburgites and dunites with mantle-like d26Mg (-0.25, -0.21 ‰). Mantle peridotite is far from equilibrium in near surface conditions leading to rapid, extensive serpentinization, carbonation and oxidation, as well as other geochemical changes. Our analyzed samples encompass most of the alteration of peridotite products observed in Oman including listvenites (completely carbonated peridotite) near the basal thrust of the ophiolite, massive magnesite veins within peridotite outcrops, and heavily altered harzburgites. Magnesite listvenites have d26Mg slightly below mantle values (-0.33, -0.33‰) while dolomite listvenites are significantly lighter (-1.46, -0.89‰). This suggests that heavy Mg isotopes were removed from the listvenites during ophiolite emplacement. Heavily altered peridotite from Wadi Fins exhibit alteration halos with drastic changes in composition. The most oxidized areas are enriched in Fe and depleted in Mg compared to the cores of the samples. These variations in Mg concentrations are complemented by a shift to heavy Mg isotopic compositions (0.74, 0.86‰), among the heaviest d26Mg values that have been reported in altered peridotite. Potential sinks for light isotopes removed from such alteration zones are massive magnesite veins with very light compositions (-3.39, -3.14‰). The fractionation of Mg isotopes observed in the mantle section of the ophiolite spans more than 50% of the known terrestrial fractionation.

Calcium Isotopic Compositions of Normal Mid-Ocean Ridge Basalts From the Southern Juan de Fuca Ridge

NASA Astrophysics Data System (ADS)

Zhu, Hongli; Liu, Fang; Li, Xin; Wang, Guiqin; Zhang, Zhaofeng; Sun, Weidong

2018-02-01

Mantle peridotites show that Ca is isotopically heterogeneous in Earth's mantle, but the mechanism for such heterogeneity remains obscure. To investigate the effect of partial melting on Ca isotopic fractionation and the mechanism for Ca isotopic heterogeneity in the mantle, we report high-precision Ca isotopic compositions of the normal Mid-Ocean Ridge Basalts (N-MORB) from the southern Juan de Fuca Ridge. δ44/40Ca of these N-MORB samples display a small variation ranging from 0.75 ± 0.05 to 0.86 ± 0.03‰ (relative to NIST SRM 915a, a standard reference material produced by the National Institute of Standards and Technology), which are slightly lower than the estimated Upper Mantle value of 1.05 ± 0.04‰ and the Bulk Silicate Earth (BSE) value of 0.94 ± 0.05‰. This phenomenon cannot be explained by fractional crystallization, because olivine and orthopyroxene fractional crystallization has limited influence on δ44/40Ca of N-MORB due to their low CaO contents, while plagioclase fractional crystallization cannot lead to light Ca isotopic compositions of the residue magma. Instead, the lower δ44/40Ca of N-MORB samples compared to their mantle source is most likely caused by partial melting. The offset in δ44/40Ca between N-MORB and BSE indicates that at least 0.1-0.2‰ fractionation would occur during partial melting and light Ca isotopes are preferred to be enriched in magma melt, which is in accordance with the fact that δ44/40Ca of melt-depleted peridotites are higher than fertile peridotites in literature. Therefore, partial melting is an important process that can decrease δ44/40Ca in basalts and induce Ca isotopic heterogeneity in Earth's mantle.

Stable carbon isotope signals in particulate organic and inorganic carbon of coccolithophores - A numerical model study for Emiliania huxleyi.

PubMed

Holtz, Lena-Maria; Wolf-Gladrow, Dieter; Thoms, Silke

2017-05-07

A recent numerical cell model, which explains observed light and carbonate system effects on particulate organic and inorganic carbon (POC and PIC) production rates under the assumption of internal pH homeostasis, is extended for stable carbon isotopes ( 12 C, 13 C). Aim of the present study is to mechanistically understand the stable carbon isotopic fractionation signal (ε) in POC and PIC and furthermore the vital effect(s) included in measured ε PIC values. The virtual cell is divided into four compartments, for each of which the 12 C as well as the 13 C carbonate system kinetics are implemented. The compartments are connected to each other via trans-membrane fluxes. In contrast to existing carbon fractionation models, the presented model calculates the disequilibrium state for both carbonate systems and for each compartment. It furthermore calculates POC and PIC production rates as well as ε POC and ε PIC as a function of given light conditions and the compositions of the external carbonate system. Measured POC and PIC production rates as well as ε PIC values are reproduced well by the model (comparison with literature data). The observed light effect on ε POC (increase of ε POC with increasing light intensities), however, is not reproduced by the basic model set-up, which is solely based on RubisCO fractionation. When extending the latter set-up by assuming that biological fractionation includes further carbon fractionation steps besides the one of RubisCO, the observed light effect on ε POC is also reproduced. By means of the extended model version, four different vital effects that superimpose each other in a real cell can be detected. Finally, we discuss potential limitations of the ε PIC proxy. Copyright © 2017 Elsevier Ltd. All rights reserved.

Colloquium: Laser probing of neutron-rich nuclei in light atoms

NASA Astrophysics Data System (ADS)

Lu, Z.-T.; Mueller, P.; Drake, G. W. F.; Nörtershäuser, W.; Pieper, Steven C.; Yan, Z.-C.

2013-10-01

The neutron-rich He6 and He8 isotopes exhibit an exotic nuclear structure that consists of a tightly bound He4-like core with additional neutrons orbiting at a relatively large distance, forming a halo. Recent experimental efforts have succeeded in laser trapping and cooling these short-lived, rare helium atoms and have measured the atomic isotope shifts along the He4-He6-He8 chain by performing laser spectroscopy on individual trapped atoms. Meanwhile, the few-electron atomic structure theory, including relativistic and QED corrections, has reached a comparable degree of accuracy in the calculation of the isotope shifts. In parallel efforts, also by measuring atomic isotope shifts, the nuclear charge radii of lithium and beryllium isotopes have been studied. The techniques employed were resonance ionization spectroscopy on neutral, thermal lithium atoms and collinear laser spectroscopy on beryllium ions. Combining advances in both atomic theory and laser spectroscopy, the charge radii of these light halo nuclei have now been determined for the first time independent of nuclear structure models. The results are compared with the values predicted by a number of nuclear structure calculations and are used to guide our understanding of the nuclear forces in the extremely neutron-rich environment.

Isotopic Enrichment of Boron in the Sputtering of Boron Nitride with Xenon Ions

NASA Technical Reports Server (NTRS)

Ray, P. K.; Shutthanandan, V.

1998-01-01

An experimental study is described to measure the isotopic enrichment of boron. Xenon ions from 100 eV to 1.5 keV were used to sputter a boron nitride target. An ion gun was used to generate the ion beam. The ion current density at the target surface was approximately 30 microA/sq cm. Xenon ions impinged on the target surface at 50 deg angle to the surface normal. Since boron nitride is an insulator, a flood electron gun was used in our experiments to neutralize the positive charge buildup on the target surface. The sputtered secondary ions of boron were detected by a quadrupole mass spectrometer. The spectrometer entrance aperture was located perpendicular to the ion beam direction and 10 mm away from the target surface. The secondary ion flux was observed to be enriched in the heavy isotopes at lower ion energies. The proportion of heavy isotopes in the sputtered secondary ion flux was found to decrease with increasing primary ion energy from 100 to 350 eV. Beyond 350 eV, light isotopes were sputtered preferentially. The light isotope enrichment factor was observed to reach an asymptotic value of 1.27 at 1.5 keV. This trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Continuously increasing δ98Mo values in Neoarchean black shales and iron formations from the Hamersley Basin

NASA Astrophysics Data System (ADS)

Kurzweil, Florian; Wille, Martin; Schoenberg, Ronny; Taubald, Heinrich; Van Kranendonk, Martin J.

2015-09-01

We present Mo-, C- and O-isotope data from black shales, carbonate- and oxide facies iron formations from the Hamersley Group, Western Australia, that range in age from 2.6 to 2.5 billion years. The data show a continuous increase from near crustal δ98Mo values of around 0.50‰ for the oldest Marra Mamba and Wittenoom formations towards higher values of up to 1.51‰ for the youngest sample of the Brockman Iron Formation. Thereby, the trend in increasing δ98Mo values is portrayed by both carbonate facies iron formations and black shales. Considering the positive correlation between Mo concentration and total organic carbon, we argue that this uniformity is best explained by molybdate adsorption onto organic matter in carbonate iron formations and scavenging of thiomolybdate onto sulfurized organic matter in black shales. A temporal increase in the seawater δ98Mo over the period 2.6-2.5 Ga is observed assuming an overall low Mo isotope fractionation during both Mo removal processes. Oxide facies iron formations show lowest Mo concentrations, lowest total organic carbon and slightly lower δ98Mo compared to nearly contemporaneous black shales. This may indicate that in iron formation settings with very low organic matter burial rates, the preferential adsorption of light Mo isotopes onto Fe-(oxyhydr)oxides becomes more relevant. A similar Mo-isotope pattern was previously found in contemporaneous black shales and carbonates of the Griqualand West Basin, South Africa. The consistent and concomitant increase in δ98Mo after 2.54 billion years ago suggests a more homogenous distribution of seawater molybdate with uniform isotopic composition in various depositional settings within the Hamersley Basin and the Griqualand West Basin. The modeling of the oceanic Mo inventory in relation to the Mo in- and outflux suggests that the long-term build-up of an isotopically heavy seawater Mo reservoir requires a sedimentary sink for isotopically light Mo. The search for this sink (i.e. adsorption onto Mn-oxides in well oxygenated surface oceans and/or subaerial environments or incomplete thiomolybdate formation in weakly sulfidic settings) remains debated, but its relevance becomes more important closer to the Great Oxidation Event and is probably related to already weakly oxidizing conditions even prior to the 2.5 Ga "whiff of oxygen".

Modified sulfur isotopic compositions of sulfides in the nakhlites and Chassigny

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greenwood, J.P.; Riciputi, L.R.; McSween, H.Y. Jr.

Variable sulfur isotopic ratios of sulfide minerals in the nakhlites and Chassigny have been measured by ion microprobe. The ranges and means of {delta}{sup 34}S values of pyrrhotite and pyrite in nakhlites become more negative in the sequence Nakhla > Governador Valadares > Lafayette. This is also the sequence of increasing degrees of subsolidus re-equilibration, suggesting that {sup 32}S enrichment may be related to the subsolidus thermal history. A chalcopyrite vein cross cutting a pyrrhotite in Nakhla, coupled with chalcopyrite having slightly lighter {delta}{sup 34}S values, suggests that subsolidus fluids may have become isotopically lighter (with respect to sulfur) inmore » Nakhla with time. Pyrite has replaced pyrrhotite in Lafayette, suggesting that {line_integral}O{sub 2} and/or {line_integral}S{sub 2} increased after pyrrhotite crystallization. A model involving subsolidus hydrothermal modification of igneous sulfide minerals (with {delta}{sup 34}S {approximately} 0{degree}) due to late-stage oxidation of fluids provides a reasonable explanation for the sulfur isotopic systematics of the nakhlites and Chassigny. Sulfur isotopic alteration is believed to have occurred during the waning stages of nakhlite magmatism, rather than during a much later low-temperature (<100 C) iddingsite formation event, based on the ineffectiveness of abiogenic sulfur isotopic fractionation below 200 C. Variable mixing of two isotopically different fluids also could have produced the observed fractionations, although an isotopically light reservoir of sulfur is problematic. Other possible mechanisms evaluated to explain the sulfur isotopic values of the sulfide minerals include martial mantle heterogeneity, possible influence of martial biological processes, and magmatic degassing of SO{sub 2}.« less

Tracing mantle processes with Fe isotopes

NASA Astrophysics Data System (ADS)

Weyer, S.; Ionov, D.

2006-12-01

High precision Fe isotope measurements have been performed on various mantle peridotites (fertile lherzolites, harzburgites, metasomatised Fe-enriched rocks) and volcanic rocks (mainly oceanic basalts) from different localities and tectonic settings. Pimitive peridotites (Mg# = 0.894) yield delta56Fe = 0.02 and are significantly lighter than the basalts (average delta56Fe = 0.11). Furthermore, the peridotites display a negative correlation of iron isotopes with Mg#. Taken together, these findings imply that Fe isotopes fractionate during partial melting, with heavy isotopes preferentially entering the melt [1, 2]. A particularly good correlation of the Fe isotope composition and Mg# shown by poorly metasomatised spinel lherzolites of three localities (Horoman, Kamchatka and Lherz) was used to model Fe isotope fractionation during partial melting, resulting in alphamantle-melt = 1.0003. This value implies higher Fe isotope fractionation between residual mantle and mantle-derived melts (i.e. Delta56Femantle-melt = 0.2-0.3) than the observed difference between the peridotites and the basalts in this study. Our data on plagioclase lherzolites from Horoman and spinel lherzolites from other localities indicate that the difference in Fe isotope composition between mantle and basalts may be reduced by partial re-equilibration between the isotopically heavy basalts and the isotopically light depleted lithospheric mantle during melt ascent. Besides partial melting, the Fe isotope composition of mantle peridotites can also be significantly modified by metasomatic events. At two localities (Tok, Siberia and Tariat, Mongolia) Fe isotopes correlates with the Fe concentration of the peridotites, which was increased up to 14.5% FeO by melt percolation. Such processes can be accompanied by chromatographic effects and produce a range of Fe isotope compositions in the percolation columns, from extremely light to heavy (delta56Fe = -0.42 to +0.17). We propose that Fe isotopes can be used as a sensitive tracer to identify such metasomatic processes in the mantle. [1] Weyer et al. (2005) EPSL 240: 251-264 [2] Williams et al. (2005) EPSL 235 : 435-452

Monitoring BTEX degradation by CSIA - chances and challenges

NASA Astrophysics Data System (ADS)

Vogt, Carsten; Dorer, Conrad; Kümmel, Steffen; Bombach, Petra; Fischer, Anko; Richnow, Hans Hermann

2014-05-01

Monitoring is crucial for evaluating the success of any geobiotechnological applications. Compound- specific stable isotope analysis (CSIA) has emerged as a key method for monitoring biogeochemical transformation processes. Isotope compositions of residual reactants may change during the first rate-limiting step in (bio)chemical reactions; measurement of these changes are the basis for CSIA. Caused by differences in the activation energy, light isotopologues often react slightly faster than heavy isotopologues, resulting in enrichment of heavy isotopes at the reactive site in the substrate or of light isotopes in the product. This is termed isotope fractionation. Upon multi-dimensional CSIA (2D-CSIA, 3D-CSIA), the isotope fractionation of two or more different elements within a molecule is determined, allowing highly resolved analyses of degradation processes as masking effects typically occurring in one-dimensional CSIA are cancelled. In the last years, 2D-CSIA making use of the ratio of stable carbon to hydrogen isotopes (13C/12C, 2H/1H), turned out to be an important tool for elucidating the environmental biodegradation pattern of BTEX compounds which are global notorious contaminants. This presentation aims to summarize the current knowledge on 2D-CSIA of BTEX, to point out the prospects and to indicate future perspectives upon monitoring in the field. Degradation experiments for determining carbon and hydrogen isotope fractionation factors were carried out using several pure and mixed cultures performing different BTEX-activating reactions. Various anaerobic key reactions showed pronounced hydrogen isotope fractionation: (i) fumarate addition to the methyl moiety of toluene, xylene isomers and probably ethylbenzene catalyzed by benzylsuccinate synthases, (ii) anaerobic hydroxylation of the ethyl side chain of ethylbenzene catalyzed by ethylbenzene dehydrogenase, and (iii) anaerobic activation of benzene by yet unknown biochemical mechanisms. Due to the high hydrogen isotope fractionation, the ratios of hydrogen vs. carbon isotope fractionation in two-dimensional plots (lambda values, Λ) were generally higher than 10 (in extreme cases > 100). Upon aerobic activation reactions at the aromatic ring catalyzed by mono- or dioxygenases, usually Λ values smaller than 10 were observed due to small, absent or inverse hydrogen isotope fractionation. An exception is the aerobic monooxygenation of methyl or methylene moieties which is linked to large hydrogen and carbon isotope fractionation. Since Λ values are highly indicative for specific transformation reactions, 2D-CSIA has a great potential for evaluating biodegradation processes of BTEX in the environment. Moreover, reactions catalyzed by benzylsuccinate synthases showed partially variable Λ values, indicating slightly different reaction mechanisms of isoenzymes, probably permitting the detection of specific isoenzymes by 2D-CSIA in field applications. In contrast, ethylbenzene dehydrogenase of three tested organisms showed similar, very characteristic isotope fractionation pattern even under different redox conditions. The major goal of future investigations is to use 2D-CSIA at contaminated field sites for elucidating specific degradation pathways. Single data for benzene are promising, demonstrating e.g., anaerobic benzene degradation by 2D-CSIA at a highly contaminated site. Nevertheless, 2D-CSIA field data for BTEX are yet lacking and need to be surveyed for a proper evaluation of the 2D-CSIA concept for BTEX.

Mercury contamination and stable isotopes reveal variability in foraging ecology of generalist California gulls

USGS Publications Warehouse

Peterson, Sarah; Ackerman, Joshua T.; Eagles-Smith, Collin A.

2017-01-01

Environmental contaminants are a concern for animal health, but contaminant exposure can also be used as a tracer of foraging ecology. In particular, mercury (Hg) concentrations are highly variable among aquatic and terrestrial food webs as a result of habitat- and site-specific biogeochemical processes that produce the bioaccumulative form, methylmercury (MeHg). We used stable isotopes and total Hg (THg) concentrations of a generalist consumer, the California gull (Larus californicus), to examine foraging ecology and illustrate the utility of using Hg contamination as an ecological tracer under certain conditions. We identified four main foraging clusters of gulls during pre-breeding and breeding, using a traditional approach based on light stable isotopes. The foraging cluster with the highest δ15N and δ34S values in gulls (cluster 4) had mean blood THg concentrations 614% (pre-breeding) and 250% (breeding) higher than gulls with the lowest isotope values (cluster 1). Using a traditional approach of stable-isotope mixing models, we showed that breeding birds with a higher proportion of garbage in their diet (cluster 2: 63–82% garbage) corresponded to lower THg concentrations and lower δ15N and δ34S values. In contrast, gull clusters with higher THg concentrations, which were more enriched in 15N and 34S isotopes, consumed a higher proportion of more natural, estuarine prey. δ34S values, which change markedly across the terrestrial to marine habitat gradient, were positively correlated with blood THg concentrations in gulls. The linkage we observed between stable isotopes and THg concentrations suggests that Hg contamination can be used as an additional tool for understanding animal foraging across coastal habitat gradients.

Calcium isotope systematics in small upland catchments affected by spruce dieback in the period of extreme acid rain (1970-1990)

NASA Astrophysics Data System (ADS)

Novak, Martin; Farkas, Juraj; Holmden, Chris; Hruska, Jakub; Curik, Jan; Stepanova, Marketa; Prechova, Eva; Veselovsky, Frantisek; Komarek, Arnost

2017-04-01

Recently, new isotope tools have become available to study the behavior of nutrients in stressed ecosystems. In this study, we focus on changes in the abundance ratio of calcium (Ca) isotopes accompanying biogeochemical processes in small forested catchments. We monitored del44Ca values in ecosystem pools and fluxes in four upland sites situated in the Czech Republic, Central Europe. A heavily acidified site in the Eagle Mts. (northern Czech Republic) experienced 13 times higher atmospheric Ca inputs, compared to the other three sites, which were less affected by forest decline. Industrial dust was responsible for the elevated Ca input. Del44Ca values of individual poos/fluxes were used to identify Ca sources for the bioavailable Ca soil reservoir and for runoff. The bedrock of the study sites differed (leucogranite, orthogneiss vs. serpentinite and amphibolite). Across the sites, mean del44Ca values increased in the order: spruce bark < fine roots < needles < soil < bedrock < canopy throughfall < open-area precipitation < runoff < soil water. Plant preferentially took up isotopically light Ca, while residual isotopically heavy Ca was sorbed to soil particles or exported via runoff. Even at sites with a low del44Ca values of bedrock, runoff had a high del44Ca value. At the base-poor site, most runoff came from atmospheric deposition and residual Ca following plant uptake. It appeared that bedrock weathering did not supply enough Ca to replenish the bioavailable Ca pool in the soil. Currently, we are analyzing Ca isotope composition of individual rock-forming minerals to better assess the effect of different weathering rates of minerals with low/high radiogenic 40Ca contents on runoff del44Ca.

Silicon Isotope Geochemistry of Ocean Island Basalts: Search for Deep Mantle Heterogeneities and Evidence for Recycled Altered Oceanic Crust

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.; Moynier, F.

2014-12-01

Analyses of Ocean Island Basalts (OIB) have shown that the Earth's mantle contains isotopically distinct components, but debate about the degree and cause of variability persists. The study of silicon (Si) isotopes in OIBs has the potential to elucidate mantle heterogeneities. Relatively large (~several per mil) Si isotopic fractionation occurs in low-temperature environments during precipitation from dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes [1], but only a limited range (~tenths of a per mil) of Si isotope fractionation has been observed due to high-temperature igneous processes [2]. Therefore, Si isotopes may be useful as tracers for the presence of crustal material in OIB source regions in a manner similar to more conventional stable isotope systems, such as oxygen. Here we present the first comprehensive suite of high-precision Si isotopic data obtained by MC-ICP-MS for a diverse set of OIBs representing the EM-1, EM-2, and HIMU mantle components. In general, the Si isotopic compositions of OIBs analyzed here are agreement with previous estimates for Bulk Silicate Earth (BSE). However, small systematic variations are present; the HIMU end-member Mangaia and HIMU-type Cape Verde island São Nicolau are enriched in the light isotopes of Si (δ30Si = -0.37 ± 0.06‰ and δ30Si = -0.39 ± 0.04‰, respectively; errors are 2sd), with compositions intermediary between Mid Ocean Ridge Basalts and chondritic values. Additionally, Iceland samples from volcanic complexes in the Northern Rift Zone show similar Si isotope compositions (on average, δ30Si = -0.40 ± 0.06‰). In contrast, the δ30Si averages of the EM-1 end-member Pitcairn (-0.28 ± 0.07‰), the EM-2 end-member Samoa (-0.31 ± 0.07‰) and other OIB localities do not show any significant difference from previous estimates for the δ30Si value of BSE [3]. The Si isotopic variability in some HIMU-type and Icelandic OIBs most likely reflects the incorporation of recycled altered oceanic crust in the plume source. However, the sampling of a primitive reservoir enriched in the light isotopes of Si, as suggested by [4], cannot be ruled out as a potential source of Si isotope variations in OIBs. References: [1] Ziegler et al., GCA 2005 [2] Savage et al., GCA 2011 [3] Savage et al., EPSL 2010 [4] Huang et al., GCA 2014

A stable isotope study of fossil mammal remains from the Paglicci cave, Southern Italy. N and C as palaeoenvironmental indicators

NASA Astrophysics Data System (ADS)

Iacumin, P.; Bocherens, H.; Delgado Huertas, A.; Mariotti, A.; Longinelli, A.

1997-04-01

A set of 102 tooth and bone samples of Pleistocene age (32,600-13,300 yr BP) belonging to the species Cervus elaphus, Bos primigenius and Equus caballus and coming from the Paglicci cave (Southern Italy) was studied for the carbon (δ 13C) and nitrogen (δ 15N) isotopic composition of bone and dentine collage and for the carbon (δ 13C c) isotopic composition of tooth enamel carbonate. The amount of collagen extracted from bone and tooth samples (mg/g) was rather variable, representing approximately only 0.5-15% of the collagen present in a fresh bone. However, the loss of an important fraction of the original collagen during diagenesis did not change the in vivo isotopic composition. In general, when the δ 13C of both collagen and carbonate and the δ 15N of collagen obtained from each level for the three species are compared, wild ox shows the most increased values, deer the most decreased values and horse shows intermediate results. These differences are probably related to distinct diets or to differences in their physiological behaviour. However, the isotopic results suggest that the three species considered lived in an open environment with a diet based on C 3 plants. The stratigraphic sequence of light and heavy nitrogen isotope values between 19,000 and 15,000 may be related to shifts from arid to humid conditions, while the overall trend shown by δ 13C toward lighter values may be related to a progressive development of a forest habitat.

Highly Efficient Quantum Sieving in Porous Graphene-like Carbon Nitride for Light Isotopes Separation

NASA Astrophysics Data System (ADS)

Qu, Yuanyuan; Li, Feng; Zhou, Hongcai; Zhao, Mingwen

2016-01-01

Light isotopes separation, such as 3He/4He, H2/D2, H2/T2, etc., is crucial for various advanced technologies including isotope labeling, nuclear weapons, cryogenics and power generation. However, their nearly identical chemical properties made the separation challenging. The low productivity of the present isotopes separation approaches hinders the relevant applications. An efficient membrane with high performance for isotopes separation is quite appealing. Based on first-principles calculations, we theoretically demonstrated that highly efficient light isotopes separation, such as 3He/4He, can be reached in a porous graphene-like carbon nitride material via quantum sieving effect. Under moderate tensile strain, the quantum sieving of the carbon nitride membrane can be effectively tuned in a continuous way, leading to a temperature window with high 3He/4He selectivity and permeance acceptable for efficient isotopes harvest in industrial application. This mechanism also holds for separation of other light isotopes, such as H2/D2, H2/T2. Such tunable quantum sieving opens a promising avenue for light isotopes separation for industrial application.

Paleoclimate Reconstruction at Lamanai, Belize Using Oxygen-Isotope Tropical Dendrochronology

NASA Astrophysics Data System (ADS)

Prentice, A.; Webb, E. A.; White, C. D.; Graham, E.

2009-05-01

Tropical dendrochronology can be complicated because many trees growing in these areas lack distinct visible annual rings. However, the oxygen-isotope composition of wood growing in tropical regions can provide a record of seasonal fluctuations in the amount of precipitation even when visible rings are absent. Variations in the oxygen-isotope compositions of cellulose as the trees grow can be related to the relative timing of wet and dry seasons and used to identify periods of drought. In this study, the oxygen-isotope composition was determined for cellulose extracted from living trees at the site of Lamanai, Belize to assess the variation in oxygen-isotope values that result from heterogeneity within individual tree rings and seasonal fluctuations in amount of precipitation. In temperate regions, the latewood rings that form during periods of reduced growth are traditionally selected for oxygen-isotope analysis of cellulose because their oxygen-isotope compositions are more directly influenced by climate and precipitation during the growing season. However, in tropical isotope dendrochronology, when visible rings are present, detailed sampling of both the light coloured earlywood and the denser latewood is required. At Lamanai, a seasonal signal was evident in the oxygen- isotope composition of the cellulose when tree rings were sectioned in very small increments (approximately every mm), sub-sampling both earlywood and latewood. However, the visible rings did not always correspond with minimum or maximum oxygen-isotope values. As a result, the amplitude of the oxygen-isotope signal obtained by considering only latewood samples is smaller than that obtained from fine-increment sampling. Hence, the oxygen-isotope values of latewood samples alone did not provide accurate data for climate reconstruction. Multiple series of latewood samples extracted from different cross-sections of the same tree did not consistently show the same trends in oxygen isotope values, which can differ by up to 2 permil around the circumference of the same ring. This indicates that even when visible rings are present in tropical trees, the rings may not be annual or continuous. However, the amplitude of variation in the oxygen-isotope values of cellulose from both early and latewood can be related to seasonal signals across the modern tree rings. These signals will be compared to the oxygen-isotope composition of tree ring cellulose extracted from a wood sample excavated from an ancient tomb at the site of Lamanai to assess the preservation of the cellulose- isotope signal in this artefact. If similar oxygen-isotope patterns are preserved in ancient cellulose they can be used as a proxy to determine past climate conditions, such as those experienced by the ancient Maya populations in Belize.

The use of oxygen isotopes of diatom silica in a decadal to centennial palaeonvironmental reconstruction

NASA Astrophysics Data System (ADS)

Hernández, A.; Giralt, S.; Bao, R.; Sáez, A.; Leng, M. J.; Barker, P. A.

2009-04-01

The Lateglacial-early Holocene transition from the Lago Chungará record (northern Chilean Altiplano) is made up of laminated sediments composed by light and dark pluriannual couplets of diatomaceous ooze. Light sediment laminae accumulated during short-term diatom blooms whereas dark sediment laminae represent the baseline limnological conditions during several years of deposition. Diatom oxygen isotope data (_18Odiatom) of dark diatom laminae from Lago Chungará show evidence that the Lateglacial-early Holocene transition (11,990-11,475 cal years BP) occurred in a series of decadal-to-centennial wet-dry oscillations. Dry periods are marked by relatively high isotope values whereas wet episodes are indicated by lower isotope values. This fact is supported by data on allochtonous inputs and water availability curves from Lago Chungará previously published (Giralt et al. 2008). They highlight the sedimentological and environmental processes that occurred during these wet and dry episodes. The delta_18Odiatom record documents at least two episodes of increased effective moisture at a centennial-scale (ca.11,800 and 11,550 cal years BP) and only one important period of increasing aridity (between ca. 11,990 and 11,800 cal years BP). However, up to seven wet episodes and at least six dry events at a decadal scale are superimposed to the normal conditions. The spectral analyses of the delta_18Odiatom values suggest that these changes could be triggered by both El Niño-Southern Oscillation (ENSO) and solar activity. Time-frequency analysis shows that the activity of these two forcings was more intense during Lateglacial than during the onset of the Holocene. This last period could be governed by La Niña-like conditions that correspond to wet conditions over the Andean Altiplano.

Authenticity of rice (Oryza sativa L.) geographical origin based on analysis of C, N, O and S stable isotope ratios: a preliminary case report in Korea, China and Philippine.

PubMed

Chung, Ill-Min; Kim, Jae-Kwang; Prabakaran, Mayakrishnan; Yang, Jin-Hee; Kim, Seung-Hyun

2016-05-01

Although rice (Oryza sativa L.) is the third largest food crop, relatively fewer studies have been reported on rice geographical origin based on light element isotope ratios in comparison with other foods such as wine, beef, juice, oil and milk. Therefore this study tries to discriminate the geographical origin of the same rice cultivars grown in different Asian countries using the analysis of C, N, O and S stable isotope ratios and chemometrics. The δ(15) NAIR , δ(18) OVSMOW and δ(34) SVCDT values of brown rice were more markedly influenced by geographical origin than was the δ(13) CVPDB value. In particular, the combination of δ(18) OVSMOW and δ(34) SVCDT more efficiently discriminated rice geographical origin than did the remaining combinations. Principal component analysis (PCA) revealed a clear discrimination between different rice geographical origins but not between rice genotypes. In particular, the first components of PCA discriminated rice cultivated in the Philippines from rice cultivated in China and Korea. The present findings suggest that analysis of the light element isotope composition combined with chemometrics can be potentially applicable to discriminate rice geographical origin and also may provide a valuable insight into the control of improper or fraudulent labeling regarding the geographical origin of rice worldwide. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Method for isotope separation by photodeflection

DOEpatents

Bernhardt, Anthony F.

1977-01-01

In the method of separating isotopes wherein a desired isotope species is selectively deflected out of a beam of mixed isotopes by irradiating the beam with a directed beam of light of narrowly defined frequency which is selectively absorbed by the desired species, the improvement comprising irradiating the deflected beam with light from other light sources whose frequencies are selected to cause the depopulation of any metastable excited states.

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

NASA Technical Reports Server (NTRS)

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

1985-01-01

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

Oxygen and carbon isotopic growth record in a reef coral from the florida keys and a deep-sea coral from blake plateau

USGS Publications Warehouse

Emiliani, C.; Harold, Hudson J.; Shinn, E.A.; George, R.Y.

1978-01-01

Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.

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.

Ubiquitous radiogenic Os in Miocene to recent basalts from diverse mantle domains beneath the Colorado Plateau, USA

NASA Astrophysics Data System (ADS)

Schlieder, T.; Reid, M. R.; Widom, E.; Blichert-Toft, J.

2015-12-01

The source of magmatism and mechanisms responsible for the observed geochemical signatures in Miocene to Recent Colorado Plateau (CP) basalts has been a renewed focus of investigation in light of Earthscope results. We report new Os and Nd isotopic data for magnesian basalts (Mg#=62-72) and interpret them in light of previously reported Hf isotope data to help constrain contributions from olivine-poor source lithologies and subduction-derived metasomatism in the genesis of recent CP volcanism. The basalts studied span a large range in Hf isotope compositions and represent melts last equilibrated at a variety of depths beneath the Colorado Plateau and its transition zones. We distinguished at least three mantle domains on the basis of paired Hf-Nd isotope, other isotopic, and geochemical characteristics of CP lavas. Domain 1 likely represents a depleted, variably metasomatized, lithospheric source, with relatively radiogenic ɛHf (+5.2 to +11.8) and highly variable ɛNd (-6.2 to +6.2). Domain 2 could represent either ancient or Farallon subduction-modified mantle and is displaced above the Hf-Nd mantle array (ɛHf=+1.0 to +7.3; ɛNd=-6.1 to -3.5). Domain 3 may be melts of pyroxenite/mica-rich veins or layers within lithospheric mantle and is characterized by unradiogenic Hf and Nd (ɛHf=-12.9 to +0.6; ɛNd=-10.0 to -2.9). The isotopic variability in CP-related lavas can largely be attributed to contributions from these mantle domains. Preliminary Os isotope data show no correlation with proxies for differentiation or crustal contamination. Osmium and Hf isotope compositions are negatively correlated between domains 1 and 2 (187Os/188Os=0.31 to 0.59), whereas the Os isotope ratios in two domain 3 basalts have both lower and higher values (187Os/188Os=0.25 and 0.68). Significantly, Os isotope signatures are highly radiogenic (vs. values of <0.12 for SW US peridotite xenoliths [1]), overlapping and extending the range for inferred melts of pyroxene- and mica-rich veins and/or layers [2]. Thus mafic magmatism associated with the CP appears to ubiquitously tap sources at least locally modified by processes such as recycling of ancient oceanic crust, introduction of terrigenous sediments, or subduction-related metasomatism. [1] Lee et al., Nature, 2001. [2] Carlson and Nowell, G-Cubed, 2001.

Carbon and nitrogen isotopic compositions of particulate organic matter and biogeochemical processes in the eutrophic Danshuei Estuary in northern Taiwan.

PubMed

Liu, Kon-Kee; Kao, Shuh-Ji; Wen, Liang-Saw; Chen, Kuan-Lun

2007-08-15

The Danshuei Estuary is distinctive for the relatively short residence time (1-2 d) of its estuarine water and the very high concentration of ammonia, which is the dominant species of dissolved inorganic nitrogen in the estuary, except near the river mouth. These characteristics make the dynamics of nitrogen cycling distinctively different from previously studied estuaries and result in unusual isotopic compositions of particulate nitrogen (PN). The delta(15)N(PN) values ranging from -16.4 per thousand to 3.8 per thousand lie in the lower end of nitrogen isotopic compositions (-16.4 to +18.7 per thousand) of suspended particulate matter observed in estuaries, while the delta(13)C values of particulate organic carbon (POC) and the C/N (organic carbon to nitrogen) ratios showed rather normal ranges from -25.5 per thousand to -19.0 per thousand and from 6.0 to 11.3, respectively. There were three major types of particulate organic matter (POM) in the estuary: natural terrigenous materials consisting mainly of soils and bedrock-derived sediments, anthropogenic wastes and autochthonous materials from the aquatic system. During the typhoon induced flood period in August 2000, the flux-weighted mean of delta(13)C(POC) values was -24.4 per thousand, that of delta(15)N(PN) values was +2.3 per thousand and that of C/N ratio was 9.3. During non-typhoon periods, the concentration-weighted mean was -23.6 per thousand for delta(13)C(POC), -2.6 per thousand for delta(15)N(PN) and 8.0 for C/N ratio. From the distribution of delta(15)N(PN) values of highly polluted estuarine waters, we identified the waste-dominated samples and calculated their mean properties: delta(13)C(POC) value of -23.6+/-0.7 per thousand, delta(15)N(PN) value of -3.0+/-0.1 per thousand and C/N ratio of 8.0+/-1.4. Using a three end-member mixing model based on delta(15)N(PN) values and C/N ratios, we calculated contributions of the three major allochthonous sources of POC, namely, wastes, soils and bedrock-derived sediments, to the estuary. Their contributions were, respectively, 83%, 12% and 5% under non-typhoon conditions, and 9%, 63% and 28% under typhoon conditions. The autochthonous POM had the most varied isotopic compositions, encompassing the full ranges of delta(13)C(POC) (-25.5 to -19.1 per thousand), delta(15)N(PN) (-16.4-3.8 per thousand) and C/N ratio (6.0-11.3). The heavy end of the carbon isotopic composition reflected the typical marine condition and the lower end the estuarine condition, which probably had elevated concentrations of dissolved inorganic carbon with low delta(13)C values due to input from decomposition of organic matter. The lack of isotopically heavy PN, as found in larger estuaries, was attributed to isotopically light starting materials, namely, anthropogenic wastes, the slow phytoplankton growth within the estuary and the rather short residence time; the latter two factors made (15)N enrichment during ammonia consumption very limited. The most isotopically light PN likely originated from phytoplankton incorporating (15)N-depleted nitrate near the river mouth, where ammonia inhibition of nitrate uptake probably stopped.

CNO isotopes in red giant stars

NASA Technical Reports Server (NTRS)

Wannier, P. G.

1985-01-01

The production and distribution of the CNO nuclides is discussed in light of observed abundance ratios in red giants and in the interstellar medium. Isotope abundances have been measured in the atmospheres and in the recent ejecta of cool giants, including carbon stars, S-type stars and red supergiants as well as in oxygen-rich giants making their first ascent of the giant branch. Several of the observations suggest revision of currently accepted nuclear cross-sections and of the mixing processes operating in giant envelopes. By comparing red giant abundances with high-quality observations of the interstellar medium, conclusions are reached about the contribution of intermediate-mass stars to galactic nuclear evolution. The three oxygen isotopes, O-16, -17 and -18, are particularly valuable for such comparison because they reflect three different stages of stellar nucleosynthesis. One remarkable result comes from observations of O-17/O-18 in several classes of red giant stars. The observed range of values for red giants excludes the entire range of values seen in interstellar molecular clouds. Furthermore, both the observations of stars and interstellar clouds exclude the isotopic ratio found in the solar system.

Determination of stable carbon and hydrogen isotopes of light hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dumke, I.; Faber, E.; Poggenburg, J.

1989-10-01

A combined system for the measurement of {sup 13}C/{sup 12}C and D/H ratios on light hydrocarbons (C{sub 1}-C{sub 3}) and CO{sub 2} is described. The system is designed for natural gas and sediment gas analyses. It comprises gas chromatographic separation with online combustion of hydrocarbons to CO{sub 2} and H{sub 2}O, reduction of H{sub 2}O to H{sub 2} on zinc in closed ampules, and mass spectrometric determination of isotope ratios ({delta}{sup 13}C, {delta}D) using a mass spectrometer inlet system especially designed for low hydrogen gas quantities. Isotope analyses can be carried out in the range of 3-10,000 {mu}L of CO{submore » 2} and 100-10,000 {mu}L of H{sub 2} (gas quantities converted from sample compounds during preparation, STP). Including all preparation steps, reproducibility of isotope values for large sample quantities (>100 {mu}L of produced CO{sub 2} and >1,000 {mu}L of produced H{sub 2}). is {plus minus}0.2{per thousand} for {delta}{sup 13}C and {plus minus}3{per thousand} for {delta}D.« less

Investigating differences in light stable isotopes between Thai jasmine rice and Sungyod rice

NASA Astrophysics Data System (ADS)

Kukusamude, C.; Kongsri, S.

2017-10-01

We report the differences in light stable isotopes between two kinds of Thai rice (Thai jasmine and Sungyod rice). Thai jasmine rice and Sungyod rice were cultivated in the northeast and the south of Thailand. Light isotopes including 13C, 15N and 18O of Thai jasmine rice and Sungyod rice samples were carried out using isotope ratio mass spectrometry (IRMS). Thai jasmine rice (Khao Dawk Mali 105) was cultivated from Thung Kula Rong Hai area, whereas Sungyod rice was cultivated from Phathalung province. Hypothesis testing of difference of each isotope between Thai jasmine rice and Sungyod rice was also studied. The study was the feasibility test whether the light stable isotopes can be the variables to identify Thai jasmine rice and Sungyod rice. The result shows that there was difference in the isotope patterns of Thai jasmine rice and Sungyod rice. Our results may provide the useful information in term of stable isotope profiles of Thai rice.

Processes controlling silicon isotopic fractionation in a forested tropical watershed: Mule Hole Critical Zone Observatory (Southern India)

NASA Astrophysics Data System (ADS)

Riotte, Jean; Meunier, Jean-Dominique; Zambardi, Thomas; Audry, Stéphane; Barboni, Doris; Anupama, Krishnamurthy; Prasad, Srinivasan; Chmeleff, Jérôme; Poitrasson, Franck; Sekhar, Muddu; Braun, Jean-Jacques

2018-05-01

Assessing the dynamics of the silica cycle in the critical zone remains challenging, particularly within the soil, where multiple processes are involved. To improve our understanding of this cycle in the Tropics, and more specifically the role played by vegetation, we combined elemental Si mass balance with the δ30Si signatures of the compartments involved in the water-plant-rock interactions of a tropical forested watershed, Mule Hole (Southern India). To accomplish this, we analysed (1) the δ30Si values of present-day litter phytoliths from tree leaves and grass, as well as soil amorphous silica (ASi); (2) the Si isotope fractionation induced by phytolith dissolution; (3) the silicon mass balance inferred from isotopes at the soil-plant scale; and (4) the consistency between water sources and the δ30Si signatures in the ephemeral stream. The δ30Si values of present-day litter phytoliths and soil ASi vary within a narrow range of 1.10-1.40‰ for all samples, but two deep vertisol samples which likely trapped phytoliths from different vegetation growing under more humid conditions, as indicated by pollen analysis. A homogeneous signature of litter is a minimum condition for using δ30Si as a proxy for the litter/phytolith source of Si. However, litter-ash dissolution experiments demonstrate that the incipient dissolution of phytoliths fractionates Si isotopes, with the preferential dissolution of 28Si over 30Si yielding δ30Si values as low as -1.41‰. Values close to the whole-sample signatures, i.e., above 1‰, were recovered in the solution after a few hours of water-ash interaction. At the soil-plant scale, the average δ30Si value of soil-infiltrating solutions is slightly lighter than the average phytolith signature, which suggests phytoliths as the source of soil dissolved Si. The isotopic budget of dissolved Si within the soil layer, which was obtained based on previous elemental fluxes, is imbalanced. Equilibrating the isotopic budget would imply that up to 4100 mol ha-1 yr-1 of silica is taken up by vegetation, which is almost twice as large as that initially estimated from the elemental budget. The additional Si flux taken up, and likely stored in woody stems, was estimated assuming that Si isotopes followed a steady-state model for the whole Si plant uptake and then followed a Rayleigh model once in the plants. The δ30Si value of the additional Si flux taken up should be close to 0‰, i.e., enriched in light Si isotopes compared to the litter. If steady-state conditions apply, the source could correspond to soil ASi dissolution or deep (saprolite) root uptake. At the outlet of the watershed, the stream exhibits low δ30Si values (0.28-0.71‰) during peak flows and high δ30Si values (1.29-1.61‰) during the recessions at the end of the rainy season. Heavy δ30Si signatures are consistent with the expected domination of seepage at the end of floods. The light δ30Si values during peak flow are slightly lower than the overland flow signature and reflect either a sampling bias of overland flow or a minor but significant contribution of another Si source within the stream, possibly the partial dissolution of phytoliths from the suspended load, with slight isotopic fractionation. This study confirms that vegetation controls the silicon cycle in this dry tropical forest. It also shows that silicon isotopes yield a better grasp of the mass balance and sources and potential mechanisms involved than the consideration of only silicon concentrations. However, this proxy still relies on working hypotheses, notably steady-state and/or Rayleigh fractionation models, which need to be confirmed in further studies.

Silurian shale origin for light oil, condensate, and gas in Algeria and the Middle East

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zumberge, J.E.; Macko, S.

1996-01-01

Two of the largest gas fields in the world, Hasi R'Mel, Algeria and North Dome, Qatar, also contain substantial condensate and light oil reserves. Gas to source rock geochemical correlation is difficult due to the paucity of molecular parameters in the former although stable isotope composition is invaluable. However, by correlating source rocks with light oils and condensates associated with gas production using traditional geochemical parameters such as biomarkers and isotopes, a better understanding of the origin of the gas is achieved. Much of the crude oil in the Ghadames/Illizi Basins of Algeria has long been thought to have beenmore » generated from Silurian shales. New light oil discoveries in Saudi Arabia have also been shown to originate in basal euxinic Silurian shales. Key sterane and terpane biomarkers as well as the stable carbon isotopic compositions of the C15+ saturate and aromatic hydrocarbon fractions allow for the typing of Silurian-sourced, thermally mature light oils in Algeria and the Middle East. Even though biomarkers are often absent due to advanced thermal maturity, condensates can be correlated to the light oils using (1) carbon isotopes of the residual heavy hydrocarbon fractions, (2) light hydrocarbon distributions (e.g., C7 composition), and (3) compound specific carbon isotopic composition of the light hydrocarbons. The carbon isotopes of the C2-C4 gas components ran then be compared to the associated condensate and light oil isotopic composition.« less

Silurian shale origin for light oil, condensate, and gas in Algeria and the Middle East

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zumberge, J.E.; Macko, S.

Two of the largest gas fields in the world, Hasi R`Mel, Algeria and North Dome, Qatar, also contain substantial condensate and light oil reserves. Gas to source rock geochemical correlation is difficult due to the paucity of molecular parameters in the former although stable isotope composition is invaluable. However, by correlating source rocks with light oils and condensates associated with gas production using traditional geochemical parameters such as biomarkers and isotopes, a better understanding of the origin of the gas is achieved. Much of the crude oil in the Ghadames/Illizi Basins of Algeria has long been thought to have beenmore » generated from Silurian shales. New light oil discoveries in Saudi Arabia have also been shown to originate in basal euxinic Silurian shales. Key sterane and terpane biomarkers as well as the stable carbon isotopic compositions of the C15+ saturate and aromatic hydrocarbon fractions allow for the typing of Silurian-sourced, thermally mature light oils in Algeria and the Middle East. Even though biomarkers are often absent due to advanced thermal maturity, condensates can be correlated to the light oils using (1) carbon isotopes of the residual heavy hydrocarbon fractions, (2) light hydrocarbon distributions (e.g., C7 composition), and (3) compound specific carbon isotopic composition of the light hydrocarbons. The carbon isotopes of the C2-C4 gas components ran then be compared to the associated condensate and light oil isotopic composition.« less

The Relative Importance of Convective and Trade-wind Orographic Precipitation to Streamflow in the Luquillo Mountains, Eastern Puerto Rico

NASA Astrophysics Data System (ADS)

Scholl, M. A.; Shanley, J. B.; Occhi, M.; Scatena, F. N.

2012-12-01

Like many mountainous areas in the tropics, watersheds in the Luquillo Mountains of Puerto Rico (18.3° N) have abundant rainfall and stream discharge, but relatively little storage capacity. Therefore, the water supply is vulnerable to drought and water availability may be affected by projected changes in regional temperature and atmospheric dynamics due to global warming. To help determine the links between climate and water availability, precipitation patterns were analyzed, and stable-isotope signatures of precipitation from different seasonal weather systems were established to identify those that are most important in maintaining streamflow and groundwater recharge. Stable isotope data include cloud water, rainfall, throughfall, streamflow, and groundwater from the Rio Mameyes and Rio Icacos/ Rio Blanco watersheds. Precipitation inputs have a wide range of stable isotope values, from fog/cloud water with δ2H and δ18O averaging +3.2‰, -1.74‰ respectively, to tropical storm rain with values as low as -154‰, -20.4‰. Spatial and temporal patterns of water isotopic values on this Caribbean island are different than higher latitude, continental watersheds. The data exhibit a 'reverse seasonality', with higher isotopic values in winter and lower values in summer; and stable isotope values of stream water do not decrease as expected with increasing altitude, because of cloud water input. Rain isotopic values vary predictably with local and mesoscale weather patterns and correlate strongly with cloud altitude. This correlation allows us to assign isotopic signatures to different sources of precipitation, and to investigate which climate patterns contribute to streamflow and groundwater recharge. At a measurement site at 615 m in the Luquillo Mountains, the average length of time between rain events was 15 h, and 45% of the rain events were <2 mm, reflecting the frequent small rain events of the trade-wind orographic rainfall weather pattern. Long-term average streamflow isotopic composition indicates a disproportionately large contribution of this trade-wind precipitation to streamflow, highlighting the importance of this climate pattern to the hydrology of the watersheds. Isotopic composition of groundwater suggests a slightly higher proportion of convective precipitation, but still smaller than in total rainfall. Hydrograph separation experiments yielded information on stormflow characteristics, with quantification of contributing sources determined from water isotopes and solute chemistry. The evidence that intense convective rain events run off and light trade-wind showers appear to contribute much of the baseflow indicates that the area may undergo a change in water supply if the trade-wind orographic precipitation dynamics in the Caribbean are affected by future climate change.

Effect of thermal decarbonation on the stable isotope composition of carbonates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durakiewicz, T.; Sharp, Z. D.; Papike, J. J.

2001-01-01

The unusual texture and stable isotope variability of carbonates in AH84001 have been used as evidence for early life on Mars (Romanek et al., 1994; McKay et al., 1996). Oxygen and carbon isotope variability is most commonly attributed to low-temperature processes, including Rayleigh-like fractionation associated with biological activity. Another possible explanation for the isotopic variability in meteoritic samples is thermal decarbonation. In this report, different carbonates were heated in a He-stream until decomposition temperatures were reached. The oxygen and carbon isotope ratios ({delta}{sup 18}O and {delta}{sup 13}C values) of the resulting gas were measured on a continuous flow isotope ratiomore » mass spectrometer. The aim of this work is to evaluate the possibility that large isotopic variations can be generated on a small scale abiogenically, by the process of thermal decarbonation. Oxygen isotope fractionations of >4{per_thousand} have been measured during decarbonation of calcite at high temperatures (McCrea, 1950), and in excess of 6{per_thousand} for dolomite decarbonated between 500 and 600 C (Sharma and Clayton, 1965). Isotopic fractionations of this magnitude, coupled with Rayleigh-like distillation behavior could result in very large isotopic variations on a small scale. To test the idea, calcite, dolomite and siderite were heated in a quartz tube in a He-stream in excess of 1 atmosphere. Simultaneous determinations of {delta}{sup 13}C and {Delta}{sup 18}O values were obtained on 250 {micro}l aliquots of the CO{sub 2}-bearing He gas using an automated 6-way switching valve system (Finnigan MAT GasBench II) and a Finnigan MAT Delta Plus mass spectrometer. It was found that decarbonation of calcite in a He atmosphere begins at 720 C, but the rate significantly increases at temperatures of 820 C. After an initial light {delta}{sup 18}O value of -14.1{per_thousand} at 720 C associated with very early decarbonation, {delta}{sup 18}0 values increase to a constant -11.8{per_thousand}, close to the accepted value of -12.09{per_thousand} (PDB). After 10 minutes at 820 C, the {delta}{sup 18}O values and signal strength both begin to decrease linearly to a {delta}{sup 18}O value of -14.75 and very low amounts of CO{sub 2} (Fig. 1). In contrast, the {delta}{sup 13}C values are extremely constant (0.12 {+-} 0.25{per_thousand}) for all measurements, in very good agreement with accepted values of 0.33{per_thousand} (PDB). There is much less isotopic variability during dolomite decarbonation. CO{sub 2} is first detected at 600 C. The signal strength increases by an order of magnitude between 670 and 700 C and again at 760 C. Both {delta}{sup 13}C and {delta}{sup 18}O values are nearly constant over the entire temperature range and sample size. For oxygen, the measured {delta}{sup 18}O values averaged -20.9 {+-} 0.7{per_thousand} (n = 30). Including only samples over 700 C, the average is -21.2 {+-} 0.2{per_thousand} compared to the accepted value of -21{per_thousand}. Carbon is similarly constant. The average {delta}{sup 13}C value is -2.50{per_thousand} compared to the accepted value of -2.62{per_thousand}. Far more variability is seen during the decomposition of siderite. Two samples were analyzed. In both samples, the initial {delta}{sup 18}O values were far lower than expected.« less

Influences of calcium availability and tree species on Ca isotope fractionation in soil and vegetation

USGS Publications Warehouse

Page, B.D.; Bullen, T.D.; Mitchell, M.J.

2008-01-01

The calcium (Ca) isotope system is potentially of great use for understanding biogeochemical processes at multiple scales in forest ecosystems, yet remains largely unexplored for this purpose. In order to further our understanding of Ca behavior in forests, we examined two nearly adjacent hardwood-dominated catchments with differing soil Ca concentrations, developed from crystalline bedrock, to determine the variability of 44Ca/ 40Ca ratios (expressed as ??44Ca) within soil and vegetation pools. For both sugar maple and American beech, the Ca isotope compositions of the measured roots and calculated bulk trees were considerably lighter than those of soil pools at these sites, suggesting that the trees were able to preferentially take up light Ca at the root-soil interface. The Ca isotope compositions of three of four root samples were among the lightest values yet reported for terrestrial materials (??44Ca ???-3.95???). Our results further indicate that Ca isotopes were fractionated along the transpiration streams of both tree species with roots having the least ??44Ca values and leaf litter the greatest. An approximately 2??? difference in ??44Ca values between roots and leaf litter of both tree species suggests a persistent fractionation mechanism along the transpiration stream, likely related to Ca binding in wood tissue coupled with internal ion exchange. Finally, our data indicate that differing tree species demand for Ca and soil Ca concentrations together may influence Ca isotope distribution within the trees. Inter-catchment differences in Ca isotope distributions in soils and trees were minor, indicating that the results of our study may have broad transferability to studies of forest ecosystems in catchments developed on crystalline substrates elsewhere. ?? 2008 Springer Science+Business Media B.V.

On-line hydrogen-isotope measurements of organic samples using elemental chromium: An extension for high temperature elemental-analyzer techniques

USGS Publications Warehouse

Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B.; Meijer, Harro A.J.; Brand, Willi A.; Schimmelmann, Arndt

2015-01-01

The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while handling water as a bulk sample. The calibration of organic samples, commonly having high δ2H values, will benefit from the availability of suitably 2H-enriched reference waters, extending the VSMOW-SLAP scale above zero.

Silicon and Zinc Isotopes in Ocean Island Basalts

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.; Moynier, F.

2013-12-01

Analyses of Ocean Island Basalts (OIB) have shown that the Earth's mantle contains isotopically distinct components, but current debate about the degree and scale of compositional variability persists. Isotopic heterogeneities in OIB for both radiogenic (e.g. Sr, Nd, Pb) and stable (e.g. Li, O, Ca) isotope systems have been attributed to the presence of recycled materials in different mantle reservoirs [1]. The study of both silicon and zinc isotopes in OIB form a complimentary approach to investigate potential heterogeneities in the mantle. Both isotope systems show limited fractionation during igneous process [2,3]. However, both Si and Zn exhibit larger (>1‰) variability in low-temperature environments (e.g. as a result of chemical weathering and biological utilization). Therefore, Si and Zn isotopes may be useful as tracers for the presence of crustal material (derived from low-T surface processes) in OIB source regions. Furthermore, characterizing the isotopic composition of the mantle is of central importance to the use of these isotopic systems as a basis for interplanetary comparisons. Here we present high-precision Si and Zn isotopic data obtained by MC-ICPMS for a diverse suite of OIB representing the EM-1, EM-2, and HIMU mantle components. Samples represent locations in the Pacific, Atlantic, and Indian Oceans. Data are reported as the permil deviation (×2 sd) from NBS28 for Si (δ30Si) and JMC-Lyon for Zn (δ66Zn). Average δ30Si values for OIB from EM-1 (-0.32×0.09‰), EM-2 (-0.30×0.03‰), and HIMU (-0.34×0.12‰) are all in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth (BSE) [4]. Similarly, the δ66Zn average values for OIB from the EM-1, EM-2, and HIMU components (0.31×0.06‰, 0.31×0.04‰, 0.31×0.05‰, respectively) agree well with previously published data for the δ66Zn value of BSE [3]. At the current levels of precision, both Si and Zn isotopes exhibit little variation in OIB, confirming the large-scale homogeneity of the mantle for these isotopic systems. Furthermore, when averaged according to surface location, neither Si nor Zn shows any variation in isotopic composition according to oceanic basin. However, some small variations in the data may be present; many HIMU samples (Mangaia, Cape Verde) are enriched in the lighter isotopes of Si (δ30Si tending toward chondritic values), which might reflect preservation of isotopic heterogeneity within the mantle, an incorporation of an isotopically light component in the source of these lavas, or isotopic fractionation during magmatic differentiation. References: [1] Hofmann, RiMG 2007 [2] Savage et al., GCA 2011 [3] Chen et al., EPSL 2013 [4] Savage et al., EPSL 2010

Examining Archean methanotrophy

NASA Astrophysics Data System (ADS)

Slotznick, Sarah P.; Fischer, Woodward W.

2016-05-01

The carbon isotope ratios preserved in sedimentary rocks can be used to fingerprint ancient metabolisms. Organic carbon in Late Archean samples stands out from that of other intervals with unusually low δ13C values (∼-45 to -60‰). It was hypothesized that these light compositions record ecosystem-wide methane cycling and methanotrophy, either of the aerobic or anaerobic variety. To test this idea, we studied the petrography and carbon and oxygen isotope systematics of well-known and spectacular occurrences of shallow water stromatolites from the 2.72 Ga Tumbiana Formation of Western Australia. We examined the carbonate cements and kerogen produced within the stromatolites, because methanotrophy is expected to leave an isotopic fingerprint in these carbon reservoirs. Mathematical modeling of Archean carbonate chemistry further reveals that methanotrophy should still have a discernible signature preserved in the isotopic record, somewhat diminished from those observed in Phanerozoic sedimentary basins due to higher dissolved inorganic carbon concentrations. These stromatolites contain kerogen with δ13Corg values of ∼ - 50 ‰. By microsampling different regions and textures within the stromatolites, we determined that the isotopic compositions of the authigenic calcite cements show a low degree of variation and are nearly identical to values estimated for seawater at this time; the lack of low and variable δ13Ccarb values implies that methanotrophy does not explain the low δ13Corg seen in the coeval kerogen. These observations do not support a methanotrophy hypothesis, but instead hint that the Late Archean may constitute an interval wherein autotrophs employed markedly different biochemical processes of energy conservation and carbon fixation.

Carbon isotope discrimination of arctic and boreal biomes inferred from remote atmospheric measurements and a biosphere-atmosphere model

NASA Astrophysics Data System (ADS)

Randerson, J. T.; Still, C. J.; Ballé, J. J.; Fung, I. Y.; Doney, S. C.; Tans, P. P.; Conway, T. J.; White, J. W. C.; Vaughn, B.; Suits, N.; Denning, A. S.

2002-07-01

Estimating discrimination against 13C during photosynthesis at landscape, regional, and biome scales is difficult because of large-scale variability in plant stress, vegetation composition, and photosynthetic pathway. Here we present estimates of 13C discrimination for northern biomes based on a biosphere-atmosphere model and on National Oceanic and Atmospheric Administration Climate Monitoring and Diagnostics Laboratory and Institute of Arctic and Alpine Research remote flask measurements. With our inversion approach, we solved for three ecophysiological parameters of the northern biosphere (13C discrimination, a net primary production light use efficiency, and a temperature sensitivity of heterotrophic respiration (a Q10 factor)) that provided a best fit between modeled and observed δ13C and CO2. In our analysis we attempted to explicitly correct for fossil fuel emissions, remote C4 ecosystem fluxes, ocean exchange, and isotopic disequilibria of terrestrial heterotrophic respiration caused by the Suess effect. We obtained a photosynthetic discrimination for arctic and boreal biomes between 19.0 and 19.6‰. Our inversion analysis suggests that Q10 and light use efficiency values that minimize the cost function covary. The optimal light use efficiency was 0.47 gC MJ-1 photosynthetically active radiation, and the optimal Q10 value was 1.52. Fossil fuel and ocean exchange contributed proportionally more to month-to-month changes in the atmospheric growth rate of δ13C and CO2 during winter months, suggesting that remote atmospheric observations during the summer may yield more precise estimates of the isotopic composition of the biosphere.

Strontium stable isotope behaviour accompanying basalt weathering

NASA Astrophysics Data System (ADS)

Burton, K. W.; Parkinson, I. J.; Gíslason, S. G. R.

2016-12-01

The strontium (Sr) stable isotope composition of rivers is strongly controlled by the balance of carbonate to silicate weathering (Krabbenhöft et al. 2010; Pearce et al. 2015). However, rivers draining silicate catchments possess distinctly heavier Sr stable isotope values than their bedrock compositions, pointing to significant fractionation during weathering. Some have argued for preferential release of heavy Sr from primary phases during chemical weathering, others for the formation of secondary weathering minerals that incorporate light isotopes. This study presents high-precision double-spike Sr stable isotope data for soils, rivers, ground waters and estuarine waters from Iceland, reflecting both natural weathering and societal impacts on those environments. The bedrock in Iceland is dominantly basaltic, d88/86Sr ≈ +0.27, extending to lighter values for rhyolites. Geothermal waters range from basaltic Sr stable compositions to those akin to seawater. Soil pore waters reflect a balance of input from primary mineral weathering, precipitation and litter recycling and removal into secondary phases and vegetation. Rivers and ground waters possess a wide range of d88/86Sr compositions from +0.101 to +0.858. Elemental and isotope data indicate that this fractionation primarily results from the formation or dissolution of secondary zeolite (d88/86Sr ≈ +0.10), but also carbonate (d88/86Sr ≈ +0.22) and sometimes anhydrite (d88/86Sr ≈ -0.73), driving the residual waters to heavier or lighter values, respectively. Estuarine waters largely reflect mixing with seawater, but are also be affected by adsorption onto particulates, again driving water to heavy values. Overall, these data indicate that the stability and nature of secondary weathering phases, exerts a strong control on the Sr stable isotope composition of silicate rivers. [1] Krabbenhöft et al. (2010) Geochim. Cosmochim. Acta 74, 4097-4109. [2] Pearce et al. (2015) Geochim. Cosmochim. Acta 157, 125-146.

Photochemical isotope separation

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

1987-01-01

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

Laser isotope separation

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Boyer, Keith; Greiner, Norman R.

1988-01-01

A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

Isotope separation by laser means

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

1982-06-15

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

Mass dependence of calcium isotope fractionations in crown-ether resin chromatography.

PubMed

Fujii, Yasuhiko; Nomura, Masao; Kaneshiki, Tositaka; Sakuma, Yoichi; Suzuki, Tatsuya; Umehara, Saori; Kishimoto, Tadahumi

2010-06-01

Benzo 18-crown-6-ether resin was synthesised by the phenol condensation polymerisation process in porous silica beads, of which particle diameter was ca 60micro Calcium adsorption chromatography was performed with the synthesised resin packed in a glass column. The effluent was sampled in fractions, and the isotopic abundance ratios of (42)Ca, (43)Ca, (44)Ca, and (48)Ca against (40)Ca were measured by a thermo-ionisation mass spectrometer. The enrichment of heavier calcium isotopes was observed at the front boundary of calcium adsorption chromatogram. The mass dependence of mutual separation of calcium isotopes was analysed by using the three-isotope-plots method. The slopes of three-isotope-plots indicate the relative values of mutual separation coefficients for concerned isotopic pairs. The results have shown the normal mass dependence; isotope fractionation is proportional to the reduced mass difference, (M - M')/MM', where M and M' are masses of heavy and light isotope, respectively. The mass dependence clarifies that the isotope fractionations are originated from molecular vibration. The observed separation coefficient epsilon is 3.1x10(-3) for the pair of (40)Ca and (48)Ca. Productivity of enriched (48)Ca by crown-ether-resin was discussed as the function of the separation coefficient and the height equivalent to the theoretical plate.

Mg isotopes in biocarbonates: new insight into vital effects associated to echinoderms and bivalves calcification

NASA Astrophysics Data System (ADS)

Planchon, F.; Hermans, J.; Borremans, C.; Dubois, P.; Poulain, C.; Paulet, Y.; Andre, L.

2007-12-01

Mg isotopes can be helpful tracers to reveal the fundamental pathways of Mg incorporation during biomineralisation. We report in this study a detailed characterisation of the Mg isotopic signatures of different biominerals: high magnesium calcitic skeletons of selected echinoderms (sea urchins and starfish) and low magnesium aragonitic shells of a bivalve species (clam). State of the art analytical procedures were applied including sample purification step followed by high precision measurements using MC-ICP-MS (Nu instrument) in dry plasma conditions. 26Mg/24Mg and 25Mg/24Mg are expressed as per mil deviations from the DSM3 (Dead Sea Metal 3) reference standard in delta notation (d26Mg and d25Mg). For echinoderms, we considered: (a) adult specimens of six starfish species (Asteria r., Marthasterias g., Anseropoda p., Asterina g., Echinaster s. and Henricia o.), sampled in Brittany (France); (b) a sea urchin species (Paracentrotus lividus) with field samples (Mediterranean Sea, Marseille, France) and culture specimen under T and S controlled conditions. In vivo endoskeletons display negative, but different d26Mg values of -3.06 for starfish (with uniform interspecies signatures) and -2.65 for sea urchin. Relative to seawater signature (-0.82), all echinoderms favour the incorporation of light isotopes during biocalcification. The d26Mg depletion is lower than theoretically expected from a inorganic calcite precipitation from seawater (at -3.5). These differences suggest that on its route from seawater to the shell, Mg isotopes are partly biologically fractionationated through "vital effects" leaving heavier Mg isotopic signatures. Taken into account that calcification in echinoderms is an intra- cellular process involving transient amorphous calcium carbonate (ACC) phase, the observed bio-fractionation factors can be related to: (1) changes in the isotopic composition of the precipitating intracellular fluids due to active pumping in and out of the cell; (2) a specific control of isotopic exchange by ACC. For bivalves, we considered one clam species (Ruditapes Philippinarum) from two different sampling sites in the gulf of Morbihan (Brittany, France). One site (Locmariaquer, Loc) is coastal and marine while the other (Le bono, BO) located upstream in the Auray river. For each site and specimen, we considered all reservoirs involved in the shell build-up: seawater, internal fluids with hemolymph (H) and extrapaleal fluid (EPF), soft tissues with mantle, muscle and remaining part (R) and finally aragonitic shells. Water d26Mg are -0.82 at Loc and -0.79 at BO and appear to be highly similar to internal fluids values (EPF and H), -0.6 for Loc and -0.8 for BO. The soft tissues with mean values of -2.7 (Mantle), -2.1 (Muscle), -2.8 (R) at both sites, show pronounced enrichments in the light isotopic fraction of Mg. The shells display the widest range of Mg isotopic signatures with -1.9 at Loc and -4.2 at BO suggesting that different routes of fractionation are acting. The shell signature at Loc similar to aragonitic coral (-1.9) suggests that moderate biological effects have influenced the shell composition at this site. In contrast, at BO, the very light signature of the shell suggests that a significant fraction of Mg has been internally recycled by the clam and used for the building of the shell.

The oceanic budgets of nickel and zinc isotopes: the importance of sulfidic environments as illustrated by the Black Sea

PubMed Central

Little, Susan H.; Archer, Corey; Cameron, Vyllinniskii; Andersen, Morten B.; Rijkenberg, Micha J. A.; Lyons, Timothy W.

2016-01-01

Isotopic data collected to date as part of the GEOTRACES and other programmes show that the oceanic dissolved pool is isotopically heavy relative to the inputs for zinc (Zn) and nickel (Ni). All Zn sinks measured until recently, and the only output yet measured for Ni, are isotopically heavier than the dissolved pool. This would require either a non-steady-state ocean or other unidentified sinks. Recently, isotopically light Zn has been measured in organic carbon-rich sediments from productive upwelling margins, providing a potential resolution of this issue, at least for Zn. However, the origin of the isotopically light sedimentary Zn signal is uncertain. Cellular uptake of isotopically light Zn followed by transfer to sediment does not appear to be a quantitatively important process. Here, we present Zn and Ni isotope data for the water column and sediments of the Black Sea. These data demonstrate that isotopically light Zn and Ni are extracted from the water column, probably through an equilibrium fractionation between different dissolved species followed by sequestration of light Zn and Ni in sulfide species to particulates and the sediment. We suggest that a similar, non-quantitative, process, operating in porewaters, explains the Zn data from organic carbon-rich sediments. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’. PMID:29035259

Silicon Isotope Geochemistry of Ocean Island Basalts: Mantle Heterogeneities and Contribution of Recycled Oceanic Crust and Lithosphere

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.; Savage, P. S.; Jackson, M. G.; Moreira, M. A.; Day, J. M.

2015-12-01

The study of Silicon (Si) isotopes in Ocean Island Basalts (OIB) has the potential to elucidate between possible heterogeneities in the mantle. Relatively large (~several per mil per atomic mass unit) Si isotope fractionation occurs in low-temperature environments during biochemical and geochemical precipitation of dissolved Si, where the precipitate is preferentially enriched in the lighter isotopes [1]. In contrast, only a limited range (~tenths of a per mil) of Si isotope fractionation has been observed in high-temperature igneous processes [2]. Therefore, Si isotopes may be useful as tracers for the presence of crustal material (derived from low-temperature surface processes) in OIB source regions in a manner similar to more conventional stable isotope systems, such as O. Here we present the first comprehensive set of high-precision Si isotope data obtained by MC-ICP-MS for a diverse suite of OIBs, including new data for the Canary Islands. Samples represent the Pacific, Atlantic, and Indian Ocean basins and include representative end-members for the EM-1, EM-2, and HIMU mantle components. Average δ30Si values for OIBs representing the EM-1 (-0.32 ± 0.06‰, 2 sd), EM-2 (-0.30 ± 0.01‰, 2 sd), and HIMU (-0.34 ± 0.09‰, 2 sd) mantle components are all in general agreement with previous estimates for the δ30Si value of Bulk Silicate Earth [3]. However, small systematic variations are present; HIMU (Mangaia, Cape Verde, La Palma) and Iceland OIBs are enriched in the lighter isotopes of Si (δ30Si values lower than MORB). Further, the difference in Si isotope composition between La Palma and El Heirro (Canary Islands) has previously been observed for O isotopes [4], suggesting a relationship between the Si and O isotope mantle systematics. The Si isotope variations among OIBs may be explained by the sampling of a primitive mantle reservoir enriched in the light isotopes of Si, as suggested by [5], but most likely reflects the incorporation of recycled altered oceanic crust and lithosphere in the plume source. References: [1] Ziegler et al., GCA 2005 [2] Savage et al., GCA 2011 [3] Savage et al., EPSL 2010 [4] Day et al., Geology 2009 [5] Huang et al., GCA 2014

Interindividual differences in embodied marginalization: Osteological and stable isotope analyses of antebellum enslaved individuals.

PubMed

Dent, Sophia C

2017-07-08

Through pathological and stable isotope analyses, this study probes the stressors, disease ecology, and diets of enslaved individuals from an antebellum plantation cemetery. The study aims to highlight how interindividual isotopic differences reveal that marginalization is not uniformly experienced or embodied. The cemetery population consists of 16 individuals; dental and skeletal pathological indicators were collected for all individuals, and light stable isotope ratios (δ 15 N, δ 13 C) were generated from the collagen and hydroxyapatite of nine individuals. The analyzed individuals have high frequencies of enamel defects-similar to contemporaneous enslaved cemetery individuals-and particularly high frequencies of carious lesions. Skeletal analysis shows evidence of chronic conditions among several individuals, two of whom likely have tuberculosis. Although the sample size is small, stable isotope values display interesting trends: there is interindividual heterogeneity in δ 13 C values, and most subadults from the cemetery have lower δ 15 N and higher δ 13 C values than the sampled adults. These relationships can be tested with larger datasets and have the potential to reveal important information about slave foodways and the broader experience of enslavement. The results of this study suggest that racial discrimination, enslavement, and age do not fully account for the heterogeneity in degree of embodied stressors. There are likely other factors at play, intersecting with the aforementioned, that influenced the lived experience of slavery and the degree of marginalization. © 2017 Wiley Periodicals, Inc.

Accounting for the effects of lipids in stable isotope (δ13C and δ15N values) analysis of skin and blubber of balaenopterid whales.

PubMed

Ryan, Conor; McHugh, Brendan; Trueman, Clive N; Harrod, Chris; Berrow, Simon D; O'Connor, Ian

2012-12-15

Stable isotope values (δ(13)C and δ(15)N) of darted skin and blubber biopsies can shed light on habitat use and diet of cetaceans, which are otherwise difficult to study. Non-dietary factors affect isotopic variability, chiefly the depletion of (13)C due to the presence of (12)C-rich lipids. The efficacy of post hoc lipid-correction models (normalization) must be tested. For tissues with high natural lipid content (e.g., whale skin and blubber), chemical lipid extraction or normalization is necessary. C:N ratios, δ(13)C values and δ(15)N values were determined for duplicate control and lipid-extracted skin and blubber of fin (Balaenoptera physalus), humpback (Megaptera novaeangliae) and minke whales (B. acutorostrata) by continuous-flow elemental analysis isotope ratio mass spectrometry (CF-EA-IRMS). Six different normalization models were tested to correct δ(13)C values for the presence of lipids. Following lipid extraction, significant increases in δ(13)C values were observed for both tissues in the three species. Significant increases were also found for δ(15)N values in minke whale skin and fin whale blubber. In fin whale skin, the δ(15)N values decreased, with no change observed in humpback whale skin. Non-linear models generally out-performed linear models and the suitability of models varied by species and tissue, indicating the need for high model specificity, even among these closely related taxa. Given the poor predictive power of the models to estimate lipid-free δ(13)C values, and the unpredictable changes in δ(15)N values due to lipid-extraction, we recommend against arithmetical normalization in accounting for lipid effects on δ(13)C values for balaenopterid skin or blubber samples. Rather, we recommend that duplicate analysis of lipid-extracted (δ(13)C values) and non-treated tissues (δ(15)N values) be used. Copyright © 2012 John Wiley & Sons, Ltd.

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science

USGS Publications Warehouse

Coplen, Tyler B.; Qi, Haiping

2016-01-01

The hydrogen isotopic composition (δ2HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)–SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ2HVSMOW-SLAPresults when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ2HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised:where mUr = 0.001 = ‰. On average, these revised δ2HVSMOW-SLAP values are 5.7 mUr more positive than those previously measured. It is critical that readers pay attention to the δ2HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ2HVSMOW–SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science.

PubMed

Coplen, Tyler B; Qi, Haiping

2016-09-01

The hydrogen isotopic composition (δ(2)HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)-SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ(2)HVSMOW-SLAP results when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ(2)HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised: [Formula: see text] [Formula: see text] where mUr=0.001=‰. On average, these revised δ(2)HVSMOW-SLAP values are 5.7mUr more positive than those previously measured. It is critical that readers pay attention to the δ(2)HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ(2)HVSMOW-SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale. Published by Elsevier Ireland Ltd.

Magnesium and iron isotopes in 2.7 Ga Alexo komatiites: Mantle signatures, no evidence for Soret diffusion, and identification of diffusive transport in zoned olivine

NASA Astrophysics Data System (ADS)

Dauphas, Nicolas; Teng, Fang-Zhen; Arndt, Nicholas T.

2010-06-01

Komatiites from Alexo, Canada, are well preserved and represent high-degree partial mantle melts (˜50%). They are thus well suited for investigating the Mg and Fe isotopic compositions of the Archean mantle and the conditions of magmatic differentiation in komatiitic lavas. High precision Mg and Fe isotopic analyses of 22 samples taken along a 15-m depth profile in a komatiite flow are reported. The δ 25Mg and δ 26Mg values of the bulk flow are -0.138 ± 0.021‰ and -0.275 ± 0.042‰, respectively. These values are indistinguishable from those measured in mantle peridotites and chondrites, and represent the best estimate of the composition of the silicate Earth from analysis of volcanic rocks. Excluding the samples affected by secondary Fe mobilization, the δ 56Fe and δ 57Fe values of the bulk flow are +0.044 ± 0.030‰, and +0.059 ± 0.044‰, respectively. These values are consistent with a near-chondritic Fe isotopic composition of the silicate Earth and minor fractionation during komatiite magma genesis. In order to explain the early crystallization of pigeonite relative to augite in slowly cooled spinifex lavas, it was suggested that magmas trapped in the crystal mush during spinifex growth differentiated by Soret effect, which should be associated with large and coupled variations in the isotopic compositions of Mg and Fe. The lack of variations in Mg and Fe isotopic ratios either rules out the Soret effect in the komatiite flow or the effect is effaced as the solidification front migrates downward through the flow crust. Olivine separated from a cumulate sample has light δ 56Fe and slightly heavy δ 26Mg values relative to the bulk flow, which modeling shows can be explained by kinetic isotope fractionation associated with Fe-Mg inter-diffusion in olivine. Such variations can be used to identify diffusive processes involved in the formation of zoned minerals.

Laser isotope separation

DOEpatents

Robinson, C.P.; Reed, J.J.; Cotter, T.P.; Boyer, K.; Greiner, N.R.

1975-11-26

A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light is described. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

Photochemical isotope separation

DOEpatents

Robinson, C.P.; Jensen, R.J.; Cotter, T.P.; Greiner, N.R.; Boyer, K.

1987-04-28

A process is described for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium. 8 figs.

Discrimination of ginseng cultivation regions using light stable isotope analysis.

PubMed

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

2015-10-01

Korean ginseng is considered to be a precious health food in Asia. Today, thieves frequently compromise ginseng farms by pervasive theft. Thus, studies regarding the characteristics of ginseng according to growth region are required in order to deter ginseng thieves and prevent theft. In this study, 6 regions were selected on the basis of Korea regional criteria (si, gun, gu), and two ginseng-farms were randomly selected from each of the 6 regions. Then 4-6 samples of ginseng were acquired from each ginseng farm. The stable isotopic compositions of H, O, C, and N of the collected ginseng samples were analyzed. As a result, differences in the hydrogen isotope ratios could be used to distinguish regional differences, and differences in the nitrogen isotope ratios yielded characteristic information regarding the farms from which the samples were obtained. Thus, stable isotope values could be used to differentiate samples according to regional differences. Therefore, stable isotope analysis serves as a powerful tool to discriminate the regional origin of Korean ginseng samples from across Korea. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Interrogating trees for isotopic archives of atmospheric sulphur deposition and comparison to speleothem records.

PubMed

Wynn, P M; Loader, N J; Fairchild, I J

2014-04-01

Palaeorecords which depict changes in sulphur dynamics form an invaluable resource for recording atmospheric pollution. Tree rings constitute an archive that are ubiquitously available and can be absolutely dated, providing the potential to explore local- to regional-scale trends in sulphur availability. Rapid isotopic analysis by a novel "on-line" method using elemental analyser isotope ratio mass spectrometry (EA-IRMS) is developed, achieving sample precision of <0.4‰ using sample sizes of 40 mg wood powder. Tree cores from NE Italy show trends in pollution, evidenced through increasing concentrations of sulphur towards the youngest growth, and inverse trends in sulphur isotopes differentiating modern growth with light sulphur isotopes (+0.7‰) from pre-industrial growth (+7.5‰) influenced by bedrock composition. Comparison with speleothem records from the same location demonstrate replication, albeit offset in isotopic value due to groundwater storage. Using EA-IRMS, tree ring archives form a valuable resource for understanding local- to regional-scale sulphur pollution dynamics. Copyright © 2013 Elsevier Ltd. All rights reserved.

Investigating the impact of light and water status on the exchange of COS, 13CO2, CO18O and H218O from bryophytes

NASA Astrophysics Data System (ADS)

Gimeno, Teresa; Royles, Jessica; Ogee, Jerome; Jones, Samuel; Burlett, Regis; West, Jason; Sauze, Joana; Wohl, Steven; Genty, Bernard; Griffiths, Howard; Wingate, Lisa

2016-04-01

Terrestrial surfaces are often covered by photoautotrophic communities that play a significant role in the biological fixation of C and N at the global scale. Bryophytes (mosses, liverworts and hornworts) are key members in these communities and are especially adapted to thrive in hostile environments, by growing slowly and surviving repeated dehydration events. Consequently, bryophyte communities can be extremely long-lived (>1500yrs) and can serve as valuable records of historic climate change. In particular the carbon and oxygen isotope compositions of mosses can be used as powerful proxies describing how growing season changes in atmospheric CO2 and rainfall have changed in the distant past over the land surface. Interpreting the climate signals of bryophyte biomass requires a robust understanding of how changes in photosynthetic activity and moisture status regulate the growth and isotopic composition of bryophyte biomass. Thus theoretical models predicting how changes in isotopic enrichment and CO2 discrimination respond to dehydration and rehydration are used to tease apart climatic and isotopic source signals. Testing these models with high resolution datasets obtained from new generation laser spectrometers can provide more information on how these plants that lack stomata cope with water loss. In addition novel tracers such as carbonyl sulfide (COS) can also be measured at high resolution and precision (<5ppt) and used to constrain understanding of diffusional and enzymatic limitations during dehydration and rehydration events in the light and the dark. Here, we will present for the first time simultaneous high-resolution chamber measurements of COS, 13CO2, CO18O and H218O fluxes by a bryophyte species (Marchantia sp.) in the light and during the dark, through complete desiccation cycles. Our measurements consistently reveal a strong enrichment dynamic in the oxygen isotope composition of transpired water over the dessication cycle that caused an increase in the oxygen isotope discrimination of CO2. These data followed closely values predicted by our process-based model. We also observed a consistent pattern in the fluxes of CO2 and COS during the desiccation cycle. Initially when the bryophyte was wet and a barrier to diffusion existed, net CO2 and COS uptake rates were low. As the water film on the bryophyte disappeared the net rates of CO2 and COS uptake increased to a steady maximum rate whilst relative water content values remained above 100%. Thereafter, the bryophyte turned from a COS sink to a source. In this talk we will further explore how the COS exchange rate of bryophytes varies with light level and whether there is any evidence for differences in the activity of the enzyme carbonic anhydrase with light and moisture status. We also use the data to develop and test a new theoretical model of COS exchange for astomatous plants for the first time.

Springs, streams, and gas vent on and near Mount Adams volcano, Washington

USGS Publications Warehouse

Nathenson, Manuel; Mariner, Robert H.

2013-01-01

Springs and some streams on Mount Adams volcano have been sampled for chemistry and light stable isotopes of water. Spring temperatures are generally cooler than air temperatures from weather stations at the same elevation. Spring chemistry generally reflects weathering of volcanic rock from dissolved carbon dioxide. Water in some springs and streams has either dissolved hydrothermal minerals or has reacted with them to add sulfate to the water. Some samples appear to have obtained their sulfate from dissolution of gypsum while some probably involve reaction with sulfide minerals such as pyrite. Light stable isotope data for water from springs follow a local meteoric water line, and the variation of isotopes with elevation indicate that some springs have very local recharge and others have water from elevations a few hundred meters higher. No evidence was found for thermal or slightly thermal springs on Mount Adams. A sample from a seeping gas vent on Mount Adams was at ambient temperature, but the gas is similar to that found on other Cascade volcanoes. Helium isotopes are 4.4 times the value in air, indicating that there is a significant component of mantle helium. The lack of fumaroles on Mount Adams and the ambient temperature of the gas indicates that the gas is from a hydrothermal system that is no longer active.

Variability in the carbon isotope composition of individual amino acids in plant proteins from different sources: 1 Leaves.

PubMed

Lynch, Anthony H; Kruger, Nicholas J; Hedges, Robert E M; McCullagh, James S O

2016-05-01

The natural carbon isotope composition of individual amino acids from plant leaf proteins has been measured to establish potential sources of variability. The plant leaves studied, taken from a range of plant groups (forbs, trees, grasses, and freshwater aquatic plants), showed no significant influence of either season or environment (water and light availability) on their Δδ(13)C values. Plant groups did, however, differ in carbon isotope composition, although no consistent differences were identified at the species level. A discriminant analysis model was constructed which allowed leaves from (1) nettles, (2) Pooideae, (3) other Poales, (4) trees and (5) freshwater higher plants to be distinguished from each other on the basis of their natural abundance (13)C/(12)C ratios of individual amino acids. Differences in carbon isotope composition are known to be retained, to some extent, in the tissues of their consumers, and hence an understanding of compound-specific variation in (13)C/(12)C fractional abundance in plants has the potential to provide dietary insights of value in archaeological and ecological studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

NASA Astrophysics Data System (ADS)

Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

2018-01-01

Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS < 0.6) of sulfhydryl groups. XANES analyses showed that the proportion of CuIIvs CuI, compared to the initial CuII/CuI ratio, decreased by 14% after the first hour of reaction and by 6% after 96 h of reaction. The value of ε65Cuinc of the biofilm exhibited a similar trend over time of exposure. Our study demonstrates the complexity of biological processes associated with live phototrophic biofilms, which produce large and contrasting isotope fractionations following rather small Cu redox and speciation changes during uptake, storage or release of the metal, i.e., favoring heavy isotopes during complexation with carboxylate ligands and light isotopes during reduction of CuII-O/N to CuI-sulfhydryl moieties.

Effects of alkalinity and salinity at low and high light intensity on hydrogen isotope fractionation of long-chain alkenones produced by Emiliania huxleyi

NASA Astrophysics Data System (ADS)

Weiss, Gabriella M.; Pfannerstill, Eva Y.; Schouten, Stefan; Sinninghe Damsté, Jaap S.; van der Meer, Marcel T. J.

2017-12-01

Over the last decade, hydrogen isotopes of long-chain alkenones have been shown to be a promising proxy for reconstructing paleo sea surface salinity due to a strong hydrogen isotope fractionation response to salinity across different environmental conditions. However, to date, the decoupling of the effects of alkalinity and salinity, parameters that co-vary in the surface ocean, on hydrogen isotope fractionation of alkenones has not been assessed. Furthermore, as the alkenone-producing haptophyte, Emiliania huxleyi, is known to grow in large blooms under high light intensities, the effect of salinity on hydrogen isotope fractionation under these high irradiances is important to constrain before using δDC37 to reconstruct paleosalinity. Batch cultures of the marine haptophyte E. huxleyi strain CCMP 1516 were grown to investigate the hydrogen isotope fractionation response to salinity at high light intensity and independently assess the effects of salinity and alkalinity under low-light conditions. Our results suggest that alkalinity does not significantly influence hydrogen isotope fractionation of alkenones, but salinity does have a strong effect. Additionally, no significant difference was observed between the fractionation responses to salinity recorded in alkenones grown under both high- and low-light conditions. Comparison with previous studies suggests that the fractionation response to salinity in culture is similar under different environmental conditions, strengthening the use of hydrogen isotope fractionation as a paleosalinity proxy.

Analytical pyrolysis and stable isotope analyses reveal past environmental changes in coralloid speleothems from Easter Island (Chile).

PubMed

Miller, Ana Z; De la Rosa, José M; Jiménez-Morillo, Nicasio T; Pereira, Manuel F C; González-Pérez, José A; Calaforra, José M; Saiz-Jimenez, Cesareo

2016-08-26

This study comprises an innovative approach based on the combination of chromatography (analytical pyrolysis and pyrolysis compound-specific isotope analysis (Py-CSIA)), light stable isotopes, microscopy and mineralogy analyses to characterize the internal layering of coralloid speleothems from the Ana Heva lava tube in Easter Island (Chile). This multidisciplinary proxy showed that the speleothems consist of banded siliceous materials of low crystallinity with different mineralogical compositions and a significant contribution of organic carbon. Opal-A constitutes the outermost grey layer of the coralloids, whereas calcite and amorphous Mg hydrate silicate are the major components of the inner whitish and honey-brown layers, respectively. The differences found in the mineralogical, elemental, molecular and isotopic composition of these distinct coloured layers are related to environmental changes during speleothem development. Stable isotopes and analytical pyrolysis suggested alterations in the water regime, pointing to wetter conditions during the formation of the Ca-rich layer and a possible increase in the amount of water dripping into the cave. The trend observed for δ(15)N values suggested an increase in the average temperature over time, which is consistent with the so-called climate warming during the Holocene. The pyrolysis compound-specific isotope analysis of each speleothem layer showed a similar trend with the bulk δ(13)C values pointing to the appropriateness of direct Py-CSIA in paleoenvironmental studies. The δ(13)C values for n-alkanes reinforced the occurrence of a drastic environmental change, indicating that the outermost Opal layer was developed under drier and more arid environmental conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Iron assimilation by the clam Laternula elliptica: Do stable isotopes (δ⁵⁶Fe) help to decipher the sources?

PubMed

Poigner, Harald; Wilhelms-Dick, Dorothee; Abele, Doris; Staubwasser, Michael; Henkel, Susann

2015-09-01

Iron stable isotope signatures (δ(56)Fe) in hemolymph (bivalve blood) of the Antarctic bivalve Laternula elliptica were analyzed by Multiple Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS) to test whether the isotopic fingerprint can be tracked back to the predominant sources of the assimilated Fe. An earlier investigation of Fe concentrations in L. elliptica hemolymph suggested that an assimilation of reactive and bioavailable Fe (oxyhydr)oxide particles (i.e. ferrihydrite), precipitated from pore water Fe around the benthic boundary, is responsible for the high Fe concentration in L. elliptica (Poigner et al., 2013 b). At two stations in Potter Cove (King George Island, Antarctica) bivalve hemolymph showed mean δ(56)Fe values of -1.19 ± 0.34‰ and -1.04 ± 0.39 ‰, respectively, which is between 0.5‰ and 0.85‰ lighter than the pool of easily reducible Fe (oxyhydr)oxides of the surface sediments (-0.3‰ to -0.6‰). This is in agreement with the enrichment of lighter Fe isotopes at higher trophic levels, resulting from the preferential assimilation of light isotopes from nutrition. Nevertheless, δ(56)Fe hemolymph values from both stations showed a high variability, ranging between -0.21‰ (value close to unaltered/primary Fe(oxyhydr)oxide minerals) and -1.91‰ (typical for pore water Fe or diagenetic Fe precipitates), which we interpret as a "mixed" δ(56)Fe signature caused by Fe assimilation from different sources with varying Fe contents and δ(56)Fe values. Furthermore, mass dependent Fe fractionation related to physiological processes within the bivalve cannot be ruled out. This is the first study addressing the potential of Fe isotopes for tracing back food sources of bivalves. Copyright © 2015 Elsevier Ltd. All rights reserved.

Clumped Isotope Thermometry Reveals Variations in Soil Carbonate Seasonal Biases Over >4 km of Relief in the Semi-Arid Andes of Central Chile

NASA Astrophysics Data System (ADS)

Burgener, L. K.; Huntington, K. W.; Hoke, G. D.; Schauer, A. J.; Ringham, M. C.; Latorre Hidalgo, C.; Díaz, F.

2015-12-01

The application of carbonate clumped isotope thermometry to soil carbonates has the potential to shed new light on questions regarding terrestrial paleoclimate. In order to better utilize this paleoclimate tool, outstanding questions regarding seasonal biases in soil carbonate formation and the relationship between soil carbonate formation temperatures (T(Δ47)) and surface temperatures must be resolved. We address these questions by comparing C, O, and clumped isotope data from Holocene/modern soil carbonates to modern meteorological data. The data were collected along a 170 km transect with >4 km of relief in central Chile (~30°S). Previous studies have suggested that soil carbonates should record a warm season bias and form in isotopic equilibrium with soil water and soil CO2. We identify two discrete climate zones separated by the local winter snow line (~3200 m). Below this boundary, precipitation falls as rain and soil carbonate T(Δ47) values at depths >40 cm resemble summer soil temperatures; at higher elevations, precipitation falls as snow and T(Δ47) values resemble mean annual soil temperatures. Soil carbonates from the highest sample site (4700 m), which is devoid of vegetation and located near perennial snow fields, yield anomalous δ18O, δ13C, and T(Δ47) values, indicative of kinetic isotope effects that we attribute to cryogenic carbonate formation. Our results suggest that soil carbonates from depths <40 cm are affected by large, high frequency variations in temperature and precipitation, and should not be used as paleotemperature proxies. These findings (1) highlight the role of soil moisture in modulating soil carbonate formation and the resulting T(Δ47) values, (2) underscore the importance of understanding past soil moisture conditions when attempting to reconstruct paleotemperatures using carbonate clumped isotope thermometry, and (3) suggest that soil carbonates from high elevation or high latitude sites may form under non-equilibrium conditions.

δ 18O(PO 43-) and δ 18O(CO 32-) from belemnite guards from Eastern Europe: implications for palaeoceanographic reconstructions and for the preservation of pristine isotopic values

NASA Astrophysics Data System (ADS)

Longinelli, Antonio; Wierzbowski, Hubert; Di Matteo, Antonella

2003-04-01

The oxygen isotopic composition of coexisting carbonate and phosphate from belemnite rostra was measured according to well established techniques in 42 samples of Early and Middle Jurassic age and in five samples of oyster shells. Most of the samples come from various locations in the Western Carpathians of Slovakia and Ukraine, and from central Poland. Three samples come from the Isle of Skye. The phosphate content of belemnite rostra, though variable, is systematically very low: consistently lower than about 0.3%. However, this phosphate concentration is close to that found in shells of modern marine organisms including pelecypods, gastropods and Sepia cuttlebones which, in some way, could be considered the modern belemnite counterpart. The measured oxygen isotopic composition of carbonate is within the normal range of values obtained from these fossils ranging from about -1.3 to about +0.6‰ (PDB-1) with the exception of three samples; the δ 13C values range from about -0.8 to about +2.8‰ (PDB-1). With the single exception of one sample from the Isle of Skye, the oxygen isotopic composition of phosphate from belemnite rostra ranges from +19.8 to +24.9‰ (V-SMOW), 22 of the samples measured showing δ 18O values equal to or heavier than +23.0‰. In contrast, the oyster values are considerably lighter, in the case of both carbonate and phosphate. 18O-enriched values can hardly be related to diagenetic processes that normally cause an oxygen isotope shift towards light values. If deposition temperatures are calculated from the heavily enriched values by means of the equation of Longinelli and Nuti [Earth Planet. Sci. Lett. 19 (1973) 373-376] and assuming the δ 18O of Jurassic ocean water to be equal to -1‰ taking into account the lack of ice caps during the Jurassic, the obtained temperatures range from about 8°C to about zero. These temperatures are obviously unreliable when Mesozoic palaeoceanographic conditions and palaeoclimate are taken into account. Two different hypotheses are suggested to explain these results, other hypotheses being rejected as unreliable. (1) Phosphate derived from the decaying organic matter of belemnites might have been introduced into belemnite rostra by early diagenetic fluids. If the phosphate of belemnite organic matter was isotopically heavy as happens nowadays in the flesh of molluscs, the inflow of this phosphate into the rostra could be responsible for the very positive δ 18O values shown by many belemnite rostra (this hypothesis is suggested by H.W.); (2) previous oxygen isotope measurements on Upper Cretaceous belemnites yielded δ 18O values very close to the most positive values obtained from Lower Tertiary pelecypods and fish teeth which are known to precipitate their phosphate under isotopic equilibrium conditions with seawater. These data suggest the possibility that the phosphate in belemnite rostra is primary phosphate so that the very positive data reported here can be considered the result of good preservation of the pristine isotopic composition of primary phosphate. Consequently, the only way to explain the very positive δ 18O values is to consider the oxygen isotopic composition of Jurassic ocean water to be more positive than nowadays by at least 3‰. This hypothesis is suggested by A.L. and A.D.M.

Provenancing Archaeological Wool Textiles from Medieval Northern Europe by Light Stable Isotope Analysis (δ13C, δ15N, δ2H)

PubMed Central

von Holstein, Isabella C. C.; Walton Rogers, Penelope; Craig, Oliver E.; Penkman, Kirsty E. H.; Newton, Jason; Collins, Matthew J.

2016-01-01

We investigate the origin of archaeological wool textiles preserved by anoxic waterlogging from seven medieval archaeological deposits in north-western Europe (c. 700–1600 AD), using geospatial patterning in carbon (δ13C), nitrogen (δ15N) and non-exchangeable hydrogen (δ2H) composition of modern and ancient sheep proteins. δ13C, δ15N and δ2H values from archaeological wool keratin (n = 83) and bone collagen (n = 59) from four sites were interpreted with reference to the composition of modern sheep wool from the same regions. The isotopic composition of wool and bone collagen samples clustered strongly by settlement; inter-regional relationships were largely parallel in modern and ancient samples, though landscape change was also significant. Degradation in archaeological wool samples, examined by elemental and amino acid composition, was greater in samples from Iceland (Reykholt) than in samples from north-east England (York, Newcastle) or northern Germany (Hessens). A nominal assignment approach was used to classify textiles into local/non-local at each site, based on maximal estimates of isotopic variability in modern sheep wool. Light element stable isotope analysis provided new insights into the origins of wool textiles, and demonstrates that isotopic provenancing of keratin preserved in anoxic waterlogged contexts is feasible. We also demonstrate the utility of δ2H analysis to understand the location of origin of archaeological protein samples. PMID:27764106

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study

NASA Astrophysics Data System (ADS)

Lauwens, Sara; Costas-Rodríguez, Marta; van Vlierberghe, Hans; Vanhaecke, Frank

2016-07-01

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient’s condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about -0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ65Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure.

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study

PubMed Central

Lauwens, Sara; Costas-Rodríguez, Marta; Van Vlierberghe, Hans; Vanhaecke, Frank

2016-01-01

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient’s condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about −0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ65Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure. PMID:27468898

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study.

PubMed

Lauwens, Sara; Costas-Rodríguez, Marta; Van Vlierberghe, Hans; Vanhaecke, Frank

2016-07-29

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient's condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about -0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ(65)Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure.

The effects of serpentinization on Mg isotopes in Mid-Atlantic ridge peridotite

NASA Astrophysics Data System (ADS)

Wimpenny, J.; Harvey, J.; Yin, Q.

2012-12-01

The magnesium isotope composition of the Earth's mantle [1], and bulk estimates for upper crustal rocks [2] overlap with values obtained from chondritic meteorites [1], suggesting broad scale homogeneity of δ26Mg on Earth. By way of contrast, weathering of continental crust results in significant fractionation of Mg isotopes [3]. Negative δ26Mg in riverine and groundwater fluxes suggest that the lighter isotopes of Mg are preferentially removed in fluid during partial weathering, leaving a heavy δ26Mg residuum [4]. Thus, riverine fluxes to the ocean result in a marine reservoir with a δ26Mg = -0.82 ± 0.01 [5], significantly lighter than that of fresh mantle material and its derivatives [1]. Abyssal peridotites recovered from Ocean Drilling Program Leg 209 display a wide range of bulk-rock compositions and have been demonstrated to have interacted with a number of low and high temperature fluids [6]. Peridotite from Hole 1274a has been variably serpentinized at low (c. 200 oC) temperatures. Serpentinized samples from Hole 1268a, have also interacted with a higher temperature fluid (c. 350 oC) with a low Mg/Si ratio resulting in abundant talc formation [6]. Serpentinites contain high concentrations of Mg and are abundantly exposed at the seafloor at slow and ultra-slow oceanic ridges [7,8]. Because peridotites are thought to be a source of Mg to seawater [9] any fractionation of Mg isotopes that accompanies serpentinization will have implications for the composition of Mg in seawater. The δ26Mg of samples from 1274a are similar to primary upper crustal rocks, (UCC δ26Mg = -0.22 ± 0.04 [2]). However, samples from 1268a have fractionated δ26Mg values that are generally enriched in isotopically heavy Mg relative to the UCC, ranging from -0.25 to -0.02‰. These results suggest that serpentinization itself does not cause fractionation of Mg, but that later formation of talc is associated with the preferential retention of isotopically heavy Mg, consistent with secondary silicates formed during continental weathering [e.g. 3]. Mass balance requires that the talc-altered serpentinite must be complimented by an isotopically light component. It seems most likely that this isotopically light Mg will be transferred and mixed into ambient temperature seawater. The impact of this transfer will be dependent on the size of the Mg exchange between peridotite and seawater and the fractionation factor associated with talc alteration. Our data suggest that this would input Mg into seawater that is isotopically light relative to the altered peridotite. [1] Pogge von Strandmann et al., (2011) GCA 75, 5247-5268. [2] Li et al. (2010) GCA 74, 6867-6884. [3] Tipper et al., (2006) EPSL 247, 267-279. [4] Wimpenny et al., (2010) GCA 74, 5259-5279. [5] Foster et al., (2010) Geochem. Geophys. Geosys. 11, doi:10.1029/2010GC003201. [6] Bach et al., (2004) Geochem. Geophys. Geosys. 5, doi:10.1029/2004GC000744. [7] Cannat et al., (1997) Tectonophys. 279, 193-213. [8] Jokat et al., (2003) Nature 423, 962-965. [9] Snow & Dick (1995) GCA, 59, 4219-4235.

Nuclear reactions in shock wave front during supernova events

NASA Technical Reports Server (NTRS)

Lavrukhina, A. K.

1985-01-01

The new unique isotopic anomalous coponent of Xe(XeX) was found in the carbonaceous chondrites. It is enriched in light shielded isotopes (124Xe and 126Xe) and in heavy nonshielded isotopes (134Xe and 136Xe. All characteristics of Xe-X can be explained by a model of nucleosynthesis of the Xe isotopes in shock wave front passed through the He envelope during supernova events. The light isotopes are created by p process and the heavy isotopes are created by n process (slow r process). They were captured with high temperature carbon grains condensing by supernova shock waves.

Shedding light on the mercury mass discrepancy by weighing Hg 52+ ions in a Penning trap

NASA Astrophysics Data System (ADS)

Fritioff, T.; Bluhme, H.; Schuch, R.; Bergström, I.; Björkhage, M.

2003-07-01

In their nuclear tables Audi and Wapstra have pointed out a serious mass discrepancy between their extrapolated values for the mercury isotopes and those from a direct measurement by the Manitoba group. The values deviate by as much as 85 ppb from each other with claimed uncertainties of about 16 and 7 ppb, respectively. In order to decide which values are correct the masses of the 198Hg and 204Hg isotopes have been measured in the Stockholm Penning trap mass spectrometer SMILETRAP using 52+ ions. This charge state corresponds to a filled Ni electron configuration for which the electron binding energy can be accurately calculated. The mass values obtained are 197.966 768 44(43) u for 198Hg and 203.973 494 10(39) u for 204Hg. These values agree with those measured by the Manitoba group, with a 3 times lower uncertainty. This measurement was made possible through the implementation of a cooling technique of the highly charged mercury ions during charge breeding in the electron beam ion source used for producing the Hg 52+ ions.

Microscale Variations in the 13C Content of the Murchison Meteorite

NASA Astrophysics Data System (ADS)

Romanek, C.; Gibson, E.; Socki, R.; Burkett, P. J.

1993-07-01

Heretofore unresolved micrometer-scale carbon isotopic zonation in the Murchison meteorite (CM3) is documented using a laser microprobe mass spectrometer. High-resolution isotopic gradients and heterogeneities between high- and low-temperature textural components help to constrain the processes that have shaped the physiochemical character of this carbonaceous chondrite. Previous bulk samples of Murchison yield an average delta ^13C value of - 5.7 +/- 4.3 per mil [1] while individual components such as micrometer-sized mineral separates (e.g., C(sub)graphite , C(sub)diamond, and SiC), acid- soluble extracts (e.g., CaCO3 and polar hydrocarbons), and insoluble residues (e.g., polycyclic aromatic hydrocarbons) are isotopically diverse (delta ^13C of -1000 to 29,000 per mil). While these studies shed light on the origin and occurrence of C-bearing phases, they fail to constrain intrinsic spatial isotopic heterogeneities. The power of the laser microprobe lies in the fact that in situ chemical and isotopic compositions are measured simultaneously for volatiles extracted from extremely small sample volumes (i.e., 0.025 mm^3 for 5 wt% C). Nd-YAG laser irradiation (1.06 micrometers) is directed onto texturally defined targets (>=50 micrometers wide) from which solid material is volatilized. Condensible gaseous phases are collected in a variable-temperature cold trap while the more volatile species (CH4 and CO) are quantified using an ion trap mass spectrometer. All gases are then converted to CO2 in a CuO furnace (containing Pt) held at 600 degrees C and analyzed for carbon and oxygen isotope ratios. The concentration and isotopic composition of condensed species are determined by stepped sublimation of unstable components and conversion to CO2. Preliminary isotopic analyses of the total volatile C content (i.e., bulk microanalysis) from distinct textural components at least 0.05 mm^3 in volume are described below. The most ^13C-depleted components within Murchison reside within the cores of chondrules and/or aggregates. Three typical cores were analyzed, with an average bulk composition of -21.0 +/- 0.5 per mil (n = 7). The bulk ^13C content of C-bearing phases increases monotonically outward in all directions within 100 to 200 micrometers of each core (i.e., within dust mantles) to a constant matrix value of -12.5 +/- 0.5 per mil (n = 40). The most isotopically enriched textural component found in Murchison is a regolith breccia clast without chondrules that has an average bulk delta ^13C value of -10 +/-0.5 per mil (n = 5). The clast was originally detectable only under cathodoluminescence, but with the aid of the laser microprobe it is now characterized by an unusually low volatile content and enriched ^13C composition. In general, the most isotopically enriched components also produce the lowest yield of gas (normalized to sampling volume). This trend of isotopic enrichment from chondrule to matrix has been documented previously for oxygen isotopes in carbonaceous chondrites [2]. Carbon isotopic gradients and heterogeneities within Murchison reflect fundamental changes in the chemical speciation and/or isotopic content of the main C-bearing components (i.e., acid-soluble and insoluble hydrocarbon fractions) within the meteorite. Perhaps core interiors and dust mantles are responding to environmental changes reflected in the speciation of C-bearing species distributed within the solar nebula or the parent body. Inverse correlations between hydrocarbon atomic mass number and ^13C abundance in the acid-soluble [3] and insoluble residues [4] of Murchison have been documented. Alternatively, micrometer-scale isotopic gradients may reflect fundamental changes in the isotopic composition of individual C-bearing species through time. Enrichments may represent kinetically controlled processes related to hydrocarbon formation. In contrast, assuming an equilibrium fractionation mechanism, isotopic enrichments may record a temperature-dependent component to hydrocarbon delta ^13C values. These opposing alternatives will be discussed in light of the isotopic composition of individual C-bearing components volatilized from tightly constrained sample volumes within Murchison. References: [1] Kerridge J. F. (1985) GCA, 49, 1707-1714. [2] Clayton R. N. and Mayeda T. K. (1984) EPSL, 67, 151-161. [3] Yuen G. et al. (1984) Nature, 307, 254. [4] Gilmour I. et al. (1991) Meteoritics, 26, 337-338.

Sulfate-dependent Anaerobic Oxidation of Methane as a Generation Mechanism for Calcite Cap Rock in Gulf Coast Salt Domes

NASA Astrophysics Data System (ADS)

Caesar, K. H.; Kyle, R.; Lyons, T. W.; Loyd, S. J.

2015-12-01

Gulf Coast salt domes, specifically their calcite cap rocks, have been widely recognized for their association with significant reserves of crude oil and natural gas. However, the specific microbial reactions that facilitate the precipitation of these cap rocks are still largely unknown. Insight into the mineralization mechanism(s) can be obtained from the specific geochemical signatures recorded in these structures. Gulf Coast cap rocks contain carbonate and sulfur minerals that exhibit variable carbon (d13C) and sulfur isotope (δ34S) signatures. Calcite d13C values are isotopically depleted and show a large range of values from -1 to -52‰, reflecting a mixture of various carbon sources including a substantial methane component. These depleted carbon isotope compositions combined with the presence of abundant sulfide minerals in cap rocks have led to interpretations that invoke microbial sulfate reduction as an important carbonate mineral-yielding process in salt dome environments. Sulfur isotope data from carbonate-associated sulfate (CAS: trace sulfate incorporated within the carbonate mineral crystal lattice) provide a more direct proxy for aqueous sulfate in salt dome systems and may provide a means to directly fingerprint ancient sulfate reduction. We find CAS sulfur isotope compositions (δ34SCAS) significantly greater than those of the precursor Jurassic sulfate-salt deposits (which exhibit δ34S values of ~ +15‰). This implies that cap rock carbonate generation occurred via microbial sulfate reduction under closed-system conditions. The co-occurrence of depleted carbonate d13C values (< ~30‰) and the enriched δ34SCAS values are evidence for sulfate-dependent anaerobic oxidation of methane (AOM). AOM, which has been shown to yield extensive seafloor carbonate authigenesis, is also potentially partly responsible for the carbonate minerals of the Gulf Coast calcite cap rocks through concomitant production of alkalinity. Collectively, these data shed new light on a potential hotspot of microbial activity in the deep biosphere.

Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.

The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol -1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gasmore » phase. Large difference in adsorption enthalpy of 2.5 kJ mol -1 between D 2 and H 2 results in D 2-over-H 2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H 2/D 2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

DOE PAGES

Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.; ...

2017-03-06

The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol -1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gasmore » phase. Large difference in adsorption enthalpy of 2.5 kJ mol -1 between D 2 and H 2 results in D 2-over-H 2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H 2/D 2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

Impact of isotopic disorders on thermal transport properties of nanotubes and nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Tao; Kang, Wei; Wang, Jianxiang, E-mail: jxwang@pku.edu.cn

2015-01-21

We present a one-dimensional lattice model to describe thermal transport in isotopically doped nanotubes and nanowires. The thermal conductivities thus predicted, as a function of isotopic concentration, agree well with recent experiments and other simulations. Our results display that for any given concentration of isotopic atoms in a lattice without sharp atomic interfaces, the maximum thermal conductivity is attained when isotopic atoms are placed regularly with an equal space, whereas the minimum is achieved when they are randomly inserted with a uniform distribution. Non-uniformity of disorder can further tune the thermal conductivity between the two values. Moreover, the dependence ofmore » the thermal conductivity on the nanoscale feature size becomes weak at low temperature when disorder exists. In addition, when self-consistent thermal reservoirs are included to describe diffusive nanomaterials, the thermal conductivities predicted by our model are in line with the results of macroscopic theories with an interfacial effect. Our results suggest that the disorder provides an additional freedom to tune the thermal properties of nanomaterials in many technological applications including nanoelectronics, solid-state lighting, energy conservation, and conversion.« less

Pristine extraterrestrial material with unprecedented nitrogen isotopic variation.

PubMed

Briani, Giacomo; Gounelle, Matthieu; Marrocchi, Yves; Mostefaoui, Smail; Leroux, Hugues; Quirico, Eric; Meibom, Anders

2009-06-30

Pristine meteoritic materials carry light element isotopic fractionations that constrain physiochemical conditions during solar system formation. Here we report the discovery of a unique xenolith in the metal-rich chondrite Isheyevo. Its fine-grained, highly pristine mineralogy has similarity with interplanetary dust particles (IDPs), but the volume of the xenolith is more than 30,000 times that of a typical IDP. Furthermore, an extreme continuum of N isotopic variation is present in this xenolith: from very light N isotopic composition (delta(15)N(AIR) = -310 +/- 20 per thousand), similar to that inferred for the solar nebula, to the heaviest ratios measured in any solar system material (delta(15)N(AIR) = 4,900 +/- 300 per thousand). At the same time, its hydrogen and carbon isotopic compositions exhibit very little variation. This object poses serious challenges for existing models for the origin of light element isotopic anomalies.

Textural and stable isotope studies of the Big Mike cupriferous volcanogenic massive sulfide deposit, Pershing County, Nevada.

USGS Publications Warehouse

Rye, R.O.; Roberts, R.J.; Snyder, W.S.; Lahusen, G.L.; Motica, J.E.

1984-01-01

The Big Mike deposit is a massive sulphide lens entirely within a carbonaceous argillite of the Palaeozoic Havallah pelagic sequence. The massive ore contains two generations of pyrite, a fine- and a coarse-grained variety; framboidal pyrite occurs in the surrounding carbonaceous argillite. Coarse grained pyrite is largely recrystallized fine-grained pyrite and is proportionately more abundant toward the margins of the lens. Chalcopyrite and sphalerite replace fine-grained pyrite and vein-fragmented coarse-grained pyrite. Quartz fills openings in the sulphide fabric. S-isotope data are related to sulphide mineralogy and textures. Isotopically light S in the early fine-grained pyrite was probably derived from framboidal biogenic pyrite. The S-isotope values of the later coarse-grained pyrite and chalcopyrite probably reflect a combination of reduced sea-water sulphate and igneous S. Combined S- and O-isotope and textural data accord with precipitation of fine-grained pyrite from a hydrothermal plume like those at the East Pacific Rise spreading centre at lat. 21oN. The primary material was recystallized and mineralized by later fluids of distinctly different S-isotope composition. -G.J.N.

[Effect of microorganisms and seasonal factors on the isotope composition of organic carbon from Black Sea suspensions].

PubMed

Ivanov, M V; Lein, A Iu; Miller, Iu M; Iusunov, S K; Pimenov, N V; Wehrli, B; Rusanov, I I; Zehnder, A

2000-01-01

The isotopic composition of particulate organic carbon (POC) from the Black Sea deep-water zone was studied during a Russian-Swiss expedition in May 1998. POC from the upper part of the hydrogen sulfide zone (the C-layer) was found to be considerably enriched with the 12C isotope, as compared to the POC of the oxycline and anaerobic zone. In the C-layer waters, the concurrent presence of dissolved oxygen and hydrogen sulfide and an increased rate of dark CO2 fixation were recorded, suggesting that the change in the POC isotopic composition occurs at the expense of newly formed isotopically light organic matter of the biomass of autotrophic bacteria involved in the sulfur cycle. In the anaerobic waters below the C-layer, the organic matter of the biomass of autotrophs is consumed by the community of heterotrophic microorganisms; this results in weighting of the POC isotopic composition. Analysis of the data obtained and data available in the literature allows an inference to be made about the considerable seasonable variability of the POC delta 13C value, which depends on the ratio of terrigenic and planktonogenic components in the particulate organic matter.

Collectivity of light Ge and As isotopes

NASA Astrophysics Data System (ADS)

Corsi, A.; Delaroche, J.-P.; Obertelli, A.; Baugher, T.; Bazin, D.; Boissinot, S.; Flavigny, F.; Gade, A.; Girod, M.; Glasmacher, T.; Grinyer, G. F.; Korten, W.; Libert, J.; Ljungvall, J.; McDaniel, S.; Ratkiewicz, A.; Signoracci, A.; Stroberg, R.; Sulignano, B.; Weisshaar, D.

2013-10-01

Background: The self-conjugate nuclei of the A˜70 mass region display rapid shape evolution over isotopic or isotonic chains. Shape coexistence has been observed in Se and Kr isotopes reflecting the existence of deformed subshell gaps corresponding to different shell configurations. As and Ge isotopes are located halfway between such deformed nuclei and the Z=28 shell closure.Purpose: The present work aims at clarifying the low-lying spectroscopy of 66Ge and 67As, and providing a better insight into the evolution of collectivity in light even-even Ge and even-odd As isotopes.Methods: We investigate the low-lying levels and collectivity of the neutron deficient 67As and 66Ge through intermediate-energy Coulomb excitation, inelastic scattering, and proton knockout measurements. The experiment was performed using a cocktail beam of 68Se, 67As, and 66Ge nuclei at an energy of 70-80 MeV/nucleon. Spectroscopic properties of the low-lying states are compared to those calculated via shell model with the JUN45 interaction and beyond-mean-field calculations with the five-dimensional collective Hamiltonian method implemented using the Gogny D1S interaction. The structure evolution of the lower-mass Ge and As isotopes is discussed.Results: Reduced electric quadrupole transition probabilities B(E2) have been extracted from the Coulomb-excitation cross sections measured in 66Ge and 67As. The value obtained for the B(E2;01+→21+) in 66Ge is in agreement with a recent measurement, ruling out the existence of a minimum at N=34 in the B(E2) systematics as previously observed. New transitions have been found in 67As and were assigned to the decay of low-lying negative-parity states.

Shell-model-based deformation analysis of light cadmium isotopes

NASA Astrophysics Data System (ADS)

Schmidt, T.; Heyde, K. L. G.; Blazhev, A.; Jolie, J.

2017-07-01

Large-scale shell-model calculations for the even-even cadmium isotopes 98Cd-108Cd have been performed with the antoine code in the π (2 p1 /2;1 g9 /2) ν (2 d5 /2;3 s1 /2;2 d3 /2;1 g7 /2;1 h11 /2) model space without further truncation. Known experimental energy levels and B (E 2 ) values could be well reproduced. Taking these calculations as a starting ground we analyze the deformation parameters predicted for the Cd isotopes as a function of neutron number N and spin J using the methods of model independent invariants introduced by Kumar [Phys. Rev. Lett. 28, 249 (1972), 10.1103/PhysRevLett.28.249] and Cline [Annu. Rev. Nucl. Part. Sci. 36, 683 (1986), 10.1146/annurev.ns.36.120186.003343].

The Boron Isotopic Composition of Elephant Dung: Inputs to the Global Boron Budget

NASA Astrophysics Data System (ADS)

Williams, L. B.; Hervig, R. L.

2011-12-01

A survey of boron in kerogen showed isotopically light δ11B values (0 to -50%) that are distinctly different from most mineral and natural water B reservoirs. Diagenesis releases this isotopically light B into pore fluids when hydrocarbons are generated, thus enriching oilfield brines in 10B. This observation suggests that borated biomolecules (BM) are primarily tetrahedral favoring 10B, whereas 11B is preferred in trigonal coordination. Plants, with optimal concentrations up to 100ppm, contribute more B than animal remains to sediment. Elephants are one of the largest herbivores on earth, consuming 200 - 250 kg of plant material/day and producing 50 kg of manure/day. They are inefficient at digestion, thus the manure contains >50% undigested plant material. Dung samples are therefore ideal for studying the δ11B of both the food input and digested output of a significant B supply to sedimentary systems. Horse and rabbit manure were studied for comparison to evaluate B isotope variations in the food supply and potential vital effects on the output. B-content and isotopic composition of dung plant material and digested fractions were measured in the solid state by secondary ion mass spectrometry. The digests were rinsed in 1.8% mannitol, a B-complexing agent, to remove surface adsorbed-B, then air dried and Au-coated for charge compensation. Results showed that the elephant diet contains 3-13 ppm B, with an average δ11B of -20 ± 0.8% (1σ), while rabbit food had 88 ppm B with a δ11B of -50 ± 1.3 %. The digested fraction of the elephant dung contains 4-10ppm B with average δ11B values of -12 ± 1.2%. In comparison, horse manure with 11-21 ppm B has a δ11B of -10.7 ± 0.5% and rabbit manure contains 2-3 ppm B with a δ11B of -8.8 ± 1%. Boron isotope compositions of these manures are indistinguishable (within error). Clearly plant material is a major contributor of isotopically light B to sediments. The herbivores studied fractionate their total B intake in favor of 11B, thus increasing the δ11B of the (solid) digested material relative to the food source. This would not affect the overall BM input to the sediment because the dung contains the undigested plants. If we assume that the average B isotopic composition of dung, ~10ppm B at -20%, represents an average BM in sediment, and that the mass of sediments (1E24 g) is comparable to the mass of seawater with an average 5ppm B at +40%, then it is clear that BM plays a major role in balancing the global B budget. Note: This research was NOT funded by taxpayer dollars. The Phoenix Zoo kindly approved the proposal to sample elephant dung for this study and their support is greatly appreciated.

Non-Rayleigh control of upper-ocean Cd isotope fractionation in the western South Atlantic

NASA Astrophysics Data System (ADS)

Xie, Ruifang C.; Galer, Stephen J. G.; Abouchami, Wafa; Rijkenberg, Micha J. A.; de Baar, Hein J. W.; De Jong, Jeroen; Andreae, Meinrat O.

2017-08-01

We present seawater Cd isotopic compositions in five depth profiles and a continuous surface water transect, from 50°S to the Equator, in the western South Atlantic, sampled during GEOTRACES cruise 74JC057 (GA02 section, Leg 3), and investigate the mechanisms governing Cd isotope cycling in the upper and deep ocean. The depth profiles generally display high ε 112 / 110Cd at the surface and decrease with increasing depth toward values typical of Antarctic Bottom Water (AABW). However, at stations north of the Subantarctic Front, the decrease in ε 112 / 110Cd is interrupted by a shift to values intermediate between those of surface and bottom waters, which occurs at depths occupied by North Atlantic Deep Water (NADW). This pattern is associated with variations in Cd concentration from low surface values to a maximum at mid-depths and is attributed to preferential utilization of light Cd by phytoplankton in the surface ocean. Our new results show that in this region Cd-deficient waters do not display the extreme, highly fractionated ε 112 / 110Cd reported in some earlier studies from other oceanic regions. Instead, in the surface and subsurface southwest (SW) Atlantic, when [Cd] drops below 0.1 nmol kg-1, ε 112 / 110Cd are relatively homogeneous and cluster around a value of +3.7, in agreement with the mean value of 3.8 ± 3.3 (2SD, n = 164) obtained from a statistical evaluation of the global ocean Cd isotope dataset. We suggest that Cd-deficient surface waters may acquire their Cd isotope signature via sorption of Cd onto organic ligands, colloids or bacterial/picoplankton extracellular functional groups. Alternatively, we show that an open system, steady-state model is in good accord with the observed Cd isotope systematics in the upper ocean north of the Southern Ocean. The distribution of ε 112 / 110Cd in intermediate and deep waters is consistent with the water mass distribution, with the north-south variations reflecting changes in the mixing proportion of NADW and either AABW or AAIW depending on the depth. Overall, the SW Atlantic Cd isotope dataset demonstrates that the large-scale ocean circulation exerts the primary control on ε 112 / 110Cd cycling in the global deep ocean.

Segregation of isotopes of heavy metals due to light-induced drift: results and problems

NASA Astrophysics Data System (ADS)

Sapar, A.; Aret, A.; Poolamäe, R.; Sapar, L.

2008-04-01

Atutov and Shalagin (1988) proposed light-induced drift (LID) as a physically well understandable mechanism to explain the formation of isotopic anomalies observed in CP stars. We have generalized the theory of LID and applied it to diffusion of heavy elements and their isotopes in quiescent atmospheres of CP stars. Diffusional segregation of isotopes of chemical elements is described by the equations of continuity and diffusion velocity. Computations of evolutionary sequences for the abundances of mercury isotopes in several model atmospheres have been made, using the Fortran 90 program SMART composed by the authors. Results confirm predominant role of LID in separation of isotopes.

Light Nuclei and Isotope Abundances in Cosmic Rays. Results from AMS-01

NASA Astrophysics Data System (ADS)

Tomassetti, N.

2011-06-01

Observations of the chemical and isotopic composition of light cosmic-ray nuclei can be used to constrain the propagation models. Nearly 200,000 light nuclei (Z > 2) have been observed by AMS-01 during the 10-day flight STS-91 in June 1998. Using these data, we have measured Li, Be, B and C in the kinetic energy range 0.35 - 45 GeV/nucleon. In this proceeding, our charge and isotopic composition results are presented and discussed.

Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

NASA Astrophysics Data System (ADS)

Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

2015-04-01

Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

Mercury (Hg) in meteorites: Variations in abundance, thermal release profile, mass-dependent and mass-independent isotopic fractionation

NASA Astrophysics Data System (ADS)

Meier, Matthias M. M.; Cloquet, Christophe; Marty, Bernard

2016-06-01

We have measured the concentration, isotopic composition and thermal release profiles of Mercury (Hg) in a suite of meteorites, including both chondrites and achondrites. We find large variations in Hg concentration between different meteorites (ca. 10 ppb to 14,000 ppb), with the highest concentration orders of magnitude above the expected bulk solar system silicates value. From the presence of several different Hg carrier phases in thermal release profiles (150-650 °C), we argue that these variations are unlikely to be mainly due to terrestrial contamination. The Hg abundance of meteorites shows no correlation with petrographic type, or mass-dependent fractionation of Hg isotopes. Most carbonaceous chondrites show mass-independent enrichments in the odd-numbered isotopes 199Hg and 201Hg. We show that the enrichments are not nucleosynthetic, as we do not find corresponding nucleosynthetic deficits of 196Hg. Instead, they can partially be explained by Hg evaporation and redeposition during heating of asteroids from primordial radionuclides and late-stage impact heating. Non-carbonaceous chondrites, most achondrites and the Earth do not show these enrichments in vapor-phase Hg. All meteorites studied here have however isotopically light Hg (δ202Hg = ∼-7 to -1) relative to the Earth's average crustal values, which could suggest that the Earth has lost a significant fraction of its primordial Hg. However, the late accretion of carbonaceous chondritic material on the order of ∼2%, which has been suggested to account for the water, carbon, nitrogen and noble gas inventories of the Earth, can also contribute most or all of the Earth's current Hg budget. In this case, the isotopically heavy Hg of the Earth's crust would have to be the result of isotopic fractionation between surface and deep-Earth reservoirs.

Tracing cadmium, zinc and lead sources in bivalves from the coasts of western Canada and the USA using isotopes

NASA Astrophysics Data System (ADS)

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

2012-01-01

Environmental monitoring and remediation require techniques to identify the source and fate of metals emissions. The measurement of heavy metal isotopic signatures, made possible by the advent of the MC-ICP-MS, is a powerful new geochemical tool, which may be used to trace the source of these metals in the environment. In a multi-tracer study, Cd, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from western Canada (British Columbia), Hawaii, and the USA East Coast. Variability in the δ 114/110Cd values of bivalves (-1.20‰ to -0.09‰) is attributed to differences in the relative contributions of Cd from natural and anthropogenic sources between sites. Cadmium isotopic compositions (δ 114/110Cd = -0.69‰ to -0.09‰) identify high Cd levels in B.C. oysters as primarily natural (i.e., upwelling of Cd rich intermediate waters in the North Pacific), with some variability attributed to anthropogenic sources (e.g., mining and smelting). Variability in the δ 66/64Zn values exhibited by the B.C. bivalves is relatively small (0.28-0.36‰). Despite the low Pb levels found in B.C. oysters, Pb isotopes are used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as significant metal sources. Although the Cd concentrations of the USA East Coast bivalves are primarily lower than those of B.C. oysters, their relatively light Cd isotopic compositions (δ 114/110Cd = -1.20‰ to -0.54‰) indicate the significance of anthropogenic Cd sources and are attributed to the high prevalence of industry on this coast. The δ 114/110Cd values of USA East Coast bivalves include the lightest ever reported, with the exception of values reported for extraterrestrial materials. In addition, the Pb isotopic compositions of bivalves from the USA East Coast indicate Pb emissions from the combustion of coal are an important source of Pb, consistent with the high consumption of coal for power production on this coast. This study demonstrates the effective use of Cd and Zn isotopes to trace anthropogenic sources in the environment and the benefit of combining these tools with Pb "fingerprinting" techniques.

Partial melting and melt percolation in the mantle: The message from Fe isotopes

NASA Astrophysics Data System (ADS)

Weyer, Stefan; Ionov, Dmitri A.

2007-07-01

High precision Fe isotope measurements have been performed on various mantle peridotites (fertile lherzolites, harzburgites, metasomatised Fe-enriched peridotites) and volcanic rocks (mainly oceanic basalts) from different localities and tectonic settings. The peridotites yield an average δ 56Fe = 0.01‰ and are significantly lighter than the basalts (average δ 56Fe = 0.11‰). Furthermore, the peridotites display a negative correlation of δ 56Fe with Mg# indicating a link between δ 56Fe and degrees of melt extraction. Taken together, these findings imply that Fe isotopes fractionate during partial melting, with heavy isotopes preferentially entering the melt. The slope of depletion trends (δ 56Fe versus Mg#) of the peridotites was used to model Fe isotope fractionation during partial melting, resulting in αmantle-melt ≈ 1.0001-1.0003 or ln αmantle-melt ≈ 0.1-0.3‰. In contrast to most other peridotites investigated in this study, spinel lherzolites and harzburgites from three localities (Horoman, Kamchatka and Lherz) are virtually unaffected by metasomatism. These three sites display a particularly good correlation and define an isotope fractionation factor of ln αmantle-melt ≈ 0.3‰. This modelled value implies Fe isotope fractionation between residual mantle and mantle-derived melts corresponding to Δ56Fe mantle-basalt ≈ 0.2-0.3‰, i.e. significantly higher than the observed difference between averages for all the peridotites and the basalts in this study (corresponding to Δ56Fe mantle-basalt ≈ 0.1‰). Either disequilibrium melting increased the modelled αmantle-melt for these particular sites or the difference between average peridotite and basalt may be reduced by partial re-equilibration between the isotopically heavy basalts and the isotopically light depleted lithospheric mantle during melt ascent. The slope of the weaker δ 56Fe-Mg# trend defined by the combined set of all mantle peridotites from this study is more consistent with the generally observed difference between peridotites and basalts; this slope was used here to estimate the Fe isotope composition of the fertile upper mantle (at Mg# = 0.894, δ 56Fe ≈ 0.02 ± 0.03‰). Besides partial melting, the Fe isotope composition of mantle peridotites can also be significantly modified by metasomatic events, e.g. melt percolation. At two localities (Tok, Siberia and Tariat, Mongolia) δ 56Fe correlates with iron contents of the peridotites, which was increased from about 8% to up to 14.5% FeO by post-melting melt percolation. This process produced a range of Fe isotope compositions in the percolation columns, from extremely light (δ 56Fe = - 0.42‰) to heavy (δ 56Fe = + 0.17‰). We propose reaction with isotopically heavy melts and diffusion (enrichment of light Fe isotopes) as the most likely processes that produced the large isotope variations at these sites. Thus, Fe isotopes might be used as a sensitive tracer to identify such metasomatic processes in the mantle.

Chlorine isotope constraints on fluid-rock interactions during subduction and exhumation of the Zermatt-Saas ophiolite

NASA Astrophysics Data System (ADS)

Selverstone, J.; Sharp, Z. D.

2013-10-01

Chlorine isotope compositions of high-pressure (˜2.3 GPa) serpentinite, rodingite, and hydrothermally altered oceanic crust (AOC) differ significantly from high- and ultrahigh-pressure (> 3.2 GPa) metasedimentary rocks in the Aosta region, Italy. Texturally early serpentinites, rodingites, and AOC have bulk δ37Cl values indistinguishable from those of modern seafloor analogues (δ37Cl = -1.0 to +1.0‰). In contrast, serpentinites and AOC samples that recrystallized during exhumation have low δ37Cl values (-2.7 to -0.5‰); 37Cl depletion correlates with progressive changes in bulk chemistry. HP/UHP metasediments have low δ37Cl values (median = -2.5‰) that differ statistically from modern marine sediments (median = -0.6‰). Cl in metasedimentary rocks is concentrated in texturally early minerals, indicating modification of seafloor compositions early in the subduction history. The data constrain fluid sources during both subduction and exhumation-related phases of fluid-rock interaction: (1) marine sediments at the top of the downgoing plate likely interacted with isotopically light pore fluids from the accretionary wedge in the early stages of subduction. (2) No pervasive interaction with externally derived fluid occurred during subsequent subduction to the maximum depths of burial. (3) Localized mixing between serpentinites and fluids released by previously isotopically modified metasediments occurred during exhumation in the subduction channel. Most samples, however, preserved protolith signatures during subduction to near-arc depths.

Developing the Molybdenum Isotopic Proxy in Marine Barite

NASA Astrophysics Data System (ADS)

Erhardt, A. M.; Paytan, A.; Aggarwal, J.

2006-12-01

Molybdenum isotope ratios in seawater fluctuate in response to changing redox conditions and can provide clues into the degree of global ocean anoxia. The isotopic ratio of molybdenum has been shown to be sensitive to the relative proportion of oxic, suboxic, and euxinic environments. Deposition in oxic environments is isotopically light (~ -1.6‰ for δ^{97/95}Mo) relative to an average crustal source (0‰). Conversely, euxinic environments have been shown to be consistently heavier (~1.3‰) than the oxic sink through time, with suboxic sediments falling between these two signals. Shifts in the relative proportion of each sink, relative to a constant source, would alter the isotopic ratio of seawater over long time scales. Previously, this seawater value, and hence the degree of global anoxia, could only be inferred through mass balance calculations. We seek to quantify the isotopic signature of seawater though time using a phase that directly records this ratio. Marine barite precipitates inorganically in the water column directly from seawater, potentially providing a direct record of seawater characteristics. Molybdenum is a trace constituent of barite, with the molybdate ion substituting for sulfate at concentrations of about 1 ppm. To accurately determine the molybdenum isotopic ratio at these low concentrations (<15 ng per sample), modifications to existing measurement techniques are required. We will present the variations made to existing separation and mass-spectrometry techniques and the calibration of these new methods. The modifications were undertaken to reduce molybdenum blank to below 1 ng per analysis, to quantitatively remove interfering zirconium and to measure precise and reproducible isotope values. Preliminary data will be presented to illustrate potential applications for this new paleoredox proxy. This technique will allow for the measurement of molybdenum isotopic ratios at low concentrations, expanding the breath of compounds and signals that potentially record changes in planetary materials.

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.

Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

NASA Astrophysics Data System (ADS)

Bryan, Allison L.; Dong, Shuofei; Wilkes, Elise B.; Wasylenki, Laura E.

2015-05-01

Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Δ66/64Znadsorbed-dissolved ∼ -0.2‰). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Δ66/64Znadsorbed-dissolved was indistinguishable from zero (+0.05 ± 0.08‰). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Δ66/64Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Δ66/64Znadsorbed-dissolved ranged from nearly +3‰ at low surface loading to +0.16‰ at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation that ferromanganese sediments are enriched in heavier isotopes of Zn relative to deep seawater. This represents a step towards building a robust mass balance model for Zn isotopes in the oceans and potentially using Zn isotopes to trace biogeochemical cycling of this important element in the modern and ancient oceans.

Steps toward identifying a biogeochemical signal in non-equilibrium methane clumped isotope measurements

NASA Astrophysics Data System (ADS)

Douglas, P. M.; Eiler, J. M.; Sessions, A. L.; Dawson, K.; Walter Anthony, K. M.; Smith, D. A.; Lloyd, M. K.; Yanay, E.

2016-12-01

Microbially produced methane is a globally important greenhouse gas, energy source, and biological substrate. Methane clumped isotope measurements have recently been developed as a new analytical tool for understanding the source of methane in different environments. When methane forms in isotopic equilibrium clumped isotope values are determined by formation temperature, but in many cases microbial methane clumped isotope values deviate strongly from expected equilibrium values. Indeed, we observe a very wide range of clumped isotope values in microbial methane, which are likely strongly influenced by kinetic isotope effects, but thus far the biological and environmental parameters controlling this variability are not understood. We will present data from both culture experiments and natural environments to explore patterns of variability in non-equilibrium clumped isotope values on temporal and spatial scales. In methanogen batch cultures sampled at different time points along a growth curve we observe significant variability in clumped isotope values, with values decreasing from early to late exponential growth. Clumped isotope values then increase during stationary growth. This result is consistent with previous work suggesting that differences in the reversibility of methanogenesis related to metabolic rates control non-equilibrium clumped isotope values. Within single lakes in Alaska and Sweden we observe substantial variability in clumped isotope values on the order of 5‰. Lower clumped isotope values are associated with larger 2H isotopic fractionation between water and methane, which is also consistent with a kinetic isotope effect determined by the reversibility of methanogenesis. Finally, we analyzed a time-series clumped isotope compositions of methane emitted from two seeps in an Alaskan lake over several months. Temporal variability in these seeps is on the order of 2‰, which is much less than the observed spatial variability within the lake. Comparing carbon isotope fractionation between CO2 and CH4 with clumped isotope data suggests the temporal variability may result from changes in methane oxidation.

Calcium isotopes in wine

NASA Astrophysics Data System (ADS)

Holmden, C. E.

2011-12-01

The δ 44/40Ca values of bottled wine vary between -0.76% to -1.55% on the seawater scale and correlate weakly with inverse Ca concentration and Mg/Ca ratio, such that the lowest δ 44/40Ca values have the highest Ca concentrations and lowest Mg/Ca ratios. The correlation is notable in the sense that the measured wines include both whites and reds sampled from different wine growing regions of the world, and cover a wide range of quality. Trends among the data yield clues regarding the cause of the observed isotopic fractionation. White wines, and wines generally perceived to be of lower quality, have lower δ 44/40Ca values compared to red wines and wines of generally perceived higher quality. Quality was assessed qualitatively through sensory evaluation, price, and scores assigned by critics. The relationship between δ 44/40Ca and wine quality was most apparent when comparing wines of one varietal from one producer from the same growing region. In the vineyard, wine quality is related to factors such as the tonnage of the crop and the ripeness of the grapes at the time of harvesting, the thickness of the skins for reds, the age of the vines, as well as the place where the grapes were grown (terroir). Quality is also influenced by winemaking practices such as fermentation temperature, duration of skin contact, and barrel ageing. Accordingly, the relationship between δ 44/40Ca and wine quality may originate during grape ripening in the vineyard or during winemaking in the cellar. We tested the grape ripening hypothesis using Merlot grapes sampled from a vineyard in the Okanagan, British Columbia, using sugar content (degrees Brix) as an indicator of ripeness. The grapes were separated into pulp, skin, and pip fractions and were analyzed separately. Thus far, there is no clear evidence for a systematic change in δ 44/40Ca values associated with progressive ripening of grapes in the vineyard. On the day of harvesting, the δ 44/40Ca value of juice squeezed from Merlot grapes was -1.94%, which is lower than any of the bottled wines measured, thus far, whether white or red. The wine made from this juice yielded -1.16%, which points to fermentation being the principal source of isotopic variability found in bottled wine. The working hypothesis is that light isotopes of Ca are preferentially stripped from the juice during maceration, fermentation, and lees contact, by ion exchange sites on solid organic-matter comprising the skins and yeast and/or by Ca-tartrate precipitation. High quality wines (especially reds) tend to involve longer contact times between juice and skins in order to increase the extraction of color and phenolic compounds (tannins) from the grape skins, a practice that might also result in greater losses of light isotopes of Ca from the juice, thus explaining the isotopic pattern in bottled wine.

Deglacial dust provenance changes in the Eastern Equatorial Pacific and implications for ITCZ movement

NASA Astrophysics Data System (ADS)

Xie, Ruifang C.; Marcantonio, Franco

2012-02-01

The provenance of eolian dust supplied to deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation. Specifically, measuring temporal changes in dust provenance can shed light on changes in the mean position of the Intertropical Convergence Zone (ITCZ), a region acting as a barrier separating wind-blown material derived from northern versus southern hemisphere sources. Here we have analyzed Nd, Sr, and Pb isotope ratios in the operationally-defined detrital component extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110°W from 3°S to 7°N (ODP Leg 138, sites 848-853). Sr isotope results show that barite Sr has a significant influence on 87Sr/86Sr isotope ratios of samples in the upwelling zone of the EEP. However, sites located >3° or more away from the equator (sites 852 and 853) are believed to not be affected by barite Sr and provide useful detrital Sr signals. 208Pb/206Pb and 207Pb/206Pb ratios in all cores fall into the Pb-isotope space of five potential dust sources (Asia, North and Central/South America, Sahara, and Australia), with no distinct isotopic fingerprinting of the dominant source(s). ɛNd values were most valuable for discerning detrital source provenance, and their values at all sites, ranging from -5.46 to -3.25, were more unradiogenic for sediments deposited during the last glacial than for those deposited during the Holocene. There are distinct latitudinal trends in the ɛNd values, with more radiogenic values further south and less radiogenic values further north, excluding site 848. This distinction holds true for both Holocene and last glacial periods. For the most southerly site, 848, we invoke, for the first time, a distinct southern hemisphere Australian source as being responsible for the unradiogenic Nd isotope ratios. Both average last glacial and Holocene ɛNd values show similar sharp gradients along the transect between 5.29°N and 2.77°N, suggesting little movement of the glacial ITCZ in the EEP. However, during the deglacial, this gradient is stronger and shifted further north between 5.29°N and 7.21°N, suggesting a more northerly, possibly stronger, deglacial ITCZ.

Marine Carbonate Component in the Mantle Beneath the Southeastern Tibetan Plateau: Evidence From Magnesium and Calcium Isotopes

NASA Astrophysics Data System (ADS)

Liu, Fang; Li, Xin; Wang, Guiqin; Liu, Yufei; Zhu, Hongli; Kang, Jinting; Huang, Fang; Sun, Weidong; Xia, Xiaoping; Zhang, Zhaofeng

2017-12-01

Tracing and identifying recycled carbonates is a key issue to reconstruct the deep carbon cycle. To better understand carbonate subduction and recycling beneath the southeastern Tibetan Plateau, high-K cal-alkaline volcanic rocks including trachy-basalts and trachy-andesites from Tengchong were studied using Mg and Ca isotopes. The low δ26Mg (-0.31 ± 0.03‰ to -0.38 ± 0.03‰) and δ44/40Ca (0.67 ± 0.07‰ to 0.80 ± 0.04‰) values of these volcanic rocks compared to those of the mantle (-0.25 ± 0.07‰ and 0.94 ± 0.05‰, respectively) indicate the incorporation of isotopically light materials into the mantle source, which may be carbonate-bearing sediments with low δ26Mg and δ44/40Ca values. In addition, no correlations of δ26Mg and δ44/40Ca with either SiO2 contents or trace element abundance ratios (e.g., Sm/Yb and Ba/Y) were observed, suggesting that limited Mg and Ca isotopic fractionation occurred during cal-alkaline magmatic differentiation. A binary mixing model using Mg-Ca isotopes shows that 5-8% carbonates dominated primarily by dolostone were recycled back into the mantle. Since Tengchong volcanism is still active and probably related to ongoing plate tectonic movement, we propose that the recycled carbonates are derived from oceanic crust related to the ongoing subduction of the Indian plate.

Biogeochemical cycling of zinc and its isotopes in the Southern Ocean

NASA Astrophysics Data System (ADS)

Zhao, Y.; Vance, D.; Abouchami, W.; de Baar, H. J. W.

2014-01-01

We report Zn concentration and isotope data for seawater samples from the Atlantic sector of the Southern Ocean, collected during the IPY/GEOTRACES ANT-XXIV/III cruise along the Greenwich Zero Meridian. Data are reported for the full depth range of the water column at three stations, as well as a transect of surface samples, using a new analytical approach that is presented in detail here. Zn concentrations increase with depth, though due to proximity to upwelling sites, surface concentrations are not as low as in some parts of the ocean such as further northward into the Sub-Antarctic Zone. For two depth profiles south of the Polar Front Zone, the physical stratification of the upper water column is reflected in sudden near-surface changes in Zn concentration with depth. In contrast, beneath 100-300 m Zn concentrations barely change with depth. Zn isotopic data beneath 1000 m, for the Southern Ocean data presented here as well as published data from the North Atlantic and North Pacific, are strikingly homogeneous, with an average δ66Zn = +0.53 ± 0.14‰ (2SD, 2SE = 0.03, n = 21). The surface Southern Ocean is more variable, with δ66Zn ranging from 0.07‰ to 0.80‰. Between the two is a thin horizon at 40-80 m which, in the Southern Ocean as well as the North Atlantic and North Pacific, is characterised by distinctly light isotopic signatures, with δ66Zn about 0.3‰ lower than surface waters. Strong correlations between Si and Zn concentrations seen here and elsewhere, coupled to the lack of any systematic relationship between Si and Zn isotopes in the Southern Ocean, suggest that the removal of Zn associated with diatom opal involves little or no isotopic fractionation. Regeneration of this Zn also explains the homogeneous Zn isotopic composition of the global deep ocean so far sampled. However, the low Zn content of opal requires that deep ocean Zn does not directly come from the opal phase itself, but rather from associated organic material external to the diatom frustule during growth. Experimental data are consistent with little or no fractionation during incorporation of Zn into this material. On the other hand, the light zinc at 40-80 m is most consistent with the regeneration of an intra-cellular pool that both culturing experiments and field data suggest will be isotopically light. The data thus imply two processes by which Zn is taken up in the surface ocean, that these pools have very different regeneration lengthscales, and that physical mixing of the oceans cannot eradicate their isotopic signatures. Finally, the deep δ66Zn ocean value is significantly higher than the current best estimate of the input to the oceans. The most obvious candidate for the required light sink is the survival of some of the cellular Zn to be buried in sediment.

Catalytic-site design for inverse heavy-enzyme isotope effects in human purine nucleoside phosphorylase

PubMed Central

Harijan, Rajesh K.; Zoi, Ioanna; Antoniou, Dimitri; Schwartz, Steven D.; Schramm, Vern L.

2017-01-01

Heavy-enzyme isotope effects (15N-, 13C-, and 2H-labeled protein) explore mass-dependent vibrational modes linked to catalysis. Transition path-sampling (TPS) calculations have predicted femtosecond dynamic coupling at the catalytic site of human purine nucleoside phosphorylase (PNP). Coupling is observed in heavy PNPs, where slowed barrier crossing caused a normal heavy-enzyme isotope effect (kchem light/kchem heavy > 1.0). We used TPS to design mutant F159Y PNP, predicted to improve barrier crossing for heavy F159Y PNP, an attempt to generate a rare inverse heavy-enzyme isotope effect (kchem light/kchem heavy < 1.0). Steady-state kinetic comparison of light and heavy native PNPs to light and heavy F159Y PNPs revealed similar kinetic properties. Pre–steady-state chemistry was slowed 32-fold in F159Y PNP. Pre–steady-state chemistry compared heavy and light native and F159Y PNPs and found a normal heavy-enzyme isotope effect of 1.31 for native PNP and an inverse effect of 0.75 for F159Y PNP. Increased isotopic mass in F159Y PNP causes more efficient transition state formation. Independent validation of the inverse isotope effect for heavy F159Y PNP came from commitment to catalysis experiments. Most heavy enzymes demonstrate normal heavy-enzyme isotope effects, and F159Y PNP is a rare example of an inverse effect. Crystal structures and TPS dynamics of native and F159Y PNPs explore the catalytic-site geometry associated with these catalytic changes. Experimental validation of TPS predictions for barrier crossing establishes the connection of rapid protein dynamics and vibrational coupling to enzymatic transition state passage. PMID:28584087

Paleoenvironmental implications of taxonomic variation among δ 15 N values of chloropigments

NASA Astrophysics Data System (ADS)

Higgins, Meytal B.; Wolfe-Simon, Felisa; Robinson, Rebecca S.; Qin, Yelun; Saito, Mak A.; Pearson, Ann

2011-11-01

Natural variations in the ratios of nitrogen isotopes in biomass reflect variations in nutrient sources utilized for growth. In order to use δ 15N values of chloropigments of photosynthetic organisms to determine the corresponding δ 15N values of biomass - and by extension, surface waters - the isotopic offset between chlorophyll and biomass must be constrained. Here we examine this offset in various geologically-relevant taxa, grown using nutrient sources that may approximate ocean conditions at different times in Earth's history. Phytoplankton in this study include cyanobacteria (diazotrophic and non-diazotrophic), eukaryotic algae (red and green), and anoxygenic photosynthetic bacteria (Proteobacteria), as well as environmental samples from sulfidic lake water. Cultures were grown using N 2, NO 3-, and NH 4+ as nitrogen sources, and were examined under different light regimes and growth conditions. We find surprisingly high variability in the isotopic difference (δ 15N biomass - δ 15N chloropigment) for prokaryotes, with average values for species ranging from -12.2‰ to +11.7‰. We define this difference as ɛpor, a term that encompasses diagenetic porphyrins and chlorins, as well as chlorophyll. Negative values of ɛpor reflect chloropigments that are 15N-enriched relative to biomass. Notably, this enrichment appears to occur only in cyanobacteria. The average value of ɛpor for freshwater cyanobacterial species is -9.8 ± 1.8‰, while for marine cyanobacteria it is -0.9 ± 1.3‰. These isotopic effects group environmentally but not phylogenetically, e.g., ɛpor values for freshwater Chroococcales resemble those of freshwater Nostocales but differ from those of marine Chroococcales. Our measured values of ɛpor for eukaryotic algae (range = 4.7-8.7‰) are similar to previous reports for pure cultures. For all taxa studied, values of ɛpor do not depend on the type of nitrogen substrate used for growth. The observed environmental control of ɛpor suggests that values of ɛpor could be useful for determining the fractional burial of eukaryotic vs. cyanobacterial organic matter in the sedimentary record.

Isotopic variants of light and heavy L-pyroglutamic acid succinimidyl esters as the derivatization reagents for DL-amino acid chiral metabolomics identification by liquid chromatography and electrospray ionization mass spectrometry.

PubMed

Mochizuki, Toshiki; Todoroki, Kenichiro; Inoue, Koichi; Min, Jun Zhe; Toyo'oka, Toshimasa

2014-02-06

L-Pyroglutamic acid succinimidyl ester (L-PGA-OSu) and its isotopic variant (L-PGA[d5]-OSu) were newly synthesized and evaluated as the chiral labeling reagents for the enantioseparation of amino acids, in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. The enantiomers of amino acids were easily labeled with the reagents at 60°C within 10 min in an alkaline medium containing triethylamine. Although all the diastereomers derived from 18 proteolytic amino acids could not be satisfactorily separated, the pairs of 9 amino acids were completely separated by reversed-phase chromatography using the small particle (1.7 μm) ODS column (Rs=1.95-8.05). The characteristic daughter ions, i.e., m/z 84.04 and m/z 89.04, were detected from all the derivatives by the collision induced dissociation of the protonated molecular ions. A highly sensitive detection at a low-fmol level (0.5-3.2 fmol) was also obtained from the selected reaction monitoring (SRM) chromatograms. An isotope labeling strategy using light and heavy L-PGA-OSu for the differential analysis of the DL-amino acids in different sample groups is also presented in this paper. The differential analysis of biological sample (i.e., human serum) and food product (i.e., yogurt) were tried to demonstrate the efficiency of the proposed method. The ratios of the DL-amino acids in human serum samples, spiked with the different concentrations of D-amino acids, were determined by the procedures using L-PGA-OSu and L-PGA[d5]-OSu. The D/L ratios in the two sample groups at different concentrations of amino acids were similar to the theoretical values. Furthermore, the ratios of D/L-alanine values in different yogurt products were comparable to the ratios obtained from the d/l values using only light reagent (i.e., L-PGA-OSu). Consequently, the proposed strategy is useful for the differential analysis not only in biological samples but also in food products. Copyright © 2013 Elsevier B.V. All rights reserved.

Manganese oxide shuttling in pre-GOE oceans - evidence from molybdenum and iron isotopes

NASA Astrophysics Data System (ADS)

Kurzweil, Florian; Wille, Martin; Gantert, Niklas; Beukes, Nicolas J.; Schoenberg, Ronny

2016-10-01

The local occurrence of oxygen-rich shallow marine water environments has been suggested to significantly predate atmospheric oxygenation, which occurred during the Great Oxidation Event (GOE) ca. 2.4 billion years ago. However, the potential influence of such 'oxygen oases' on the mobility, distribution and isotopic composition of redox sensitive elements remains poorly understood. Here, we provide new molybdenum and iron isotopic data from shallow marine carbonate and silicate iron formations of the Koegas Subgroup, South Africa, that confirm local ocean redox stratification prior to the GOE. Mn concentrations correlate negatively with both δ98 Mo and δ56 Fe values, which highlights the substantial role of particulate manganese for the cycling of Mo and Fe in the Paleoproterozoic oceans. Based on these trends we propose that pore water molybdate was recharged (1) by the diffusional transport of seawater molybdate with high δ98 Mo and (2) by the re-liberation of adsorbed molybdate with low δ98 Mo during Mn oxide dissolution within the sediment. The relative contribution of isotopically light Mo is highest close to a Mn chemocline, where the flux of Mn oxides is largest, causing the negative correlation of Mn concentrations and δ98 Mo values in the Koegas sediments. The negative correlation between δ56 Fe values and Mn concentrations is likely related to Fe isotope fractionation during Fe(II) oxidation by Mn oxides, resulting in lower δ56 Fe values in the uppermost water column close to a Mn chemocline. We argue that the preservation of these signals within Paleoproterozoic sediments implies the existence of vertically extended chemoclines with a smoother gradient, probably as a result of low atmospheric oxygen concentrations. Furthermore, we suggest that abiotic oxidation of Fe(II) by a Mn oxide particle shuttle might have promoted the deposition of the Koegas iron formations.

Lifetime Stable isotopes profiles in whale earplug: assessment of foraging and migrations in the Northern Hemisphere

NASA Astrophysics Data System (ADS)

Mansouri, F.; Crain, D.; Winfield, Z.; Trumble, S.; Usenko, S.

2017-12-01

Whale earplugs, historically used for aging, were used to reconstruct lifetime stable isotope profiles for carbon (δ13C) and nitrogen (δ15N) for individual whales by delaminating lamina within the earplug. These stable isotope profile, which provide Continuous lifetime records of feeding, foraging ecology, and migration, were determined for 20 individuals from 4 baleen species including fin, minke, humpback, and blue whales spanning more than a century (1869 - 2014) using stable isotope analysis. Approximately 1 mg tissue from each lamina (n=1200) was analyzed for carbon and nitrogen stable isotope using continuous flow isotope ratio mass spectrometer (CF-IRMS). This research using whale earplugs have combined age estimates with stable isotope measurements to reconstruct lifetime foraging profiles with a 6-month resolution, providing an unprecedented opportunity to assess periods and trends in dietary fluctuations as well as migration between different foraging area which have distinct isotope values. Trends with these profiles suggest long-term changing in migration, while annual variability highlights seasonal fasting and feeding. Isotopic ratios were also used to identify subpopulations of Atlantic fin whales, which enabled us to assign unidentified humpback and minke whales to the Atlantic or Pacific Oceans. This historical archive of data provides us an unprecedented tool to assess long term marine ecosystem and subsequently marine organism transition to alternate foraging area and shed light on the whale's population status in the Northern hemisphere.

The influence of melt infiltration on the Li and Mg isotopic composition of the Horoman Peridotite Massif

NASA Astrophysics Data System (ADS)

Lai, Yi-Jen; Pogge von Strandmann, Philip A. E.; Dohmen, Ralf; Takazawa, Eiichi; Elliott, Tim

2015-09-01

We have analysed the Li and Mg isotope ratios of a suite of samples from the Horoman Peridotite Massif. Our results show that most Li and all Mg isotopic compositions of the Horoman peridotites are constant over 100 metres of continuous outcrop, yielding values for pristine mantle of δ7Li = 3.8 ± 1.4‰ (2SD, n = 9), δ25Mg = -0.12 ± 0.02‰ and δ26Mg = -0.23 ± 0.04‰ (2SD, n = 17), in keeping with values for undisturbed mantle xenoliths. However, there are also some anomalously low δ7Li values (-0.2‰ to 1.6‰), which coincide with locations that show enrichment of incompatible elements, indicative of the prior passage of small degree melts. We suggest Li diffused from infiltrating melts with high [Li] into the low [Li] minerals and kinetically fractionated 7Li/6Li as a result. Continued diffusion after the melt flow had ceased would have resulted in the disappearance of this isotopically light signature in less than 15 Ma. In order to preserve this feature, the melt infiltration must have been a late stage event and the massif must have subsequently cooled over a maximum of ∼0.3 Ma from peak temperature (950 °C, assuming the melts were hydrous) to Li closure temperature (700 °C), likely during emplacement. The constant δ26Mg values of Horoman peridotites suggest that chemical potential gradients caused by melt infiltration were insufficient to drive associated δ26Mg fractionation greater than our external precision of 0.03‰.

Origin of the volcanic-hosted Yamansu Fe deposit, Eastern Tianshan, NW China: constraints from pyrite Re-Os isotopes, stable isotopes, and in situ magnetite trace elements

NASA Astrophysics Data System (ADS)

Huang, Xiao-Wen; Zhou, Mei-Fu; Beaudoin, Georges; Gao, Jian-Feng; Qi, Liang; Lyu, Chuan

2018-01-01

The Yamansu Fe deposit (32 Mt at 51% Fe) in the Eastern Tianshan Orogenic Belt of NW China is hosted in early Carboniferous volcano-sedimentary rocks and spatially associated with skarn. The paragenetic sequence includes garnet-diopside (I), magnetite (II), hydrous silicate-sulfide (III), and calcite-quartz (IV) stages. Pyrite associated with magnetite has a Re-Os isochron age of 322 ± 7 Ma, which represents the timing of pyrite and, by inference, magnetite mineralization. Pyrite has δ 34SVCDT values of - 2.2 to + 2.9‰, yielding δ 34SH2S values of - 3.1 to 2‰, indicating the derivation of sulfur from a magmatic source. Calcite from stages II and IV has δ 13CVPDB values from - 2.5 to - 1.2‰, and - 1.1 to 1.1‰, and δ 18OVSMOW values from 11.8 to 12.0‰ and - 7.7 to - 5.2‰, respectively. Calculated δ 13C values of fluid CO2 and water δ 18O values indicate that stage II hydrothermal fluids were derived from magmatic rocks and that meteoric water mixed with the hydrothermal fluids in stage IV. Some ores contain magnetite with obvious chemical zoning composed of dark and light domains in BSE images. Dark domains have higher Mg, Al, Ca, Mn, and Ti but lower Fe and Cr contents than light domains. The chemical zoning resulted from a fluctuating fluid composition and/or physicochemical conditions (oscillatory zoning), or dissolution-precipitation (irregular zoning) via infiltration of magmatic-hydrothermal fluids diluted by late meteoric water. Iron was mainly derived from fluids similar to that in skarn deposits.

The earliest Lunar Magma Ocean differentiation recorded in Fe isotopes

NASA Astrophysics Data System (ADS)

Wang, Kun; Jacobsen, Stein B.; Sedaghatpour, Fatemeh; Chen, Heng; Korotev, Randy L.

2015-11-01

Recent high-precision isotopic measurements show that the isotopic similarity of Earth and Moon is unique among all known planetary bodies in our Solar System. These observations provide fundamental constraints on the origin of Earth-Moon system, likely a catastrophic Giant Impact event. However, in contrast to the isotopic composition of many elements (e.g., O, Mg, Si, K, Ti, Cr, and W), the Fe isotopic compositions of all lunar samples are significantly different from those of the bulk silicate Earth. Such a global Fe isotopic difference between the Moon and Earth provides an important constraint on the lunar formation - such as the amount of Fe evaporation as a result of a Giant Impact origin of the Moon. Here, we show through high-precision Fe isotopic measurements of one of the oldest lunar rocks (4.51 ± 0.10 Gyr dunite 72 415), compared with Fe isotope results of other lunar samples from the Apollo program, and lunar meteorites, that the lunar dunite is enriched in light Fe isotopes, complementing the heavy Fe isotope enrichment in other lunar samples. Thus, the earliest olivine accumulation in the Lunar Magma Ocean may have been enriched in light Fe isotopes. This new observation allows the Fe isotopic composition of the bulk silicate Moon to be identical to that of the bulk silicate Earth, by balancing light Fe in the deep Moon with heavy Fe in the shallow Moon rather than the Moon having a heavier Fe isotope composition than Earth as a result of Giant Impact vaporization.

Atomic line emission analyzer for hydrogen isotopes

DOEpatents

Kronberg, J.W.

1993-03-30

Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using a metal hydride.

Atomic line emission analyzer for hydrogen isotopes

DOEpatents

Kronberg, J.W.

1991-05-08

Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using, a metal hydride.

Atomic line emission analyzer for hydrogen isotopes

DOEpatents

Kronberg, James W.

1993-01-01

Apparatus for isotopic analysis of hydrogen comprises a low pressure chamber into which a sample of hydrogen is introduced and then exposed to an electrical discharge to excite the electrons of the hydrogen atoms to higher energy states and thereby cause the emission of light on the return to lower energy states, a Fresnel prism made at least in part of a material anomalously dispersive to the wavelengths of interest for dispersing the emitted light, and a photodiode array for receiving the dispersed light. The light emitted by the sample is filtered to pass only the desired wavelengths, such as one of the lines of the Balmer series for hydrogen, the wavelengths of which differ slightly from one isotope to another. The output of the photodiode array is processed to determine the relative amounts of each isotope present in the sample. Additionally, the sample itself may be recovered using a metal hydride.

Hydrogen isotopic compositions of organic compounds in plants reflect the plant's carbon metabolism

NASA Astrophysics Data System (ADS)

Cormier, M. A.; Kahmen, A.; Werner, R. A.

2015-12-01

The main factors controlling δ2H of plant organic compounds are generally assumed to be the plant's source water and the evaporative deuterium enrichment of leaf water. Hydrogen isotope analyses of plant compounds from sediments or tree rings are therefore mainly applied to assess hydrological conditions at different spatial and temporal scales. However, the biochemical hydrogen isotope fractionation occurring during biosynthesis of plant organic compounds (ɛbio) also accounts for a large part of the variability observed in the δ2H values. Nevertheless, only few studies have directly addressed the physiological basis of this variability and even fewer studies have thus explored possible applications of hydrogen isotope variability in plant organic compounds for plant physiological research. Here we show two datasets indicating that the plant's carbon metabolism can have a substantial influence on δ2H values of n-alkanes and cellulose. First, we performed a controlled experiment where we forced plants into heterotrophic and autotrophic C-metabolism by growing them under four different light treatments. Second, we assessed the δ2H values of different parasitic heterotrophic plants and their autotrophic host plants. Our two datasets show a systematic shift in ɛbio of up to 80 ‰ depending on the plant's carbon metabolism (heterotrophic or autotrophic). Differences in n-alkane and cellulose δ2H values in plants with autotrophic vs. heterotrophic metabolisms can be explained by different NADPH pools that are used by the plants to build their compounds either with assimilates that originate directly from photosynthesis or from stored carbohydrates. Our results have significant implications for the calibration and interpretation of geological records. More importantly, as the δ2H values reflect the plant's carbon metabolism involved during the tissue formation, our findings highlight the potential of δ2H values as new tool for studying plant and ecosystem carbon metabolism.

Potassium isotope abundances in Australasian tektites and microtektites.

NASA Astrophysics Data System (ADS)

Herzog, G. F.; O'D. Alexander, C. M.; Berger, E. L.; Delaney, J. S.; Glass, B. P.

2008-10-01

We report electron microprobe determinations of the elemental compositions of 11 Australasian layered tektites and 28 Australasian microtektites; and ion microprobe determinations of the 41K/39K ratios of all 11 tektites and 13 of the microtektites. The elemental compositions agree well with literature values, although the average potassium concentrations measured here for microtektites, 1.1 1.6 wt%, are lower than published average values, 1.9 2.9 wt%. The potassium isotope abundances of the Australasian layered tektites vary little. The average value of δ41K, 0.02 ± 0.12‰ (1σ mean), is indistinguishable from the terrestrial value (= 0 by definition) as represented by our standard, thereby confirming four earlier tektite analyses of Humayun and Koeberl (2004). In agreement with those authors, we conclude that evaporation has significantly altered neither the isotopic nor the elemental composition of Australasian layered tektites for elements less volatile than potassium. Although the average 41K/39K ratio of the microtektites, 1.1 ± 1.7‰ (1σ mean), is also statistically indistinguishable from the value for the standard, the individual ratios vary over a very large range, from -10.6 ± 1.4‰ to +13.8 ± 1.5‰ and at least three of them are significantly different from zero. We interpret these larger variations in terms of the evaporation of isotopically light potassium; condensation of potassium in the vapor plume; partial or complete stirring and quenching of the melts; and the possible uptake of potassium from seawater. That the average 41K/39K ratio of the microtektites equals the terrestrial value suggests that the microtektite-forming system was compositionally closed with respect to potassium and less volatile elements. The possibility remains open that 41K/39K ratios of microtektites vary systematically with location in the strewn field.

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 during magmatic differentiation and the isotopic composition of the bulk Earth. Earth and Planetary Science Letters 369, 34-42 (2013). [2] Little et al., The oceanic mass balance of copper and zinc isotopes, investigated by analysis of their inputs, and outputs to ferromanganese oxide sediments. Geochimica et Cosmochimica Acta 125, 673-693 (2014).

Rapid enhancement of chemical weathering recorded by extremely light seawater lithium isotopes at the Permian–Triassic boundary

PubMed Central

Sun, He; Xiao, Yilin; Zhang, Guijie; Casey, John F.; Shen, Yanan

2018-01-01

Lithium (Li) isotope analyses of sedimentary rocks from the Meishan section in South China reveal extremely light seawater Li isotopic signatures at the Permian–Triassic boundary (PTB), which coincide with the most severe mass extinction in the history of animal life. Using a dynamic seawater lithium box model, we show that the light seawater Li isotopic signatures can be best explained by a significant influx of riverine [Li] with light δ7Li to the ocean realm. The seawater Li isotope excursion started ≥300 Ky before and persisted up to the main extinction event, which is consistent with the eruption time of the Siberian Traps. The eruption of the Siberian Traps exposed an enormous amount of fresh basalt and triggered CO2 release, rapid global warming, and acid rains, which in turn led to a rapid enhancement of continental weathering. The enhanced continental weathering delivered excessive nutrients to the oceans that could lead to marine eutrophication, anoxia, acidification, and ecological perturbation, ultimately resulting in the end-Permian mass extinction. PMID:29581278

Rapid enhancement of chemical weathering recorded by extremely light seawater lithium isotopes at the Permian-Triassic boundary

NASA Astrophysics Data System (ADS)

Sun, He; Xiao, Yilin; Gao, Yongjun; Zhang, Guijie; Casey, John F.; Shen, Yanan

2018-04-01

Lithium (Li) isotope analyses of sedimentary rocks from the Meishan section in South China reveal extremely light seawater Li isotopic signatures at the Permian–Triassic boundary (PTB), which coincide with the most severe mass extinction in the history of animal life. Using a dynamic seawater lithium box model, we show that the light seawater Li isotopic signatures can be best explained by a significant influx of riverine [Li] with light δ7Li to the ocean realm. The seawater Li isotope excursion started ≥300 Ky before and persisted up to the main extinction event, which is consistent with the eruption time of the Siberian Traps. The eruption of the Siberian Traps exposed an enormous amount of fresh basalt and triggered CO2 release, rapid global warming, and acid rains, which in turn led to a rapid enhancement of continental weathering. The enhanced continental weathering delivered excessive nutrients to the oceans that could lead to marine eutrophication, anoxia, acidification, and ecological perturbation, ultimately resulting in the end-Permian mass extinction.

Sulfur isotope geochemistry of the central Japan Sea sediments (IODP Exp. 346) 20 150 kyr ago: Implications for the evolution of Asian Monsoon climate system

NASA Astrophysics Data System (ADS)

Oshio, S.; Yamaguchi, K. E.; Takahashi, S.; Naraoka, H.; Ikehara, M.

2016-12-01

Asian monsoon climate system has started about 50 Ma, after the collision of the Indian and Eurasian continents followed by uplift of the Himalaya and Tibetan Plateau. It has influenced sediments in the Japan Sea, where cm-scale alternation of Corg-rich dark layers and Corg-poor light layers occurs. This is most likely due to temporal changes in the nutrient status and/or oceanic redox conditions, which are likely caused by the fluctuations in the intensity of continental weathering and ocean currents, both of which were ultimately caused by the variable monsoon system. In order to obtain insights into the evolving oceanic redox state and the monsoon system, we conducted sulfur speciation and isotope study for the marine sediment core samples recovered in the central Japan Sea by IODP Exp. 346. The light layers have lower Spy (0.03-0.25 wt.%) contents when compared to the dark layers (0.26-1.49 wt.%). The Corg contents have similar distribution (0.34-1.10 wt.% for light layers and 1.16-3.38 wt.% for dark layers). However, the SSO4 contents (0.02-.64 wt.%) and the δ34S values (-34 to -38‰) did not show such light-dark distinction. Elevated Spy/Corg ratios (0.03-1.00) in the dark layers are interpreted to represent sulfide formation in the anoxic water column by bacterial sulfate reduction. During deposition of light layers, oxidation of sulfide minerals could have resulted in formation of sulfate minerals without significant isotope fractionation, as observed in this study. Regardless of the type of the sediments (dark vs. light), sulfate was not limiting during bacterial sulfate reduction, as reflected in the sulfur isotope compositions. We speculate that, during deposition of dark layers, enhanced summer monsoon activity caused heavy rainfall and increased source-rock weathering, runoff of the Yangtze River, and nutrient input into the East China Sea and the Tsushima Warm Current. Inflow of nutrient-rich and less salty water into the Japan Sea triggered enhanced biological activity, water-column density stratification, transport of organic matter into deeper ocean and consumption of dissolved oxygen, and ultimately the creation of anoxic water body to allow bacterial sulfate reduction. (syngenetic sulfide formation)

Neodymium Isotope associated with planktonic foraminifera as a proxy of deglacial changes in Pacific ocean circulation

NASA Astrophysics Data System (ADS)

Hu, R.

2015-12-01

Neodymium isotopes of ferromanganese oxide coatings precipitated on planktonic foraminifera have been intensively used as a proxy for water mass reconstruction in the deep Atlantic and Indian Ocean, but their suitability is not well constrained in the Pacific and may be affected by enhanced inputs and scavenging relative to advection. In this study, Nd isotopes and Rare Earth Element (REE) concentrations of planktonic foraminifera from ~60 sites widely distributed throughout the Pacific are presented. We found that the REE pattern associated with planktonic foraminifera in our study and Fe-Mn oxides/coatings in the global ocean have a common heavy REE depleted pattern when normalized to their ambient seawater due to preferential removal of light REEs onto particles relative to heavy REEs during scavenging. The core-top ɛNd results agree with the proximal seawater compositions, indicating that planktonic foraminiferal coatings can give a reliable record of past changes in bottom water Nd isotopes in the Pacific. A good correlation between foraminifera Nd isotopes and seawater phosphate suggests that Nd with a predominantly radiogenic isotopic composition was probably added gradually along continental boundaries so that the Nd isotopic composition change paralleled the accumulation of nutrients in the deep Pacific. By confirming Nd isotopes as a reliable water mass tracer in the Pacific Ocean, this proxy is then applied to reconstruct how the water mass circulation changes during the Last Glacial Maximum (LGM). Most of the cores in deep North Pacific show essentially invariant Nd isotopic compositions during the LGM compared with core-top values, suggesting that Nd isotope of Pacific end-member did not change during glacial times. However, the LGM Southwest Pacific cores have more radiogenic ɛNd than core-tops corroborating the previous findings of reduced inflow of North Atlantic Deep Water. The Eastern Equatorial Pacific cores above ~2 km showed consistently lower LGM ɛNd values, which might suggest a reduced influence of more radiogenic North Pacific Deep Water return flow. Taken together, our results indicate a slower Pacific overturning circulation during the glacial times, and the inflow and return flow of the Pacific meridional overturning were closely linked in the glacial-interglacial cycles.

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 to explain the reason for this decoupling. Our current work that also includes leaf water isotopic measurements will provide further details regarding the role of transpiration in controlling the deltaD values of leaf lipids.

Non-Destructive X-ray Computed Tomography (XCT) of Gas Hydrate Bearing Fractures in Marine Sediment

NASA Astrophysics Data System (ADS)

Oti, E.; Buchwalter, E.; Cook, A.; Crandall, D.

2017-12-01

Hydrate-filled fractures are found in many environments, both related to methane vents and constrained to lithologic layers; how hydrate filled fractures form in layered environments is not well understood. We focus on understanding hydrate origins and fracture formation by examining hydrate-bearing fractures in conventional cores taken from Gulf of Mexico sites from JIP Leg 1 and UT-GOM, Keathley Canyon 151. There are two main methane sources available for hydrate formation. The first is the hydrocarbon reservoir underlying the Gulf sediments. This reservoir formed when deeply buried organic matter of high molecular weight was exposed to high temperature and pressures and degraded. A second source is the biogenesis of organic material, which occurs when microbial activity breaks down organic materials. Biogenic methane is more enriched in lighter carbon isotopes as the reduction or fermentation reactions preferentially consume lighter carbon isotopes. As a result, we hypothesize that sediment surrounding biogenically derived methane will have heavier carbon isotopes when compared to non-host sediment, due to the consumption of the lighter carbon isotopes during methanogenesis. We use non-destructive X-ray Computed Tomography (XCT) scanning to visualize and identify hydrate-bearing fractures. The presence of hydrate fractures is further confirmed with a salinity analysis, as hydrate dissociation freshens the pore water and lowers the salinity. After hydrate fracture location is inferred, carbon isotope analysis is used to identify hydrocarbon source. XCT scans of Keathley Canyon core JIP-1 17H-4 revealed 10 total fractures, five of which XCT and salinity analysis indicated as formerly containing hydrate. All ten fractures, in addition to background sediment, underwent a carbon isotope analysis in which organic isotopes were measured. In the background sediment and the non hydrate-bearing fractures, DOC values were relatively light, with dC13 percentages ranging from -27.8% to -30.8%. In the five hydrate fracture regions, DOC was comparatively heavy, with DOC dC13 values ranging from -23.2% to -30.3%. These values suggest that biogenic methane was formed adjacent to the fracture and likely migrated into the hydrate filled fracture.

Mates but not sexes differ in migratory niche in a monogamous penguin species.

PubMed

Thiebot, Jean-Baptiste; Bost, Charles-André; Dehnhard, Nina; Demongin, Laurent; Eens, Marcel; Lepoint, Gilles; Cherel, Yves; Poisbleau, Maud

2015-09-01

Strong pair bonds generally increase fitness in monogamous organisms, but may also underlie the risk of hampering it when re-pairing fails after the winter season. We investigated whether partners would either maintain contact or offset this risk by exploiting sex-specific favourable niches during winter in a migratory monogamous seabird, the southern rockhopper penguin Eudyptes chrysocome. Using light-based geolocation, we show that although the spatial distribution of both sexes largely overlapped, pair-wise mates were located on average 595 ± 260 km (and up to 2500 km) apart during winter. Stable isotope data also indicated a marked overlap between sex-specific isotopic niches (δ¹³C and δ¹⁵N values) but a segregation of the feeding habitats (δ¹³C values) within pairs. Importantly, the tracked females remained longer (12 days) at sea than males, but all re-mated with their previous partners after winter. Our study provides multiple evidence that migratory species may well demonstrate pair-wise segregation even in the absence of sex-specific winter niches (spatial and isotopic). We suggest that dispersive migration patterns with sex-biased timings may be a sufficient proximal cause for generating such a situation in migratory animals.

Lithium isotopes and implications on chemical weathering in the catchment of Lake Donggi Cona, northeastern Tibetan Plateau

NASA Astrophysics Data System (ADS)

Weynell, Marc; Wiechert, Uwe; Schuessler, Jan A.

2017-09-01

This study presents lithium (Li) isotope ratios (δ7Li) for rocks, sediments, suspended particulate material, and dissolved Li from the Lake Donggi Cona catchment, located on the northeastern Tibetan Plateau, China. The average δ7Li = +1.9‰ of the bedrocks is estimated from local loess. δ7Li values decrease progressively within the sediment cascade from loess, to river and lake floor sediments. The lake floor sediments average at -0.7‰. The difference between bedrock and lake sediments reflects the preferential fractionation of dissolved 6Li into clay minerals (mostly illite) in the weathering zone and grain-size sorting during fluvial sediment transport. The δ7Li values of stream and lake water samples range from +13.6 to +20.8‰, whereas thermal waters fall between +5.9 and +11.6‰. The δ7Li values of lake water samples are close to +17‰ and reflect mixing of waters from two perennial inflows and thermal waters. Dissolved Li in streams represents an integrated isotopic signal derived from soil solutions in the weathering zone. An apparent isotopic fractionation of -17.8 ± 1.6‰ (αsec-sol ∼ 0.982) between secondary minerals and solution was determined. An inflow that drains a sub-catchment in the north carries a high proportion of thermal waters. Despite of the high proportion of admixed thermal waters with high Li concentrations and low δ7Li, this stream has the highest δ7Li values of about +21‰. This is consistent with admixing of thermal waters to solutions in the weathering zone and subsequent fractionation by preferential uptake of isotopically light dissolved Li into secondary phases. Based on Li isotope ratios of the dissolved and solid export flux from the weathering zone we calculated that around five times more Li is exported in particles than dissolved in streams. An average δ7Li value of about +17‰ of most streams and the lake is reflecting a low weathering intensity and chemical weathering rate of about 4 t/km2/a. Low weathering rates and an erosion dominated weathering system are consistent with moderate precipitations, the cold climate, and the high relief of the study area.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

1987-01-01

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

1977-01-01

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, in the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

Photodegradation of polycyclic aromatic hydrocarbons in soils under a climate change base scenario.

PubMed

Marquès, Montse; Mari, Montse; Audí-Miró, Carme; Sierra, Jordi; Soler, Albert; Nadal, Martí; Domingo, José L

2016-04-01

The photodegradation of polycyclic aromatic hydrocarbons (PAHs) in two typical Mediterranean soils, either coarse- or fine-textured, was here investigated. Soil samples, spiked with the 16 US EPA priority PAHs, were incubated in a climate chamber at stable conditions of temperature (20 °C) and light (9.6 W m(-2)) for 28 days, simulating a climate change base scenario. PAH concentrations in soils were analyzed throughout the experiment, and correlated with data obtained by means of Microtox(®) ecotoxicity test. Photodegradation was found to be dependent on exposure time, molecular weight of each hydrocarbon, and soil texture. Fine-textured soil was able to enhance sorption, being PAHs more photodegraded than in coarse-textured soil. According to the EC50 values reported by Microtox(®), a higher detoxification was observed in fine-textured soil, being correlated with the outcomes of the analytical study. Significant photodegradation rates were detected for a number of PAHs, namely phenanthrene, anthracene, benzo(a)pyrene, and indeno(123-cd)pyrene. Benzo(a)pyrene, commonly used as an indicator for PAH pollution, was completely removed after 7 days of light exposure. In addition to the PAH chemical analysis and the ecotoxicity tests, a hydrogen isotope analysis of benzo(a)pyrene was also carried out. The degradation of this specific compound was associated to a high enrichment in (2)H, obtaining a maximum δ(2)H isotopic shift of +232‰. This strong isotopic effect observed in benzo(a)pyrene suggests that compound-specific isotope analysis (CSIA) may be a powerful tool to monitor in situ degradation of PAHs. Moreover, hydrogen isotopes of benzo(a)pyrene evidenced a degradation process of unknown origin occurring in the darkness. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence

USGS Publications Warehouse

Bullen, Thomas D.; Chadwick, Oliver A.

2016-01-01

Nutrient biolifting is an important pedogenic process in which plant roots obtain inorganic nutrients such as phosphorus (P) and calcium (Ca) from minerals at depth and concentrate those nutrients at the surface. Here we use soil chemistry and stable isotopes of the alkaline earth elements Ca, strontium (Sr) and barium (Ba) to test the hypothesis that biolifting of P has been an important pedogenic process across a soil climosequence developed on volcanic deposits at Kohala Mountain, Hawaii. The geochemical linkage between these elements is revealed as generally positive site-specific relationships in soil mass gains and losses, particularly for P, Ba and Ca, using the ratio of immobile elements titanium and niobium (Ti/Nb) to link individual soil samples to a restricted compositional range of the chemically and isotopically diverse volcanic parent materials. At sites where P is enriched in surface soils relative to abundances in deeper soils, the isotope compositions of exchangeable Ca, Sr and Ba in the shallowest soil horizons (< 10 cm depth) are lighter than those of the volcanic parent materials and trend toward those of plants growing on fresh volcanic deposits. In contrast the isotope composition of exchangeable Ba in deeper soil horizons (> 10 cm depth) at those sites is consistently heavier than the volcanic parent materials. The isotope compositions of exchangeable Ca and Sr trend toward heavier compositions with depth more gradually, reflecting increasing leakiness from these soils in the order Ba < Sr < Ca and downward transfer of light biocycled Ca and Sr to deeper exchange sites. Given the long-term stability of ecosystem properties at the sites where P is enriched in surface soils, a simple box model demonstrates that persistence of isotopically light exchangeable Ca, Sr and Ba in the shallowest soil horizons requires that the uptake flux to plants from those near-surface layers is less than the recycling flux returned to the surface as litterfall. This observation implicates an uptake flux from an additional source which we attribute to biolifting. We view the heavy exchangeable Ba relative to soil parent values in deeper soils at sites where P is enriched in surface soils, and indeed at all but the wettest site across the climosequence, to represent the complement of an isotopically light Ba fraction removed from these soils by plant roots consistent with the biolifting hypothesis. We further suggest that decreasing heaviness of depth-integrated exchangeable Ba in deeper soils with increasing median annual precipitation across the climosequence reflects greater reliance on shallow nutrient sources as site water balance increases. While the Ca, Sr and Ba isotopes considered together were useful in confirming an important role for nutrient biolifting across the climosequence, the Ba isotopes provided the most robust tracer of biolifting and have the greatest potential to find application as an isotopic proxy for P dynamics in soils.

Repeated occurrences of methanogenic zones, diagenetic dolomite formation and linked silicate alteration in southern Bering Sea sediments (Bowers Ridge, IODP Exp. 323 Site U1341)

NASA Astrophysics Data System (ADS)

Wehrmann, L. M.; Ockert, C.; Mix, A. C.; Gussone, N.; Teichert, B. M. A.; Meister, P.

2016-03-01

Diagenetic precipitates, such as dolomite, and the chemistry of residual deeply buried porewater often represent the only traces of past biogeochemical activity in marine sediments. A 600 m thick sedimentary section, recently drilled at Integrated Ocean Drilling Program (IODP) Site U1341 on Bowers Ridge (southern Bering Sea), provides insight into such a 4.3 Ma old paleo-diagenetic archive. Hard-lithified calcite-dolomite layers, and laminae of disseminated carbonate, were recovered in diatom-rich sediments over a depth range of 400 m. Carbon isotope values of the diagenetic carbonates between -16.6 and -14.4‰ (VPDB) and strontium isotope ratios of dolomites close to past seawater values suggest carbonate precipitation induced by the production of dissolved inorganic carbon (DIC) during elevated rates of organic carbon mineralization, primarily via sulfate reduction, at shallow sediment depth below the paleo-seafloor. Diagenetic carbonates at 280-440 m below seafloor were likely also produced by the intermittent onset of sulfate reduction coupled to the anaerobic oxidation of methane (AOM) at sulfate-methane transition zones (SMTZ). These microbially mediated processes do not occur in the sediment at this site at present but were likely connected to the presence of a methanogenic zone at 2.58-2.51 Ma. A minimum in sulfate concentrations in modern porewaters and low sedimentary Ba/Al ratios resulting from former sulfate depletion are reminiscent of the presence of this large methanogenic zone. The minimum in sulfate concentrations is reflected in a minimum in magnesium concentrations, less radiogenic strontium and isotopically light calcium in the porewater. It is proposed that magnesium was removed from the porewater during carbonate precipitation and volcanic ash alteration which occurred in the former methanogenic zone and also released strontium with a less radiogenic isotope ratio and isotopically light calcium into the porewater. The isotopic composition of porewater calcium was also influenced by ammonium-calcium exchange on clay minerals and carbonate recrystallization. Our study elucidates the response of porewater element concentrations and isotopic profiles interlinked with the formation of diagenetic carbonates to changes in the deposition of organic carbon in sediments of deeper water sites (>2000 m water depth) over prolonged timescales. It shows that variations in biogeochemical processes in response to changes in oceanographic conditions and a dynamic subseafloor biogeochemical zonation have to also be taken into account at these deep water sites for a global assessment of organic carbon burial fluxes and remineralization.

Light and variable 37Cl/35Cl ratios in rocks from Gale Crater, Mars: Possible signature of perchlorate

NASA Astrophysics Data System (ADS)

Farley, K. A.; Martin, P.; Archer, P. D.; Atreya, S. K.; Conrad, P. G.; Eigenbrode, J. L.; Fairén, A. G.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Malespin, C.; Ming, D. W.; Navarro-Gonzalez, R.; Sutter, B.

2016-03-01

Cl isotope ratios measured on HCl thermally evolved from as-yet-unknown phases in sedimentary rocks and sand in Gale Crater provide unexpected insights to the Martian surficial Cl cycle. The seven samples yield δ37Cl values ranging from - 1 ± 25 ‰ to - 51 ± 5 ‰. Five analyses from two samples of the Sheepbed mudstone (Yellowknife Bay study area) are analytically indistinguishable with a mean δ37Cl of - 11 ± 7 ‰ (1 σ). In contrast, four mudstones/sandstones from the Kimberley and Pahrump study areas also yielded indistinguishable ratios, but with a mean δ37Cl of - 43 ± 6 ‰. The Rocknest sand deposit gave a highly uncertain δ37Cl value of - 7 ± 44 ‰. These light and highly variable δ37Cl values are unique among known solar system materials. Two endmember models are offered to account for these observations, and in both, perchlorate, with its extreme ability to fractionate Cl isotopes, is critical. In the first model, SAM is detecting HCl from an oxychlorine compound (e.g., perchlorate) produced from volcanic gas emissions by atmospheric chemical reactions. Similar reactions in Earth's atmosphere may be responsible for the isotopically lightest known Cl outside of this study, in perchlorate from the Atacama Desert. Some of the Gale Crater δ37Cl values are more negative than those in Atacama perchlorate, but because reaction mechanisms and associated fractionation factors are unknown, it is impossible to assess whether this difference is prohibitive. If the negative δ37Cl signal is produced in this fashion, the isotopic variability among samples could arise either from variations in the relative size of the reactant chloride and product perchlorate reservoirs, or from variations in the fraction of perchlorate reduced back to chloride after deposition. Such reduction strongly enriches 37Cl in the residual perchlorate. Perchlorate reduction alone offers an alternative endmember model that can explain the observed data if SAM measured HCl derived from chloride. In this model isotopically normal perchlorate produced by an unspecified mechanism is reduced to chloride. Depending on the relative size of the reduced reservoir, the integrated product chloride can vary in isotopic composition from - 70 ‰ in the first increment all the way to the starting composition if the perchlorate is fully reduced. Thus, variable degrees of perchlorate reduction can produce chloride with the appropriate δ37Cl range. Combination of the two endmember models, in which the perchlorate subject to post-deposition reduction is isotopically negative from atmospheric reactions, is also possible. Determination of the phase hosting the Cl measured by SAM, an oxychlorine compound or chloride, is critical for selecting between these models, and for developing implications of the results for the Mars surficial Cl cycle. At present it is not possible to conclusively establish which phase is responsible (possibly both), but limited evidence favors the conclusion that the measured Cl derives mostly from an oxychlorine compound.

Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China.

PubMed

Song, Shiming; Mathur, Ryan; Ruiz, Joaquin; Chen, Dandan; Allin, Nicholas; Guo, Kunyi; Kang, Wenkai

2016-02-15

Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS2 has a 'tight' cluster of Cu isotope values (-0.15‰ to +1.65‰; +0.37 ± 0.6‰, 1σ, n=10), and the second mineral source, pyrite (FeS2), has a much larger range of Cu isotope values (-4‰ to +11.9‰; 2.7 ± 4.3‰, 1σ, n=16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately +1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (<0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ(65)Cu ranging between +2 to +5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems. Copyright © 2015 Elsevier B.V. All rights reserved.

Colored dissolved organic matter in shallow estuaries: relationships between carbon sources and light attenuation

NASA Astrophysics Data System (ADS)

Oestreich, W. K.; Ganju, N. K.; Pohlman, J. W.; Suttles, S. E.

2016-02-01

Light availability is of primary importance to the ecological function of shallow estuaries. For example, benthic primary production by submerged aquatic vegetation is contingent upon light penetration to the seabed. A major component that attenuates light in estuaries is colored dissolved organic matter (CDOM). CDOM is often measured via a proxy, fluorescing dissolved organic matter (fDOM), due to the ease of in situ fDOM sensor measurements. Fluorescence must be converted to CDOM absorbance for use in light attenuation calculations. However, this CDOM-fDOM relationship varies among and within estuaries. We quantified the variability in this relationship within three estuaries along the mid-Atlantic margin of the eastern United States: West Falmouth Harbor (MA), Barnegat Bay (NJ), and Chincoteague Bay (MD/VA). Land use surrounding these estuaries ranges from urban to developed, with varying sources of nutrients and organic matter. Measurements of fDOM (excitation and emission wavelengths of 365 nm (±5 nm) and 460 nm (±40 nm), respectively) and CDOM absorbance were taken along a terrestrial-to-marine gradient in all three estuaries. The ratio of the absorption coefficient at 340 nm (m-1) to fDOM (QSU) was higher in West Falmouth Harbor (1.22) than in Barnegat Bay (0.22) and Chincoteague Bay (0.17). The CDOM : fDOM absorption ratio was variable between sites within West Falmouth Harbor and Barnegat Bay, but consistent between sites within Chincoteague Bay. Stable carbon isotope analysis for constraining the source of dissolved organic matter (DOM) in West Falmouth Harbor and Barnegat Bay yielded δ13C values ranging from -19.7 to -26.1 ‰ and -20.8 to -26.7 ‰, respectively. Concentration and stable carbon isotope mixing models of DOC (dissolved organic carbon) indicate a contribution of 13C-enriched DOC in the estuaries. The most likely source of 13C-enriched DOC for the systems we investigated is Spartina cordgrass. Comparison of DOC source to CDOM : fDOM absorption ratios at each site demonstrates the relationship between source and optical properties. Samples with 13C-enriched carbon isotope values, indicating a greater contribution from marsh organic material, had higher CDOM : fDOM absorption ratios than samples with greater contribution from terrestrial organic material. Applying a uniform CDOM : fDOM absorption ratio and spectral slope within a given estuary yields errors in modeled light attenuation ranging from 11 to 33 % depending on estuary. The application of a uniform absorption ratio across all estuaries doubles this error. This study demonstrates that light attenuation coefficients for CDOM based on continuous fDOM records are highly dependent on the source of DOM present in the estuary. Thus, light attenuation models for estuaries would be improved by quantification of CDOM absorption and DOM source identification.

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 origin of the volatile element depletion of the Moon compared to Earth remains a key question in planetary science. It has recently been shown that both high-Ti and low-Ti lunar basalts are enriched in the heavier isotopes of Zn compared to Earth with an effect of ~1.3 permil on the 66Zn/64Zn ratio (Paniello et al., Nature, 2012). In order to obtain a better understanding of Zn behavior in and on the Moon, we present new measurements of lunar basalts, pyroclastic green glass 15426, highland anorthosites, cataclastic dunite 77215, cataclastic norite 72415 and some lunar soils. Samples were analyzed using a Thermo-Fisher Neptune Plus multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) at Washington University in St Louis. The data presented below are reported as the permil deviation of the 66Zn/64Zn ratio from the JMC-Lyon standard (δ66Zn). Four new high Ti basalts and three low Ti basalts confirm the observations of Paniello et al. (2012), that there is an enrichment in the heavier isotopes of Zn compared with chondrites and terrestrial samples. Combining these data together with Paniello et al. (2012) and Herzog et al. (GCA, 2009) we calculate a new average for lunar basalts of δ66Zn= 1.4×0.4 (1sd, n = 27). A few exceptions (5 samples out of 32) are isotopically light and probably represent addition of isotopically light Zn condensed onto the lunar surface from Zn isotopic fractionation during meteoritic impact, creating correspondingly isotopically heavy soils. In contrast to the homogeneity of mare basalts, highland samples show large Zn isotopic variability (δ66Zn -11.4 up to +4.24 permil) which encompasses the entire Zn isotopic variability measured so far in the Solar System. These δ66Zn variations are negatively correlated with the Zn abundance, with the isotopically light samples having the highest Zn concentrations. We interpret these results as the consequence of meteoritic bombardment and volatilization/condensation of Zn at 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.

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 -0.02‰). Our results suggest that the source of the distal dry fallouts is the main chimney plume, whose light Zn isotopic signature they preserve. Based on Zn isotopic analysis in combination with morphological and chemical characteristics of airborne particles, the present study suggests the traceability of smelter dusts by Zn isotopes.

AMS Observations of Light Cosmic Ray Isotopes and Implications for their Production in the Galaxy

NASA Astrophysics Data System (ADS)

Tomassetti, Nicola

2012-08-01

Observations of light isotopes in cosmic rays provide information on their origin and propagation in the Galaxy. Using the data collected by AMS-01 in the STS-91 space mission, we report our final results on the isotopic composition of hydrogen and helium between 200 MeV and 1.4 GeV per nucleon. These measurements are in good agreement with the previous data and set new standards of precision. We discuss the role of isotopic composition data in modeling the cosmic ray production, acceleration and diffusive transport in the Galaxy.

Evidence for a Light-Rare-Earth-Element-Depleted Source for Some Ferroan Anorthosites

NASA Astrophysics Data System (ADS)

Borg, L. E.; Norman, M.; Nyquist, L. E.; Bogard, D.; Snyder, G.; Taylor, L.

1998-01-01

In the lunar magma ocean model, ferroan anorthosites (FANs) are expected to be derived from a relatively undifferentiated source with chondritic REE abundances and yield the oldest radiometric ages of any lunar rocks. Samarium-neodymium-isotopic analyses of 60025 and 67016 yielded ages of 4.44 +/- 0.02 Ga and 4.53 +/- 0.12 Ga and initial EpsilonNd(sup 143) values in excess of -0.5. These ages are within error of ages determined on some Mg-suite rocks by researchers. Thus, the existing data are not completely consistent with the standard magma ocean model. We have completed isotopic analysis on the pristine FAN 62236 in order to place further constraints on lunar crust-forming processes.

Evidence for a Light-Rare-Earth-Element-Depleted Source for Some Ferroan Anorthosites

NASA Technical Reports Server (NTRS)

Borg, L. E.; Norman, M.; Nyquist, L. E.; Bogard, D.; Snyder, G.; Taylor, L.

1998-01-01

In the lunar magma ocean model, ferroan anorthosites (FANs) are expected to be derived from a relatively undifferentiated source with chondritic REE abundances and yield the oldest radiometric ages of any lunar rocks. Samarium-neodymium-isotopic analyses of 60025 and 67016 yielded ages of 4.44 +/- 0.02 Ga and 4.53 +/- 0.12 Ga and initial Epsilon(sub Nd)(sup 143) values in excess of -0.5. These ages are within error of ages determined on some Mg-suite rocks by researchers. Thus, the existing data are not completely consistent with the standard magma ocean model. We have completed isotopic analysis on the pristine FAN 62236 in order to place further constraints on lunar crust-forming processes.

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.

Alteration, oxygen isotope, and fluid inclusion study of the Meishan iron oxide-apatite deposit, SE China

NASA Astrophysics Data System (ADS)

Yu, Jinjie; Che, Linrui; Wang, Tiezhu

2015-10-01

The Meishan deposit (338 Mt at 39 % Fe) comprises massive ores in the main orebody and stockwork and disseminated ores along the main orebody. Four stages of mineralization and related alteration have been identified. The second stage of mineralization, which was the main stage of iron mineralization, formed stringer, disseminated iron ores, as well as the main Meishan orebody. The fourth stage formed small pyrite and/or gold orebodies above or alongside the main magnetite orebody. Stage 2 apatites have homogenization temperatures of 257-485 °C and salinities of 7.3-11 wt% NaCleq. Calculated δ18Ofluid values of magnetite and apatite from the disseminated ores vary between 7.7 and 14.9 ‰, which is similar to values observed in the massive ores (8.1-12.9 ‰). The high-18O fluids at Meishan have been interpreted as being of magmatic-hydrothermal origin. These fluids are indicative of the boiling of ore-forming fluids. Quartz, occurring as cavity fillings, gives homogenization temperatures from 202 to 344 °C, with most values lying between 250 and 330 °C. Corresponding salinities are ˜5 wt% NaCleq. Calculated δ18Ofluid values are +6.4 to +6.8 ‰. These values indicate that the lower-temperature (250-330 °C) quartz was deposited from a cooling magmatic-hydrothermal fluid. Stage 3 siderites contain fluid inclusions that homogenized between 190 and 310 °C, mainly between 210 and 290 °C. Corresponding salinities are 4-8 wt% NaCleq. Stage 4 quartz-carbonate veinlets contain fluid inclusions that homogenized at moderate to low temperatures (150-230 °C) and exhibit low salinities (2-10 wt% NaCl eq). δ18Ofluid values of the mineralizing fluids for the quartz and calcite can be calculated to vary from -0.7 to +5.6 ‰ and +6.3 to +10.2 ‰, respectively. While there is some overlap, the δ18O values of the fluids are generally lower than those observed in the massive and disseminated magnetite ores. δD values for the quartz and calcite vary between -154 and -123 ‰ and -123 and -111 ‰, respectively. These values suggest late-stage input of a shallow-sourced, isotopically light meteoric fluid at the temperature of pyrite and gold deposition. The fluid inclusion and stable isotope data indicate a cooling magmatic-hydrothermal system that progressed from isotopically heavy to isotopically depleted fluids as it cooled. Such fluid evolution is comparable with those of other Kiruna-type deposits worldwide.

Bayesian Integration of Isotope Ratio for Geographic Sourcing of Castor Beans

DOE PAGES

Webb-Robertson, Bobbie-Jo; Kreuzer, Helen; Hart, Garret; ...

2012-01-01

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

Bayesian Integration of Isotope Ratios for Geographic Sourcing of Castor Beans

DOE Office of Scientific and Technical Information (OSTI.GOV)

Webb-Robertson, Bobbie-Jo M.; Kreuzer, Helen W.; Hart, Garret L.

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

Bayesian Integration of Isotope Ratio for Geographic Sourcing of Castor Beans

DOE Office of Scientific and Technical Information (OSTI.GOV)

Webb-Robertson, Bobbie-Jo; Kreuzer, Helen; Hart, Garret

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

Bayesian Integration of Isotope Ratio for Geographic Sourcing of Castor Beans

PubMed Central

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

2012-01-01

Recent years have seen an increase in the forensic interest associated with the poison ricin, which is extracted from the seeds of the Ricinus communis plant. Both light element (C, N, O, and H) and strontium (Sr) isotope ratios have previously been used to associate organic material with geographic regions of origin. We present a Bayesian integration methodology that can more accurately predict the region of origin for a castor bean than individual models developed independently for light element stable isotopes or Sr isotope ratios. Our results demonstrate a clear improvement in the ability to correctly classify regions based on the integrated model with a class accuracy of 60.9 ± 2.1% versus 55.9 ± 2.1% and 40.2 ± 1.8% for the light element and strontium (Sr) isotope ratios, respectively. In addition, we show graphically the strengths and weaknesses of each dataset in respect to class prediction and how the integration of these datasets strengthens the overall model. PMID:22919270

Isotope reference materials

USGS Publications Warehouse

Coplen, Tyler B.

2010-01-01

Measurement of the same isotopically homogeneous sample by any laboratory worldwide should yield the same isotopic composition within analytical uncertainty. International distribution of light element isotopic reference materials by the International Atomic Energy Agency and the U.S. National Institute of Standards and Technology enable laboratories to achieve this goal.

VAPOR PRESSURE ISOTOPE EFFECTS IN THE MEASUREMENT OF ENVIRONMENTAL TRITIUM SAMPLES.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuhne, W.

2012-12-03

Standard procedures for the measurement of tritium in water samples often require distillation of an appropriate sample aliquot. This distillation process may result in a fractionation of tritiated water and regular light water due to the vapor pressure isotope effect, introducing either a bias or an additional contribution to the total tritium measurement uncertainty. The magnitude of the vapor pressure isotope effect is characterized as functions of the amount of water distilled from the sample aliquot and the heat settings for the distillation process. The tritium concentration in the distillate is higher than the tritium concentration in the sample earlymore » in the distillation process, it then sharply decreases due to the vapor pressure isotope effect and becomes lower than the tritium concentration in the sample, until the high tritium concentration retained in the boiling flask is evaporated at the end of the process. At that time, the tritium concentration in the distillate again overestimates the sample tritium concentration. The vapor pressure isotope effect is more pronounced the slower the evaporation and distillation process is conducted; a lower heat setting during the evaporation of the sample results in a larger bias in the tritium measurement. The experimental setup used and the fact that the current study allowed for an investigation of the relative change in vapor pressure isotope effect in the course of the distillation process distinguish it from and extend previously published measurements. The separation factor as a quantitative measure of the vapor pressure isotope effect is found to assume values of 1.034 {+-} 0.033, 1.052 {+-} 0.025, and 1.066 {+-} 0.037, depending on the vigor of the boiling process during distillation of the sample. A lower heat setting in the experimental setup, and therefore a less vigorous boiling process, results in a larger value for the separation factor. For a tritium measurement in water samples, this implies that the tritium concentration could be underestimated by 3 - 6%.« less

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C.P.; Rockwood, S.D.; Jensen, R.J.; Lyman, J.L.; Aldridge, J.P. III.

1987-04-07

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO[sub 2] laser light may be used to highly enrich [sup 34]S in natural SF[sub 6] and [sup 11]B in natural BCl[sub 3]. 8 figs.

Authigenic carbon entombed in methane-soaked sediments from the northeastern transform margin of the Guaymas Basin, Gulf of California

NASA Astrophysics Data System (ADS)

Paull, Charles K.; Ussler, William; Peltzer, Edward T.; Brewer, Peter G.; Keaten, Rendy; Mitts, Patrick J.; Nealon, Jeffrey W.; Greinert, Jens; Herguera, Juan-Carlos; Elena Perez, M.

2007-06-01

Extensive ROV-based sampling and exploration of the seafloor was conducted along an eroded transform-parallel fault scarp on the northeastern side of the Guaymas Basin in the Gulf of California to observe the nature of fluids venting from the seafloor, measure the record left by methane-venting on the carbonates from this area, and determine the association with gas hydrate. One gas vent vigorous enough to generate a water-column gas plume traceable for over 800 m above the seafloor was found to emanate from a ˜10-cm-wide orifice on the eroded scarp face. Sediment temperature measurements and topography on a sub-bottom reflector recorded in a transform-parallel seismic reflection profile identified a subsurface thermal anomaly beneath the gas vent. Active chemosynthetic biological communities (CBCs) and extensive authigenic carbonates that coalesce into distinct chemoherm structures were encountered elsewhere along the eroded transform-parallel scarp. The carbon isotopic composition of methane bubbles flowing vigorously from the gas vent (-53.6±0.8‰ PDB) is comparable to methane found in sediment cores taken within the CBCs distributed along the scarp (-51.9±8.1‰ PDB). However, the δ13C value of the CO 2 in the vent gas (+12.4±1.1‰ PDB) is very distinct from those for dissolved inorganic carbon (DIC) (-35.8‰ to -2.9‰ PDB) found elsewhere along the scarp, including underneath CBCs. The δ13C values of the carbonate-rich sediments and rocks exposed on the seafloor today also span an unusually large range (-40.9‰ to +12.9‰ PDB) and suggest two distinct populations of authigenic carbonate materials were sampled. Unconsolidated sediments and some carbonate rocks, which have lithologic evidence for near-seafloor formation, have negative δ13C values, while carbonate rocks that clearly formed in the subsurface have positive δ13C values (up to +23.0‰) close to that measured for CO 2 in the vent gas. There appears to be two carbon sources for the authigenic carbonates: (1) deeply-sourced, isotopically heavy CO 2 (˜+12‰); and (2) isotopically light DIC derived from local anaerobic oxidation of methane at the sulfate-methane interface in the shallow subsurface. Addition of isotopically light methane-derived carbon at the seafloor may completely mask the isotopically heavy CO 2 signature (+12.4‰) in the underlying sediments. Thus, the authigenic carbonates may have formed from the same methane- and carbon dioxide-bearing fluid, but under different migration and alteration conditions, depending on how it migrated through the sediment column.

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 ...

Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy

NASA Astrophysics Data System (ADS)

Nowak-Lovato, K.

2014-12-01

Seepage from enhanced oil recovery, carbon storage, and natural gas sites can emit trace gases such as carbon dioxide, methane, and hydrogen sulfide. Trace gas emission at these locations demonstrate unique light stable isotope signatures that provide information to enable source identification of the material. Light stable isotope detection through surface monitoring, offers the ability to distinguish between trace gases emitted from sources such as, biological (fertilizers and wastes), mineral (coal or seams), or liquid organic systems (oil and gas reservoirs). To make light stable isotope measurements, we employ the ultra-sensitive technique, frequency modulation spectroscopy (FMS). FMS is an absorption technique with sensitivity enhancements approximately 100-1000x more than standard absorption spectroscopy with the advantage of providing stable isotope signature information. We have developed an integrated in situ (point source) system that measures carbon dioxide, methane and hydrogen sulfide with isotopic resolution and enhanced sensitivity. The in situ instrument involves the continuous collection of air and records the stable isotope ratio for the gas being detected. We have included in-line flask collection points to obtain gas samples for validation of isotopic concentrations using our in-house isotope ratio mass spectroscopy (IRMS). We present calibration curves for each species addressed above to demonstrate the sensitivity and accuracy of the system. We also show field deployment data demonstrating the capabilities of the system in making live dynamic measurements from an active source.

Rapidly Assessing Changes in Bone Mineral Balance Using Natural Stable Calcium Isotopes

NASA Technical Reports Server (NTRS)

Morgan, J. L. L.; Gordon, G. W.; Romaniello, S. J.; Skulan, J. L.; Smith, S. M.; Anbar, A. D.

2011-01-01

We demonstrate that variations in the Ca isotope ratios in urine rapidly and quantitatively reflect changes in bone mineral balance. This variation occurs because bone formation depletes soft tissue of light Ca isotopes, while bone resorption releases that isotopically light Ca back into soft tissue. In a study of 12 individuals confined to bed rest, a condition known to induce bone resorption, we show that Ca isotope ratios shift in a direction consistent with net bone loss after just 7 days, long before detectible changes in bone density occur. Consistent with this interpretation, the Ca isotope variations track changes observed in N-teleopeptide, a bone resorption biomarker, while bone-specific alkaline phosphatase, a bone formation biomarker, is unchanged. Ca isotopes can in principle be used to quantify net changes in bone mass. Ca isotopes indicate an average loss of 0.62 +/- 0.16 % in bone mass over the course of this 30-day study. The Ca isotope technique should accelerate the pace of discovery of new treatments for bone disease and provide novel insights into the dynamics of bone metabolism.

Paleoenvironmental implications of taxonomic variation among δ15N values of chloropigments

USGS Publications Warehouse

Higgins, Meytal B.; Wolfe-Simon, Felisa; Robinson, Rebecca S.; Qin, Yelun; Saito, Mark A.; Pearson, Ann

2011-01-01

Natural variations in the ratios of nitrogen isotopes in biomass reflect variations in nutrient sources utilized for growth. In order to use δ15N values of chloropigments of photosynthetic organisms to determine the corresponding δ15N values of biomass – and by extension, surface waters – the isotopic offset between chlorophyll and biomass must be constrained. Here we examine this offset in various geologically-relevant taxa, grown using nutrient sources that may approximate ocean conditions at different times in Earth’s history. Phytoplankton in this study include cyanobacteria (diazotrophic and non-diazotrophic), eukaryotic algae (red and green), and anoxygenic photosynthetic bacteria (Proteobacteria), as well as environmental samples from sulfidic lake water. Cultures were grown using N2, NO3−, and NH4+ as nitrogen sources, and were examined under different light regimes and growth conditions. We find surprisingly high variability in the isotopic difference (δ15Nbiomass − δ15Nchloropigment) for prokaryotes, with average values for species ranging from −12.2‰ to +11.7‰. We define this difference as εpor, a term that encompasses diagenetic porphyrins and chlorins, as well as chlorophyll. Negative values of εpor reflect chloropigments that are 15N-enriched relative to biomass. Notably, this enrichment appears to occur only in cyanobacteria. The average value of εpor for freshwater cyanobacterial species is −9.8 ± 1.8‰, while for marine cyanobacteria it is −0.9 ± 1.3‰. These isotopic effects group environmentally but not phylogenetically, e.g., εpor values for freshwater Chroococcales resemble those of freshwater Nostocales but differ from those of marine Chroococcales. Our measured values of εpor for eukaryotic algae (range = 4.7–8.7‰) are similar to previous reports for pure cultures. For all taxa studied, values of εpor do not depend on the type of nitrogen substrate used for growth. The observed environmental control of εpor suggests that values of εpor could be useful for determining the fractional burial of eukaryotic vs. cyanobacterial organic matter in the sedimentary record.

Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid

Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasingmore » synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.« less

Chemical evolution with rotating massive star yields - I. The solar neighbourhood and the s-process elements

NASA Astrophysics Data System (ADS)

Prantzos, N.; Abia, C.; Limongi, M.; Chieffi, A.; Cristallo, S.

2018-05-01

We present a comprehensive study of the abundance evolution of the elements from H to U in the Milky Way halo and local disc. We use a consistent chemical evolution model, metallicity-dependent isotopic yields from low and intermediate mass stars and yields from massive stars which include, for the first time, the combined effect of metallicity, mass loss, and rotation for a large grid of stellar masses and for all stages of stellar evolution. The yields of massive stars are weighted by a metallicity-dependent function of the rotational velocities, constrained by observations as to obtain a primary-like 14N behaviour at low metallicity and to avoid overproduction of s-elements at intermediate metallicities. We show that the Solar system isotopic composition can be reproduced to better than a factor of 2 for isotopes up to the Fe-peak, and at the 10 per cent level for most pure s-isotopes, both light ones (resulting from the weak s-process in rotating massive stars) and the heavy ones (resulting from the main s-process in low and intermediate mass stars). We conclude that the light element primary process (LEPP), invoked to explain the apparent abundance deficiency of the s-elements with A < 100, is not necessary. We also reproduce the evolution of the heavy to light s-elements abundance ratio ([hs/ls]) - recently observed in unevolved thin disc stars - as a result of the contribution of rotating massive stars at sub-solar metallicities. We find that those stars produce primary F and dominate its solar abundance and we confirm their role in the observed primary behaviour of N. In contrast, we show that their action is insufficient to explain the small observed values of ^{12}C/^{13}C in halo red giants, which is rather due to internal processes in those stars.

A 1000-year record of dry conditions in the eastern Canadian prairies reconstructed from oxygen and carbon isotope measurements on Lake Winnipeg sediment organics

USGS Publications Warehouse

Buhay, W.M.; Simpson, S.; Thorleifson, H.; Lewis, M.; King, J.; Telka, A.; Wilkinson, Philip M.; Babb, J.; Timsic, S.; Bailey, D.

2009-01-01

A short sediment core (162 cm), covering the period AD 920-1999, was sampled from the south basin of Lake Winnipeg for a suite of multi-proxy analyses leading towards a detailed characterisation of the recent millennial lake environment and hydroclimate of southern Manitoba, Canada. Information on the frequency and duration of major dry periods in southern Manitoba, in light of the changes that are likely to occur as a result of an increasingly warming atmosphere, is of specific interest in this study. Intervals of relatively enriched lake sediment cellulose oxygen isotope values (??18Ocellulose) were found to occur from AD 1180 to 1230 (error range: AD 1104-1231 to 1160-1280), 1610-1640 (error range: AD 1571-1634 to 1603-1662), 1670-1720 (error range: AD 1643-1697 to 1692-1738) and 1750-1780 (error range: AD 1724-1766 to 1756-1794). Regional water balance, inferred from calculated Lake Winnipeg water oxygen isotope values (??18Oinf-lw), suggest that the ratio of lake evaporation to catchment input may have been 25-40% higher during these isotopically distinct periods. Associated with the enriched d??18Ocellulose intervals are some depleted carbon isotope values associated with more abundantly preserved sediment organic matter (d??13COM). These suggest reduced microbial oxidation of terrestrially derived organic matter and/or subdued lake productivity during periods of minimised input of nutrients from the catchment area. With reference to other corroborating evidence, it is suggested that the AD 1180-1230, 1610-1640, 1670-1720 and 1750-1780 intervals represent four distinctly drier periods (droughts) in southern Manitoba, Canada. Additionally, lower-magnitude and duration dry periods may have also occurred from 1320 to 1340 (error range: AD 1257-1363), 1530-1540 (error range: AD 1490-1565 to 1498-1572) and 1570-1580 (error range: AD 1531-1599 to 1539-1606). ?? 2009 John Wiley & Sons, Ltd.

New Carbonate Standard Reference Materials for Boron Isotope Geochemistry

NASA Astrophysics Data System (ADS)

Stewart, J.; Christopher, S. J.; Day, R. D.

2015-12-01

The isotopic composition of boron (δ11B) in marine carbonates is well established as a proxy for past ocean pH. Yet, before palaeoceanographic interpretation can be made, rigorous assessment of analytical uncertainty of δ11B data is required; particularly in light of recent interlaboratory comparison studies that reported significant measurement disagreement between laboratories [1]. Well characterised boron standard reference materials (SRMs) in a carbonate matrix are needed to assess the accuracy and precision of carbonate δ11B measurements throughout the entire procedural chemistry; from sample cleaning, to ionic separation of boron from the carbonate matrix, and final δ11B measurement by multi-collector inductively coupled plasma mass spectrometry. To date only two carbonate reference materials exist that have been value-assigned by the boron isotope measurement community [2]; JCp-1 (porites coral) and JCt-1 (Giant Clam) [3]. The National Institute of Standards and Technology (NIST) will supplement these existing standards with new solution based inorganic carbonate boron SRMs that replicate typical foraminiferal and coral B/Ca ratios and δ11B values. These new SRMs will not only ensure quality control of full procedural chemistry between laboratories, but have the added benefits of being both in abundant supply and free from any restrictions associated with shipment of biogenic samples derived from protected species. Here we present in-house δ11B measurements of these new boron carbonate SRM solutions. These preliminary data will feed into an interlaboratory comparison study to establish certified values for these new NIST SRMs. 1. Foster, G.L., et al., Chemical Geology, 2013. 358(0): p. 1-14. 2. Gutjahr, M., et al., Boron Isotope Intercomparison Project (BIIP): Development of a new carbonate standard for stable isotopic analyses. Geophysical Research Abstracts, EGU General Assembly 2014, 2014. 16(EGU2014-5028-1). 3. Inoue, M., et al., Geostandards and Geoanalytical Research, 2004. 28(3): p. 411-416.

From soil to grape and wine: Variation of light and heavy elements isotope ratios.

PubMed

Durante, Caterina; Bertacchini, Lucia; Bontempo, Luana; Camin, Federica; Manzini, Daniela; Lambertini, Paolo; Marchetti, Andrea; Paolini, Mauro

2016-11-01

In the development of a geographical traceability model, it is necessary to understand if the value of the monitored indicators in a food is correlated to its origin or if it is also influenced by 'external factors' such as those coming from its production. In this study, a deeper investigation of the trend of direct geographical traceability indicators along the winemaking process of two traditional oenological products was carried out. Different processes were monitored, sampling each step of their production (grape juice, intermediate products and wine). The results related to the determinations of δ(18)O, (D/H)I, (D/H)II, δ(13)C, δ(15)N and (87)Sr/(86)Sr have been reported. Furthermore, correspondence with the isotopic values coming from the respective soil and vine-branch samples have been investigated as well, showing the optimal traceability power of the monitored geographical tracers. Copyright © 2016 Elsevier Ltd. All rights reserved.

Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

PubMed Central

Platzner, Thomas I.; Segal, Irina

2007-01-01

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

Method and apparatus for tritiated water separation

DOEpatents

Nelson, David A.; Duncan, James B.; Jensen, George A.

1995-01-01

The present invention is a membrane method and apparatus for separating isotopic water constituents from light water. The method involves providing a supported membrane of an aromatic polyphosphazene and pressurizing the water on one side of the membrane thereby forcing the light water through the supported membrane while isotopic water constituents are retained or vice versa. The apparatus of the present invention includes an aromatic polyphosphazene placed on a porous support and means for pressurizing water through the membrane while certain isotopic water constituents are retained.

Method and apparatus for tritiated water separation

DOEpatents

Nelson, D.A.; Duncan, J.B.; Jensen, G.A.

1995-09-19

The present invention is a membrane method and apparatus for separating isotopic water constituents from light water. The method involves providing a supported membrane of an aromatic polyphosphazene and pressurizing the water on one side of the membrane thereby forcing the light water through the supported membrane while isotopic water constituents are retained or vice versa. The apparatus of the present invention includes an aromatic polyphosphazene placed on a porous support and means for pressurizing water through the membrane while certain isotopic water constituents are retained. 1 fig.

Stable isotope analysis of Dacryoconarid carbonate microfossils: a new tool for Devonian oxygen and carbon isotope stratigraphy.

PubMed

Frappier, Amy Benoit; Lindemann, Richard H; Frappier, Brian R

2015-04-30

Dacryoconarids are extinct marine zooplankton known from abundant, globally distributed calcite microfossils in the Devonian, but their shell stable isotope composition has not been previously explored. Devonian stable isotope stratigraphy is currently limited to less common invertebrates or bulk rock analyses of uncertain provenance. As with Cenozoic planktonic foraminifera, isotopic analysis of dacryoconarid shells could facilitate higher-resolution, geographically widespread stable isotope records of paleoenvironmental change, including marine hypoxia events, climate changes, and biocrises. We explored the use of Dacryoconarid isotope stratigraphy as a viable method in interpreting paleoenvironments. We applied an established method for determining stable isotope ratios (δ(13) C, δ(18) O values) of small carbonate microfossils to very well-preserved dacryoconarid shells. We analyzed individual calcite shells representing five common genera using a Kiel carbonate device coupled to a MAT 253 isotope ratio mass spectrometer. Calcite shell δ(13) C and δ(18) O values were compared by taxonomic group, rock unit, and locality. Single dacryoconarid calcite shells are suitable for stable isotope analysis using a Kiel-IRMS setup. The dacryoconarid shell δ(13) C values (-4.7 to 2.3‰) and δ(18) O values (-10.3 to -4.8‰) were consistent across taxa, independent of shell size or part, but varied systematically through time. Lower fossil δ(18) O values were associated with warmer water temperature and more variable δ(13) C values were associated with major bioevents. Dacryoconarid δ(13) C and δ(18) O values differed from bulk rock carbonate values. Dacryoconarid individual microfossil δ(13) C and δ(18) O values are highly sensitive to paleoenvironmental changes, thus providing a promising avenue for stable isotope chemostratigraphy to better resolve regional to global paleoceanographic changes throughout the upper Silurian to the upper Devonian. Our results warrant further exploration of dacryoconarid stable isotope proxy sensitivity, the isotopic contrast among dacryoconarids, other taxa, and bulk rock, as well as other potential dacryoconarid proxies (Mg/Ca, Sr/Ca, (87) Sr/(86) Sr, microlaser and ion microprobe isotope techniques, and clumped isotopes) for stratigraphic research. Copyright © 2015 John Wiley & Sons, Ltd.

Methylamphetamine synthesized from cold medication as precursor source via two different routes show significantly different stable isotope signatures

NASA Astrophysics Data System (ADS)

Jayaram, S.; Daeid, N. Nic; Kerr, W. J.; Kemp, H. F.; Meier-Augenstein, W.

2012-04-01

This work exposes the variation in light element stable isotopic abundance values of 13C, 2H and 15N) derived from the analysis of methylamphetamine synthesized via 2 different synthetic routes popular with clandestine laboraties, the Hypophosphorous and the Moscow route. We repeatedly prepared the final product using known clandestine synthetic methods where the precursors, catalysts and reducing agents have themselves been derived from house hold products and commonly available cold medications. Methylamphetamine was prepared from both lab grade pseudoephedrine and pseudoephedrine extracted (using three different solvent systems) from Sudafed®, an over-the-counter cold medication widely available in the United Kingdom. Six repetitive batches of the final product were produced in each case to provide within and between batch variations thus yielding a total of 48 samples (24 for each route). We have demonstrated that stable isotope analysis by Isotope Ratio Mass Spectrometry (IRMS) is potentially useful in the comparison and discrimination of batches of methylamphetamine produced for each route and for each precursor depending on the solvent used for extracting the pseudoephedrine starting material. To our knowledge this is the first time multivariate stable isotope analysis has been applied to methylamphetamine samples synthesized from pseudoephedrine extracted from over-the-counter cold medications.

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

NASA Astrophysics Data System (ADS)

Gajos, Norbert A.; Lundstrom, Craig C.; Taylor, Alexander H.

2016-11-01

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ56Fe and δ30Si with increasing silica content as well as a systematic increase in δ56Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ56Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ56Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ56Fe = +0.05 ± 0.02 ‰; δ30Si = -0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.

Water stable isotope measurements of Antarctic samples by means of IRMS and WS-CRDS techniques

NASA Astrophysics Data System (ADS)

Michelini, Marzia; Bonazza, Mattia; Braida, Martina; Flora, Onelio; Dreossi, Giuliano; Stenni, Barbara

2010-05-01

In the last years in the scientific community there has been an increasing interest for the application of stable isotope techniques to several environmental problems such as drinking water safeguarding, groundwater management, climate change, soils and paleoclimate studies etc. For example, the water stable isotopes, being natural tracers of the hydrological cycle, have been extensively used as tools to characterize regional aquifers and to reconstruct past temperature changes from polar ice cores. Here the need for improvements in analytical techniques: the high request for information calls for technologies that can offer a great quantity of analyses in short times and with low costs. Furthermore, sometimes it is difficult to obtain big amount of samples (as is the case for Antarctic ice cores or interstitial water) preventing the possibility to replicate the analyses. Here, we present oxygen and hydrogen measurements performed on water samples covering a big range of isotopic values (from very negative antarctic precipitation to mid-latitude precipitation values) carried out with both the conventional Isotope Ratio Mass Spectrometry (IRMS) technique and with a new method based on laser absorption techniques, the Wavelenght Scanned Cavity Ringdown Spectroscopy (WS-CRDS). This study is focusing on improving the precision of the measurements carried out with WS-CRDS in order to extensively apply this method to Antarctic ice core paleoclimate studies. The WS-CRDS is a variation of the CRDS developed in 1988 by O'Keef and Deacon. In CRDS a pulse of light goes through a box with high reflective inner surfaces; when there is no sample in the box the light beam doesn't find any obstacle in its path, but the reflectivity of the walls is not perfect so eventually there will be an absorption of the light beam; when the sample is injected in the box there is absorption and the difference between the time of absorption without and with sample is proportional to the quantity of the sample in the box. In the WS-CRDS the path of laser is longer, producing higher-sensitivity measurements. The instrument is paired with an autosampler and can be used without it and the vaporizer to analyze directly the isotopic composition of the water vapour in the atmosphere. In addition, the instrument can be moved from the laboratory and also used for outdoor measurements. The more important improvements over traditional IRMS techniques are that WS-CRDS needs less sample in order to perform the analysis (<2 ul vs. 3/5 ml); that it doesn't need manipulation of the sample (like the gas/water equilibration techniques) and the analyses are faster. Coversely, memory effects may affect the measurements so there is the need to increase the number of injection to have a high precision measurement. The laboratory of Isotope Geochemistry of the Department of Geosciences has recently acquired a WS-CRDS system from PICARRO. The isotopic data obtained with this new method have been compared with the ones obtained by means of IRMS methods. An HDO device coupled with a Thermo Finnigan Delta Plus Advantage mass spectrometer has been used, using the well know CO2 and H2/water equilibration technique. At the moment of the writing of the abstract the mean difference between the values obtained using PICARRO and using the traditional IRMS method is of the order of 0.1 per mil for the ratio 18O/16O and 1.00 per mil for the ratio D/H, but further measurements are currently underway. O'Keef A., Deacon D.A.G., 1988. Cavity ring-down optical spectrometer for absorption measurements using pulsed laser sources, Rev. Sci. Instrum., 59, 2544.

Stable mercury isotope ratios as tracers for Hg cycling at the inoperative New Idria Hg mine, California

NASA Astrophysics Data System (ADS)

Wiederhold, J. G.; Jew, A. D.; Brown, G. E.; Bourdon, B.; Kretzschmar, R.

2010-12-01

The seven stable isotopes of Hg are fractionated in the environment as a result of mass-dependent (MDF) and mass-independent (MIF) fractionation processes that can be studied in parallel by analyzing the ratios of even and odd mass Hg isotopes. MDF and MIF Hg isotope signatures of natural samples may provide a new tool to trace sources and transformations in environmental Hg cycling. However, the mechanisms controlling the extent of kinetic and equilibrium Hg isotope fractionations are still only partially understood. Thus, development of this promising tracer requires experimental calibration of relevant fractionation factors as well as assessment of natural variations of Hg isotope ratios under different environmental conditions. The inoperative Hg mine in New Idria (California, USA) represents an ideal case study to explore Hg isotope fractionation during Hg transformation and transport processes. More than a century of Hg mining and on-site thermal refining to obtain elemental Hg until 1972 produced large volumes of contaminated mine wastes which now represent sources of Hg pollution for the surrounding ecosystems. Here, we present Hg isotope data from various materials collected at New Idria using Cold-Vapor-MC-ICPMS with a long-term δ202Hg reproducibility of ±0.1‰ (2SD). Uncalcined mine waste samples were isotopically similar to NIST-3133 and did not exhibit any MIF signatures. In contrast, calcine samples, which represent the residue of the thermal ore processing at 700°C, had significantly heavier δ202Hg values of up to +1.5‰. In addition, we observed small negative MIF anomalies of the odd-mass Hg isotopes in the calcine samples, which could be caused either by nuclear volume fractionation or a magnetic isotope effect during or after the roasting process. The mass-dependent enrichment of heavy Hg isotopes in the calcine materials indicates that light Hg isotopes were preferentially removed during the roasting process, in agreement with a previous study by Stetson et al. (ES&T, 2009, 43:7331-7336). In order to further elucidate the Hg isotope signatures of the New Idria samples, we performed a three-step sequential extraction procedure to separate different Hg pools. The calcine samples exhibited a higher proportion of leachable Hg phases compared with the unrefined ore waste samples. The most soluble Hg pool (HAc/HCl, pH 2) had a significantly heavier MDF and more negative MIF signature than the bulk calcine samples, suggesting that the dissolution of more soluble Hg phases from calcine materials results in an enhanced flux of leached Hg which is isotopically distinct from the original ore. Moreover, this finding demonstrates that the Hg isotope fractionation during the ore roasting cannot be solely explained by a kinetic Rayleigh-type process which removes light Hg isotopes, but must additionally involve the formation of isotopically heavy secondary Hg phases in the calcine. The analysis of additional samples will enable us to test this hypothesis and to gain further insights into the applicability of stable Hg isotope ratios as source and process tracers in Hg-contaminated environments.

Continental warming preceding the Palaeocene-Eocene thermal maximum.

PubMed

Secord, Ross; Gingerich, Philip D; Lohmann, Kyger C; Macleod, Kenneth G

2010-10-21

Marine and continental records show an abrupt negative shift in carbon isotope values at ∼55.8 Myr ago. This carbon isotope excursion (CIE) is consistent with the release of a massive amount of isotopically light carbon into the atmosphere and was associated with a dramatic rise in global temperatures termed the Palaeocene-Eocene thermal maximum (PETM). Greenhouse gases released during the CIE, probably including methane, have often been considered the main cause of PETM warming. However, some evidence from the marine record suggests that warming directly preceded the CIE, raising the possibility that the CIE and PETM may have been linked to earlier warming with different origins. Yet pre-CIE warming is still uncertain. Disentangling the sequence of events before and during the CIE and PETM is important for understanding the causes of, and Earth system responses to, abrupt climate change. Here we show that continental warming of about 5 °C preceded the CIE in the Bighorn Basin, Wyoming. Our evidence, based on oxygen isotopes in mammal teeth (which reflect temperature-sensitive fractionation processes) and other proxies, reveals a marked temperature increase directly below the CIE, and again in the CIE. Pre-CIE warming is also supported by a negative amplification of δ(13)C values in soil carbonates below the CIE. Our results suggest that at least two sources of warming-the earlier of which is unlikely to have been methane-contributed to the PETM.

Gradients in seasonality and seawater oxygen isotopic composition along the early Permian Gondwanan coast, SE Australia

NASA Astrophysics Data System (ADS)

Beard, J. Andrew; Ivany, Linda C.; Runnegar, Bruce

2015-09-01

Oxygen isotope compositions of marine carbonates are commonly employed for understanding ancient temperatures, but this approach is complicated in the very distant past due to uncertainties about the effects of diagenesis and the isotopic composition of seawater, both locally and globally. Microsampled accretionary calcite from two species of the fossil bivalve Eurydesma Sowerby and Morris 1845 collected from sediments of Cisuralian age in high latitude marine sediments along the SE coast of Australia records cyclic seasonal fluctuations in shell δ18O values during growth, demonstrating the primary nature of the isotope signal and thus allowing investigation of early Permian seawater isotopic composition and water temperature in the high southern latitudes. The mean and seasonal range of δ18Ocarb decreases poleward across about 10° of paleolatitude (∼67°S-77°S). The presence of co-occurring dropstones and stratigraphically associated glendonites constrains winter temperatures across the region to near-freezing, thus permitting calculation of realistic estimates of water composition and summer temperatures. Summer δ18Ocarb values indicate water temperatures between 5 °C and 12 °C, with warmer values at lower latitudes. The decrease in both mean sea surface temperature and seasonal amplitude with increasing latitude on the Gondwanan coast is much like that observed along high-latitude coastlines today. Calculated δ18Owater decreases toward the pole, likely associated with an increasing contribution of isotopically light fresh water derived from summer snow-melt. The gradient in δ18Owater is similar to that documented over a similar span of latitude on the modern SE Greenland coast. We infer the presence of a north-flowing coastal current of cold, O18-depleted water that entrains progressively greater amounts of more typical seawater as it moves away from the pole. δ18O values in SE Australia, however, are about 3‰ lower than those off Greenland, suggesting comparatively lower salinity water or more O18-depleted glacial ice/runoff in the Permian Gondwanan high latitudes, perhaps augmented by more depleted (negative) global average seawater. Conditions in southeastern Australia during the largest of the Permian deglaciations were warmer than present-day Antarctica at similar latitudes, but may approximate those of early-mid Miocene Antarctica, with frozen winters but summers closer to 10 °C.

Sulfur, carbon, and oxygen isotope variations in submarine hydrothermal deposits of Guaymas Basin, Gulf of California, USA

USGS Publications Warehouse

Peter, J.M.; Shanks, Wayne C.

1992-01-01

Sulfur, carbon, and oxygen isotope values were measured in sulfide, sulfate, and carbonate from hydrothermal chimney, spire, and mound samples in the southern trough of Guaymas Basin, Gulf of California, USA. ??34S values of sulfides range from -3.7 to 4.5%. and indicate that sulfur originated from several sources: 1. (1) dissolution of 0??? sulfide contained within basaltic rocks, 2. (2) thermal reduction of seawater sulfate during sediment alteration reactions in feeder zones to give sulfide with positive ??34S, and 3. (3) entrainment or leaching of isotopically light (negative-??34S) bacteriogenic sulfide from sediments underlying the deposits. ??34S of barite and anhydrite indicate sulfur derivation mainly from unfractionated seawater sulfate, although some samples show evidence of sulfate reduction and sulfide oxidation reactions during mixing within chimneys. Oxygen isotope temperatures calculated for chimney calcites are in reasonable agreement with measured vent fluid temperatures and fluid inclusion trapping temperatures. Hydrothermal fluids that formed calcite-rich chimneys in the southern trough of Guaymas Basin were enriched in 18O with respect to seawater by about 2.4??? due to isotopic exchange with sedimentary and/or basaltic rocks. Carbon isotope values of calcite range from -9.6 to -14.0??? ??34CpDB, indicating that carbon was derived in approximately equal quantities from the dissolution of marine carbonate minerals and the oxidation of organic matter during migration of hydrothermal fluid through the underlying sediment column. Statistically significant positive, linear correlations of ??34S, ??34C, and ??18O of sulfides and calcites with geographic location within the southern trough of Guaymas Basin are best explained by variations in water/rock ( w r) ratios or sediment reactivity within subsurface alteration zones. Low w r ratios and the leaching of detrital carbonates and bacteriogenic sulfides at the southern vent sites result in relatively high ??13C and low ??34S in chimney carbonates and sulfides, respectively. In the north, where the depletion of alkalis in vent fluids indicates higher w r ratios, positive ??34S and more negative ??13c are due to increased contributions from organic matter oxidation and sulfate reduction reactions. ?? 1992.

Carbon, oxygen, and strontium isotopic composition of methane-derived authigenic carbonates in methane seep areas, eastern margin of Japan Sea

NASA Astrophysics Data System (ADS)

Kakizaki, Y.; Ishikawa, T.; Hiruta, A.; Matsumoto, R.

2016-12-01

We report the occurrence, mineralogy, and isotopic composition (δ13C; δ18O) of methane-derived authigenic carbonates (MDACs) from three methane seep areas with shallow gas hydrate (Umitaka Spur, Joetsu Knoll, and off-Tobishima Island), in the southeastern margin of Japan Sea. Furthermore, we present strontium isotopic ratios (87Sr/86Sr) of MDACs, pore waters, and seawater from Umitaka Spur. MDACs range from a few mm to several tens of cm in diameter. Their shape is quite varied, e.g. nodular, platy, and indetermine form. Most MDACs are composed of high-Mg calcite. The δ13C values of MDACs from Umitaka Spur range from -30 to -4 permil. These isotopic values are higher than those of Joetsu Knoll and off-Tobishima Island. This difference is dependent upon the formation depth of MDACs in the sediment column. It probably indicates a difference in the formation environment of MDACs (e.g. methane flux). Meanwhile, range of the δ18O values of MDACs from those three areas is mostly equal. The 87Sr/86Sr ratios in MDACs from shallow sediment depth of Umitaka Spur are equal to those of modern surface seawater just above Umitaka Spur. The 87Sr/86Sr ratios of MDACs from deeper sediment depth are lower, and the Sr-isotopic trend indicates an upward increase. This trend can be correlated to the global Sr-isotopic trend of the seawater from late Pleistocene to present. It means that 87Sr/86Sr ratios of MDACs reflect the 87Sr/86Sr ratio of seawater at the formation age. However, the 87Sr/86Sr ratios in pore water are lower than those of MDACs, yet follow a parallel trend. This would suggest that the pore water includes a source of light Sr, presumably released from tuff and volcaniclastics during diagenetic processes. This study was conducted under the commission from AIST as a part of the methane hydrate research project funded by METI (the Ministry of Economy, Trade and Industry, Japan).

Deuterium excess reveals diurnal sources of water vapor in forest air.

PubMed

Lai, Chun-Ta; Ehleringer, James R

2011-01-01

An understanding of atmospheric water vapor content and its isotopic composition is important if we are to be able to model future water vapor dynamics and their potential feedback on future climate change. Here we present diurnal and vertical patterns of water isotope ratios in forest air (δ(2)H(v) and δ(18)O(v)) not observed previously. Water vapor observed at three heights over 3 consecutive days in a coniferous forest in the Pacific Northwest of the United States, shows a stratified nocturnal structure of δ(2)H(v) and δ(18)O(v), with the most positive values consistently observed above the canopy (60 m). Differences between 0.5 m and 60 m range between 2-6‰ for δ(18)O and 20-40‰ for δ(2)H at night. Using a box model, we simulated H(2)O isotope fluxes and showed that the low to high δ(2)H(v) and δ(18)O(v) profiles can be explained by the vapor flux associated with evaporation from the forest floor and canopy transpiration. We used d-excess as a diagnostic tracer to identify processes that contribute to the diurnal variation in atmospheric moisture. Values of d-excess derived from water vapor measurements showed a repeated diel pattern, with the lowest values occurring in the early morning and the highest values occurring at midday. The isotopic composition of rain water, collected during a light rain event in the first morning of our experiment, suggested that considerable below-cloud secondary evaporation occurred during the descent of raindrops. We conclude that atmospheric entrainment appears to drive the isotopic variation of water vapor in the early morning when the convective boundary layer rapidly develops, while evapotranspiration becomes more important in the mid-afternoon as a primary moisture source of water vapor in this forest. Our results demonstrate the interplay between the effects of vegetation and boundary layer mixing under the influence of rain evaporation, which has implications for larger-scale predictions of precipitation across the terrestrial landscape.

The Early Differentiation History of Mars from W-182-Nd-142 Isotope Systematics in the SNC Meteorites

NASA Technical Reports Server (NTRS)

Foley, C. Nicole; Wadhwa, M.; Borg, L. E.; Janney, P. E.; Hines, R.; Grove, T. L.

2005-01-01

We report here the results of an investigation of W and Nd isotopes in the SNC (Shergottite-Nakhlite-Chassignite (martian)) meteorites. We have determined that epsilon W-182 values in the nakhlites are uniform within analytical uncertainties and have an average value of approx. 3. Also, while epsilon W-182 values in the shergottites have a limited range (from 0.3-0.7), their epsilon Nd-142 values vary considerably (from -0.2-0.9). There appears to be no correlation between epsilon W-182 and epsilon Nd-142 in the nakhlites and shergottites. These results shed new light on early differentiation processes on Mars, particularly on the timing and nature of fractionation in silicate reservoirs. Assuming a two-stage model, the metallic core is estimated to have formed at approx. 12 Myr after the beginning of the solar system. Major silicate differentiation established the nakhlite source reservoir before approx. 4542 Ma and the shergottite source reservoirs at 4525 [sup +19 sub -21] Ma. These ages imply that, within the uncertainties afforded by the Hf-182-W-182 and Sm-146-Nd-142 chronometers, the silicate differentiation events that established the source reservoirs of the nakhlites and shergottites may have occurred contemporaneously, possibly during crystallization of a global magma ocean. The distinct W-182-Nd-142 isotope systematics in the nakhlites and the shergottites imply the presence of at least three isotopically distinct silicate reservoirs on Mars, two of which are depleted in incompatible lithophile elements relative to chondrites, and the third is enriched. The two depleted silicate reservoirs most likely reside in the Martian mantle, while the enriched reservoir could be either in the crust or the mantle. Therefore, the W-182-Nd-142 isotope systematics indicate that the nakhlites and the shergottites originated from distinct source reservoirs and cannot be petrogenetically related. A further implication is that the source reservoirs of the nakhlites and shergottites on Mars have been isolated since their establishment before approx. 4.5 Ga. Therefore, there has been no giant impact or efficient global mantle convection to thoroughly homogenize the Martian mantle following the establishment of the SNC source reservoirs.

Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

USGS Publications Warehouse

Hackley, Keith C.; Liu, Chao-Li; Trainor, D.

1999-01-01

The major source of methane (CH4) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH4 and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH4 up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH4 included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments. Isotopic analyses included ??13C, ??D, 14C, and 3H on select CH4 samples and ??D and ??18O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had ??13C values from -79 to -82???, typical of natural 'drift gas' generated by microbial CO2-reduction. The CH4 from the shallow lacustrine deposits had ??13C values from -63 to -76???, interpreted as a mixture between CH4 generated by microbial fermentation and the CO2-reduction processes within the subsurface sediments. The ??D values of all the CH4 samples were quite negative ranging from -272 to -299???. Groundwater sampled from the deeper zones also showed quite negative ??D values that explained the light ??D observed for the CH4. Radiocarbon analyses of the CH4 showed decreasing 14C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH4 detected in the fill deposits of this site was microbial CH4 generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH4 from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH4 could not be completely ruled out.

Intraspecific carbon and nitrogen isotopic variability in foxtail millet (Setaria italica).

PubMed

Lightfoot, Emma; Przelomska, Natalia; Craven, Martha; O Connell, Tamsin C; He, Lu; Hunt, Harriet V; Jones, Martin K

2016-07-15

Isotopic palaeodietary studies generally focus on bone collagen from human and/or animal remains. While plant remains are rarely analysed, it is known that plant isotope values can vary as a result of numerous factors, including soil conditions, the environment and type of plant. The millets were important food crops in prehistoric Eurasia, yet little is known about the isotopic differences within millet species. Here we compare the stable isotope ratios within and between Setaria italica plants grown in a controlled environment chamber. Using homogenised samples, we compare carbon isotope ratios of leaves and grains, and nitrogen isotope ratios of grains, from 29 accessions of Setaria italica. We find significant isotopic variability within single leaves and panicles, and between leaves and panicles within the same plant, which must be considered when undertaking plant isotope studies. We find that the leaves and grains from the different accessions have a ca 2‰ range in δ(13) C values, while the nitrogen isotope values in the grains have a ca 6‰ range. We also find an average offset of 0.9‰ between leaves and grains in their δ(13) C values. The variation found is large enough to have archaeological implications and within- and between-plant isotope variability should be considered in isotope studies. The range in δ(15) N values is particularly significant as it is larger than the typical values quoted for a trophic level enrichment, and as such may lead to erroneous interpretations of the amount of animal protein in human or animal diets. It is therefore necessary to account for the variability in plant stable isotope values during palaeodietary reconstructions. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Stable Te isotope fractionation in tellurium-bearing minerals from precious metal hydrothermal ore deposits

NASA Astrophysics Data System (ADS)

Fornadel, Andrew P.; Spry, Paul G.; Haghnegahdar, Mojhgan A.; Schauble, Edwin A.; Jackson, Simon E.; Mills, Stuart J.

2017-04-01

The tellurium isotope compositions of naturally-occurring tellurides, native tellurium, and tellurites were measured by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) and compared to theoretical values for equilibrium mass-dependent isotopic fractionation of representative Te-bearing species estimated with first-principles thermodynamic calculations. Calculated fractionation models suggest that 130/125Te fractionations as large as 4‰ occur at 100 °C between coexisting tellurates (Te VI) and tellurides (Te -II) or or native tellurium Te(0), and smaller, typically <1‰, fractionations occur between coexisting Te(-I) or Te(-II) (Au,Ag)Te2 minerals (i.e., calaverite, krennerite) and (Au,Ag)2Te minerals (i.e., petzite, hessite). In general, heavyTe/lightTe is predicted to be higher for more oxidized species, and lower for reduced species. Tellurides in the system Au-Ag-Te and native tellurium analyzed in this study have values of δ130/125Te = -1.54‰ to 0.44‰ and δ130/125Te = -0.74‰ to 0.16‰, respectively, whereas those for tellurites (tellurite, paratellurite, emmonsite and poughite) range from δ130/125Te = -1.58‰ to 0.59‰. Thus, the isotopic composition for both oxidized and reduced species are broadly coincident. Calculations of per mil isotopic variation per amu for each sample suggest that mass-dependent processes are responsible for fractionation. In one sample of coexisting primary native tellurium and secondary emmonsite, δ130/125Te compositions were identical. The coincidence of δ130/125Te between all oxidized and reduced species in this study and the apparent lack of isotopic fractionation between native tellurium and emmonsite in one sample suggest that oxidation processes cause little to no fractionation. Because Te is predominantly transported as an oxidized aqueous phase or as a reduced vapor phase under hydrothermal conditions, either a reduction of oxidized Te in hydrothermal liquids or deposition of Te from a reduced vapor to a solid is necessary to form the common tellurides and native tellurium in ore-forming systems. Our data suggest that these sorts of reactions during mineralization may account for a ∼3‰ range of δ130/125Te values. Based on the data ranges for Te minerals from various ore deposits, the underpinning geologic processes responsible for mineralization seem to have primary control on the magnitude of fractionation, with tellurides in epithermal gold deposits showing a narrower range of isotope values than those in orogenic gold and volcanogenic massive sulfide deposits.

Carnivore specific bone bioapatite and collagen carbon isotope fractionations: Case studies of modern and fossil grey wolf populations

NASA Astrophysics Data System (ADS)

Fox-Dobbs, K.; Wheatley, P. V.; Koch, P. L.

2006-12-01

Stable isotope analyses of modern and fossil biogenic tissues are routinely used to reconstruct present and past vertebrate foodwebs. Accurate isotopic dietary reconstructions require a consumer and tissue specific understanding of how isotopes are sorted, or fractionated, between trophic levels. In this project we address the need for carnivore specific isotope variables derived from populations that are ecologically well- characterized. Specifically, we investigate the trophic difference in carbon isotope values between mammalian carnivore (wolf) bone bioapatite and herbivore (prey) bone bioapatite. We also compare bone bioapatite and collagen carbon isotope values collected from the same individuals. We analyzed bone specimens from two modern North American grey wolf (Canis lupus) populations (Isle Royale National Park, Michigan and Yellowstone National Park, Wyoming), and the ungulate herbivores that are their primary prey (moose and elk, respectively). Because the diets of both wolf populations are essentially restricted to a single prey species, there were no confounding effects due to carnivore diet variability. We measured a trophic difference of approximately -1.3 permil between carnivore (lower value) and herbivore (higher value) bone bioapatite carbon isotope values, and an average inter-tissue difference of 5.1 permil between carnivore bone collagen (lower value) and bioapatite (higher value) carbon isotope values. Both of these isotopic differences differ from previous estimates derived from a suite of African carnivores; our carnivore-herbivore bone bioapatite carbon isotope spacing is smaller (-1.3 vs. -4.0 permil), and our carnivore collagen-bioapatite carbon difference is larger (5.1 vs. 3.0 permil). These discrepancies likely result from comparing values measured from a single hypercarnivore (wolf) to average values calculated from several carnivore species, some of which are insectivorous or partly omnivorous. The trophic and inter-tissue differences we measured for wolves are applicable to future isotopic studies of consumers with purely carnivorous diets. For example, we collected bone bioapatite and collagen carbon isotope data from late Pleistocene grey wolf fossils from eastern Beringia (Fairbanks, Alaska), and used the modern inter-tissue difference presented here to verify bioapatite preservation. We then compared the wolves to herbivores (horse and caribou) from the same locality, and found the difference in their bone bioapatite carbon isotope values corresponded to the modern carnivore-herbivore trophic spacing given above. We therefore were able to conclude that horse and caribou were part of Beringian wolf diet.

A Continuous Holocene Record of Hydroclimate from Kartchner Cavern, AZ, Supported by Multiyear Dripwater Monitoring

NASA Astrophysics Data System (ADS)

Cole, J. E.; Hlohowskyj, S.; Vetter, L.; King, J.; Casavant, R. R.; Woodhead, J. D.; Drysdale, R.; Truebe, S.; Henderson, G. M.

2017-12-01

In the arid southwest, hydroclimatic variability is critical to natural and human systems. Cave records provide the chance to reconstruct past variations in moisture, including the seasonal hydroclimatic response to known forcings such as the seasonal distribution of insolation. At Kartchner Caverns State Park, AZ, a sample dating to 12,000 years before present reveals a continuous Holocene history of the Southwest monsoon in its stable isotope content. We interpret the large ( 4‰) changes in speleothem d18O in terms of seasonal precipitation balance, based on modern isotope studies. The Kartchner record confirms a shorter ( 6500 yr) reconstruction from the neighboring Cave of the Bells in describing a strong trend of declining monsoon moisture during the Holocene. The Kartchner sample reveals an early Holocene monsoon peak defined by a broad δ18O peak between 7000 and 9000 years ago, following a gradual strengthening from the start of the record. Between 7000-2000 years ago, the monsoon weakened, and the oxygen isotope values show no trend over the past 2000 years. Substantial multidecadal-multicentury variability is present throughout the record. This pattern is consistent with a sensitive response of the Southwest monsoon to orbital forcing of seasonal radiation. A new laser-ICPMS multi-element dataset spans the past 2400 years and adds information to our isotope-based reconstruction. In particular, Ba and Sr highlight intervals of overall wet and dry conditions, complementing the isotopic record of seasonal precipitation distribution. Dripwater monitoring since 2011 at 4 sites in the cave allows us to identify seasonal and interannual controls on the isotopic and elemental variations of dripwater. Drips differ in their isotopic behavior, with some dominated by relatively steady, low (winter) values and others exhibiting highly variable δ18O. This study provides one of the first cave-based reconstructions of the North American monsoon spanning the entire Holocene. The modern dripwater data shed light on how isotopic and elemental signals vary over space and time and create the multivariate climate record preserved in cave calcite.

Biology and air-sea gas exchange controls on the distribution of carbon isotope ratios (δ13C) in the ocean

NASA Astrophysics Data System (ADS)

Schmittner, A.; Gruber, N.; Mix, A. C.; Key, R. M.; Tagliabue, A.; Westberry, T. K.

2013-09-01

Analysis of observations and sensitivity experiments with a new three-dimensional global model of stable carbon isotope cycling elucidate processes that control the distribution of δ13C of dissolved inorganic carbon (DIC) in the contemporary and preindustrial ocean. Biological fractionation and the sinking of isotopically light δ13C organic matter from the surface into the interior ocean leads to low δ13CDIC values at depths and in high latitude surface waters and high values in the upper ocean at low latitudes with maxima in the subtropics. Air-sea gas exchange has two effects. First, it acts to reduce the spatial gradients created by biology. Second, the associated temperature-dependent fractionation tends to increase (decrease) δ13CDIC values of colder (warmer) water, which generates gradients that oppose those arising from biology. Our model results suggest that both effects are similarly important in influencing surface and interior δ13CDIC distributions. However, since air-sea gas exchange is slow in the modern ocean, the biological effect dominates spatial δ13CDIC gradients both in the interior and at the surface, in contrast to conclusions from some previous studies. Calcium carbonate cycling, pH dependency of fractionation during air-sea gas exchange, and kinetic fractionation have minor effects on δ13CDIC. Accumulation of isotopically light carbon from anthropogenic fossil fuel burning has decreased the spatial variability of surface and deep δ13CDIC since the industrial revolution in our model simulations. Analysis of a new synthesis of δ13CDIC measurements from years 1990 to 2005 is used to quantify preformed and remineralized contributions as well as the effects of biology and air-sea gas exchange. The model reproduces major features of the observed large-scale distribution of δ13CDIC as well as the individual contributions and effects. Residual misfits are documented and analyzed. Simulated surface and subsurface δ13CDIC are influenced by details of the ecosystem model formulation. For example, inclusion of a simple parameterization of iron limitation of phytoplankton growth rates and temperature-dependent zooplankton grazing rates improves the agreement with δ13CDIC observations and satellite estimates of phytoplankton growth rates and biomass, suggesting that δ13C can also be a useful test of ecosystem models.

Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

NASA Astrophysics Data System (ADS)

Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

2017-12-01

The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical results, measurements of site-specific isotopic fractionation properties could improve our understanding and the interpretation of isotopic records in apatites.

Distinguishing wild vs. stocked lake trout (Salvelinus namaycush) in Lake Ontario: Evidence from carbon and oxygen stable isotope values of otoliths

USGS Publications Warehouse

Schaner, T.; Patterson, W.P.; Lantry, B.F.; O'Gorman, R.

2007-01-01

We investigated the potential for using carbon and oxygen isotope values of otolith carbonate as a method to distinguish naturally produced (wild) lake trout (Salvelinus namaycush) from hatchery-reared lake trout in Lake Ontario. We determined δ 13C(CaCO3) and δ 18O(CaCO3) values of otoliths from juvenile fish taken from two hatcheries, and of otoliths from wild yearlings. Clear differences in isotope values were observed between the three groups. Subsequently we examined otoliths from large marked and unmarked fish captured in the lake, determining isotope values for regions of the otolith corresponding to the first year of life. Marked (i.e., stocked) fish showed isotope ratios similar to one of the hatchery groups, whereas unmarked fish, (wild fish or stocked fish that lost the mark) showed isotope ratios similar either to one of the hatchery groups or to the wild group. We interpret these data to suggest that carbon and oxygen isotope values can be used to determine the origin of lake trout in Lake Ontario, if a catalogue of characteristic isotope values from all candidate years and hatcheries is compiled.

Biologically mediated isotope fractionations - Biochemistry, geochemical significance and preservation in the earth's oldest sediments

NASA Technical Reports Server (NTRS)

Schidlowski, M.

1983-01-01

Preferential metabolization of isotopically light carbon and sulfur has resulted in a fractionation of the stable isotopes of these elements on a global scale, with the light species (C-12, S-32) markedly concentrated in biogenic materials. Since the biological effects are basically retained when carbon and sulfur are incorporated in sediments, the respective fractionations are propagated into the rock section of the geochemical cycle, this having consequently caused a characteristic bipartition of both elements between 'light' and 'heavy' crustal reservoirs. Preservation of the biological isotope effects in sedimentary rocks makes it possible to trace the underlying biochemical processes back over most of the geological record. According to the available evidence, biological (autotrophic) carbon fixation arose prior to 3.5(if not 3.8) billion years ago, while the emergence of dissimilatory sulfate reduction antedates the appearance of the oldest presumably bacteriogenic sulfur isotope patterns in rocks between 2.7 and 2.8 billion years old. Hence, biological control of the terrestrial carbon and sulfur cycles has been established very early in the earth's history.

Iron isotope behavior during fluid/rock interaction in K-feldspar alteration zone - A model for pyrite in gold deposits from the Jiaodong Peninsula, East China

NASA Astrophysics Data System (ADS)

Zhu, Zhi-Yong; Jiang, Shao-Yong; Mathur, Ryan; Cook, Nigel J.; Yang, Tao; Wang, Meng; Ma, Liang; Ciobanu, Cristiana L.

2018-02-01

Mechanisms for Fe isotope fractionation in hydrothermal mineral deposits and in zones of associated K-feldspar alteration remain poorly constrained. We have analyzed a suite of bulk samples consisting of granite displaying K-feldspar alteration, Precambrian metamorphic rocks, and pyrite from gold deposits of the Jiaodong Peninsula, East China, by multi-collector inductively-coupled plasma mass spectrometry. Pyrites from disseminated (J-type) ores show a δ56Fe variation from +0.01 to +0.64‰, overlapping with the signature of the host granites (+0.08 to +0.39‰). In contrast, pyrites from quartz veins (L-type ores) show a wide range of Fe-isotopic composition from -0.78 to +0.79‰. Negative values are never seen in the J-type pyrites. The Fe isotope signature of the host granite with K-feldspar alteration is significantly heavier than that of the bulk silicate Earth. The Fe isotopic compositions of Precambrian metamorphic rocks across the district display a narrow range between -0.16‰ and +0.19‰, which is similar to most terrestrial rocks. Concentrations of major and trace elements in bulk samples were also determined, so as to evaluate any correlation between Fe isotope composition and degree of alteration. We note that during progressive K-feldspar alteration to rocks containing >70 wt% SiO2, >75 ppm Rb, and <1.2 wt% total Fe2O3, the Fe isotope composition of the granite changes systematically. The Fe isotope signature becomes heavier as the degree of alteration increases. The extremely light Fe isotopic compositions in L-type gold deposits may be explained by Rayleigh fractionation during pyrite precipitation in an open fracture system. We note that the sulfur isotopic compositions of pyrite in the two types of ores are also different. Pyrite from J-type ores has a systematically 3.5‰-higher δ34S value (11.2‰) than those of pyrite from the L-type ores (7.7‰). There is, however, no correlation between Fe and S isotope signatures. The isotopic fractionation of sulfur is used to constrain a change in the fO2 of the hydrothermal fluids from which pyrite precipitated. This work demonstrates that the Fe isotope composition of pyrite displays a significant response to the process of pyrite precipitation in hydrothermal systems, and that systematic fractionation of iron isotopes occurs during fluid/rock reaction in the K-feldspar alteration zone of the Linglong granite. The implications of the results are that processes of mineralization and associated fluid-rock interaction, which are ubiquitously observed in porphyry-style Cu-Au-Mo and other hydrothermal deposits, may be readily traceable using Fe isotopes.

Nitrogen Isotopic Composition of Proteinaceous Coral Skeletal Amino Acids Records Change in Source Nitrate to the Euphotic Zone in the Western Tropical Pacific

NASA Astrophysics Data System (ADS)

Williams, B.; Thibodeau, B.; Chikaraishi, Y.; Ohkouchi, N.; Grottoli, A. G.

2014-12-01

Instrumental and proxy data and global climate model experiments indicate a multi-decadal shoaling of the western tropical Pacific (WTP) thermocline potentially related to a shift in ENSO frequency. In the WTP, the nutricline coincides with the thermocline, and a shoaling of the nutricline brings more nitrate-rich seawater higher in the water column and within the sunlit euphotic zone. In the nutrient-poor WTP, this incursion of nitrate-rich water at the bottom of the euphotic zone may stimulate productivity in the water column. However, there is a general paucity of measurements below the surface with which to investigate recent changes in seawater chemistry. Nitrogen isotope (δ15N) measurements of particulate organic matter (POM) can elucidate the source of nitrogen to the WTP and related trophic dynamics. This POM is the food source to the long-lived proteinaceous corals, and drives the nitrogen isotopic composition of their skeleton. Here, we report time series δ15N values from the banded skeletons of proteinaceous corals from offshore Palau in the WTP that provide proxy information about past changes in euphotic zone nitrogen dynamics. Bulk skeletal δ15N values declined between 1977 and 2010 suggesting a progressively increasing contribution of deep water with isotopically-light nitrate to the euphotic zone and/or a shortening of the planktonic food web. Since only some amino acids are enriched in δ15N with each trophic transfer in a food web, we measured the δ15N composition of seven individual amino acids in the same coral skeleton. The δ15N time series of the individual amino acids also declined over time, mirroring the bulk values. These new data indicate that the changes in the source nitrogen to the base of the euphotic zone drives a decline in coral skeletal δ15N values, consistent with the shoaling nutricline, with no coinciding alteration of the trophic structure in the WTP.

Geochemical and isotopic (Nd-Pb-Sr-O) variations bearing on the genesis of volcanic rocks from Vesuvius, Italy

USGS Publications Warehouse

Ayuso, R.A.; de Vivo, B.; Rolandi, G.; Seal, R.R.; Paone, A.

1998-01-01

Alkaline volcanism produced by Monte Somma-Vesuvius volcano includes explosive plinian and subplinian activity in addition to effusive lava flows. Pumice, scoria, and lava (150 samples) exhibit major- and trace-element gradients as a function of SiO2 (58.9-47.2 wt%) and MgO (0-7.8 wt%); Mg value are ???50. Internally gradational chemical groups or cycles are distinguished by age: (1) 25 000 to 14 000 yr B.P.; (2) 8000 yr B.P. to A.D. 79; and (3) A.D. 79 to 1944. A small number of lavas, dikes and scora were also analysed from the Somma formation (~ 35 000 to 25 000 yr B.P.). Within each group, contents of Na2O + K2O increas with decreasing MgO along distinct rocks. Nb/Y values are variable from 0.66 to 3.14 (at SiO2 ??? 50 wt%) generally in the range of alkaline and ultra-alkaline rocks. Variations in contents of some majro elements (e.g., P and Ti), and trace elements (e.g., Th, Nb, Ta, Zr, Hf, Pb, La, and Sc), as well as contrasting trends in ratios of various elements (e.g., Ta/Yb, Hf/U, Th/Ta, Th/Hf, Th/Yb, etc.) are also generally consistent with the group subdivisions. For example, Th/Hf increases from ??? 5 to ??? 10 with decreasing age for the Vesuvius system as a whole, yielding similar compositions in the least evolved rocks (low-silica, high-MgO, imcompatible element-poor) erupted at the end of each cycle. Internal variations within individual eruptions also systematically changed generally towards a common mafic composition at the end of each cycle, thus reflecting the dominanit volume in the magma chamber. At the start of a new eruptive cycle, the rocks are relatively enriched in incompatible elements; younger groups also contain higher abundances than other groups. N-MORB-normalized multielement diagrams exhibit selective enrichments of Sr, K, Rb, Th, and the light rare-earth elements; deep Nb and Ta negative anomalies commonly seen in rocks generated at orogenic margins are absent in the light rare-earth elements; deep Nb and Ta netgative anomalies commonly seen in rocks generated at orogenic margins are absent in our samples. Sr isotopic compositions are known to be variable within some of the units, in agreement with our data (87Sr/86Sr ~ 0.70699 to 0.70803) and with contributions from several isotopic components. Isotopic compositions for ??18O (7.3 to 10.2%), Pb for mineral separates and whole rocks (206Pb/204Pb ~ 18.947 to 19.178, 207Pb/204/Pb ~ 15.617 to 15.769, 208Pb/204Pb ~38.915 to 39.345), and Nd (143Nd ~ 0.51228 to 0.51251) also show variability. Oxygen isotope data show that pumices have higher ??18O values than cogenetic lavas, and that ??18O values and SiO2 are correlated. Radiogenic and stable isotope data plot within range of isotopic compositions for the Roman comagmatic province. Fractional crystallization cannot account for the radiogenic isotopic compositions of the Vesuvius magmas. We favor instead the combined effects of heterogeneous magma sources, together with isotopic exchange near the roof of the magma chamber. We suggest that metasomatized continental mantle lithosphere is the principal source of the magmas. This kind of enriched mantle was melted and reactivated in an area of continental extension (incipient rift setting) without direct reliance on contemporaneous subduction processes but possibly with input from mantle sources that resemble those that produce ocean island basalts.

Reassessment of the 13C/12C and 14C/12C isotopic fractionation ratio and its impact on high-precision radiocarbon dating

NASA Astrophysics Data System (ADS)

Fahrni, Simon M.; Southon, John R.; Santos, Guaciara M.; Palstra, Sanne W. L.; Meijer, Harro A. J.; Xu, Xiaomei

2017-09-01

The vast majority of radiocarbon measurement results (14C/12C isotopic ratios or sample activities) are corrected for isotopic fractionation processes (measured as 13C/12C isotopic ratios) that occur in nature, in sample preparation and measurement. In 1954 Harmon Craig suggested a value of 2.0 for the fractionation ratio b that is used to correct 14C/12C ratios for shifts in the 13C/12C ratios and this value has been applied by the radiocarbon community ever since. While theoretical considerations suggest moderate deviations of b from 2.0, some measurements have suggested larger differences (e.g. b = 2.3, measured by Saliège and Fontes in 1984). With the high precision attained in radiocarbon measurements today (±2‰), even a relatively small deviation of b from 2.0 can impact the accuracy of radiocarbon data, and it is, therefore, of interest to re-evaluate the fractionation corrections. In the present study, the fractionation ratio b was determined by independent experiments on the chemical reduction of carbon dioxide (CO2) to elemental carbon (graphitization reaction) and on the photosynthetic uptake of CO2 by C3 and C4 plants. The results yielded b = 1.882 ± 0.019 for the reduction of CO2 to solid graphite and b = 1.953 ± 0.025 for the weighted mean of measurements involving C3 and C4 photosynthesis pathways. In addition, the analysis of over 9600 full-sized OX-I and OX-II normalizing standards measured between 2002 and 2012 confirms b values lower than 2.0. The obtained values are in good agreement with quantum mechanical estimates of the equilibrium fractionation and classic kinetic fractionation as well as with results from other light three-isotope systems (oxygen, magnesium, silicon and sulfur). While the value of the fractionation ratio varies with the relative importance of kinetic and equilibrium fractionation, the values obtained in the present study cluster around b = 1.9. Our findings suggest that a significant fraction of all samples ("unknowns") would be shifted by 2‰ (16 radiocarbon years) or more due to this effect: for example, for b = 1.882, between 16.8% and 25.9% of almost 60,000 radiocarbon values measured at the Keck Carbon Cycle AMS facility between 2002 and 2012 would be affected. The implications for radiocarbon dating and its accuracy are discussed.

Sub-seasonal oxygen and carbon isotope variations in shells of modern Radix sp. (Gastropoda) from the Tibetan Plateau: potential of a new archive for palaeoclimatic studies

NASA Astrophysics Data System (ADS)

Taft, Linda; Wiechert, Uwe; Riedel, Frank; Weynell, Marc; Zhang, Hucai

2012-02-01

Carbon and oxygen isotope ratios have been measured for nine aragonite shells of the gastropod genus Radix from the lake Bangda Co (30°29'N, 97°04'E, 4450 m a.s.l.) at the south-eastern edge and from two characteristic sites at the lake Kyaring Co (31°09'N, 88°17'E, 4650 m a.s.l.) on the central Tibetan Plateau. Radix shells were sampled for isotope ratio analysis with high spatial resolution along the ontogenetic spiral of growth providing the basis of isotope records with a sub-seasonal time-resolution. δ18O values of shells from Bangda Co are on average ˜-15.0‰ relative to PDB and the pattern exhibits a clear onset and progression of the summer monsoon precipitation indicated by a strong "amount effect". This pattern mirrors the precipitation pattern in the respective year and region as expected for a small (surface area ca 0.3 km2) and shallow (<5 m) lake or habitat with short water residence times and little evaporative 18O enrichment of the lake water. In contrast, δ18O values of Radix shells from Kyaring Co habitat A which is connected to the deep (several tens of metres) and big (surface area ca 660 km2) lake, average at ˜-13.0‰ consistent with a higher evaporation rate and longer water residence time. The latter is supported by more 18O enriched water in this habitat. The δ18O values of Radix shells from Kyaring Co habitat B are nearly as low as shells from Bangda Co due to the similar habitat characteristic but isotopic patterns of these shells exhibit a weaker "amount effect". In both lake systems δ13C values of the shells are coupled with oxygen isotopes because a large amount of isotopically light carbon is washed from mountain slopes into the lake during the rainy season. Although other processes influence the isotopic patterns, e.g. biological productivity (δ13C) or temperature (δ18O), these influences are minor compared with the monsoon signal or the effect of evaporation in the Radix shell records. The overall weaker amount effect in Radix shells from Kyaring Co habitat B compared with shells from Bangda Co are consistent with a current decreasing monsoon influence from the south-eastern edge towards the central Tibetan Plateau. Thus, fossil shells of the gastropod genus Radix are a valuable archive for reconstructing climatic and environmental changes on the Tibetan Plateau and provide information about former habitat sizes and depths.

Sulfur isotope and porewater geochemistry of Florida escarpment seep sediments

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Paull, C.K.; Coston, J.A.

1993-01-01

Distributions of porewater constituents, SO4=, NH4+, Cl-, ???CO2, and H2S, solid phase iron, and sulfur concentrations, and the sulfur isotopic composition of dissolved and solid phases were investigated in sediments from abyssal seeps at the base of the Florida escarpment. Despite the apparent similarity of seep sediment porewater chemistry to that of typical marine sediments undergoing early diagenesis, relationships between chemical distributions and isotopic measurements revealed that the distribution of pore fluid constituents was dominated by processes occurring within the platform rather than by in situ microbial processes. Ammonium and sulfate concentrations were linearly correlated with chloride concentrations, indicating that variations in porewater chemistry were controlled by the admixture of seawater and a sulfate depleted brine with a chlorinity of 27.5 ?? 1.9%. and 2.2 ?? 1.3 mM ammonium concentration. At sites dominated by seepage, dissolved sulfate isotopic composition remained near seawater values despite depletion in porewater concentrations. Porewater ???CO2 concentrations were found to be elevated relative to seawater, but not to the extent predicted from the observed sulfate depletion. Sediment solid phase sulfur was predominantly pyrite, at concentrations as high as 20% S by weight. In contrast to typical marine deposits, pyrite concentrations were not related to the quantity of sedimentary organic matter. Pyrite ??34S values ranged from -29%. to + 21%. (CDT). However, only positive ??34S values were observed at sites associated with high pyrite concentrations. Isotopically heavy pyrite was observed at sites with porewater sulfate of seawater-like isotopic composition. Isotopically light pyrite was associated with sites where porewater sulfate exhibited ??34S values greater than those in seawater, indicating the activity of in situ microbial sulfate reduction. Thus, dual sulfide sources are suggested to explain the range in sediment pyrite isotopic composition: a ??34S enriched (+10 to +20%.) source adverted from within the Florida platform, and a lighter 34S depleted component generated in situ from microbial reduction of seawater sulfate. The degree of pyritization of seep sediments was as high as 0.9 and was controlled by pyrite concentrations, which varied over a wider range than did the non-pyrite solid phase iron concentrations. The highest non-sulfide solid phase iron concentrations were observed in sediments that are believed to be at the "front" of the advancing seep fluids (i.e., hemipelagic sediments newly exposed to the seep fluids), indicating that dissolution of hemipelagic background sediment may be the source of at least half of the iron to the highly pyritized seep sediments. Porewater sulfide concentrations were variable, reaching a maximum of 5.7 mM, and were not correlated with the degree of pyritization of the sediments, suggesting that iron was not particularly limiting to pyrite formation. ?? 1993.

Distribution of oxygen isotopes in the water masses of Drake Passage and the South Atlantic

NASA Astrophysics Data System (ADS)

Meredith, Michael P.; Grose, Katie E.; McDonagh, Elaine L.; Heywood, Karen J.; Frew, Russell D.; Dennis, Paul F.

1999-09-01

Measurements of the ratio of stable isotopes of oxygen (18O and 16O) from samples collected on World Ocean Circulation Experiment sections SR1b (eastern Drake Passage) and A11 (Punta Arenas to Cape Town) are used, together with hydrographic data, to deduce information about the formation and variability of South Atlantic and Southern Ocean water masses. The Drake Passage surface waters south of the Polar Front (PF) are isotopically light (δ18O around -0.4‰) owing to the influence of meteoric waters. The salinity and δ18O of the A11 surface waters yield an apparent freshwater end-member which is much isotopically lighter than the local precipitation, thus advection of these waters from farther south dominates over local effects in determining the surface water properties. The Drake Passage section shows unusual proximity of the two main fronts of the Antarctic Circumpolar Current (the PF and Subantarctic Front (SAF)), and we observe cold, fresh, and isotopically light water derived from the temperature-minimum Winter Water at the SAF. This water is of the correct density to freshen the intermediate water north of the SAF and thus play a role in the formation of the comparatively fresh Antarctic Intermediate Water (AAIW) of the South Atlantic. This confirms the role of Antarctic water in forming the South Atlantic variety of AAIW. Across the A11 section the oxygen isotope and salinity data at the AAIW core show very similar traces, with waters in the Malvinas Current loop showing lowest values of both. At the eastern boundary of the South Atlantic, the input of Red Sea Water from east of South Africa is observed via the presence of anomalously isotopically heavy AAIW. We deduce potentially significant temporal variability in the isotopic composition of Weddell Sea Deep Water (WSDW) by comparing the Drake Passage data to earlier data covering the outflow of the Weddell Sea. The A11 data show WSDW consistent with such variability, indicating that its effects could persist in the waters as they flow north into the western South Atlantic. We speculate that such variability could be due to small changes in the amount of glacial ice melt in WSDW.

Fossil Fuel Combustion-Related Emissions Dominate Atmospheric Ammonia Sources during Severe Haze Episodes: Evidence from 15N-Stable Isotope in Size-Resolved Aerosol Ammonium

NASA Astrophysics Data System (ADS)

Pan, Y.; Tian, S.; Liu, D.; Fang, Y.; Zhu, X.; Zhang, Q.; Zheng, B.; Michalski, G. M.; Wang, Y.

2016-12-01

The reduction of ammonia (NH3) emissions is urgently needed due to its major contributions to nitrogen deposition and particle pollution. However, the relative contributions of individual NH3 sources are unclear, and debate remains over whether agricultural emissions dominate atmospheric NH3 in urban areas. Based on the chemical and isotopic measurements of size-resolved aerosols in urban Beijing, China, we find that the natural abundance of 15N (expressed using δ15N values) of ammonium (NH4+) in fine particles varies with the development of haze episodes, ranging from -37.1‰ to -21.7‰ during clean/dusty days (relative humidity: ˜ 40%), to -13.1‰ to +5.8‰ during hazy days (relative humidity: 70-90%). After factoring the isotope exchange between NH3 gas and aerosol NH4+, the δ15N value of the initial NH3 during hazy days is found to be -14.5‰ to -1.6‰, which indicates fossil fuel-based emissions. These emissions contribute 90% of the total NH3 during hazy days in urban Beijing. This work demonstrates the analysis of δ15N values of aerosol NH4+ to be a promising new tool for partitioning atmospheric NH3 sources, providing policy makers with insights into NH3 emissions and secondary aerosols for regulation in urban environments. This work also shed lights on the sources of nitrogen deposition in downwind ecosystems.

Production of medical isotopes from a thorium target irradiated by light charged particles up to 70 MeV

NASA Astrophysics Data System (ADS)

Duchemin, C.; Guertin, A.; Haddad, F.; Michel, N.; Métivier, V.

2015-02-01

The irradiation of a thorium target by light charged particles (protons and deuterons) leads to the production of several isotopes of medical interest. Direct nuclear reaction allows the production of Protactinium-230 which decays to Uranium-230 the mother nucleus of Thorium-226, a promising isotope for alpha radionuclide therapy. The fission of Thorium-232 produces fragments of interest like Molybdenum-99, Iodine-131 and Cadmium-115g. We focus our study on the production of these isotopes, performing new cross section measurements and calculating production yields. Our new sets of data are compared with the literature and the last version of the TALYS code.

Production of medical isotopes from a thorium target irradiated by light charged particles up to 70 MeV.

PubMed

Duchemin, C; Guertin, A; Haddad, F; Michel, N; Métivier, V

2015-02-07

The irradiation of a thorium target by light charged particles (protons and deuterons) leads to the production of several isotopes of medical interest. Direct nuclear reaction allows the production of Protactinium-230 which decays to Uranium-230 the mother nucleus of Thorium-226, a promising isotope for alpha radionuclide therapy. The fission of Thorium-232 produces fragments of interest like Molybdenum-99, Iodine-131 and Cadmium-115g. We focus our study on the production of these isotopes, performing new cross section measurements and calculating production yields. Our new sets of data are compared with the literature and the last version of the TALYS code.

Light charged clusters emitted in 32 MeV/nucleon Xe,124136+Sn,112124 reactions: Chemical equilibrium and production of 3He and 6He

NASA Astrophysics Data System (ADS)

Bougault, R.; Bonnet, E.; Borderie, B.; Chbihi, A.; Dell'Aquila, D.; Fable, Q.; Francalanza, L.; Frankland, J. D.; Galichet, E.; Gruyer, D.; Guinet, D.; Henri, M.; La Commara, M.; Le Neindre, N.; Lombardo, I.; Lopez, O.; Manduci, L.; Marini, P.; Pârlog, M.; Roy, R.; Saint-Onge, P.; Verde, G.; Vient, E.; Vigilante, M.; Indra Collaboration

2018-02-01

Background: The isovector part of the nuclear equation of state remains partly unknown and is the subject of many studies. The degree of equilibration between the two main collision partners in heavy ion reactions may be used to study the equation of state since it is connected to isospin (N /Z ) transport properties of nuclear matter. Purpose: We aim to test chemical equilibrium attainment by measuring isotopic characteristics of emitted elements as a function of impact parameter. Method: We study four Xe,124136+Sn,112124 reactions at 32 MeV/nucleon. The data were acquired with the INDRA detector at the GANIL (Caen, France) facility. Combined (projectile+target) systems are identical for two studied reactions, therefore it is possible to study the path towards chemical equilibrium from different neutron to proton ratio (N /Z ) entrance channels. The study is limited to identified isotopes detected in the forward part of the center of mass in order to focus on the evolution of projectile-like fragment isotopic content and the benefit of excellent detection performances of the forward part of the apparatus. Results: Light charged particle productions, multiplicities, and abundance ratios dependence against impact parameter are studied. It is measured to almost identical mean characteristics for the two 124Xe+124Sn and 136Xe+112Sn systems for central collisions. Comparing all four studied systems it is shown that mean values evolve from projectile N /Z to projectile+target N /Z dependence. Those identical mean characteristics concern all light charged particles except 3He whose mean behavior is strongly different. Conclusions: Our inclusive analysis (no event selection) shows that N /Z equilibration between the projectile-like and the target-like is realized to a high degree for central collisions. The light charged particle production mean value difference between 124Xe+124Sn and 136Xe+112Sn systems for central collisions is of the order of a few %. This slight difference could be explained by pre-equilibrium particle emission whose intensity may differ for the two reactions. This point is demonstrated using 3He mean characteristics whose production takes place before chemical equilibrium attainment. The realized N /Z balance between projectile-like and target-like does not imply a pure two-body mechanism. Indeed a midrapidity production of light charged particle does exist and its N /Z is different as compared to the projectile-like one: it is n enriched. This point is touched using 6He midrapidity production which is favored by the drift phenomenon.

The Distinct Genetics of Carbonaceous and Non-Carbonaceous Meteorites Inferred from Molybdenum Isotopes

NASA Astrophysics Data System (ADS)

Budde, G.; Burkhardt, C.; Kleine, T.

2017-07-01

Mo isotope systematics manifest a fundamental dichotomy in the genetic heritage of carbonaceous and non-carbonaceous meteorites. We discuss its implications in light of the most recent literature data and new isotope data for primitive achondrites.

Colored dissolved organic matter in shallow estuaries: relationships between carbon sources and light attenuation

USGS Publications Warehouse

Oestreich, W.K.; Ganju, Neil K.; Pohlman, John; Suttles, Steven E.

2016-01-01

Light availability is of primary importance to the ecological function of shallow estuaries. For example, benthic primary production by submerged aquatic vegetation is contingent upon light penetration to the seabed. A major component that attenuates light in estuaries is colored dissolved organic matter (CDOM). CDOM is often measured via a proxy, fluorescing dissolved organic matter (fDOM), due to the ease of in situ fDOM sensor measurements. Fluorescence must be converted to CDOM absorbance for use in light attenuation calculations. However, this CDOM–fDOM relationship varies among and within estuaries. We quantified the variability in this relationship within three estuaries along the mid-Atlantic margin of the eastern United States: West Falmouth Harbor (MA), Barnegat Bay (NJ), and Chincoteague Bay (MD/VA). Land use surrounding these estuaries ranges from urban to developed, with varying sources of nutrients and organic matter. Measurements of fDOM (excitation and emission wavelengths of 365 nm (±5 nm) and 460 nm (±40 nm), respectively) and CDOM absorbance were taken along a terrestrial-to-marine gradient in all three estuaries. The ratio of the absorption coefficient at 340 nm (m−1) to fDOM (QSU) was higher in West Falmouth Harbor (1.22) than in Barnegat Bay (0.22) and Chincoteague Bay (0.17). The CDOM : fDOM absorption ratio was variable between sites within West Falmouth Harbor and Barnegat Bay, but consistent between sites within Chincoteague Bay. Stable carbon isotope analysis for constraining the source of dissolved organic matter (DOM) in West Falmouth Harbor and Barnegat Bay yielded δ13C values ranging from −19.7 to −26.1 ‰ and −20.8 to −26.7 ‰, respectively. Concentration and stable carbon isotope mixing models of DOC (dissolved organic carbon) indicate a contribution of 13C-enriched DOC in the estuaries. The most likely source of 13C-enriched DOC for the systems we investigated is Spartina cordgrass. Comparison of DOC source to CDOM : fDOM absorption ratios at each site demonstrates the relationship between source and optical properties. Samples with 13C-enriched carbon isotope values, indicating a greater contribution from marsh organic material, had higher CDOM : fDOM absorption ratios than samples with greater contribution from terrestrial organic material. Applying a uniform CDOM : fDOM absorption ratio and spectral slope within a given estuary yields errors in modeled light attenuation ranging from 11 to 33 % depending on estuary. The application of a uniform absorption ratio across all estuaries doubles this error. This study demonstrates that light attenuation coefficients for CDOM based on continuous fDOM records are highly dependent on the source of DOM present in the estuary. Thus, light attenuation models for estuaries would be improved by quantification of CDOM absorption and DOM source identification.

Biogeochemical cycling of Mg and its isotopes in a sugar maple forest in Québec

NASA Astrophysics Data System (ADS)

Kimmig, Sara R.; Holmden, Chris; Bélanger, Nicolas

2018-06-01

A Mg isotope study of sugar maple (Acer saccharum Marsh.) in a field site in southern Québec, Canada, and seedlings grown in sterile soil substrate in the laboratory, both demonstrate per mil level within-tree Mg isotope fractionation. However, only sugar maple seedlings grown in the laboratory fractionate Mg isotopes during uptake into fine roots, favoring heavy isotope enrichment in the plant compared to the growth medium. Absence of uptake-related Mg isotope fractionation in field stands of sugar maple is tentatively attributed to the activities of the arbuscular mycorrhizal fungi that colonize fine roots of the trees in the field, but were absent from the laboratory grown specimens. The fungi facilitate nutrient uptake for the tree, while the tree provides valuable carbohydrates to the fungi. Without the symbiotic fungi, pot-grown trees in the laboratory are visibly stressed and often die. The mechanisms responsible for Mg isotopic fractionation in stressed trees remain to be elucidated. Rivers are isotopically light compared to bedrock weathering sources of Mg, and this has bearing on the δ26Mg value of the continental weathering flux of Mg to the oceans, which is an important parameter in studies of ocean Mg cycling in the geological past. If uptake-related fractionation is negligible in many other naturally growing tree species, as it is in sugar maple, then forest growth will exert little or no influence on the δ26Mg value of the export flux of Mg to first-order streams and rivers, and in turn the ocean Mg cycle. Above the tree line, preferential retention of heavy Mg isotopes in clay minerals formed during silicate weathering has been linked to the low δ26Mg values in rivers. In the forested catchment of this study there is no clear evidence for these effects. The 1 N HNO3 leach of the Bf-BC and C mineral soils, which are often used to identify minerals that may be releasing Mg and other base cations to plant-available pools, have the same average δ26Mg value (-0.66‰, n = 2) as the litter layer and exchangeable leach of the forest floor, all soil solutions, and the stream (-0.63 ± 0.17‰ 2σ, n = 23). More revealing is the molar Mg/Ca ratio of the 1 N HNO3 treatment (0.17), which is nearly identical to the bulk Mg/Ca ratio of the aboveground biomass (0.14). We conclude that the 1 N HNO3 leach in this setting releases Mg from secondary minerals, such as vermiculite, other clays, and amorphous phases, which have taken up plant-recycled Mg and Ca that has filtered down through the soil from the litter layer of the forest floor. A single mineral, chlorite, with an estimated δ26Mg value of -0.78‰, appears to be responsible for supplying most of the Mg that is circulating between the forest and soils in this setting, which is weathered and cached over timescales of thousands of years.

Thallium isotopes track fluctuations in global manganese oxide burial during the Ediacaran Period

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Nielsen, S.; Owens, J. D.; Jiang, G.; Planavsky, N.; Sahoo, S. K.; Zhang, F.; Lyons, T. W.; Anbar, A. D.

2017-12-01

Complex marine ecosystems appear in the geologic record for the first time during the Ediacaran (635 - 541 Ma), after the Marinoan Glaciation but before the Cambrian Explosion. Much debate surrounds the redox-state of global oceans during this diversification, with some arguing for pervasive anoxic conditions and others for increased oxygenation, including the possibility of episodic oxygen increases. Here, we use thallium (Tl) isotopes preserved in organic-rich shales from a deep-water section at Wuhe, South China, to track large-scale perturbations in Mn oxide burial during the Ediacaran. Changes to the Tl isotope composition of seawater over geologic timescales are driven dominantly by fluctuations in global Mn oxide burial, which require persistent O2 at the sediment-water interface. Importantly, the suite of sedimentary rocks analyzed is thought to have been deposited beneath persistent localized euxinia, which is an environment shown to effectively capture the Tl isotope composition of seawater. Within samples previously suggested to host oceanic oxygenation episodes (OOEs) because of high redox-sensitive element (RSE) enrichments (Sahoo et al. 2016, Geobiology), we find Tl isotope values as light as -5 epsilon units, which are indicative of removal of heavy Tl by Mn oxides elsewhere in the Ediacaran ocean and in-line with the presence of deep-marine O2. Intriguingly, between these events, during periods previously viewed as dominantly anoxic, we find Tl isotope excursions to values that are even lighter than during the OOEs (less than -10 epsilon units). To first order, these results imply that an even larger Mn oxide sink was present between the OOEs, which would require pervasive oceanic oxygenation. This interpretation is in direct conflict with interpretations of low RSE enrichments in these same samples, which invoke reservoir drawdown due to widespread anoxia—as well as many other data that suggest dominantly anoxic deep marine conditions through the Ediacaran (e.g. Sperling et al. 2015, Nature). Further work is needed to interpret this paradox.

Stable Isotope Tracking of Endangered Sea Turtles: Validation with Satellite Telemetry and δ15N Analysis of Amino Acids

PubMed Central

Seminoff, Jeffrey A.; Benson, Scott R.; Arthur, Karen E.; Eguchi, Tomoharu; Dutton, Peter H.; Tapilatu, Ricardo F.; Popp, Brian N.

2012-01-01

Effective conservation strategies for highly migratory species must incorporate information about long-distance movements and locations of high-use foraging areas. However, the inherent challenges of directly monitoring these factors call for creative research approaches and innovative application of existing tools. Highly migratory marine species, such as marine turtles, regularly travel hundreds or thousands of kilometers between breeding and feeding areas, but identification of migratory routes and habitat use patterns remains elusive. Here we use satellite telemetry in combination with compound-specific isotope analysis of amino acids to confirm that insights from bulk tissue stable isotope analysis can reveal divergent migratory strategies and within-population segregation of foraging groups of critically endangered leatherback sea turtles (Dermochelys coriacea) across the Pacific Ocean. Among the 78 turtles studied, we found a distinct dichotomy in δ15N values of bulk skin, with distinct “low δ15N” and “high δ15N” groups. δ15N analysis of amino acids confirmed that this disparity resulted from isotopic differences at the base of the food chain and not from differences in trophic position between the two groups. Satellite tracking of 13 individuals indicated that their bulk skin δ15N value was linked to the particular foraging region of each turtle. These findings confirm that prevailing marine isoscapes of foraging areas can be reflected in the isotopic compositions of marine turtle body tissues sampled at nesting beaches. We use a Bayesian mixture model to show that between 82 and 100% of the 78 skin-sampled turtles could be assigned with confidence to either the eastern Pacific or western Pacific, with 33 to 66% of all turtles foraging in the eastern Pacific. Our forensic approach validates the use of stable isotopes to depict leatherback turtle movements over broad spatial ranges and is timely for establishing wise conservation efforts in light of this species’ imminent risk of extinction in the Pacific. PMID:22666354

Stable isotope tracking of endangered sea turtles: validation with satellite telemetry and δ15N analysis of amino acids.

PubMed

Seminoff, Jeffrey A; Benson, Scott R; Arthur, Karen E; Eguchi, Tomoharu; Dutton, Peter H; Tapilatu, Ricardo F; Popp, Brian N

2012-01-01

Effective conservation strategies for highly migratory species must incorporate information about long-distance movements and locations of high-use foraging areas. However, the inherent challenges of directly monitoring these factors call for creative research approaches and innovative application of existing tools. Highly migratory marine species, such as marine turtles, regularly travel hundreds or thousands of kilometers between breeding and feeding areas, but identification of migratory routes and habitat use patterns remains elusive. Here we use satellite telemetry in combination with compound-specific isotope analysis of amino acids to confirm that insights from bulk tissue stable isotope analysis can reveal divergent migratory strategies and within-population segregation of foraging groups of critically endangered leatherback sea turtles (Dermochelys coriacea) across the Pacific Ocean. Among the 78 turtles studied, we found a distinct dichotomy in δ(15)N values of bulk skin, with distinct "low δ(15)N" and "high δ(15)N" groups. δ(15)N analysis of amino acids confirmed that this disparity resulted from isotopic differences at the base of the food chain and not from differences in trophic position between the two groups. Satellite tracking of 13 individuals indicated that their bulk skin δ(15)N value was linked to the particular foraging region of each turtle. These findings confirm that prevailing marine isoscapes of foraging areas can be reflected in the isotopic compositions of marine turtle body tissues sampled at nesting beaches. We use a Bayesian mixture model to show that between 82 and 100% of the 78 skin-sampled turtles could be assigned with confidence to either the eastern Pacific or western Pacific, with 33 to 66% of all turtles foraging in the eastern Pacific. Our forensic approach validates the use of stable isotopes to depict leatherback turtle movements over broad spatial ranges and is timely for establishing wise conservation efforts in light of this species' imminent risk of extinction in the Pacific.

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

NASA Astrophysics Data System (ADS)

Elardo, Stephen M.; Shahar, Anat

2017-02-01

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

Oxygen isotope corrections for online δ34S analysis

USGS Publications Warehouse

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

2002-01-01

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

Involvement of magmatic fluids at the Laloki and Federal Flag massive sulfide Cu-Zn-Au-Ag deposits, Astrolabe mineral district, Papua New Guinea: sulfur isotope evidence

NASA Astrophysics Data System (ADS)

Noku, Shadrach K.; Espi, Joseph O.; Matsueda, Hiroharu

2015-01-01

We present the first sulfur (S) isotope data of sulfides, sulfates, pyrite in host mudstone, and bulk sulfur of gabbroic rocks from the Laloki and Federal Flag massive Cu-Zn-Au-Ag deposits in the Astrolabe mineral district, Papua New Guinea. Early-stage pyrite-marcasite, chalcopyrite, and sphalerite from Laloki display wide range of δ34S values from -4.5 to +7.0 ‰ ( n = 16). Late-stage pyrite, chalcopyrite, and sphalerite have restricted δ34S values of -1.9 to +4.7 ‰ ( n = 16). The mineralizing stage these correspond to had moderately saline (5.9-8.4 NaCl eq. wt%) mineralizing fluids of possible magmatic origin. A single analysis of late-stage barite has a value of δ34S +17.9 ‰, which is likely similar to coexisting seawater sulfate. Pyrite from the foot-wall mudstone at Laloki has very light δ34S values of -36.1 to -33.8 ‰ ( n = 2), which suggest an organic source for S. Pyrite-marcasite and chalcopyrite from Federal Flag show δ34S values of -2.4 to -1.9 ‰ ( n = 2), consistent with a magmatic origin, either leached from intrusive magmatic rocks or derived from magmatic-hydrothermal fluids. The very narrow range and near-zero δ34S values (-1.0 to +0.6 ‰) of bulk gabbroic samples is consistent with mantle-derived magmatic S. Sulfur isotope characteristics of sulfides and sulfates are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and sedimented mid-ocean ridges. The most reasonable interpretation is that the range of the sulfide and sulfate δ34S values from both Laloki and Federal Flag massive sulfide deposits is indicative of the complex interaction of magmatic fluids, seawater, gabbroic rocks, and mudstone.

Reaction paths and host phases of uranium isotopes (235U; 238U), Saanich Inlet

NASA Astrophysics Data System (ADS)

Amini, M.; Holmden, C. E.; Francois, R. H.

2009-12-01

In recent times, Uranium has become increasingly the focus of stable isotope fractionation studies. Variations in 238U/235U have been reported as a result of redox reactions [1,2] from the nuclear field shift effect [3], and a mass-dependent, microbially-mediated, kinetic isotope effect [4]. The 238U/235U variability caused by changes in environmental redox conditions leads to an increase in the 238U/235U ratios of the reduced U species sequestered into marine sediments. This points to U isotope variability as a new tool to study ancient ocean redox changes. However, the process by which reduced sediments become enriched in the heavy isotopes of U is not yet known, and hence the utility of 238U/235U as a redox tracer remains to be demonstrated. In order to further constrain sedimentary U enrichment and related isotope effect, we are investigating U isotopic compositions of water samples and fresh surface sediment grab samples over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. U was sequentially extracted from sediments in order to characterize specific fractions for their isotopic composition. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10‰ (2sd). Fifteeen analyses of seawater yielded δ238U of -0.42±0.08‰ (2sd). The results for the water samples indicate a homogenous δ238U value throughout the Saanich Inlet water column that matches the global seawater signature. All of the water samples from above and below average -0.42±0.05‰ (2sd). In contrast, a plankton net sample yielded a distinctly different, (about 0.5‰ lighter) isotope value. Bacterial reduction experiments [4] have also shown isotope enrichment factors of about -0.3‰. In addition, metal isotope fractionation occurs during adsorption with the light isotope being preferentially adsorbed [5]. Whether plankton mediated chemical reduction or scavenging causes this fractionation will be further investigated by leaching experiments on sediment trap samples. By contrast, weak acidic leachates (at pH 6) of suboxic bottom sediments, tend towards higher δ238U values. For oxic sediments, U contents of this fraction were below detection limit. Stronger leaching at pH 3 removed most of the uranium from suboxic and oxic sediments. For oxic sediments, this fraction yields the seawater δ238U signature, while the U released from the suboxic sample is about 0.2‰ heavier. This matches the value for previously reported bulk analyses of suboxic sediments [1] implying that the reduced sedimentary U is released by this treatment,. Major and trace element analyses and XRD patterns will help relating this fraction to a specific mineral or reactive phase. [1] Weyer et al. (2007) GCA 72, 345-399. [2] Stirling et al. (2007) EPSL 264, 208-225. [3] Schauble (2007) GCA 71, 2170-2189. [4] Rademacher et al. (2006) Environ. Sci. Technol. 40,6943-6948. [5] Wasylenki (2009) GCA A1419.

Absolute Isotopic Abundance Ratios and the Accuracy of Δ47 Measurements

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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.

Magnesium isotope fractionation between brucite [Mg(OH)2] and Mg aqueous species: Implications for silicate weathering and biogeochemical processes

NASA Astrophysics Data System (ADS)

Li, Weiqiang; Beard, Brian L.; Li, Chengxiang; Johnson, Clark M.

2014-05-01

Brucite, with its octahedral structure, has a lattice configuration that is similar to the Mg-bearing octahedral layers in phyllosilicates. Understanding stable Mg isotope fractionation between brucite and aqueous solution therefore bears on interpretation of Mg isotope data in natural weathering systems. In this study, we experimentally determined Mg isotope fractionation between brucite and two Mg aqueous species, the free Mg aquo ion ([Mg(OH2)6]2+) and EDTA-bonded Mg (Mg-EDTA2-). Results from recrystallization and brucite synthesis experiments suggest mild preferential partitioning of light Mg isotopes into brucite compared to Mg aquo ions at low temperatures, where measured ΔMgbrucite-Mg26 fractionation increased from ca. -0.3‰ at 7 °C, to ca. -0.2‰ at 22 °C, to ca. 0‰ at 40 °C. MgO hydrolysis experiments in EDTA-bearing solutions suggest that the ΔMgbrucite-Mg-EDTA26 fractionation is ⩾+2.0‰ at 22 °C, indicating that light Mg isotopes strongly partition into Mg-EDTA complex relative to brucite, as well as relative to Mg aquo ions. Magnesium atoms in brucite, Mg aquo ions, and Mg-EDTA complexes are all octahedrally coordinated, and the measured Mg isotope fractionations correlate with average bond lengths for Mg. Aqueous Mg ions have the shortest bond length among the three phases, and enrich heavy Mg isotopes relative to brucite and Mg-EDTA. In contrast, Mg-EDTA has the longest average bond length for Mg, and enriches light Mg isotopes relative to Mg aquo ions and brucite; the relatively long Mg-EDTA bond suggests that organically bound Mg may commonly have low 26Mg/24Mg ratios, which may explain proposed "vital" effects for stable Mg isotopes. Such relations between bond length and Mg isotope fractionation could be extended to other phyllosilicates such as serpentine- and clay-group minerals where Mg is also octahedrally coordinated.

Reduction of Thermal Conductivity in Nanowires by Combined Engineering of Crystal Phase and Isotope Disorder.

PubMed

Mukherjee, S; Givan, U; Senz, S; de la Mata, M; Arbiol, J; Moutanabbir, O

2018-05-09

Nanowires are a versatile platform to investigate and harness phonon and thermal transport phenomena in nanoscale systems. With this perspective, we demonstrate herein the use of crystal phase and mass disorder as effective degrees of freedom to manipulate the behavior of phonons and control the flow of local heat in silicon nanowires. The investigated nanowires consist of isotopically pure and isotopically mixed nanowires bearing either a pure diamond cubic or a cubic-rhombohedral polytypic crystal phase. The nanowires with tailor-made isotopic compositions were grown using isotopically enriched silane precursors 28 SiH 4 , 29 SiH 4 , and 30 SiH 4 with purities better than 99.9%. The analysis of polytypic nanowires revealed ordered and modulated inclusions of lamellar rhombohedral silicon phases toward the center in otherwise diamond-cubic lattice with negligible interphase biaxial strain. Raman nanothermometry was employed to investigate the rate at which the local temperature of single suspended nanowires evolves in response to locally generated heat. Our analysis shows that the lattice thermal conductivity in nanowires can be tuned over a broad range by combining the effects of isotope disorder and the nature and degree of polytypism on phonon scattering. We found that the thermal conductivity can be reduced by up to ∼40% relative to that of isotopically pure nanowires, with the lowest value being recorded for the rhombohedral phase in isotopically mixed 28 Si x 30 Si 1- x nanowires with composition close to the highest mass disorder ( x ∼ 0.5). These results shed new light on the fundamentals of nanoscale thermal transport and lay the groundwork to design innovative phononic devices.

The selenium isotopic variations in chondrites are mass-dependent; Implications for sulfide formation in the early solar system

NASA Astrophysics Data System (ADS)

Labidi, J.; König, S.; Kurzawa, T.; Yierpan, A.; Schoenberg, R.

2018-01-01

Element transfer from the solar nebular gas to solids occurred either through direct condensation or via heterogeneous reactions between gaseous molecules and previously condensed solid matter. The precursors of altered sulfides observed in chondrites are for example attributed to reactions between gaseous hydrogen sulfide and metallic iron grains. The transfer of selenium to solids likely occurred through a similar pathway, allowing the formation of iron selenides concomitantly with sulfides. The formation rate of sulfide however remains difficult to assess. Here we investigate whether the Se isotopic composition of meteorites contributes to constrain sulfide formation during condensation stages of our solar system. We present high precision Se concentration and δ 82 / 78 Se data for 23 chondrites as well as the first δ 74 / 78 Se , δ 76 / 78 Se and δ 77 / 78 Se data for a sub-set of seven chondrites. We combine our dataset with previously published sulfur isotopic data and discuss aspects of sulfide formation for various types of chondrites. Our Se concentration data are within uncertainty to literature values and are consistent with sulfides being the dominant selenium host in chondrites. Our overall average δ 82 / 78 Se value for chondrites is - 0.21 ± 0.43 ‰ (n = 23, 2 s.d.), or - 0.14 ± 0.21 ‰ after exclusion of three weathered chondrites (n = 20, 2 s.d.). These average values are within uncertainty indistinguishable from a previously published estimate. For the first time however, we resolve distinct δ 82 / 78 Se between ordinary (- 0.14 ± 0.07 ‰, n = 9, 2 s.d.), enstatite (- 0.27 ± 0.05 ‰, n = 3, 2 s.d.) and CI carbonaceous chondrites (- 0.01 ± 0.06 ‰, n = 2, 2 s.d.). We also resolve a Se isotopic variability among CM carbonaceous chondrites. In addition, we report on δ 74 / 78 Se , δ 76 / 78 Se and δ 77 / 78 Se values determined for 7 chondrites. Our data allow evaluating the mass dependency of the δ 82 / 78 Se variations. Mass-independent deficits ro excesses of 74Se, 76Se and 77Se are calculated relative to the observed 82Se/78Se ratios, and were observed negligible. This rules out poor mixing of nucleosynthetic components to account for the δ 82 / 78 Se variability and implies that the mass dependent Se isotopic variations were produced in a once-homogeneous disk. The mass-dependent isotopic difference between enstatite and ordinary chondrites may reflect the contribution of a kinetic sulfidation process at anomalously high H2S-H2Se contents in the region of enstatite chondrite formation. Experimental studies showed that high H2S contents favor the formation of compact sulfide layers around metallic grains. This decreases the reactive surface, which tends to inhibit the continuation of the sulfidation reaction. Under these conditions sulfide growth likely occurs under isotopic disequilibrium and favors the trapping of light S and Se isotopes in solids; This hypothesis provides an explanation for our Se isotope as well as for previously published S isotope data. On the other hand, high δ 82 / 78 Se values in carbonaceous chondrites may result from sample heterogeneities generated by parent body aqueous alteration, or could reflect the contribution of ices carrying photo-processed Se from the outer solar system.

Uranium Isotope Systematic in Saanich Inlet

NASA Astrophysics Data System (ADS)

Amini, M.; Holmden, C.; Francois, R.

2008-12-01

As a redox-sensitive element Uranium has become the focus of stable isotope studies. Based on the nuclear field shift effect [1], U isotope fractionation was predicted as a function of U(IV)-U(VI) exchange reactions with the insoluble reduced U(IV) species being heavier than the soluble oxidized U(VI) species. Recently, variations in 238U/235U were reported in low temperature aqueous and sedimentary environments [2,3] indicating that U deposited in well-oxygenated environments is characterized by light isotopic composition, whereas suboxic and anoxic deposits tend towards a heavy isotopic signature. U isotope fractionation has been hence proposed as a promising new paleo-redox proxy. In order to test the efficacy of U isotope fractionation to record oxidation states in marine systems, we are investigating sediment samples deposited over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. We have also made δ238U measurements for water samples from above and below the redoxcline. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10 permil (2sd). Eleven analyses of seawater performed over the course of this work yielded δ238U of -0.41±0.07 permil (2sd). No clear difference in δ238U values has been found, thus far, in water samples collected at 10m (O2~380μM) and 200m (O2~1μM) depths from a single location in the middle of the inlet. The mean of two measurements of the deepwater sample yielded -0.43±0.01 permil (2sd). Two measurements of the shallow water sample yielded a mean value of -0.38±0.03 permil (2sd). The δ238U values for HF-HNO3 digestions of the organic rich sediments, one taken in the middle of the basin (3.11% organic carbon) below seasonally anoxic bottom waters (-0.22±0.01 permil, n=2), and the other taken from the sill (1.29% organic carbon) below well-oxygenated bottom waters (-0.22 permil, n=1) are identical. The δ238U value matches previously reported values for suboxic sediments from the Peru margin [3], but is lighter than organic rich sediments from the Black Sea [3], where the bottom waters are strongly euxinic. The consistency in δ238U vaues between previously investigated suboxic sediment samples [3] and our two sediment samples indicates that the magnitude of the U isotopic fractionation is identical between seawater and sediments deposited under a range of bottom water oxygen conditions from oxygenated to anoxic. However, differences between the U isotope compositions in Saanich Inlet and those from the Black Sea remain to be explained, if U isotope fractionation is be used as a quantitative proxy for paleoredox in ancient oceans. [1] Schauble (2007) GCA 71, 2170- 2189. [2] Stirling et al. (2007) EPSL 264, 208-225. [3] Weyer et al. (2007) GCA 72, 345-399.

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 are relatively uniform and homogeneous in Sm-Nd isotopic system and thus can serve as ideal reference materials for external calibration during in situ Sm-Nd analysis.

Position-Specific Hydrogen and Carbon Isotope Fractionations of Light Hydrocarbons by Quantitative NMR

NASA Astrophysics Data System (ADS)

Liu, C.; Mcgovern, G. P.; Horita, J.

2015-12-01

Traditional isotope ratio mass spectrometry methods to measure 2H/1H and 13C/12C ratios of organic molecules only provide average isotopic values of whole molecules. During the measurement process, valuable information of position-specific isotope fractionations (PSIF) between non-equivalent H and C positions is lost, which can provide additional very useful information about the origins and history of organic molecules. Quantitative nuclear magnetic resonance (NMR) spectrometry can measure 2H and 13C PSIF of organic molecules without destruction. The 2H and 13C signals from different positions of a given molecule show up as distinctive peaks in an NMR spectrum, and their peak areas are proportional to the 2H and 13C populations at each position. Moreover, quantitative NMR can be applied to a wide variety of organic molecules. We have been developing quantitative NMR methods to determine 2H and 13C PSIF of light hydrocarbons (propane, butane and pentane), using J-Young and custom-made high-pressure NMR cells. With careful conditioning of the NMR spectrometer (e.g. tuning, shimming) and effective 1H -13C decoupling, precision of ± <10‰ (2H) and ± <1‰ (13C) can be readily attainable after several hours of acquisition. Measurement time depends on the relaxation time of interested nucleus and the total number of scans needed for high signal-to-noise ratios. Our data for commercial, pure hydrocarbon samples showed that 2H PSIF in the hydrocarbons can be larger than 60‰ and that 13C PSIF can be as large as 15‰. Comparison with theoretical calculations indicates that the PSIF patterns of some hydrocarbon samples reflect non-equilibrium processes in their productions.

Hydrogen and Oxygen Isotope Ratios in Body Water and Hair: Modeling Isotope Dynamics in Nonhuman Primates

PubMed Central

O’Grady, Shannon P.; Valenzuela, Luciano O.; Remien, Christopher H.; Enright, Lindsey E.; Jorgensen, Matthew J.; Kaplan, Jay R.; Wagner, Janice D.; Cerling, Thure E.; Ehleringer, James R.

2012-01-01

The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water (2H/1H, 18O/16O expressed as δ2H and δ18O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ2H and δ18O values of body water and a second model to predict the δ2H and δ18O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ2H and δ18O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ2H and δ18O values of gut water and the 18O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (αow). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of αow was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. PMID:22553163

Hydrogen and oxygen isotope ratios in body water and hair: modeling isotope dynamics in nonhuman primates.

PubMed

O'Grady, Shannon P; Valenzuela, Luciano O; Remien, Christopher H; Enright, Lindsey E; Jorgensen, Matthew J; Kaplan, Jay R; Wagner, Janice D; Cerling, Thure E; Ehleringer, James R

2012-07-01

The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water ((2)H/(1)H, (18)O/(16)O expressed as δ(2) H and δ(18)O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ(2)H and δ(18)O values of body water and a second model to predict the δ(2)H and δ(18)O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ(2)H and δ(18)O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ(2)H and δ(18)O values of gut water and the (18)O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (α(ow)). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of α(ow) was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. © 2012 Wiley Periodicals, Inc.

Large effect of irradiance on hydrogen isotope fractionation of alkenones in Emiliania huxleyi

NASA Astrophysics Data System (ADS)

van der Meer, Marcel T. J.; Benthien, Albert; French, Katherine L.; Epping, Eric; Zondervan, Ingrid; Reichart, Gert-Jan; Bijma, Jelle; Sinninghe Damsté, Jaap S.; Schouten, Stefan

2015-07-01

The hydrogen isotopic (δD) composition of long-chain alkenones produced by certain haptophyte algae has been suggested as a potential proxy for reconstructing paleo sea surface salinity. However, environmental parameters other than salinity may also affect the δD of alkenones. We investigated the impact of the level of irradiance on hydrogen isotopic fractionation of alkenones versus growth water by cultivating two strains of the cosmopolitan haptophyte Emiliania huxleyi at different light intensities. The hydrogen isotope fractionation decreased by approximately 40‰ when irradiance was increased from 15 to 200 μmol photons m-2 s-1 above which it was relatively constant. The response is likely a direct effect of photosystem I and II activity as the relationship of the fractionation factor α versus light intensity can be described by an Eilers-Peeters photosynthesis model. This irradiance effect is in agreement with published δD data of alkenones derived from suspended particulate matter collected from different depths in the photic zone of the Gulf of California and the eastern tropical North Pacific. However, haptophyte algae tend to bloom at relatively high light intensities (>500 μmol photons m-2 s-1) occurring at the sea surface, at which hydrogen isotope fractionation is relatively constant and not affected by changes in light intensity. Alkenones accumulating in the sediment are likely mostly derived from these surface water haptophyte blooms, when the largest amount of biomass is produced. Therefore, the observed irradiance effect is unlikely to affect the applicability of the hydrogen isotopic composition of sedimentary long chain alkenones as a proxy for paleosalinity.

Distinguishing sources of ground water recharge by using δ2H and δ18O

USGS Publications Warehouse

Blasch, Kyle W.; Bryson, Jeannie R.

2007-01-01

Stable isotope values of hydrogen and oxygen from precipitation and ground water samples were compared by using a volumetrically based mixing equation and stable isotope gradient to estimate the season and location of recharge in four basins. Stable isotopes were sampled at 11 precipitation sites of differing elevation during a 2-year period to quantify seasonal stable isotope contributions as a function of elevation. Supplemental stable isotope data collected by the International Atomic Energy Association during a 14-year period were used to reduce annual variability of the mean seasonal stable isotope data. The stable isotope elevation relationships and local precipitation elevation relationships were combined by using a digital elevation model to calculate the total volumetric contribution of water and stable isotope values as a function of elevation within the basins. The results of these precipitation calculations were compared to measured ground water stable isotope values at the major discharge points near the terminus of the basins. Volumetric precipitation contributions to recharge were adjusted to isolate contributing elevations. This procedure provides an improved representation of recharge contributions within the basins over conventional stable isotope methods. Stable isotope values from wells and springs at the terminus of each basin were used to infer the elevations of precipitation important for recharge of the regional ground water flow system. Ancillary climatic, geologic, and stable isotope values were used to further constrain the location where precipitation is entering the ground water flow system.

Isotopic signature of atmospheric xenon released from light water reactors.

PubMed

Kalinowski, Martin B; Pistner, Christoph

2006-01-01

A global monitoring system for atmospheric xenon radioactivity is being established as part of the International Monitoring System to verify compliance with the Comprehensive Nuclear-Test-Ban Treaty (CTBT). The isotopic activity ratios of (135)Xe, (133m)Xe, (133)Xe and (131m)Xe are of interest for distinguishing nuclear explosion sources from civilian releases. Simulations of light water reactor (LWR) fuel burn-up through three operational reactor power cycles are conducted to explore the possible xenon isotopic signature of nuclear reactor releases under different operational conditions. It is studied how ratio changes are related to various parameters including the neutron flux, uranium enrichment and fuel burn-up. Further, the impact of diffusion and mixing on the isotopic activity ratio variability are explored. The simulations are validated with reported reactor emissions. In addition, activity ratios are calculated for xenon isotopes released from nuclear explosions and these are compared to the reactor ratios in order to determine whether the discrimination of explosion releases from reactor effluents is possible based on isotopic activity ratios.

Red deer bone and antler collagen are not isotopically equivalent in carbon and nitrogen.

PubMed

Stevens, Rhiannon E; O'Connell, Tamsin C

2016-09-15

Bone and antler collagen δ(13) C and δ(15) N values are often assumed to be equivalent when measured in palaeodietary, palaeoclimate and palaeocological studies. Although compositionally similar, bone grows slowly and is remodelled whereas antler growth is rapid and remodelling does not occur. These different patterns of growth could result in isotopic difference within antler and between the two tissue types. Here we test whether red deer (Cervus elaphus) bone and antler δ(13) C and δ(15) N values are equivalent, and whether intra-antler isotopic values are uniform. Bone and antler were isotopically analysed from six stags that lived in a temperate maritime climate on the Isle of Rum, Scotland. Multiple antlers from different years were sampled per individual, together with a single bone sample per individual. Up to 12 samples were taken along the length of each antler (total of 25 antlers, 259 samples) so that a chronological record of the isotopic composition during antler growth could be obtained. Collagen was extracted and its δ(13) C and δ(15) N values were measured by continuous-flow isotope ratio mass spectrometry. Intra-antler collagen isotope signatures vary, and show that not all antlers from an individual or a growth year are equivalent in carbon and nitrogen isotopic ratios. δ(15) N values typically increase with distance along antler length, but no overall trend is observed in δ(13) C values. An isotopic offset is visible between bone and antler, with bone δ(13) C and δ(15) N values being higher in most cases. Bone and antler collagen δ(13) C and δ(15) N values are not isotopically equivalent and are therefore not directly comparable in palaeodietary, palaeoclimate and palaeocological studies. Bone and antler collagen isotopic differences probably relate to differential metabolic processes during the formation of the two tissues. Intra- and inter-antler isotopic variations probably reflect the isotopic composition of an individual's diet rather than physiological parameters, and may have the potential to provide high-resolution individual-specific information in modern and ancient cervid populations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Measurement of isotope ratio of Ca{sup +} ions in a linear Paul Trap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hashimoto, Y.; Minamino, K.; Nagamoto, D.

2009-03-17

Measurement of isotope ratios of Calcium is very useful in many fields. So we demonstrated the measurement of isotope ratios of {sup 40}Ca{sup +}(abundance 96.4%) to {sup 44}Ca{sup +}(2.09%) ions in a linear Paul trap with several laser lights tuning to the isotope shifts. And we found that the experimental parameters had large influences on the measurement of the isotope ratios.

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.

Tracing anthropogenic aerosol Fe sources in the North Atlantic Ocean using dissolved Fe isotope ratios

NASA Astrophysics Data System (ADS)

Conway, T. M.; Shelley, R.; Aguilar-Islas, A. M.; Landing, W. M.; Mahowald, N. M.; John, S.

2016-02-01

Supply of iron (Fe) to the surface ocean from atmospheric deposition plays a vital role in marine biogeochemical cycles, especially in Fe-limited areas or regions close to dust sources. However, large uncertainties remain over the fluxes, solubility and bioavailability of Fe supplied by aerosol dust. Additionally, aerosol Fe is likely to consist of a mixture of natural and anthropogenic (urban, biomass burning and combustion) components, which may have very different solubilities in seawater [e.g. 1]. To constrain soluble Fe supply to the oceans, it is thus vitally important to understand the relative contributions of different types of aerosol Fe, their solubilities and spatial distributions. Stable Fe isotopes (δ56Fe) may offer a way to discriminate between different dust sources [2], because of differential fractionation during a range of chemical processes. In this study, we measured δ56Fe in North Atlantic marine aerosols collected during two US GEOTRACES GA03 cruises (Lisbon to Woods Hole via Cape Verde, 2010-11) and we present δ56Fe measurements (relative to IRMM-014) from both the bulk aerosol (HF-HNO3 digested) and the water-soluble (10s ultrapure water leach) fractions. Aerosols collected from different air-masses (Saharan, European and N. American) allowed us to investigate the variability in δ56Fe due to different regional dust sources. The bulk phase was characterized by near-crustal δ56Fe values of +0.1±0.2‰, indicating the dominance of mineral dust. In contrast, the water-soluble fraction showed great variability; aerosols from European and North American air-masses were very isotopically light (-1.2±0.2‰ and -1.1±0.7‰) while those from Saharan air-masses were crustal (+0.1‰). Comparison of this data with isotope-informed model predictions of soluble Fe from mineral and anthropogenic sources (combustion, biofuels and biomass burning) [1], suggests that the data is consistent with mixing of either 1) Fe from mineral dust (+0.1‰) and a distinctly light anthropogenic Fe (-1.6‰), or 2) Fe from crustal mineral dust, isotopically heavy combustion Fe (+0.1 to +0.3‰), and biomass Fe that is both isotopically light (-1.6‰) and very soluble (>50%). [1] Luo, C. et al. (2008), Glob. Biogeochem. Cyc., 22, GB1012. [2] Mead, C. et al. (2013), Geophys. Res. Lett., 40, 5722-5727.

Isotopic ecology and dietary profiles of Liberian chimpanzees.

PubMed

Smith, Catherine C; Morgan, Michèle E; Pilbeam, David

2010-01-01

An extensive suite of isotopic data (delta(13)C, delta(15)N, and delta(18)O) from enamel apatite and bone collagen of adult male and female wild chimpanzees establishes baseline values for Pan troglodytes verus in a primary rainforest setting. The Ganta chimpanzee sample derives from a restricted region in northern Liberia. Diet is examined using stable light isotopes at three life stages-infant, young juvenile, and adult-and developmental differences are investigated within and between individual males and females. The isotopic data are very homogeneous with few exceptions. Juvenile females show consistent enrichment in (13)C relative to infants, while juvenile males do not. These data suggest that age at weaning may be more variable for male offspring who survive to adulthood than for female offspring. Alternatively, or additionally, the weaning diet of males and females may differ, with greater consumption of technologically extracted insects and/or nuts by young females. Metabolic differences, including growth and hormone-mediated responses, may also contribute to the observed variation. The Ganta chimpanzee data offer an independent and objective line of evidence to primatologists interested in the dietary strategies of the great apes and to paleoanthropologists seeking comparative models for reconstructing early hominin subsistence patterns. Despite the high diversity of dietary items consumed by chimpanzees, isotopic signatures of chimpanzees from a primary rainforest setting exhibit narrow ranges of variation similar to chimpanzees in more open habitats.

Ca-rich carbonates associated with ultrabasic-ultramafic melts: Carbonatite or limestone xenoliths? A case study from the late Miocene Morron de Villamayor volcano (Calatrava Volcanic Field, central Spain)

NASA Astrophysics Data System (ADS)

Lustrino, Michele; Prelević, Dejan; Agostini, Samuele; Gaeta, Mario; Di Rocco, Tommaso; Stagno, Vincenzo; Capizzi, Luca Samuele

2016-07-01

The volcanic products of the late Miocene Morron de Villamayor volcano (Calatrava Volcanic Field, central Spain) are known for being one of the few outcrops of leucitites in the entire circum-Mediterranean area. These rocks are important because aragonite of mantle origin has been reported as inclusion in olivine macrocrysts. We use petrographic observations, mineral compositions, as well as oxygen and carbon isotope ratios coupled with experimental petrology to understand the origin of carbonate phase in these olivine-phyric rocks. Groundmass and macrocryst olivines range from δ18OVSMOW of +4.8‰, typical of mantle olivine values, to +7.4‰, indicating contamination by sedimentary carbonate. Carbonates are characterized by heavy oxygen isotope compositions (δ18OVSMOW >+24‰), and relatively light carbon isotopes (δ13CPDB <-11‰), resembling skarn values, and distinct from typical mantle carbonatite compositions. Petrography, mineral compositions such as low Mg# of clinopyroxene and biotite, low Ca# and low incompatible element abundance of the carbonate, and isotopic ratios of O and C, do not support a mantle origin for the carbonate. Rather, the carbonate inclusions found in the olivine macrocrysts are interpreted as basement limestone fragments entrapped by the rising crystallizing magma. Comparison with experimental carbonatitic and silicate-carbonatitic melts indicates that low-degree partial melts of a carbonated peridotite must have a dolomitic rather than the aragonitic/calcitic composition as those found trapped in the Morron de Villamayor olivine macrocrysts.

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

USGS Publications Warehouse

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

2011-01-01

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

Characterisation of the input signal to aquifers in the French Basque Country: Emphasis on parameters influencing the chemical and isotopic composition of recharge waters

NASA Astrophysics Data System (ADS)

Jaunat, J.; Celle-Jeanton, H.; Huneau, F.; Dupuy, A.; Le Coustumer, P.

2013-07-01

A hydrochemical and isotopic survey of rainwater and groundwater has been carried out during almost two years on the Ursuya Mount in the northern Basque Country (southwestern France) with the aim of enhancing the understanding of the behaviour of this aquifer and more peculiarly the recharge mode of groundwater. The input signal of this aquifer is defined thanks to 112 rainwater samples. The computed meteoric water line (δD = 7.3 δ18O + 5.1; r = 0.96) is consistent with that defined in the European IAEA/WMO network stations. The weighted mean deuterium excess about 9.7‰ is really close to the value obtained for Atlantic precipitations and clearly demonstrates an oceanic major origin. The computations conducted on the chemical dataset show that the rainwater composition is controlled by four major factors: (1) a mixed source of anthropogenic pollution and crustal material; (2) a marine source; (3) an urban source; (4) an acid source. Further, the quantification of neutralizing potentials clearly revealed below cloud processes in which crustal and anthropogenic components are responsible for the neutralization of anions. Besides the major Atlantic origin of the recharge water, the chemical and isotopic content of the samples coupled with the corresponding air mass back trajectories revealed four major geographical origins of the components: (1) northwestern part of Atlantic Ocean and (2) Southwestern part of Atlantic Ocean. The oceanic influence in airmasses from these origins is highlighted by the stable isotopic content (weighted mean close to the Atlantic Ocean signature) and by the chemical concentrations dominated by sea salt elements. (3) Northern Europe with a continental influence shown by a light depletion on isotopic signal besides purely oceanic origin and a higher concentration of crustal and anthropogenic components. 4) Southeastern area (Southeastern Europe, Northern Africa and Mediterranean Sea) with an isotopic signature consistent with the Mediterranean one and a chemical composition clearly influenced by the industrial activities of this region. The dataset is confronted with the chemical and isotopic characteristics of groundwater in order to assess the recharge water signature of the aquifer of the Ursuya Mount. The groundwater isotopic signal is close to the defined LMWL, showing actual and local recharge. Nevertheless, a slightly difference is observed between the mean value of stable isotopic content in groundwater and in rainwater. The slightly depleted values of groundwater besides rainwater can be attributed to a preferential winter/autumn recharge. An altitudinal gradient about -0.11‰ δ18O/100 m is defined and both water-rock interactions and physicochemical processes fingerprint on the groundwater composition are characterised.

Constraints on Nucleosynthesis from Xenon Isotopes in Presolar Material

NASA Astrophysics Data System (ADS)

Gilmour, J. D.; Turner, G.

2007-03-01

By applying theoretical constraints to three-dimensional fits of xenon isotope data from presolar grains, we show that they strongly suggest a nucleosynthesis process that produces ``r-process'' isotopes without producing s-process isotopes (128Xe, 130Xe) and without producing the conventional r-process isotope 136Xe. It is one of three distinct nucleosynthetic sources that are necessary and sufficient to explain the gross variation in xenon isotopic data across all presolar material. The other source contributing r-process isotopes is responsible for the heavy isotope signature identified in nanodiamonds, which is also present in presolar SiC, and is associated with light isotope enrichment. The relative enrichments of heavy and light isotopes in this component in nanodiamonds and SiC grains are different, implying that the parent nucleosynthetic processes are not inextricably linked. Because minor variations in the isotopic compositions of xenon trapped in nanodiamonds show that two distinct sites contributed nanodiamonds to the early solar system within the average grain lifetime, it is suggested that Type IIa supernovae (SNe IIa) are not the source of the nanodiamonds. The s-process signature derived is consistent with that derived from mixing lines between grain subpopulations for isotopes on the s-process path. This implies that a pure end-member is present in the grains (although not approached in analyses). Our approach is more general and provides a less restrictive set of numerical constraints to be satisfied by proposed theoretical treatments of nucleosynthesis.

Metrology for stable isotope reference materials: 13C/12C and 18O/16O isotope ratio value assignment of pure carbon dioxide gas samples on the Vienna PeeDee Belemnite-CO2 scale using dual-inlet mass spectrometry.

PubMed

Srivastava, Abneesh; Michael Verkouteren, R

2018-07-01

Isotope ratio measurements have been conducted on a series of isotopically distinct pure CO 2 gas samples using the technique of dual-inlet isotope ratio mass spectrometry (DI-IRMS). The influence of instrumental parameters, data normalization schemes on the metrological traceability and uncertainty of the sample isotope composition have been characterized. Traceability to the Vienna PeeDee Belemnite(VPDB)-CO 2 scale was realized using the pure CO 2 isotope reference materials(IRMs) 8562, 8563, and 8564. The uncertainty analyses include contributions associated with the values of iRMs and the repeatability and reproducibility of our measurements. Our DI-IRMS measurement system is demonstrated to have high long-term stability, approaching a precision of 0.001 parts-per-thousand for the 45/44 and 46/44 ion signal ratios. The single- and two-point normalization bias for the iRMs were found to be within their published standard uncertainty values. The values of 13 C/ 12 C and 18 O/ 16 O isotope ratios are expressed relative to VPDB-CO 2 using the [Formula: see text] and [Formula: see text] notation, respectively, in parts-per-thousand (‰ or per mil). For the samples, value assignments between (-25 to +2) ‰ and (-33 to -1) ‰ with nominal combined standard uncertainties of (0.05, 0.3) ‰ for [Formula: see text] and [Formula: see text], respectively were obtained. These samples are used as laboratory reference to provide anchor points for value assignment of isotope ratios (with VPDB traceability) to pure CO 2 samples. Additionally, they serve as potential parent isotopic source material required for the development of gravimetric based iRMs of CO 2 in CO 2 -free dry air in high pressure gas cylinder packages at desired abundance levels and isotopic composition values. Graphical abstract CO 2 gas isotope ratio metrology.

Methanotrophic gastropods from a bathyal hydrocarbon seep, Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, L.C.; Aharon, P.; Gupta, S.

Two gastropods, Neritina sp. and Truncatella sp., collected live from a Gulf of Mexico active gas seep with the submersible Johnson Sea Link in September 1991, apparently incorporate methane-derived carbon in their soft tissues. Flesh of an individual Neritina sp. had a delta C-13 of [minus]50.92 per mil PDB, and that of two coexisting individuals of Truncatella sp. had values of [minus]45.11 and [minus]49.27 per mil. These isotope values are comparable to those reported for the methanotrophic mytilid bivalve Bathymodiolus sp. from other hydrocarbon seeps on the Gulf of Mexico, and are lighter than published isotopic values of chemosynthetic organismsmore » with sulfur-oxidizing symbionts. The anomalously light carbon-isotopic values of Neritina sp. and Truncatella sp. may steam from one of three causes: (1) these gastropods host symbiotic methanotrophic bacteria, (2) their chief food is methane-oxidizing bacteria present at the seep, or (3) they incorporate some carbon from the periostracum of mussels on which they may graze. The presence of abundant juveniles of Bathymodiolus, reported to settle preferentially in areas of active seepage and high methane release, indicates that methane was abundant and supported a community with multiple trophic levels. Generally, studies of hydrocarbon-seep communities have focused on larger community members, especially bivalves and tube worms. The presence of living Neritina and Truncatella at the authors sampling site, however, draws attention to the fact that these gastropods are integral and significant parts of hydrocarbon-seep communities. Both gastropod species are members of genera that characteristically inhabit shallow marine, intertidal, and semiterrestrial environments. The presence of these genera in bathyal hydrocarbon seeps indicates that they have very broad environmental ranges, thus limiting their utility in paleoecologic reconstructions.« less

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

USGS Publications Warehouse

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

2012-01-01

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

Extreme 13C depletions in seawater-derived brines and their implications for the past geochemical carbon cycle

NASA Astrophysics Data System (ADS)

Lazar, Boaz; Erez, Jonathan

1990-12-01

Extreme depletions in the 13C content of the total dissolved inorganic carbon (CT) were found in brines overlying microbial mat communities. Total alkalinity (AT) and CT in the brines suggest that intense photosynthetic activity of the microbial mat communities depletes the CT from the brine. We suggest that this depletion drives a large, kinetic, negative fractionation of carbon isotopes similar to that observed in highly alkaline solutions. In brines of extreme salinity where microbial mat communities no longer exist, the 13C content of the CT increases, probably because photosynthesis no longer dominates the gas-exchange processes. This mechanism explains light carbon-isotope compositions of carbonate rocks from evaporitic sections and bears on the interpretation of δ13C values in bedded stromatolitic limestones that are ca. 3.5 b.y. old.

Diet-tissue stable isotope (Δ(13)C and Δ(15)N) discrimination factors for multiple tissues from terrestrial reptiles.

PubMed

Steinitz, Ronnie; Lemm, Jeffrey M; Pasachnik, Stesha A; Kurle, Carolyn M

2016-01-15

Stable isotope analysis is a powerful tool for reconstructing trophic interactions to better understand drivers of community ecology. Taxon-specific stable isotope discrimination factors contribute to the best use of this tool. We determined the first Δ(13)C and Δ(15)N values for Rock Iguanas (Cyclura spp.) to better understand isotopic fractionation and estimate wild reptile foraging ecology. The Δ(13)C and Δ(15)N values between diet and skin, blood, and scat were determined from juvenile and adult iguanas held for 1 year on a known diet. We measured relationships between iguana discrimination factors and size/age and quantified effects of lipid extraction and acid treatment on stable isotope values from iguana tissues. Isotopic and elemental compositions were determined by Dumas combustion using an elemental analyzer coupled to an isotope ratio mass spectrometer using standards of known composition. The Δ(13)C and Δ(15)N values ranged from -2.5 to +6.5‰ and +2.2 to +7.5‰, respectively, with some differences among tissues and between juveniles and adults. The Δ(13)C values from blood and skin differed among species, but not the Δ(15)N values. The Δ(13)C values from blood and skin and Δ(15)N values from blood were positively correlated with size/age. The Δ(13)C values from scat were negatively correlated with size (not age). Treatment with HCl (scat) and lipid extraction (skin) did not affect the isotope values. These results should aid in the understanding of processes driving stable carbon and nitrogen isotope discrimination factors in reptiles. We provide estimates of Δ(13)C and Δ(15)N values and linear relationships between iguana size/age and discrimination factors for the best interpretation of wild reptile foraging ecology. Copyright © 2015 John Wiley & Sons, Ltd.

Potential of calcium isotopes to identify fractionations in vegetation: experimental approach

NASA Astrophysics Data System (ADS)

Cobert, F.; Schmitt, A.; Bourgade, P.; Stille, P.; Chabaux, F. J.; Badot, P.; Jaegler, T.

2010-12-01

This study aims to better understand the role of vegetation on the Ca cycle at the level of the critical zone of the Earth, in order to specify the mechanisms controlling the Ca absorption by plants at the rock/plant interface. To do this, we performed experiments using hydroponic plant cultures in a way that we could control the cooccuring geochemical and biological processes and determine the impact of the nutritive solution on the Ca cycle within plants. A dicotyledon and calcicole plant with rapid growth, the French bean (Phaseolus vulgaris L.), has been chosen to have access to one complete growth cycle. Several experiments have been conducted with two Ca concentrations, 5 (L) and 60 (H) ppm and two pH values (4 and 6) in the nutritive solution, for which the Ca concentration was maintained constant, so its Ca content is considered to be infinite. We determined Ca concentrations and isotopic ratios in the nutritive solution and in different organs (main roots, secondary roots, old and young stems, old and young leaves and fruits) at two different growth stages (10 days and 6 weeks). Our results show, in accord with previously published field studies, that the bean organs are all enriched in the light 40Ca isotope compared to the nutritive solution (e.g. Wigand et al., 2005; Page et al., 2008; Cenki-Tok et al., 2009; Holmden and Bélanger, 2010). We identify two fractionation levels. The first occurs during the uptake of the nutrient elements by the lateral roots. This implies that the main mechanisms of light isotope enrichments in the plant are due to electrochemical gradient transport processes taking place at this interface. The second fractionation can be observed within the plant itself and is due to the nature of the considered organ itself. Indeed structural reservoirs (primary roots, stem, reproductive organs) incorporate more the light 40Ca isotope compared to the transfer reservoirs (lateral roots, xylem sap, leaves). This could be linked to ion-exchange reactions with the pectins in the cell walls of the conducting xylem. However, we also observe that bean organs from L4 experiment growing in nutrient solutions with lower Ca concentrations and low pH behave slightly differently and show reduced Ca isotopic fractionations compared with beans from the other experiments. All these results indicate that there is no simple correlation between Ca isotopic variations, Ca content and pH of the nutrient solution, and that also biological effects have to be involved. The data confirm the potential of the Ca isotopic system for tracing biological fractionations in natural ecosystems. Wiegand et al., (2005). Geophys. Res. Lett., 32, L11404 Page et al., (2008). Biogeochemistry, 88, 1-13 Cenki-Tok et al,. (2009). Geochim. Cosmochim. Acta, 73, 2215-2228 Holmden and Bélanger(2010). Geochim. Cosmochim. Acta, 74, 995-1015

Effects of preservation methods of muscle tissue from upper-trophic level reef fishes on stable isotope values (δ (13)C and δ (15)N).

PubMed

Stallings, Christopher D; Nelson, James A; Rozar, Katherine L; Adams, Charles S; Wall, Kara R; Switzer, Theodore S; Winner, Brent L; Hollander, David J

2015-01-01

Research that uses stable isotope analysis often involves a delay between sample collection in the field and laboratory processing, therefore requiring preservation to prevent or reduce tissue degradation and associated isotopic compositions. Although there is a growing literature describing the effects of various preservation techniques, the results are often contextual, unpredictable and vary among taxa, suggesting the need to treat each species individually. We conducted a controlled experiment to test the effects of four preservation methods of muscle tissue from four species of upper trophic-level reef fish collected from the eastern Gulf of Mexico (Red Grouper Epinephelus morio, Gag Mycteroperca microlepis, Scamp Mycteroperca phenax, and Red Snapper Lutjanus campechanus). We used a paired design to measure the effects on isotopic values for carbon and nitrogen after storage using ice, 95% ethanol, and sodium chloride (table salt), against that in a liquid nitrogen control. Mean offsets for both δ (13)C and δ (15)N values from controls were lowest for samples preserved on ice, intermediate for those preserved with salt, and highest with ethanol. Within species, both salt and ethanol significantly enriched the δ (15)N values in nearly all comparisons. Ethanol also had strong effects on the δ (13)C values in all three groupers. Conversely, for samples preserved on ice, we did not detect a significant offset in either isotopic ratio for any of the focal species. Previous studies have addressed preservation-induced offsets in isotope values using a mass balance correction that accounts for changes in the isotope value to that in the C/N ratio. We tested the application of standard mass balance corrections for isotope values that were significantly affected by the preservation methods and found generally poor agreement between corrected and control values. The poor performance by the correction may have been due to preferential loss of lighter isotopes and corresponding low levels of mass loss with a substantial change in the isotope value of the sample. Regardless of mechanism, it was evident that accounting for offsets caused by different preservation methods was not possible using the standard correction. Caution is warranted when interpreting the results from specimens stored in either ethanol or salt, especially when using those from multiple preservation techniques. We suggest the use of ice as the preferred preservation technique for muscle tissue when conducting stable isotope analysis as it is widely available, inexpensive, easy to transport and did not impart a significant offset in measured isotopic values. Our results provide additional evidence that preservation effects on stable isotope analysis can be highly contextual, thus requiring their effects to be measured and understood for each species and isotopic ratio of interest before addressing research questions.

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

Insights into iron sources and pathways in the Amazon River provided by isotopic and spectroscopic studies

NASA Astrophysics Data System (ADS)

Mulholland, Daniel Santos; Poitrasson, Franck; Boaventura, Geraldo Resende; Allard, Thierry; Vieira, Lucieth Cruz; Santos, Roberto Ventura; Mancini, Luiz; Seyler, Patrick

2015-02-01

The present study investigated the weathering and transport mechanisms of Fe in the Amazon River. A particular emphasis was placed on Fe partitioning, speciation, and isotopic fractionation in the contrasting waters of the Solimões and Negro rivers and their mixing zone at the beginning of the Amazon River. Samples collected in the end-member rivers and thirteen sites distributed throughout the mixing zone were processed through frontal vacuum filtration and tangential-flow ultrafiltration to separate the different suspended solid fractions, i.e., particulate (P > 0.45 μm and P > 0.22 μm), colloidal (0.22 μm > C > 5 kDa) and truly dissolved elements (TD < 5 kDa). The Fe isotopic composition and electron paramagnetic resonance (EPR) species were measured on these different pore-sized fractions. The acidic and organo-Fe-rich waters of the Negro River displayed dissolved and colloidal fractions enriched in heavy isotopes (∼1.2‰, in δ57Fe values relative to IRMM-14), while the particulate fractions yielded light isotopic compositions of -0.344‰ for P > 0.22 μm and -0.104‰ for P > 0.45 μm fractions). The mineral particulate-rich waters of the Solimões River had dissolved and colloidal fractions with light isotopic composition (-0.532‰ and -0.176‰, respectively), whereas the particulate fractions yielded δ57Fe values close to those of the continental crust (i.e., -0.029‰ for P > 0.22 μm and 0.028‰ for P > 0.45 μm). Ten kilometers downstream from the Negro and Solimões junction, the concentrations of colloidal and dissolved Fe species deviate markedly from conservative mixing. A maximum Fe loss of 43 μg/L (i.e., 50% of the dissolved and colloidal Fe) is observed 110 km downstream from the rivers junction. The contrasting Negro and Solimões Rivers isotopic compositions along the pore-sized water fractions is attributable to the biogeochemical processes involving different types of upland soils and parental materials. For instance, the isotopic composition of colloidal and dissolved Fe from the Negro River are consistent with Fe oxidation and complexation mechanisms at the interface between waterlogged podzols and river networks, as supported by strong organo-Fe complexes signals observed by EPR. Conversely, the particulate and colloidal fractions from the Solimões River have δ57Fe consistent with strong mechanical erosion in the Andean Cordillera and upland soils, as evidenced by high concentrations of Fe3+-oxides sensu lato measured by EPR. The massive dissolved and colloidal Fe removal is associated with the evolution of the physical and chemical composition of the waters (i.e., ionic strength) during mixing, which influences organo-Fe3+ and Fe3+-oxyhydroxides stability. Several models are discussed to explain Fe non-conservative behavior, including dissociation of organo-Fe complexes and the subsequent formation of solid Fe3+-oxyhydroxides and semiquinone free radicals, as evidenced by EPR spectra demonstrating that organo-Fe signals decrease as Fe3+-oxyhydroxides and free radicals signals increase. As in estuarine regions, the mechanisms involving Fe transfer and loss in the mixing zone has a negligible effect on the bulk water Fe isotopic composition. This result suggests that a tropical basin similar to the Amazon River Basin delivers to the ocean waters with an Fe isotopic composition similar to that of the Earth's continental crust.

Fractionation of Cu and Mo isotopes caused by vapor-liquid partitioning, evidence from the Dahutang W-Cu-Mo ore field

NASA Astrophysics Data System (ADS)

Yao, Junming; Mathur, Ryan; Sun, Weidong; Song, Weile; Chen, Huayong; Mutti, Laurence; Xiang, Xinkui; Luo, Xiaohong

2016-05-01

The study presents δ65Cu and δ97Mo isotope values from cogenetic chalcopyrite and molybdenite found in veins and breccias of the Dahutang W-Cu-Mo ore field in China. The samples span a 3-4 km range. Both isotopes show a significant degree of fractionation. Cu isotope values in the chalcopyrite range from -0.31‰ to +1.48‰, and Mo isotope values in the molybdenite range from -0.03‰ to +1.06‰. For the cogenetic sulfide veined samples, a negative slope relationship exists between δ65Cu and δ97Mo values, which suggest a similar fluid history. Rayleigh distillation models the vein samples' change in isotope values. The breccia samples do not fall on the trend, thus indicating a different source mineralization event. Measured fluid inclusion and δD and δ18O data from cogenetic quartz indicate changes in temperature, and mixing of fluids do not appear to cause the isotopic shifts measure. Related equilibrium processes associated with the partitioning of metal between the vapor-fluid in the hydrothermal system could be the probable cause for the relationship seen between the two isotope systems.

Temperature dependence of the isotope chemistry of the heavy elements.

PubMed Central

Bigeleisen, J

1996-01-01

The temperature coefficient of equilibrium isotope fractionation in the heavy elements is shown to be larger at high temperatures than that expected from the well-studied vibrational isotope effects. The difference in the isotopic behavior of the heavy elements as compared with the light elements is due to the large nuclear isotope field shifts in the heavy elements. The field shifts introduce new mechanisms for maxima, minima, crossovers, and large mass-independent isotope effects in the isotope chemistry of the heavy elements. The generalizations are illustrated by the temperature dependence of the isotopic fractionation in the redox reaction between U(VI) and U(IV) ions. PMID:8790340

Mass Measurements of Proton-Rich Isotopes between Mo and Pd using the Canadian Penning Trap Mass Spectrometer

NASA Astrophysics Data System (ADS)

Fallis, J.; Sharma, K. S.; Sharma, H.; Savard, G.; Levand, A. F.; Sun, T.; Clark, J. A.; Deibel, C.; Parikh, A.; Wrede, C.; Lascar, D.; Segel, R.; Caldwell, S.; Sternberg, M.; van Schelt, J.; Buchinger, F.; Crawford, J. E.; Gulick, S.; Lee, J. K. P.; Li, G.; Scielzo, N. D.; Hecht, A. A.

2008-04-01

In our understanding of the origin of elemental abundances the means of producing the observed abundances of ^92Mo and ^94Mo have long been unknown. These ``light p'' nuclei cannot be adequately produced by the classic p-process alone. The νp-process however, which occurs due to the neutrino wind in core collapse supernovae explosions, involves both proton-capture and neutron-capture reactions and can produce ^92Mo and ^94Mo. The final abundances of these isotopes depend directly on the values of the proton separation energies, Sp, along the reaction path of this process. Recent mass measurements performed with the Canadian Penning Trap Mass Spectrometer have dramatically reduced the uncertainties of Sp values of proton-rich nuclei between Mo and Pd. These measurements and the resulting implications for both the νp-process path and the ^92Mo/^94Mo abundance ratio will be discussed. This work was supported by grants from NSERC, Canada and the U.S. DOE, Nucl. Phys. Div.,under Contract W-31-109-ENG-38

Occurrence and morphology of carbonate concretions in the Beulah-Zap coal bed, Williston basin, North Dakota

USGS Publications Warehouse

Keighin, C.W.M.; Flores, R.M.; Rowland, T.

1996-01-01

Carbonate concretionary bodies were encountered during mining of the Beulah-Zap lignite seam in the Coteau Properties' Freedom mine, Mercer County, North Dakota. Preliminary studies show that areal and vertical distribution of the concretions are variable. All concretions examined are composed almost entirely of calcite. They occur as thin tabular bodies, as more or less elliptical forms, or as tear shaped bodies, and may occur individually or as clusters of buff-colored, poorly consolidated to solidly crystalline material. The carbonate masses vary in size from a few millimeters to tens of centimeters. Bedding in the lignite may display some compactional folding over dense spheroidal to elliptical concretions, indicating formation of the concretions prior to compaction. Internal morphology of the concretions is complex, and includes cone-in-cone structure, cross-cutting calcite veinlets, and multiple generations of calcite. Carbon isotope values suggest the concretions are composed of biogenic carbonate, probably related to early diagenesis and decomposition of organic matter (peat); oxygen isotope values are light, and consistent with a freshwater origin.

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

USGS Publications Warehouse

Ni, Y.; Ma, Q.; Ellis, G.S.; Dai, J.; Katz, B.; Zhang, S.; Tang, Y.

2011-01-01

Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using ??D values in ethane from several basins in the world are in close agreement with similar predictions based on the ??13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that ??D values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that ??D values in ethane might be more suitable for modeling than comparable values in methane and propane. ?? 2011 Elsevier Ltd.

Deglacial Dust Provenance Changes in the Eastern Equatorial Pacific and Implications for ITCZ Movement

NASA Astrophysics Data System (ADS)

Xie, R.; Marcantonio, F.

2009-12-01

The provenance of the eolian dust component of deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation patterns. Measuring temporal changes in dust provenance can shed more light on changes in the position of the Intertropical Convergence Zone (ITCZ), a region in which dust is removed from the upper troposphere by deep convection and scavenged by precipitation. The ITCZ should, therefore, act as a barrier separating wind-blown northern versus southern sources. Perhaps the best way to trace for provenance of dust sources is through the measurement of radiogenic isotope ratios. Here, we have analyzed Nd, Sr, and Pb isotope ratios in the detrital components extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110W from 3S to 7N (ODP Leg 138, Sites 848 - 853). At each site, the sediments ranged in age from 0 to 25 ka. Detrital component extraction involved the chemical removal of the biogenic and authigenic sedimentary fractions. Preliminary detrital Nd isotope ratios show a range of 2.4 ɛNd units (from -5.7 to -3.3). There are distinct latitudinal trends in the ɛNd values, with more radiogenic values further south and less radiogenic values further north. This distinction holds true for both Holocene and glacial time. The difference in Nd isotope ratios at any one site between Holocene and glacial is smaller for the sites furthest North. The greatest Holocene-glacial differences in ɛNd occur at sites south of 3N, suggesting a distinct detrital component boundary at this latitude. The sites furthest north (7N and 5.29N) show the greatest variability in detrital 87Sr/86Sr isotope ratios, while sites furthest south (equator and 1.5N) show negligible variability. The detrital component of sediment at Site 851 (2.77N) has a Sr isotope variability that is intermediate between the northern and southern values, again suggesting a detrital boundary of some sort. We interpreted these preliminary results to suggest that the ITCZ position was displaced toward the south, with a paleo-position located between Site 851 (2.77N) and Site 852 (5.29N), from its average current location, which is approximately 7N. This supports one hypothesis put forward by McGee et al. [1], based on changes in dust flux for the same transect, that the ITCZ was displaced toward the south during the last glacial period. [1] McGee et al., 2007, EPSL 257, 215-230 .

Reporting of nitrogen-isotope abundances (Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Krouse, H.R.; Böhlke, John Karl

1992-01-01

To eliminate possible confusion in the reporting of nitrogen-isotope analyses, the Commission on Atomic Weights and Isotopic Abundances recommends that the value 272 be employed for the 14N/15N value of N2 in air for calculating atom percent 15N from measured δ15N values.

Sedimentary input into the source of Martinique lavas: a Li perspective

NASA Astrophysics Data System (ADS)

Tang, M.; Chauvel, C.; Rudnick, R. L.

2013-12-01

The Lesser Antilles arc is known for the prominent continental crustal signatures in its lavas. It thus provides an ideal target for studying crustal recycling in subduction zones. Martinique Island, located in the middle of the Lesser Antilles arc, has been well characterized for its elemental and radiogenic isotope geochemistry (Labanieh et al., 2012). We measured Li isotopes in the Martinique lavas as well as sediments cored at the southern (Site 144) and northern part (Site 543) of the subducting slab. The sediments show a large isotopic variation (δ7Li ~ -4.2‰ to +3.2‰) but the average δ7Li of -1.1 × 2.4‰ (1 σ, n = 15) is significantly lower than that of N-MORB (δ7Li = + 3.4 × 0.7‰, 1 σ, Tomascak et al., 2008), reflecting the influence of chemical weathering in the continental provenance. Although the subducting sediments display marked mineralogical and chemical shifts from south to north due to different deposition distances to the continental platform (Carpentier et al., 2009), their average Li isotopic compositions are indiscernible from each other. With a few exceptions, the Li isotopic compositions of the Martinique lavas are systematically lighter than MORB, giving an average δ7Li of 1.6 × 1.4‰ (1 σ, n = 25, 4 exceptions excluded). The δ7Li values show no correlation with any radiogenic isotope ratios (206Pb/204Pb, 87Sr/86Sr, 143Nd/144Nd and 176Hf/177Hf), Li/Y ratio, La/Sm ratio and SiO2 content. Therefore, the light Li isotopic composition likely reflects the source characteristics rather than contamination within the arc crust. Incorporation of the isotopically light sediments from Site 144 and 543 in the source may explain the depletion of 7Li in the Martinique lavas. A two-end-member mixing model requires 2-5% addition of the sediments into the depleted mantle source, compared with 1-10% sediments constrained by radiogenic isotopes (Carpentier et al., 2008). References Carpentier, M., Chauvel, C., & Mattielli, N., 2008. Pb-Nd isotopic constraints on sedimentary input into the Lesser Antilles arc system. Earth and Planetary Science Letters, 272(1), 199-211. Carpentier, M., Chauvel, C., Maury, R. C., & Mattielli, N., 2009. The 'zircon effect' as recorded by the chemical and Hf isotopic compositions of Lesser Antilles forearc sediments. Earth and Planetary Science Letters, 287(1), 86-99. Labanieh, S., Chauvel, C., Germa, A., & Quidelleur, X., 2012. Martinique: a Clear Case for Sediment Melting and Slab Dehydration as a Function of Distance to the Trench. Journal of Petrology, 53(12), 2441-2464. Tomascak, P. B., Langmuir, C. H., le Roux, P. J., & Shirey, S. B. (2008). Lithium isotopes in global mid-ocean ridge basalts. Geochimica et Cosmochimica Acta, 72(6), 1626-1637.

Pre-scission model predictions of fission fragment mass distributions for super-heavy elements

NASA Astrophysics Data System (ADS)

Carjan, N.; Ivanyuk, F. A.; Oganessian, Yu. Ts.

2017-12-01

The total deformation energy just before the moment of neck rupture for the heaviest nuclei for which spontaneous fission has been detected (Ds281279-, 281Rg and Cn284282-) is calculated. The Strutinsky's prescription is used and nuclear shapes just before scission are described in terms of Cassinian ovals defined for the fixed value of elongation parameter α = 0.98 and generalized by the inclusion of four additional shape parameters: α1, α3, α4, and α6. Supposing that the probability of each point in the deformation space is given by Boltzmann factor, the distribution of the fission-fragment masses is estimated. The octupole deformation α3 at scission is found to play a decisive role in determining the main feature of the mass distribution: symmetric or asymmetric. Only the inclusion of α3 leads to an asymmetric division. Finally, the calculations are extended to an unexplored region of super-heavy nuclei: the even-even Fl (Z = 114), Lv (Z = 116), Og (Z = 118) and (Z = 126) isotopes. For these nuclei, the most probable mass of the light fragment has an almost constant value (≈136) like in the case of the most probable mass of the heavy fragment in the actinide region. It is the neutron shell at 82 that makes this light fragment so stable. Naturally, for very neutron-deficient isotopes, the mass division becomes symmetric when N = 2 × 82.

Iron isotope fractionation during hydrothermal ore deposition and alteration

NASA Astrophysics Data System (ADS)

Markl, Gregor; von Blanckenburg, Friedhelm; Wagner, Thomas

2006-06-01

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ56Fe between -2.3‰ and +1.3‰. Primary hematite ( δ56Fe: -0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe ( δ56Fe: -0.5‰) leached from the crystalline basement. Occasional input of CO 2-rich waters resulted in precipitation of isotopically light siderite ( δ56Fe: -1.4 to -0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.

Diet of the prehistoric population of Rapa Nui (Easter Island, Chile) shows environmental adaptation and resilience

PubMed Central

Larsen, Thomas; Hunt, Terry; Lipo, Carl; Solsvik, Reidar; Wallsgrove, Natalie; Ka'apu‐Lyons, Cassie; Close, Hilary G.; Popp, Brian N.

2017-01-01

Abstract Objectives The Rapa Nui “ecocide” narrative questions whether the prehistoric population caused an avoidable ecological disaster through rapid deforestation and over‐exploitation of natural resources. The objective of this study was to characterize prehistoric human diets to shed light on human adaptability and land use in an island environment with limited resources. Materials and methods Materials for this study included human, faunal, and botanical remains from the archaeological sites Anakena and Ahu Tepeu on Rapa Nui, dating from c. 1400 AD to the historic period, and modern reference material. We used bulk carbon and nitrogen isotope analyses and amino acid compound specific isotope analyses (AA‐CSIA) of collagen isolated from prehistoric human and faunal bone, to assess the use of marine versus terrestrial resources and to investigate the underlying baseline values. Similar isotope analyses of archaeological and modern botanical and marine samples were used to characterize the local environment. Results Results of carbon and nitrogen AA‐CSIA independently show that around half the protein in diets from the humans measured came from marine sources; markedly higher than previous estimates. We also observed higher δ15N values in human collagen than could be expected from the local environment. Discussion Our results suggest highly elevated δ15N values could only have come from consumption of crops grown in substantially manipulated soils. These findings strongly suggest that the prehistoric population adapted and exhibited astute environmental awareness in a harsh environment with nutrient poor soils. Our results also have implications for evaluating marine reservoir corrections of radiocarbon dates. PMID:28664976

Geochemical and isotopic tracing of water in nested southern Minnesota corn-belt watersheds.

PubMed

Magner, J A; Alexander, S C

2002-01-01

Land-use changes over the last century in southern Minnesota have influenced riverine water chemistry. A nested watershed approach was used to examine hydrologic pathways of water movement in this now agriculturally intensive region. From field scale subsurface tile-drains of the Beauford ditch to the respective outlets of the Cobb River and Blue Earth River, more than 125 samples were collected for major dissolved ions and isotopes between March 1994 and June 1996 over a range of climatic conditions that included snowmelt and storm-flows. Results indicate that riverine water chemistry is dominated by subsurface tile-drained row crop agriculture. In the mid-1990s, regional ground water discharge into the Cobb and Blue Earth Rivers comprised less than 10% of the total flow based on ionic mixing calculations. Ammonia, present in manure or as anhydrous, is readily exchanged in the soil. This ion exchange releases increasing ratios of magnesium, sodium and strontium relative to calcium, the dominant cation. Soil thaw and snowmelt recharge influenced March-April tile-drain and ditch water isotopic values. Light deltaD values increased as spring infiltration-derived water was displaced from the soil zone by heavier summer precipitation. Delta15N followed a similar but opposite pattern with relatively heavy March-April tile-drain and ditch values trending to lighter delta15N through the growing season. The future of southern Minnesota riverine water quality is closely linked to the management of the landscape. To improve the riverine environment, land owners and managers will need to address cropping systems, fertilization practices and drainage.

Diet of the prehistoric population of Rapa Nui (Easter Island, Chile) shows environmental adaptation and resilience.

PubMed

Jarman, Catrine L; Larsen, Thomas; Hunt, Terry; Lipo, Carl; Solsvik, Reidar; Wallsgrove, Natalie; Ka'apu-Lyons, Cassie; Close, Hilary G; Popp, Brian N

2017-10-01

The Rapa Nui "ecocide" narrative questions whether the prehistoric population caused an avoidable ecological disaster through rapid deforestation and over-exploitation of natural resources. The objective of this study was to characterize prehistoric human diets to shed light on human adaptability and land use in an island environment with limited resources. Materials for this study included human, faunal, and botanical remains from the archaeological sites Anakena and Ahu Tepeu on Rapa Nui, dating from c. 1400 AD to the historic period, and modern reference material. We used bulk carbon and nitrogen isotope analyses and amino acid compound specific isotope analyses (AA-CSIA) of collagen isolated from prehistoric human and faunal bone, to assess the use of marine versus terrestrial resources and to investigate the underlying baseline values. Similar isotope analyses of archaeological and modern botanical and marine samples were used to characterize the local environment. Results of carbon and nitrogen AA-CSIA independently show that around half the protein in diets from the humans measured came from marine sources; markedly higher than previous estimates. We also observed higher δ 15 N values in human collagen than could be expected from the local environment. Our results suggest highly elevated δ 15 N values could only have come from consumption of crops grown in substantially manipulated soils. These findings strongly suggest that the prehistoric population adapted and exhibited astute environmental awareness in a harsh environment with nutrient poor soils. Our results also have implications for evaluating marine reservoir corrections of radiocarbon dates. © 2017 Wiley Periodicals, Inc.

Deciphering Seasonal Variations of Diet and Water in Modern White-Tailed Deer by In Situ Analysis of Osteons in Cortical Bone

NASA Astrophysics Data System (ADS)

Larson, T. E.; Longstaffe, F. J.

2004-12-01

In situ stable carbon and oxygen isotope compositions of biogenic apatite were obtained from longitudinally-cut sections of cortical bone from femurs of modern domesticated sheep and free-range White-Tailed deer, using an IR-laser and a GC-continuous flow interface. Ablation pits averaged 200x50 microns, making it possible to analyze individual osteons. Since cortical bone is remodelled along osteons throughout a mammal's lifetime, isotopic data at this resolution provides information about seasonal variations in diet and drinking water. The O-isotope results were calibrated using laser analyses of NBS-18 and NBS-19, which produced a value of 26.39±0.46 permil (n=27) for WS-1 calcite (accepted value, 26.25 permil). C-isotope results were calibrated using a CO2 reference gas, producing a value of 0.76±0.40permil (n=27) for WS-1, also in excellent agreement with its accepted value of 0.74 permil. Average O- and C-isotope values for a local domestic sheep (southwestern Ontario, Canada) were 12.20±0.58 and -15.70±0.35 permil (n=27), respectively. No isotopic trend occurred along or across individual osteons. This pattern is consistent with the sheep's relatively unchanging food and water sources. The free-range White-Tailed deer came from Pinery Provincial Park (PPP), southwestern Ontario. Its O- and C-isotope compositions varied systematically across individual osteons and were negatively correlated (R2=0.56). O-isotope values ranged from 13.4 to 15.5 permil; the highest values correlated with summer and the lowest values, with winter. The O-isotope compositions of the main water source (Old Ausable River Channel) varied similarly during the deer's lifetime: winter average, -10.7±0.5 permil; summer average, -8.6±0.4 permil. The C-isotope results for the deer osteons varied from -19.7 to -15.9 permil. This variation can be explained by changes in food sources. Summer diets of deer in PPP consist mainly of leafy fractions of C3 vegetation, especially sumac, cedar, oak and pine (average leaf C-isotope value, -28.4±0.8 permil). During winter, when leafy material is unavailable and deep snow inhibits access to vegetation in general, deer strip bark from vegetation (average bark C-isotope value, -25.6±0.8 permil). Certain C4 grasses (little bluestem and sandreed grass, average C-isotope value, -12.7±0.2 permil), which are abundant in unforested dune areas of PPP, commonly stand above the snow cover, and hence are also available for consumption. Deer may also range more widely in the winter, feeding on corn stalks and husks that escaped both harvest and snow cover (average C-isotope value, -11.3±0.2 permil).

Fractionation of 238U/235U by reduction during low temperature uranium mineralisation processes

NASA Astrophysics Data System (ADS)

Murphy, Melissa J.; Stirling, Claudine H.; Kaltenbach, Angela; Turner, Simon P.; Schaefer, Bruce F.

2014-02-01

Investigations of ‘stable’ uranium isotope fractionation during low temperature, redox transformations may provide new insights into the usefulness of the 238U/235U isotope system as a tracer of palaeoredox processes. Sandstone-hosted uranium deposits accumulate at an oxidation/reduction interface within an aquifer from the low temperature reduction of soluble U(VI) complexes in groundwaters, forming insoluble U(IV) minerals. This setting provides an ideal environment in which to investigate the effects of redox transformations on 238U/235U fractionation. Here we present the first coupled measurements of 238U/235U isotopic compositions and U concentrations for groundwaters and mineralised sediment samples from the same redox system in the vicinity of the high-grade Pepegoona sandstone-hosted uranium deposit, Australia. The mineralised sediment samples display extremely variable 238U/235U ratios (herein expressed as δUCRM145238, the per-mil deviation from the international NBL standard CRM145). The majority of mineralised sediment samples have δUCRM145238 values between -1.30±0.05 and 0.55±0.12‰, spanning a ca. 2‰ range. However, one sample has an unusually light isotopic composition of -4.13±0.05‰, which suggests a total range of U isotopic variability of up to ca. 5‰, the largest variation found thus far in a single natural redox system. The 238U/235U isotopic signature of the mineralised sediments becomes progressively heavier (enriched in 238U) along the groundwater flow path. The groundwaters show a greater than 2‰ variation in their 238U/235U ratios, ranging from δUCRM145238 values of -2.39±0.07 to -0.71±0.05‰. The majority of the groundwater data exhibit a clear systematic relationship between 238U/235U isotopic composition and U concentration; samples with the lowest U concentrations have the lowest 238U/235U ratios. The preferential incorporation of 238U during reduction of U(VI) to U(IV) and precipitation of uranium minerals leaves the groundwaters enriched in 235U, resulting in a progressive shift in 238U/235U towards lighter values in the aqueous phase as U is removed. These data can be modelled by a closed system Rayleigh fractionation model, with a fractionation factor (α, representing the 238U/235U composition of the groundwater relative to the solid uranium minerals) ranging from ∼0.9996 to 1.0000, with the majority of datapoints ranging from α values of 0.9998 to 0.9999. The sense and magnitude of the results of this study imply that 238U/235U fractionation is likely to be controlled by volume-dependent nuclear field shift effects during the reduction of U(VI) to U(IV) during mineralisation processes. These findings support the use of the 238U/235U isotopic system as a tracer to constrain the nature and timing of palaeoredox conditions.

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-aluminum-rich inclusions in the proto planetary disc is thus not required to explain the Mg isotopic composition of the Earth.

Are carbon and nitrogen exchange between fungi and the orchid Goodyera repens affected by irradiance?

PubMed Central

Liebel, Heiko T.; Bidartondo, Martin I.; Gebauer, Gerhard

2015-01-01

Background and Aims The green orchid Goodyera repens has been shown to transfer carbon to its mycorrhizal partner, and this flux may therefore be affected by light availability. This study aimed to test whether the C and N exchange between plant and fungus is dependent on light availability, and in addition addressed the question of whether flowering and/or fruiting individuals of G. repens compensate for changes in leaf chlorophyll concentration with changes in C and N flows from fungus to plant. Methods The natural abundances of stable isotopes of plant C and N were used to infer changes in fluxes between orchid and fungus across natural gradients of irradiance at five sites. Mycorrhizal fungi in the roots of G. repens were identified by molecular analyses. Chlorophyll concentrations in the leaves of the orchid and of reference plants were measured directly in the field. Key Results Leaf δ13C values of G. repens responded to changes in light availability in a similar manner to autotrophic reference plants, and different mycorrhizal fungal associations also did not affect the isotope abundance patterns of the orchid. Flowering/fruiting individuals had lower leaf total N and chlorophyll concentrations, which is most probably explained by N investments to form flowers, seeds and shoot. Conclusions The results indicate that mycorrhizal physiology is relatively fixed in G. repens, and changes in the amount and direction of C flow between plant and fungus were not observed to depend on light availability. The orchid may instead react to low-light sites through increased clonal growth. The orchid does not compensate for low leaf total N and chlorophyll concentrations by using a 13C- and 15N-enriched fungal source. PMID:25538109

The Mineralogical Record of Oxygen Fugacity Variation and Alteration in Northwest Africa 8159: Evidence for Interaction Between a Mantle Derived Martian Basalt and a Crustal Component(s)

NASA Technical Reports Server (NTRS)

Shearer, Charles K.; Burger, Paul V.; Bell, Aaron S.; McCubbin, Francis M.; Agee, Carl; Simon, Justin I.; Papike, James J.

2015-01-01

A prominent geochemical feature of basaltic magmatism on Mars is the large range in initial Sr isotopic ratios (approx. 0.702 - 0.724) and initial epsilon-Nd values (approx. -10 to greater than +50). Within this range, the shergottites fall into three discreet subgroups. These subgroups have distinct bulk rock REE patterns, mineral chemistries (i.e. phosphate REE patterns, Ni, Co, V in olivine), oxygen fugacity of crystallization, and stable isotopes, such as O. In contrast, nakhlites and chassignites have depleted epsilon-Nd values (greater than or equal to +15), have REE patterns that are light REE enriched, and appear to have crystallized near the FMQ buffer. The characteristics of these various martian basalts have been linked to different reservoirs in the martian crust and mantle, and their interactions during the petrogenesis of these magmas. These observations pose interesting interpretive challenges to our understanding of the conditions of the martian mantle (e.g. oxygen fugacity) and the interaction of mantle derived magmas with the martian crust and surface. Martian meteorite NWA 8159 is a unique fine-grained augite basalt derived from a highly depleted mantle source as reflected in its initial epsilon-Nd value, contains a pronounced light REE depleted pattern, and crystallized presumably under very oxidizing conditions. Although considerably older than both shergottites and nahklites, it has been petrogenetically linked to both styles of martian magmatism. These unique characteristics of NWA 8159 may provide an additional perspective for deciphering the petrogenesis of martian basalts and the nature of the crust of Mars.

Environmental regulation of carbon isotope composition and crassulacean acid metabolism in three plant communities along a water availability gradient.

PubMed

Ricalde, M Fernanda; Andrade, José Luis; Durán, Rafael; Dupuy, Juan Manuel; Simá, J Luis; Us-Santamaría, Roberth; Santiago, Louis S

2010-12-01

Expression of crassulacean acid metabolism (CAM) is characterized by extreme variability within and between taxa and its sensitivity to environmental variation. In this study, we determined seasonal fluctuations in CAM photosynthesis with measurements of nocturnal tissue acidification and carbon isotopic composition (δ(13)C) of bulk tissue and extracted sugars in three plant communities along a precipitation gradient (500, 700, and 1,000 mm year(-1)) on the Yucatan Peninsula. We also related the degree of CAM to light habitat and relative abundance of species in the three sites. For all species, the greatest tissue acid accumulation occurred during the rainy season. In the 500 mm site, tissue acidification was greater for the species growing at 30% of daily total photon flux density (PFD) than species growing at 80% PFD. Whereas in the two wetter sites, the species growing at 80% total PFD had greater tissue acidification. All species had values of bulk tissue δ(13)C less negative than -20‰, indicating strong CAM activity. The bulk tissue δ(13)C values in plants from the 500 mm site were 2‰ less negative than in plants from the wetter sites, and the only species growing in the three communities, Acanthocereus tetragonus (Cactaceae), showed a significant negative relationship between both bulk tissue and sugar δ(13)C values and annual rainfall, consistent with greater CO(2) assimilation through the CAM pathway with decreasing water availability. Overall, variation in the use of CAM photosynthesis was related to water and light availability and CAM appeared to be more ecologically important in the tropical dry forests than in the coastal dune.

Hydrological cycle during the early Eocene: What can we learn from leaf waxes?

NASA Astrophysics Data System (ADS)

Krishnan, S.; Pagani, M.; Huber, M.

2012-12-01

Understanding how rapid warming modified global precipitation patterns during periods of global warming is essential to forecasting the impact of future climate change. The early Eocene (~55-52 Ma) represents a period of peak warmth for the past 65 million years with global temperatures ~10 degrees C warmer than present. This period is also known for at least three, greenhouse gas-induced episodes of rapid global warming (hyperthermals: PETM; ~55 Ma, ETM-2; ~53.7 Ma and ETM-3; 52.8 Ma), often considered extreme analogues to modern climate change. Hyperthermals are also characterized by negative carbon isotope excursions (CIE), which reflect the input of isotopically light carbon responsible for observed temperature increases. A novel proxy used for hydrological reconstructions uses the hydrogen isotopic composition of compound-specific biomarkers preserved in the sedimentary record. For terrestrial leaf-wax lipids (e.g., n-alkanes), the hydrogen isotopic composition primarily reflects the isotopic composition of meteoric waters, which is dependent on distance of vapor transport, number of rainout events, precipitation amount, and evapotranspiration. Isotopic compositions of PETM n-alkanes (δDalkanes) recovered from the Arctic Ocean show a substantial deuterium (D)-enrichment at the onset of the CIE which was argued to potentially reflect reduced rainout in the mid-latitudes, resulting in increased precipitation in the Arctic (Pagani et al., 2006). D-depleted values of n-alkanes during peak warmth of the PETM suggest either modification of local precipitation or a global change in the fraction of rainout. In this study, we evaluate the veracity of previous conclusions by compiling existing δDalkanes records (including from Mar-2X, Venezuela; Tawanui, New Zealand; Wilkes Land, Antarctica; and the Lomonsov Ridge, Arctic) with new records from the Pacific and Atlantic oceans and marginal marine sections (including Cicogna, Italy; Giraffe Core, Canadian High Arctic). To determine the background state of the hydrological cycle in a warmer world, we measured early Eocene δDalkanes at these sites. This compilation was then compared against results from the isotope-coupled National Center for Atmospheric Research (NCAR) Community Climate System Model v3.0 (CCSM) global climate model, with Eocene boundary conditions and two different pCO2 levels (2240 and 4480 ppm). Preliminary analyses suggest that the model is able to simulate the equator-pole trends in precipitation δD. However, predicted values are offset from the n-alkane data by up to 40‰. To study changes in the hydrological cycle with rapid warming, we analyze n-alkane δD and δ13C values for the PETM and ETM-2. Leads and lags between the carbon and hydrogen isotopic records help constrain the timing and type of hydrological shifts with respect to carbon input. Preliminary results from the ETM-2 recovered from the Arctic indicate similar hydrological changes during both hyperthermals. A pre-event increase in δD values (of 60‰ during the PETM and 25‰ during ETM-2) is observed, followed by a decrease in δD (~10-15‰ for both the events) during the peak of the CIE. A significant pre-PETM D-enrichment at mid-latitudes is not evident, however, more negative δD values during the CIE is observed in some sites. The reasons for these isotopic shifts and their implication for the local and global water cycles will be discussed.

Climatic signals registered as Carbon isotopic values in Metasequoia leaf tissues: A statistical analysis

NASA Astrophysics Data System (ADS)

Yang, H.; Blais, B.; Perez, G.; Pagani, M.

2006-12-01

To examine climatic signals registered as carbon isotopic values in leaf tissues of C3 plants, we collected mature leaf tissues from sun and shade leaves of Metasequoia trees germinated from the 1947 batch of seeds from China and planted along a latitudinal gradient of the United States. Samples from 40 individual trees, along with fossilized material from the early Tertiary of the Canadian Arctic, were analyzed for C and concentration and isotopic values using EA-IRMS after the removal of free lipids. The generated datasets were then merged with climate data compiled from each tree site recorded as average values over the past thirty years (1971-2002, NOAA database). When the isotope data were cross plotted against each geographic and climatic indicator, Latitude, Mean Annual Temperature (MAT), Average Summer Mean Temperature (ASMT)(June-August), Mean Annual Precipitation (MAP), and Average Summer Mean Precipitation (ASMP) respectively correlation patterns were revealed. The best correlating trend was obtained between temperature parameters and C isotopic values, and this correlation is stronger in the northern leaf samples than the southern samples. We discovered a strong positive correlation between latitude and the offset of C isotopic values between shade and sun leaves. This investigation represents a comprehensive examination on climatic signals registered as C isotopic values on a single species that is marked by single genetic source. The results bear implications on paleoclimatic interpretations of C isotopic signals obtained from fossil plant tissues.

Is the Sun Lighter than the Earth? Isotopic CO in the Photosphere, Viewed through the Lens of Three-dimensional Spectrum Synthesis

NASA Astrophysics Data System (ADS)

Ayres, Thomas R.; Lyons, J. R.; Ludwig, H.-G.; Caffau, E.; Wedemeyer-Böhm, S.

2013-03-01

We consider the formation of solar infrared (2-6 μm) rovibrational bands of carbon monoxide (CO) in CO5BOLD 3D convection models, with the aim of refining abundances of the heavy isotopes of carbon (13C) and oxygen (18O, 17O), to compare with direct capture measurements of solar wind light ions by the Genesis Discovery Mission. We find that previous, mainly 1D, analyses were systematically biased toward lower isotopic ratios (e.g., R 23 ≡ 12C/13C), suggesting an isotopically "heavy" Sun contrary to accepted fractionation processes that were thought to have operated in the primitive solar nebula. The new 3D ratios for 13C and 18O are R 23 = 91.4 ± 1.3 (R ⊕ = 89.2) and R 68 = 511 ± 10 (R ⊕ = 499), where the uncertainties are 1σ and "optimistic." We also obtained R 67 = 2738 ± 118 (R ⊕ = 2632), but we caution that the observed 12C17O features are extremely weak. The new solar ratios for the oxygen isotopes fall between the terrestrial values and those reported by Genesis (R 68 = 530, R 67 = 2798), although including both within 2σ error flags, and go in the direction favoring recent theories for the oxygen isotope composition of Ca-Al inclusions in primitive meteorites. While not a major focus of this work, we derive an oxygen abundance, epsilonO ~ 603 ± 9 ppm (relative to hydrogen; log epsilon ~ 8.78 on the H = 12 scale). The fact that the Sun is likely lighter than the Earth, isotopically speaking, removes the necessity of invoking exotic fractionation processes during the early construction of the inner solar system.

Temporal δ13C records from bottlenose dolphins (Tursiops truncatus) reflect variation in foraging location and global carbon cycling

NASA Astrophysics Data System (ADS)

Rossman, S. L.; Barros, N. B.; Ostrom, P. H.; Gandhi, H.; Wells, R. S.

2010-12-01

With four decades of data on a population of bottlenose dolphins (Tursiops truncatus) resident to Sarasota Bay (SB), The Sarasota Dolphin Research Program offers an unparalleled platform for ground-truthing stable isotope data and exploring bottlenose dolphin ecology in a natural setting. We explored carbon isotope value fidelity to habitat utilization by comparing δ13C data from whole teeth and muscle to the individual dolphin's proclivity towards foraging in seagrass beds based on observational data. We then examined variation in habitat use based on temporal isotope records. Whole tooth protein isotope values do not show a significant correlation with the observed percentage of foraging in seagrass habitat. In contrast, δ13C values from muscle showed a significant positive relationship with the observational data. Differences in the degree of tissue turn over may account for this distinction between tooth and muscle. Dolphin teeth consist of annually deposited layers that are inert once formed. Thus, the isotopic composition of protein in annuli reflect foraging at the time of deposition. In addition to incorporating variation associated with differences in foraging over the lifetime of the individual, whole tooth isotope values are confounded because a disproportionate amount of tooth protein derives from the first few years of life. Given the turnover time of muscle tissue, isotope values reflect diet over the past several months. From 1991 to 2008, muscle δ13C values showed a significant decline, -13.5‰ to -15.1‰.This time period encompasses a state wide net fishing ban (1995) however other factors such as a series of red tide harmful algal blooms, a decline in predators, increases in shallow water boat traffic and an increase in string ray abundance may also contribute to the temporal isotope trend. To examine changes in dolphin foraging habitat further back in time we analyzed the tip of crown of the tooth which records the isotopic signal from the first year of life. Given the age of bottlenose dolphins from SB (ca. 60 years), our isotopic data provide a record beginning in 1944. While carbon isotope values show a striking decline over time, the data must be corrected for the Suess effect. The Suess effect results from burning of 13C depleted hydrocarbons which causes a decrease in the δ13C of atmospheric CO2 that subsequent depresses isotope values in food webs. To account for the Suess effect, δ13C values are adjusted by 0.15‰ per decade. Suess corrected δ13C values do not show a temporal linear trend however the average isotope value prior to 1960 is significantly higher than that after 1960 (-10.1 vs -11.66, p=0.038). While documented declines in seagrass abundance prior to 1980 may influence our data, the decline in δ13C of atmospheric CO2 is likely an important factor that controls the isotopic composition of dolphin tissues. Our results suggest that isotope-based estimates of foraging should account for the Suess effect, and that dolphins act as environmental sentinels whose δ13C values records perturbations in global carbon cycling.

Magnesium isotopic evidence for chemical disequilibrium among cumulus minerals in layered mafic intrusion

NASA Astrophysics Data System (ADS)

Chen, Lie-Meng; Teng, Fang-Zhen; Song, Xie-Yan; Hu, Rui-Zhong; Yu, Song-Yue; Zhu, Dan; Kang, Jian

2018-04-01

Magnesium isotopic compositions of olivine, clinopyroxene, and ilmenite from the Baima intrusion, SW China, for the first time, are investigated to constrain the magnitude and mechanisms of Mg isotope fractionation among cumulus minerals in layered mafic intrusions and to evaluate their geological implications. Olivine and clinopyroxene have limited Mg isotope variations, with δ26Mg ranging from -0.33 to +0.05‰ and from -0.29 to -0.13‰, respectively, similar to those of mantle xenolithic peridotites. By contrast, ilmenites display extremely large Mg isotopic variation, with δ26Mg ranging from -0.50 to +1.90‰. The large inter-mineral fractionations of Mg isotopes between ilmenite and silicates may reflect both equilibrium and kinetic processes. A few ilmenites have lighter Mg isotopic compositions than coexisting silicates and contain high MgO contents without compositional zoning, indicating equilibrium fractionation. The implication is that the light Mg isotopic compositions of lunar high-Ti basalts may result from an isotopically light source enriched in cumulate ilmenites. On the other hand, most ilmenites have heavy Mg isotopic compositions, coupled with high MgO concentration and chemical zoning, which can be quantitatively modeled by kinetic Mg isotope fractionations induced by subsolidus Mg-Fe exchange between ilmenite and ferromagnesian silicates during the cooling of the Baima intrusion. The extensive occurrence of kinetic Mg isotope fractionation in ilmenites implies the possibility of widespread compositional disequilibrium among igneous minerals in magma chambers. Consequently, disequilibrium effects need to be considered in studies of basaltic magma evolution, magma chamber processes, and magmatic Fe-Ti oxide ore genesis.

Fish fins as non-lethal surrogates for muscle tissues in freshwater food web studies using stable isotopes.

PubMed

Hette Tronquart, Nicolas; Mazeas, Laurent; Reuilly-Manenti, Liana; Zahm, Amandine; Belliard, Jérôme

2012-07-30

Dorsal white muscle is the standard tissue analysed in fish trophic studies using stable isotope analyses. However, sampling white muscle often implies the sacrifice of fish. Thus, we examined whether the non-lethal sampling of fin tissue can substitute muscle sampling in food web studies. Analysing muscle and fin δ(15)N and δ(13)C values of 466 European freshwater fish (14 species) with an elemental analyser coupled with an isotope ratio mass spectrometer, we compared the isotope values of the two tissues. Correlations between fin and muscle isotope ratios were examined for all fish together and specifically for 12 species. We further proposed four methods of assessing muscle from fin isotope ratios and estimated the errors made using these muscle surrogates. Despite significant differences between isotope values of the two tissues, fin and muscle isotopic signals are strongly correlated. Muscle values, estimated with raw fin isotope ratios (1st method), induce an error of ca. 1‰ for both isotopes. In comparison, specific (2nd method) or general (3rd method) correlations provide meaningful corrections of fin isotope ratios (errors <0.6‰). On the other hand, relationships, established for Australian tropical fish, only give poor muscle estimates (errors >0.8‰). There is little chance that a global model can be created. However, the 2nd and 3rd methods of estimating muscle values from fin isotope ratios should provide an acceptable level of error for the studies of European freshwater food web. We thus recommend that future studies use fin tissue as a non-lethal surrogate for muscle. Copyright © 2012 John Wiley & Sons, Ltd.

A manual for a laboratory information management system (LIMS) for light stable isotopes

USGS Publications Warehouse

Coplen, Tyler B.

1997-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program is presented herein. Major benefits of this system include (i) an increase in laboratory efficiency, (ii) reduction in the use of paper, (iii) reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) decreased errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for stable isotope laboratories. Since the original publication of the manual for LIMS for Light Stable Isotopes, the isotopes 3 H, 3 He, and 14 C, and the chlorofluorocarbons (CFCs), CFC-11, CFC-12, and CFC-113, have been added to this program.

A manual for a Laboratory Information Management System (LIMS) for light stable isotopes

USGS Publications Warehouse

Coplen, Tyler B.

1998-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program is presented herein. Major benefits of this system include (i) an increase in laboratory efficiency, (ii) reduction in the use of paper, (iii) reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) decreased errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for stable isotope laboratories. Since the original publication of the manual for LIMS for Light Stable Isotopes, the isotopes 3 H, 3 He, and 14 C, and the chlorofluorocarbons (CFCs), CFC-11, CFC-12, and CFC-113, have been added to this program.

Chromium isotope inventory of Cr(VI)-polluted groundwaters at four industrial sites in Central Europe

NASA Astrophysics Data System (ADS)

Novak, Martin; Martinkova, Eva; Chrastny, Vladislav; Stepanova, Marketa; Curik, Jan; Szurmanova, Zdenka; Cron, Marcel; Tylcer, Jiri; Sebek, Ondrej

2016-04-01

Chromium is one of the most toxic elements, especially in its dissolved Cr(VI) form. In the Czech Republic (Central Europe), massive contamination of groundwater has been reported at more than 200 industrial operations. Under suitable conditions, i.e., low Eh, and high availability of reductive agents, Cr(VI) in groundwater may be spontaneously reduced to solid, largely non-toxic Cr(III). This process is associated with a Cr isotope fractionation, with the residual liquid Cr(VI) becoming enriched in the heavier isotope 53Cr. At industrial operations that have been closed and/or where no further leakage of Cr(VI) occurs, the contaminated groundwater plume may be viewed as a closed system. At such sites, an increasing degree of Cr(VI) reduction should result in an increasing del53/52Cr value of the residual liquid. Here we present del53/52Cr systematics at four contaminated Czech sites, focusing on groundwaters. At two of the four sites (Zlate Hory, Loucna) we were also able to analyze the source of contamination. Chromium in the electroplating solutes was isotopically relatively light, with del53/52Cr values <1 per mil. At the remaining two sites (Letnany and Velesin), the Cr isotope signature of the source of contamination was not known. At all four sites, most del53/52Cr values were positive, with means higer than 1 per mil: At Zlate Hory, del53/52Cr ranged between -2.2 and +3.0 per mil (mean of +1.5 per mil); at Loucna, del53/52Cr ranged between 0 and +4.0 per mil (mean of +1.7 per mil); at Letnany, del53/52Cr ranged between +2.0 and +4.5 per mil (mean of +3.2 per mil); and at Velesin, del53/52Cr ranged between +0.5 and +4.5 per mil (mean of +2.7 per mil). Cr(VI) reduction may proceed at Zlate Hory and Loucna, where del53/52Cr(VI) values in groundwater were on average higher than those of the contamination source. At these two sites, our Cr isotope data are not consistent with the existing estimates of the amount of dissolved and precipitated Cr: The pool size of solid Cr(III) in the soil was estimated at 6600 and 500 kg at Zlate Hory and Loucna, respectively. At the same time, the pool size of dissolved Cr(VI) was estimated at 50 and 1.2 kg at Zlate Hory and Loucna, respectively. It follows that, at both sites, less than 1 % of the entire Cr that had leaked into the aquifer an a liquid form remained in the liquid form. If, indeed, most solid Cr now present in the saturated zone had undergone anaerobic reduction, we would expect much higher del53/52Cr values of the residual liquid Cr(VI) than those actually observed. Our understanding of the system is incomplete. Currently, del53/52Cr values of the contaminated soils are being determined in an attempt to close a Cr isotope mass balance.

Boron Isotopic Composition Correlates with Ultra-Structure in a - Sea Coral Lophelia Pertusa: Implications for Biomineralization and - PH

NASA Astrophysics Data System (ADS)

Blamart, D.; Rollion-Bard, C.; Meibom, A.; Cuif, J.; Juillet-Leclerc, A.; Dauphin, Y.; Douarin, M.

2007-12-01

The geochemistry (stable isotopes and trace elements) of biogenic carbonates has been widely used for more than fifty years to reconstruct past climatic variability. During this time, the studies were mainly based on bulk sampling limiting sometimes the interpretations of the geochemical data as paleoclimatic proxies. Recently, high spatial resolution sampling techniques, such as micro-mill and SIMS, have been employed in the study of C, O and B isotopic compositions and trace elements (Mg, Sr) in the skeletons of a variety of (deep-sea) coral species. These studies have documented dramatic 'vital effects' and uncovered a systematic relationship between skeletal ultra-structure and stable isotopic composition. The formation of skeleton corals follows a universal two-step growth process. At the tips of the skeletal structures, the mineralizing cell layer produces centers of calcification (COC) or, equivalently, Early Mineralization Zone (EMZ). These EMZ are subsequently overgrown by fibrous aragonite(FA) consisting of cyclically added layers. The EMZ are characterized by systematically lighter C and O isotopic compositions compared with the adjacent FA. A number of geochemical models have been proposed, in which this systematic stable isotopic difference between EMZ and FA is ascribed to a biologically induced variation in the pH of a proposed Extra-cytoplasmic Calcifying Fluid (ECF) reservoir. In these models, relatively high pH conditions during the formation of EMZ result in relatively light C and O isotopic compositions compared with FA, which form under generally lower pH conditions. A direct test of such models would be possible if the Boron isotopic composition, which is pH sensitive, of EMZ and FA could be measured. We performed ion microprobe d11B measurements for EMZ and FA in Lophelia pertusa, a deep-sea coral common in the North-East Atlantic Ocean. We observe a systematic difference in B isotopic composition between the EMZ and FA skeleton. In EMZ, the measured δ11B values are consistently low. Fibrous aragonite is characterized by systematically higher d11B values, but also display B isotopic heterogeneity associated with specific growth bands in the calyx wall. The magnitude of the observed B isotopic variations cannot be explained by changes in environmental conditions and are likely caused by biological processes involved in the biomineralization of new skeleton; i.e. 'vital' effects. The observed B isotopic variations are opposite to the predictions of geochemical models for vital effects. Our data indicate that pH variations are not responsible for the observed stable isotopic fractionations. Geochemical models therefore do not provide an adequate framework within which to understand coral skeletal formation. Without a better understanding of these processes, which require experiments, the use of B isotopic composition to reconstruct paleo-pH variations in the oceans must be considered problematic - at least as far as Lophelia pertusa is concerned.

Standardization for oxygen isotope ratio measurement - still an unsolved problem.

PubMed

Kornexl; Werner; Gehre

1999-07-01

Numerous organic and inorganic laboratory standards were gathered from nine European and North American laboratories and were analyzed for their delta(18)O values with a new on-line high temperature pyrolysis system that was calibrated using Vienna standard mean ocean water (VSMOW) and standard light Antartic precipitation (SLAP) internationally distributed reference water samples. Especially for organic materials, discrepancies between reported and measured values were high, ranging up to 2 per thousand. The reasons for these discrepancies are discussed and the need for an exact and reliable calibration of existing reference materials, as well as for the establishment of additional organic and inorganic reference materials is stressed. Copyright 1999 John Wiley & Sons, Ltd.

Habitat use of migratory bats killed during autumn at wind turbines.

PubMed

Voigt, Christian C; Lindecke, Oliver; Schönborn, Sophia; Kramer-Schadt, Stephanie; Lehmann, David

2016-04-01

The killing of large numbers of migratory bats at wind turbines is a pressing conservation problem. Even though avoidance and mitigation measures could benefit from a better knowledge of the species' migratory habits, we lack basic information about what habitats and corridors bats use during migration. We studied the isotopic niche dimensions of three bat species that are frequently killed at wind turbines in Germany: non-migratory Pipistrellus pipistrellus, mid-distance migratory Nyctalus noctula, and long- distance migratory Pipistrellus nathusii. We measured stable carbon and nitrogen isotope ratios (δ¹³C, δ¹⁵N) in five tissues that differed in isotopic retention time (fur, wing membrane tissue, muscle, liver, blood) to shed light on the species-specific habitat use during the autumn migration period using standard ellipse areas (SEAc). Further, we used stable isotope ratios of non-exchangeable hydrogen (δ²H(K)) in fur keratin to assess the breeding origin of bats. We inferred from isotopic composition (δ¹³C, δ¹⁵N) of fur keratin that isotopic niche dimensions of P. nathusii was distinct from that of N. noctula and P. pipistrellus, probably because P. nathusii was using more aquatic habitats than the other two species. Isoscape origin models supported that traveled distances before dying at wind turbines was largest for P. nathusii, intermediate for N. noctula, and shortest for P. pipistrellus. Isotopic niche dimensions calculated for each sample type separately reflected the species' migratory behavior. Pipistrellus pipistrellus and N. noctula showed similar isotopic niche breadth across all tissue types, whereas SEAc values of P. nathusii increased in tissues with slow turnaround time. Isotopic data suggested that P. nathusii consistently used aquatic habitats throughout the autumn period, whereas N. noctula showed a stronger association with terrestrial habitats during autumn compared to the pre-migration period.

Iron isotope evidence for the origin of the Moon through partial vaporisation

NASA Astrophysics Data System (ADS)

Poitrasson, F.; Halliday, A. N.; Lee, D. C.; Levasseur, S.; Teutsch, N.

2003-04-01

The currently favoured scenario of the origin of the Moon through a Giant Impact, in which a body approaching the size of Mars hit the proto-Earth and yielded ejecta leading to the Moon remains hypothetical. This theory predicts extremely high temperatures, sufficient to induce planetary-scale vaporisation. We have thus measured the Fe isotope composition of the Earth, Moon and meteorites thought to come from Mars and asteroid Vesta to see if this highly energetic process left an imprint. Our analytical method involves Fe purification through anionic exchange chromatography and iron isotope measurement by MC-ICP-MS. Repeat analyses of standards define 57Fe/54Fe reproducibility of 0.09 per mil (2SD). Meteorites from Mars and Vesta, give δ57Fe/54Fe values indistinguishable to the international IRMM-14 Fe isotopic standard. In contrast, ten lunar samples, spanning a large range in composition give a mean 0.2 per mil heavier than IRMM-14. Mantle-derived terrestrial samples yield a mean δ57Fe/54Fe intermediate between the Moon and Mars. Student's t-tests show that the terrestrial mean is significantly different from the averages of Mars, Vesta and the Moon at a confidence level of more than 99%. These new Fe isotope measurements, combined with previous oxygen isotope data rule out alternative theories of the origin of the Moon through co-accretion, capture or fission from the proto-Earth. In contrast, vaporisation of bodies in space can generate kinetic isotope fractionation, leaving residues with a relatively heavier isotope signature. Hence, the Earth, and especially the Moon, can represent such heavy residues having lost part of their light iron through vaporisation. Only the Giant Impact can account for the energy required to partially melt and vaporise major portion of the Earth and the impactor. Rayleigh kinetic isotope calculations suggest that the Moon lost up to 1% of its iron, whereas the Earth lost up to 0.5% during partial vaporisation.

Patterns of Storage, Synthesis and Changing Light Levels Revealed by Carbon Isotope Microsampling within Eocene Metasequoia Tree Rings

NASA Astrophysics Data System (ADS)

Jahren, H.; Sternberg, L.

2005-12-01

Fossil tree rings from Axel Heiberg Island were microanalyzed for δ13C value in order to assess patterns of tree growth and carbon storage within the Middle Eocene (~45 Ma) Arctic paleoenvironment. Wood from four Metasequoia-type individuals was subsampled for analysis: each individual fossil consisted of between 4 and 10 large (~1 cm thick) consecutive tree rings. One of the fossils displayed an obvious concentric pattern, allowing for the determination of the direction of growth with isotopic pattern. Each ring was divided into ~1 mm thick subsamples, resulting in 5-10 δ13C value determinations per period of ring growth (i.e., growing season). All rings revealed a distinct pattern that was characteristic across growing seasons and across individual fossils. Early in the season, δ13C was at its highest value but descended systematically and sharply to its lowest value at the end of the growing season. Total decrease ranged between 3 and 5 ‰ over the course of each growing season. Identical patterns were observed in the δ13C value of alpha-cellulose isolated from each subsample, indicating that the trends observed did not represent changing levels of secondary metabolites, but rather a seasonal adjustment in the bulk source of carbon used during biosynthesis. Our results are consistent with the following annual pattern of wood synthesis 1.) complete dependence on the mobilization of stored carbon compounds early in the growing season; 2.) systematically increasing use of actively-acquired photosynthate during the growing season; 3.) complete reliance on active photosynthate by the end of the growing season. An additional and significant source of 13C discrimination is declining light levels late in the growing season, and likely contributes to the extreme pattern of δ13C decrease seen across each ring. Our results mimic those seen from modern broadleaf deciduous trees (Helle & Schlesser 2004), but differ from those seen in modern conifers (Barbour et al 2002), underlining the important influence of dormancy, storage and changing light levels on carbon cycling within the Paleogene polar forests. Helle & Schleser 2004: Plant, Cell and Environment 27:367-380. Barbour, Walcroft & Farquhar 2002: Plant, Cell and Environment 25: 1483-1499.

Stable isotopes in nitrous oxide emitted from tropical rain forest soils and agricultural fields: Implications for the global atmospheric nitrous oxide budget

NASA Astrophysics Data System (ADS)

Perez, Tibisay Josefina

Nitrous oxide (N2O) is an important greenhouse gas and is the primary source of NOx in the stratosphere. Large uncertainties exist in the global N2O budget, mainly due to the high uncertainty associated with source estimates. Recently, stable isotopes of 15N and 18O have been proposed as a tool to better constrain the N2O global budget. This thesis develops analytical methods for constraining and measuring stable isotopes in N2O emitted from soils and reports initial investigations of N2O isotopes from the largest sources in the global N2O budget: tropical rain forest soils and agricultural fields. We found significant differences in the isotopic composition of N 2O emitted from tropical rain forest soils and fertilized agricultural fields. Differences were largest for 15N. Emission-weighted δ 15N-N2O were -26 +/- 2.5‰ s.d., n = 3 (Costa Rican forest), -6.6 +/- 11.3‰ s.d. n = 14 (Brazilian forest) and -36.7 +/- 9.2‰ s.d. n = 19 (Mexican agricultural field and Costa Rican Papaya plantation). We attribute the large range in δ 15N from tropical rain forests, where denitrification is the main source of N2O, to differences in the degree of N2O to N2 reduction. We attribute the very light δ15N values in fertilized agricultural fields to the enhanced nitrogen availability in the soils which facilitates higher fractionation between substrates and products. Similarly, in the Brazilian tropical forest lighter δ 15N-N2O from a local area of enhanced emission is attributed to locally more abundant N- substrate in that particular soil site. If the increase of N2O in the troposphere over the past 100 years is attributable to increased use of N fertilizer, and assuming that light δ 15N- N2O isotopic values are associated with agricultural practices, we expect the δ15N-N2O in the troposphere to have decreased since pre-industrial times. Theoretically, comparison of 15N and 18O signature of emitted N2O with precursors species (NO3 -, NH4+, H2O and O 2) should uniquely determine (a)the fraction of N2O produced by nitrification versus denitrification and (b)the fractionation of N2O reduced to N2. However, for this approach to be useful, in situ determinations of fractionation factors associated with nitrification and denitrification in soils are required.

Zircon oxygen isotopes reveal Ivrea-Verbano Zone source characteristics of the Sesia Valley Caldera

NASA Astrophysics Data System (ADS)

Economos, R. C.; Quick, J. E.; Sinigoi, S.; de Silva, S. L.

2013-12-01

The Sesia Valley, in the Italian Alpine foothills, contains >14 km diameter caldera adjacent to and structurally shallower than the famous Ivrea-Verbano Zone deep crustal section. The caldera and its associated eruptive sequence presents opportunity to explore volcanic magmatism in light of exposed and well characterized source candidates, namely lower crustal gabbros and the mid-crustal metasedimentary Kinzigite formation. Original geochemical characteristics of volcanic units have been obscured by the effects of subsequent hydrothermal alteration. The resistance of the mineral zircon to fluid alteration makes it a prime candidate for the preservation and exploration of these geochemical signals, such as O isotopes. Lower crustal gabbros in the Ivrea-Verbano Zone have broadly monotonic whole-rock δ18O values between +8 and +9‰VSMOW (Sinigoi et al., 1994). Kinzigites preserve a much higher and more heterogeneous δ18O values, typically ranging from +10‰ up to +15‰ (Baker, 1990). Zircons from the caldera-forming rhyolitic eruption units and a pre-caldera rhyodacitic unit were analyzed by ion microprobe at UCLA for in-situ oxygen isotope ratios. External reproducibility of within-mount standard R33 grains range from 0.27 to 0.36‰. Rhyolites from the caldera-forming eruption yield a range of δ18O(zircon) values from 6.3‰ to 8.3‰. This range displays rough correlation with CL activity - CL active grains have lower δ18O(zircon) values while CL dark grains have higher δ18O(zircon) values. This variation may correlate with U contents, which are notoriously low in zircons from Ivrea-Verbano Zone gabbros. We argue that the range in O isotope values suggests zircons are a good fit for magmas influenced by gabbro and Kinzigite sources. However, these zircons do not appear to be inherited directly from either the gabbro or Kinzigite sources as their O isotope signatures are typically intermediate between the two. The pre-caldera rhyodacite sample displays a much broader range of δ18O(zircon) values, from +6 to +10‰. These values, when corrected for melt-zircon isotopic fractionation, are an excellent match for mafic and felsic sources in the Ivrea-Verbano Zone. Thus, volcanic rocks of the Sesia Valley share spatial, temporal, and geochemical affinities for Ivrea-Verbano Zone sources, strengthening the body of evidence that the Sesia Valley Caldera represents the upper crustal portions of a complete crustal section contiguous with these mid- and lower-crustal Alpine exposures. These data demonstrate a difference in extent of hybridization of source signals in the rhyodacite (little homogenization) compared to the caldera-forming eruption (more homogenization). This suggests a record of variation in magmatic processes for precursor and climactic eruptions that is potentially related to the thermal maturation of the volcanic system and warrants additional study. Additional work on trace element concentrations, including Ti thermometry, on these grains will further elucidate these processes and their relationship to known zircon-bearing sources in the mid- to deep-crust of the Ivrea-Verbano Zone.

Exploring Archean seawater sulfate via triple S isotopes in carbonate associated sulfate.

NASA Astrophysics Data System (ADS)

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

2015-12-01

Multiple sulfur isotope ratios in Archean sedimentary rocks provide powerful insights into the behavior of the ancient sulfur cycle, the redox state of fluid Earth, and the timing of the rise of atmospheric oxygen [1]. The Archean sulfur isotope record is marked by pronounced mass-independent fractionation (Δ33S≠0)—signatures widely interpreted as the result of SO2 photolysis from "short-wavelength" UV light resulting in a reduced phase carrying positive Δ33S values (ultimately recorded in pyrite) and an oxidized phase carrying negative Δ33S values carried by sulfate [2]. Support for this hypothesis rests on early laboratory experiments and observations of negative Δ33S from barite occurrences in mixed volcanic sedimentary strata in Mesoarchean greenstone terrains. Despite forming the framework for understanding Archean sulfur cycle processes, this hypothesis is still largely untested, notably due to the lack of sulfate minerals in Archean strata. Using a new MC-ICP-MS approach combined with petrography and X-ray spectroscopy we have generated a growing S isotope dataset from CAS extracted from Archean carbonates from a range of sedimentary successions, including: the 2.6 to 2.521 Ga Campbellrand-Malmani carbonate platform (Transvaal Supergroup, South Africa), 2.7 Ga Cheshire Formation (Zimbabwe), and 2.9 Ga Steep Rock Formation (Canada). Importantly, we observe positive δ34S and Δ33S values across a range of different lithologies and depositional environments. These results demonstrate that dissolved sulfate in seawater was characterized by positive Δ33S values—a result that receives additional support from recent laboratory and theoretical experiments [e.g. 4, 5]. [1] Farquhar et al., 2000, Science [2] Farquhar et al., 2001, Journal of Geophysical Research: Planets [3] Paris et al., 2014, Science. [4] Whitehill et al., 2013, Proceedings of the National Academy of Sciences. [5] Claire et al., 2014 Geochimica et Cosmochimica Acta

Effect of a Jurassic oceanic anoxic event on belemnite ecology and evolution

PubMed Central

Ullmann, Clemens Vinzenz; Thibault, Nicolas; Ruhl, Micha; Hesselbo, Stephen P.; Korte, Christoph

2014-01-01

The Toarcian oceanic anoxic event (T-OAE; ∼183 million y ago) is possibly the most extreme episode of widespread ocean oxygen deficiency in the Phanerozoic, coinciding with rapid atmospheric pCO2 increase and significant loss of biodiversity in marine faunas. The event is a unique past tipping point in the Earth system, where rapid and massive release of isotopically light carbon led to a major perturbation in the global carbon cycle as recorded in organic and inorganic C isotope records. Modern marine ecosystems are projected to experience major loss in biodiversity in response to enhanced ocean anoxia driven by anthropogenic release of greenhouse gases. Potential consequences of this anthropogenic forcing can be approximated by studying analog environmental perturbations in the past such as the T-OAE. Here we present to our knowledge the first organic carbon isotope record derived from the organic matrix in the calcite rostra of early Toarcian belemnites. We combine both organic and calcite carbon isotope analyses of individual specimens of these marine predators to obtain a refined reconstruction of the early Toarcian global exogenic carbon cycle perturbation and belemnite paleoecology. The organic carbon isotope data combined with measurements of oxygen isotope values from the same specimens allow for a more robust interpretation of the interplay between the global carbon cycle perturbation, environmental change, and biotic response during the T-OAE. We infer that belemnites adapted to environmental change by shifting their habitat from cold bottom waters to warm surface waters in response to expanded seafloor anoxia. PMID:24982187

Isotope shift, nonlinearity of King plots, and the search for new particles

NASA Astrophysics Data System (ADS)

Flambaum, V. V.; Geddes, A. J.; Viatkina, A. V.

2018-03-01

We derive a mean-field relativistic formula for the isotope shift of an electronic energy level for arbitrary angular momentum; we then use it to predict the spectra of superheavy metastable neutron-rich isotopes belonging to the hypothetical island of stability. Our results may be applied to the search for superheavy atoms in astrophysical spectra using the known values of the transition frequencies for the neutron-deficient isotopes produced in the laboratory. An example of a relevant astrophysical system may be the spectra of the Przybylski's star where superheavy elements up to Z =99 have been possibly identified. In addition, it has been recently suggested to use the measurements of King plot nonlinearity in a search for hypothetical new light bosons. On the other hand, one can find the nonlinear corrections to the King plot arising already in the standard model framework. We investigate contributions to the nonlinearity arising from relativistic effects in the isotope field shift, the nuclear polarizability, and many-body effects. It is found that the nuclear polarizability contribution can lead to the significant deviation of the King plot from linearity. Therefore, the measurements of the nonlinearity of King plots may be applied to obtain the nuclear polarizability change between individual isotopes. We then proceed with providing a rough analytical estimate of the nonlinearity arising solely from the effect of a hypothetical scalar boson. Our predictions give theoretical limitations on the sensitivity of the search for new interactions and should help to identify the most suitable atoms for corresponding experiments.

Energy and lighting

NASA Astrophysics Data System (ADS)

Berman, Samuel

1985-11-01

Advances in research for new types of lighting with increased efficacies (lumens/watt) are discussed in the following areas: (1) high-frequency, solid-state ballasts, (2) isotopic enhancement of mercury isotopes, (3) magnetic augmentation, (4) electrodeless, ultra-high frequency, (5) tuned phosphors, (6) two-photon phosphors, (7) heat mirrors, and (8) advanced control circuits to take advantage of daylight and occupancy. As of 1985, improvements in efficacy have been accomplished on an economic basis to save energy for (1) high frequency ballasts (25%), (2) isotopic enhancement (5%), and (8) advanced control circuits (up to 50%). Most of these advances depend on a deeper understanding of the weakly ionized plasma as a radiating and diffusing medium.

Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9-10°N

USGS Publications Warehouse

Rouxel, O.; Shanks, Wayne C.; Bach, W.; Edwards, K.J.

2008-01-01

In this study, we report on coupled Fe- and S-isotope systematics of hydrothermal fluids and sulfide deposits from the East Pacific Rise at 9–10°N to better constrain processes affecting Fe-isotope fractionation in hydrothermal environments. We aim to address three fundamental questions: (1) Is there significant Fe-isotope fractionation during sulfide precipitation? (2) Is there significant variability of Fe-isotope composition of the hydrothermal fluids reflecting sulfide precipitation in subsurface environments? (3) Are there any systematics between Fe- and S-isotopes in sulfide minerals? The results show that chalcopyrite, precipitating in the interior wall of a hydrothermal chimney displays a limited range of δ56Fe values and δ34S values, between − 0.11 to − 0.33‰ and 2.2 to 2.6‰ respectively. The δ56Fe values are, on average, slightly higher by 0.14‰ relative to coeval vent fluid composition while δ34S values suggest significant S-isotope fractionation (− 0.6 ± 0.2‰) during chalcopyrite precipitation. In contrast, systematically lower δ56Fe and δ34S values relative to hydrothermal fluids, by up to 0.91‰ and 2.0‰ respectively, are observed in pyrite and marcasite precipitating in the interior of active chimneys. These results suggest isotope disequilibrium in both Fe- and S-isotopes due to S-isotopic exchange between hydrothermal H2S and seawater SO42− followed by rapid formation of pyrite from FeS precursors, thus preserving the effects of a strong kinetic Fe-isotope fractionation during FeS precipitation. In contrast, δ56Fe and δ34S values of pyrite from inactive massive sulfides, which show evidence of extensive late-stage reworking, are essentially similar to the hydrothermal fluids. Multiple stages of remineralization of ancient chimney deposits at the seafloor appear to produce minimal Fe-isotope fractionation. Similar affects are indicated during subsurface sulfide precipitation as demonstrated by the lack of systematic differences between δ56Fe values in both high-temperature, Fe-rich black smokers and lower-temperature, Fe-depleted vents.

Dry season limnological conditions and basin geology exhibit complex relationships with δ13C and δ15N of carbon sources in four Neotropical floodplains.

PubMed

Zaia Alves, Gustavo H; Hoeinghaus, David J; Manetta, Gislaine I; Benedito, Evanilde

2017-01-01

Studies in freshwater ecosystems are seeking to improve understanding of carbon flow in food webs and stable isotopes have been influential in this work. However, variation in isotopic values of basal production sources could either be an asset or a hindrance depending on study objectives. We assessed the potential for basin geology and local limnological conditions to predict stable carbon and nitrogen isotope values of six carbon sources at multiple locations in four Neotropical floodplain ecosystems (Paraná, Pantanal, Araguaia, and Amazon). Limnological conditions exhibited greater variation within than among systems. δ15N differed among basins for most carbon sources, but δ13C did not (though high within-basin variability for periphyton, phytoplankton and particulate organic carbon was observed). Although δ13C and δ15N values exhibited significant correlations with some limnological factors within and among basins, those relationships differed among carbon sources. Regression trees for both carbon and nitrogen isotopes for all sources depicted complex and in some cases nested relationships, and only very limited similarity was observed among trees for different carbon sources. Although limnological conditions predicted variation in isotope values of carbon sources, we suggest the resulting models were too complex to enable mathematical corrections of source isotope values among sites based on these parameters. The importance of local conditions in determining variation in source isotope values suggest that isotopes may be useful for examining habitat use, dispersal and patch dynamics within heterogeneous floodplain ecosystems, but spatial variability in isotope values needs to be explicitly considered when testing ecosystem models of carbon flow in these systems.

Dry season limnological conditions and basin geology exhibit complex relationships with δ13C and δ15N of carbon sources in four Neotropical floodplains

PubMed Central

Hoeinghaus, David J.; Manetta, Gislaine I.; Benedito, Evanilde

2017-01-01

Studies in freshwater ecosystems are seeking to improve understanding of carbon flow in food webs and stable isotopes have been influential in this work. However, variation in isotopic values of basal production sources could either be an asset or a hindrance depending on study objectives. We assessed the potential for basin geology and local limnological conditions to predict stable carbon and nitrogen isotope values of six carbon sources at multiple locations in four Neotropical floodplain ecosystems (Paraná, Pantanal, Araguaia, and Amazon). Limnological conditions exhibited greater variation within than among systems. δ15N differed among basins for most carbon sources, but δ13C did not (though high within-basin variability for periphyton, phytoplankton and particulate organic carbon was observed). Although δ13C and δ15N values exhibited significant correlations with some limnological factors within and among basins, those relationships differed among carbon sources. Regression trees for both carbon and nitrogen isotopes for all sources depicted complex and in some cases nested relationships, and only very limited similarity was observed among trees for different carbon sources. Although limnological conditions predicted variation in isotope values of carbon sources, we suggest the resulting models were too complex to enable mathematical corrections of source isotope values among sites based on these parameters. The importance of local conditions in determining variation in source isotope values suggest that isotopes may be useful for examining habitat use, dispersal and patch dynamics within heterogeneous floodplain ecosystems, but spatial variability in isotope values needs to be explicitly considered when testing ecosystem models of carbon flow in these systems. PMID:28358822

Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways

NASA Astrophysics Data System (ADS)

Albarede, F.; Telouk, P.; Lamboux, A.; Jaouen, K.; Balter, V.

2011-12-01

Despite its potential importance for understanding perturbations in the Fe-Cu homeostatic pathways, the natural isotopic variability of these metals in the human body remains unexplored. We measured the Fe, Cu, and Zn isotope compositions of total blood, serum, and red blood cells of ~50 young blood donors by multiple-collector ICP-MS after separation and purification by anion exchange chromatography. Zn is on average 0.2 permil heavier in erythrocytes (δ 66Zn=0.44±0.33 permil) with respect to serum but shows much less overall isotopic variability than Fe and Cu, which indicates that isotope fractionation depends more on redox conditions than on ligand coordination. On average, Fe in erythrocytes (δ 56Fe=-2.59±0.47 permil) is isotopically light by 1-2 permil with respect to serum, whereas Cu in erythrocytes (δ 65Cu=0.56±0.50 permil) is 0.8 percent heavier. Fe and Cu isotope compositions clearly separate erythrocytes of men and women. Fe and Cu from B-type men erythrocytes are visibly more fractionated than all the other blood types. Isotope compositions provide an original method for evaluating metal mass balance and homeostasis. Natural isotope variability shows that the current models of Fe and Cu erythropoiesis, which assume that erythropoiesis is restricted to bone marrow, violate mass balance requirements. It unveils unsuspected major pathways for Fe, with erythropoietic production of isotopically heavy ferritin and hemosiderin, and for Cu, with isotopically light Cu being largely channeled into blood and lymphatic circulation rather than into superoxide dismutase-laden erythrocytes. Iron isotopes provide an intrinsic measuring rod of the erythropoietic yield, while Cu isotopes seem to gauge the relative activity of erythropoiesis and lymphatics.

Chemical leaching methods and measurements of marine labile particulate Fe

NASA Astrophysics Data System (ADS)

Revels, B. N.; John, S.

2012-12-01

Iron (Fe) is an essential nutrient for life. Yet its low solubility and concentration in the ocean limits marine phytoplankton productivity in many regions of the world. Dissolved phase Fe (<0.4μm) has traditionally been considered the most biologically accessible form, however, the particulate phase (>0.4μm) may contain an important, labile reservoir of Fe that may also be available to phytoplankton. However, concentration data alone cannot elucidate the sources of particulate Fe to the ocean and to what extent particulate iron may support phytoplankton growth. Isotopic analysis of natural particles may help to elucidate the biogeochemical cycling of Fe, though it is important to find a leaching method which accesses bioavailable Fe. Thirty-three different chemical leaches were performed on a marine sediment reference material, MESS-3. The combinations included four different acids (25% acetic acid, 0.01M HCl, 0.5M HCl, 0.1M H2SO4 at pH2), various redox conditions (0.02M hydroxylamine hydrochloride or 0.02M H2O2), three temperatures (25°C, 60°C, 90°C), and three time points (10 minutes, 2 hours, 24 hours). Leached Fe concentrations varied from 1mg/g to 35mg/g, with longer treatment times, stronger acids, and hotter temperatures generally associated with an increase in leached Fe. δ56Fe in these leaches varied from -1.0‰ to +0.2‰. Interestingly, regardless of leaching method used, there was a very similar relationship between the amount of Fe leached from the particles and the δ56Fe of this iron. Isotopically lighter δ56Fe values were associated with smaller amounts of leached Fe whereas isotopically heavier δ56Fe values were associated with larger amounts of leached Fe. Two alternate hypotheses could explain these data. Either, the particles may contain pools of isotopically light Fe that are easily accessed early in dissolution, or isotopically light Fe may be preferentially leached from the particle due to a kinetic isotope effect during dissolution. To explore the first hypothesis, we modeled dissolution of Fe from particles assuming two separate pools, labile and refractory. The model produces a good fit to the data assuming 3mg/g of a labile Fe pool with δ56Fe = -0.9‰ and a refractory Fe pool with δ56Fe = +0.1‰. If the second hypothesis is true, and there is a kinetic isotope effect during dissolution, the similar relationship between amount of Fe leached and δ56Fe for both organic and mineral acids suggests that Fe is leached from particles via proton-promoted dissolution. Several of these leaching techniques will be employed on sediment trap material from the Cariaco Basin to further investigate the relationship between δ56Fe and the labile, bioavailable fraction of iron particles. A leach or series of leaches will be chosen to provide the most useful information about the bioavailability of iron from particles, and they will be applied to filtered particle samples from portions of the US GEOTRACES A10 (North Atlantic) transect. δ56Fe values from particulate material in these regions will provide a better understanding of the sources of particulate iron to the ocean, and may help to trace how particulate iron is involved in global biogeochemical cycles.

Using Triple Oxygen Isotope Analyses of Biogenic Carbonate to Reconstruct Early Triassic Ocean Oxygen Isotopic Values and Temperatures

NASA Astrophysics Data System (ADS)

Gibbons, J. A.; Sharp, Z. D.; Atudorei, V.

2017-12-01

The calcite-water triple oxygen isotope fractionation is used to determine isotopic equilibrium and ancient ocean oxygen isotopic values and temperatures. Unlike conventional δ18O analysis where the formation water's isotopic value is assumed, paired δ17O-δ18O measurements allow for the water's isotopic composition to be calculated because there is only one unique solution for equilibrium fractionation using Δ17O-δ18O values (where Δ17O=δ17O-0.528δ18O). To a first approximation, the calcite-water equilibrium fractionation factor, θ (where θ=ln17α/ln18α), varies with temperature by 0.00001/°. The calcite-water equilibrium fractionation line was determined at two temperatures, 30° and 0°, by using modern carbonate samples that formed in ocean water with a δ18O value of 0‰. The θ values for the 30° and 0° samples are 0.52515 and 0.52486, respectively. Oxygen values were measured using complete fluorination in nickel tubes with BrF5 as the reaction reagent. We calibrated all oxygen values to the SMOW-SLAP scale by measuring SMOW, SLAP, San Carlos olivine, NBS-18, NBS-19, and PDB. The triple oxygen isotope calcite-water equilibrium fractionation line was applied to well preserved Early Triassic ammonite shells from the Western United States. Based on paired δ17O-δ18O measurements, the samples did not form in equilibrium with an ice-free ocean with an oxygen isotopic value of -1‰ or the modern ocean value of 0‰. Assuming the calcite is still primary and formed in equilibrium with the ocean water, our data indicate that the δ18O value of the ocean in the early Triassic was 3-5‰ lower than modern. Samples from the Smithian thermal maximum formed in water 10° warmer than samples from after the thermal maximum. Paired δ17O-δ18O measurements of pristine ancient carbonates may provide a better understanding of past ocean conditions during climate change events.

N-loss isotope effects in the Peru oxygen minimum zone studied using a mesoscale eddy as a natural tracer experiment

NASA Astrophysics Data System (ADS)

Bourbonnais, Annie; Altabet, Mark A.; Charoenpong, Chawalit N.; Larkum, Jennifer; Hu, Haibei; Bange, Hermann W.; Stramma, Lothar

2015-06-01

Mesoscale eddies in Oxygen Minimum Zones (OMZs) have been identified as important fixed nitrogen (N) loss hotspots that may significantly impact both the global rate of N-loss as well as the ocean's N isotope budget. They also represent "natural tracer experiments" with intensified biogeochemical signals that can be exploited to understand the large-scale processes that control N-loss and associated isotope effects (ɛ; the ‰ deviation from 1 in the ratio of reaction rate constants for the light versus heavy isotopologues). We observed large ranges in the concentrations and N and O isotopic compositions of nitrate (NO3-), nitrite (NO2-), and biogenic N2 associated with an anticyclonic mode-water eddy in the Peru OMZ during two cruises in November and December 2012. In the eddy's center where NO3- was nearly exhausted, we measured the highest δ15N values for both NO3- and NO2- (up to ~70‰ and 50‰) ever reported for an OMZ. Correspondingly, N deficit and biogenic N2-N concentrations were also the highest near the eddy's center (up to ~40 µmol L-1). δ15N-N2 also varied with biogenic N2 production, following kinetic isotopic fractionation during NO2- reduction to N2 and, for the first time, provided an independent assessment of N isotope fractionation during OMZ N-loss. We found apparent variable ɛ for NO3- reduction (up to ~30‰ in the presence of NO2-). However, the overall ɛ for N-loss was calculated to be only ~13-14‰ (as compared to canonical values of ~20-30‰) assuming a closed system and only slightly higher assuming an open system (16-19‰). Our results were similar whether calculated from the disappearance of DIN (NO3- + NO2-) or from the appearance of N2 and changes in isotopic composition. Further, we calculated the separate ɛ values for NO3- reduction to NO2- and NO2- reduction to N2 of ~16-21‰ and ~12‰, respectively, when the effect of NO2- oxidation could be removed. These results, together with the relationship between N and O of NO3- isotopes and the difference in δ15N between NO3- and NO2-, confirm a role for NO2- oxidation in increasing the apparent ɛ associated with NO3- reduction. The lower ɛ for N-loss calculated in this study could help reconcile the current imbalance in the global N budget if representative of global OMZ N-loss.

Method and apparatus for separation of heavy and tritiated water

DOEpatents

Lee, Myung W.

2001-01-01

The present invention is a bi-thermal membrane process for separating and recovering hydrogen isotopes from a fluid containing hydrogen isotopes, such as water and hydrogen gas. The process in accordance with the present invention provides counter-current cold and hot streams of the fluid separated with a thermally insulating and chemically transparent proton exchange membrane (PEM). The two streams exchange hydrogen isotopes through the membrane: the heavier isotopes migrate into the cold stream, while the lighter isotopes migrate into the hot stream. The heavy and light isotopes are continuously withdrawn from the cold and hot streams respectively.

Food-web structure of seep sediment macrobenthos from the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Demopoulos, Amanda W. J.; Gualtieri, Daniel; Kovacs, Kaitlin

2010-11-01

The slope environment of the Gulf of Mexico (GOM) supports dense communities of seep megafaunal invertebrates that rely on endosymbiotic bacteria for nutrition. Seep sediments also contain smaller macrofaunal invertebrates whose nutritional pathways are not well understood. Using stable-isotope analysis, we investigate the utilization of chemosynthetically fixed and methane-derived organic matter by macrofauna. Biological sampling was conducted in three lower-slope GOM seep environs: Green Canyon (GC852, 1428 m), Atwater Valley (AT340, 2230 m), and Alaminos Canyon (AC601, 2384 m). Infaunal δ13C and δ15N exhibited a broad range of values; most infauna appeared to be heterotrophic, although several taxa had very light δ15N and δ13C values, indicating possible reliance on chemoautotrophic symbioses. The lightest δ13C and δ15N values were observed in nematodes (δ13C=-54.6±0.1‰, δ15N=-6.1±0.2‰) and one gastropod (δ13C=-54.1‰, δ15N=-1.1‰) from Green Canyon. Mixing-model results indicated that sulfur-oxidizing Beggiatoa may be an important food source for seep infauna; the rate of utilization ranged from 60% to 100% at Green Canyon and Atwater Valley. The overall range in isotope values was similar across the three sites, suggesting that biogeochemical processes may be very similar in these geographically distinct areas.

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 isotopic composition toward natural values. The Mediterranean samples have isotopic compositions within error of the lighter end of the range reported for Mediterranean seawater. The Zn isotopic compositions of French oysters and mussels (δ66/64Zn = 0.39 to 0.46‰) are identical to those reported for North Atlantic seawater, with the exception of the much heavier compositions of oysters (δ66/64Zn = 1.03 to 1.15‰) from the polluted Gironde estuary. In agreement with Cd and Zn isotopic compositions, the Pb isotopic compositions of the French bivalves indicate primarily industrial (as opposed to automotive) sources; this is consistent with the collection of most of the French bivalve samples in 2004, after the complete phase-out of leaded gasoline in France. This study demonstrates the effective use of Cd and Zn isotopes to trace anthropogenic sources in the environment and the benefit of combining these tools with Pb isotope “fingerprinting” techniques to identify processes contributing metals. Use of these new geochemical tools requires site-specific knowledge of potential metal sources and their isotopic compositions.

Origin of low δ26Mg basalts with EM-I component: Evidence for interaction between enriched lithosphere and carbonated asthenosphere

NASA Astrophysics Data System (ADS)

Tian, H.; Yang, W.; Li, S. G.; Ke, S.; Chu, Z. Y.

2016-12-01

Many studies have focused on the interactions between recycled materials and depleted mantle to explain the origins of EM and HIMU components (e.g., Cohen and O'Nions, 1982; White and Hofmann, 1982). However, little is known about the interactions between recycled materials and enriched mantle and the associated consequences, e.g., late recycled crustal material overprints mantle previously enriched by earlier recycling events of the crust. Recently, light Mg isotopic composition of the basalts from North China Craton (NCC) and South China Block (SCB) has been attributed to recycled carbonate metasomatism from subducted Pacific slab (Yang et al., 2012; Huang et al., 2015). If this explanation is correct, the Cenozoic basalts from Northeast (NE) China should also contain light Mg isotopic compositions. The basalts from NE China have EMI Sr-Nd-Pb isotopic features that are distinct from the NCC and SCB basalts, indicating the contribution of an enriched mantle source (Choi et al., 2006; Chu et al., 2013). Therefore, Mg isotopic compositions of the Cenozoic basalts from NE China will help to determine the interaction between recycled sedimentary carbonates and an enriched mantle. Consistent with the hypothesis, our results show that the Cenozoic basalts from Wudalianchi and Erkeshan, NE China, have homogeneous and light Mg isotopic compositions (δ26Mg =-0.57 to -0.46‰). Based on the similarity to the basalts from NCC and SCB, their light Mg isotopic feature should also be derived from carbonate metasomatism (i.e. carbonated asthenosphere). In addition to that, a question arise that why the interaction between carbonated asthenosphere and the EM-I SLCM significantly modify the trace element and Sr-Nd-Pb isotopic composition of the mantle-derived melt, but have little effect on the Mg isotopes? The possible mechanism is the interaction between low SiO2 melt and peridotite, which converts pyroxene to olivine, as reported in previous studies (e.g., Kelemen et al., 1992; Edwards and Malpas, 1996; Zhou et al., 1996, 2014). During the interaction, the trace elements of the EM-I SCLM largely entered the melt, and all Mg was transferred from Opx and Cpx into the newly formed olivine. Consequently, the Wudalianchi and Erkeshan basalts preserve low δ26Mg and obtain EM-I Sr-Nd-Pb isotopic compositions (Fig. 1).

Patterns in Stable Isotope Values of Nitrogen and Carbon in ...

EPA Pesticide Factsheets

Stable isotope measurements of nitrogen and carbon (15N, 13ddC) are often used to characterize estuarine, nearshore, and open ocean ecosystems. Reliable information about the spatial distribution of base-level stable isotope values, often represented by primary producers, is critical to interpreting values in these ecosystems. While base-level isotope data are generally readily available for estuaries, nearshore coastal waters, and the open ocean, the continental shelf is less studied. To address this, and as a first step toward developing a surrogate for base-level isotopic signature in this region, we collected surface and deep water samples from the United States’ eastern continental shelf in the Western Atlantic Ocean, from the Gulf of Maine to Cape Hatteras, periodically between 2000 and 2013. During the study, particulate matter 15dN values ranged from 0.8 to 17.4‰, and 13dC values from −26.4 to −15.6‰over the region. We used spatial autocorrelation analysis and random forest modeling to examine the spatial trends and potential environmental drivers of the stable isotope values. We observed general trends toward lower values for both nitrogen and carbon isotopes at the seaward edge of the shelf. Conversely, higher 15dN and 13dC values were observed on the landward edge of the shelf, in particular in the southern portion of the sampling area. Across all sites, the magnitude of the difference between the 15dN of subsurface and surface particulate m

A status of progress for the Laser Isotope Separation (LIS) process

NASA Technical Reports Server (NTRS)

Delionback, L. M.

1976-01-01

An overview of the Laser Isotope Separation (LIS) methodology is given together with illustrations showing a simplified version of the LIS technique, an example of the two-photon photoionization category, and a diagram depicting how the energy levels of various isotope influence the LIS process. Applications were proposed for the LIS system which, in addition to enriching uranium, could in themselves develop into programs of tremendous scope and breadth. These include the treatment of radioactive wastes from light-water nuclear reactors, enriching the deuterium isotope to make heavy-water, and enriching the light isotopes of such elements as titanium for aerospace weight-reducing programs. Economic comparisons of the LIS methodology with the current method of gaseous diffusion indicate an overwhelming advantage; the laser process promises to be 1000 times more efficient. The technique could also be utilized in chemical reactions with the tuned laser serving as a universal catalyst to determine the speed and direction of a chemical reaction.

Solar wind noble gases and nitrogen in metal from lunar soil 68501

NASA Technical Reports Server (NTRS)

Becker, Richard H.; Pepin, Robert O.

1994-01-01

Noble gases and N were analyzed in handpicked metal separates from lunar soil 68501 by a combination of step-wise combustions and pyrolyses. Helium and Ne were found to be unfractionated with respect to one another when normalized to solar abundances, for both the bulk sample and for all but the highest temperature steps. However, they are depleted relative to Ar, Kr and Xe by at least a factor of 5. The heavier gases exhibit mass-dependent fractionation relative to solar system abundance ratios but appear unfractionated, both in the bulk metal and in early temperature steps, when compared to relative abundances derived from lunar ilmenite 71501 by chemical etching, recently put forward as representing the abundance ratios in solar wind. Estimates of the contribution of solar energetic particles (SEP) to the originally implanted solar gases, derived from a basic interpretation of He and Ne isotopes, yield values of about 10%. Analysis of the Ar isotopes requires a minimum of 20% SEP, and Kr isotopes, using our preferred composition for solar wind Kr, yield a result that overlaps both these values. It is possible to reconcile the data from these gases if significant loss of solar wind Ar, Kr and presumably Xe has occurred relative to the SEP component, most likely by erosive processes that are mass independent, although mass-dependent losses (Ar greater than Kr greater than Xe) cannot be excluded. If such losses did occur, the SEP contribution to the solar implanted gases must have been no more than a few percent. Nitrogen is a mixture of indigenous meteoritic N, whose isotopic composition is inferred to be relatively light, and implanted solar N, which has probably undergone diffusive redistribution and fractionation. If the heavy noble gases have not undergone diffusive loss, then N/Ar in the solar wind can be inferred to be at least several times the accepted solar ratio. The solar wind N appears, even after correction for fractionation effects, to have a minimum delta N-15 value equal to or greater than +150% and a more probable value equal to or greater than +200%.

Chlorine Isotope Ratios in M Giants and S Stars

NASA Astrophysics Data System (ADS)

Maas, Zachary; Pilachowski, C. A.

2018-01-01

Chlorine is an odd-Z, light element that has been poorly studied in stars. Recently, the first stellar abundance measurements of the isotopologue 35Cl were made and the 35Cl/37Cl ratio was derived in RZ Ari (Maas et al. 2016). Additional abundance measurements are necessary to understand the Galactic chemical evolution and complex nucleosynthesis of Cl. The Cl isotope ratio in particular is important in distinguishing contributions from different nucleosynthesis sites to the surface abundances of stars. For example, current nucloesynthesis models predict that both isotopes of Cl are produced primarily during core collapse supernovae (CCSNe) with the energy and progenitor mass impacting the isotopic ratio of the ejected material. In addition to CCSNe, 37Cl is formed by the s-process both in massive stars and in AGB stars, and 35Cl may be produced from neutrino spallation. Understanding the formation of the Cl isotopes is also important to studies of the interstellar medium (ISM). A range of Cl isotope ratios mainly between 2 - 3.5 have been measured in star forming regions, in the circumstellar envelopes of evolved stars, and in proto-stellar cores using Cl bearing molecules. Additional measurements of the Cl isotope ratio in nearby stars will test nucleosynthesis models and allow comparisons with the range of isotope ratios observed in the ISM.We build on the results of Maas et al. (2016) by measuring the Cl isotope ratio in six M giants and four S stars using R~50,000 resolution spectra from Phoenix on Gemini South. We find no significant difference between the average Cl isotope ratios in the M stars and S stars and our measurements are consistent with the range of values seen in the ISM. We also find the average Cl ratio to be larger than the predicted isotope ratio of 1.8 for the solar neighborhood. Finally, two S stars, GG Pup and WY Pyx, show anomalously strong HCl features with equivalent widths ~3-5 times larger than the HCl features of other stars of similar temperature.

Small-scale studies of roasted ore waste reveal extreme ranges of stable mercury isotope signatures

NASA Astrophysics Data System (ADS)

Smith, Robin S.; Wiederhold, Jan G.; Jew, Adam D.; Brown, Gordon E.; Bourdon, Bernard; Kretzschmar, Ruben

2014-07-01

Active and closed Hg mines are significant sources of Hg contamination to the environment, mainly due to large volumes of mine waste material disposed of on-site. The application of Hg isotopes as source tracer from such contaminated sites requires knowledge of the Hg isotope signatures of different materials potentially released to the environment. Previous work has shown that calcine, the waste residue of the on-site ore roasting process, can exhibit distinct Hg isotope signatures compared with the primary ore. Here, we report results from a detailed small-scale study of Hg isotope variations in calcine collected from the closed New Idria Hg mine, San Benito County, CA, USA. The calcine samples exhibited different internal layering features which were investigated using optical microscopy, micro X-ray fluorescence, micro X-ray absorption spectroscopy (μ-XAS), and stable Hg isotope analysis. Significant Fe, S, and Hg concentration gradients were found across the different internal layers. Isotopic analyses revealed an extreme variation with pronounced isotopic gradients across the internal layered features. Overall, δ202Hg (±0.10‰, 2 SD) describing mass-dependent fractionation (MDF) ranged from -5.96 to 14.49‰, which is by far the largest range of δ202Hg values reported for any environmental sample. In addition, Δ199Hg (±0.06‰, 2 SD) describing mass-independent fractionation (MIF) ranged from -0.17 to 0.21‰. The μ-XAS analyses suggested that cinnabar and metacinnabar are the dominant Hg-bearing phases in the calcine. Our results demonstrate that the incomplete roasting of HgS ores in Hg mines can cause extreme mass-dependent Hg isotope fractionations at the scale of individual calcine pieces with enrichments in both light and heavy Hg isotopes relative to the primary ore signatures. This finding has important implications for the application of Hg isotopes as potential source tracers for Hg released to the environment from closed Hg mines and highlights the need for detailed source signature identification.

Sulfur isotopic disequilibrium and fluid-rock interaction during metamorphism of sulfidic black shales from the Waterville-Augusta area, Maine, USA

USGS Publications Warehouse

Oliver, N.H.S.; Hoering, T.C.; Johnson, T.W.; Rumble, D.; Shanks, Wayne C.

1992-01-01

Sulfur isotope ratios of pyrite (py) and pyrrhotite (po) from regionally metamorphosed graphitic sulfidic schists and related rocks from south-central Maine, USA, were analysed using SO2 and SF6 techniques. There is a broad range in ??34S values for both pyrite and pyrrhotite at most outcrops, up to 8%. and overall the values are isotopically light, averaging ~ -27??? for the entire data set, suggesting that the rocks have not been grossly isotopically disturbed by regional metamorphism from their inferred organic-rich sedimentary origins. At all temperatures from chlorite to sillimanite grades, sulfide analysed from veins and blebs within the schists show predominantly disequilibrium fractionations ranging from ??34Spy-po -3.0 to +3.5???, as do matrix sulfides from rocks that attained temperatures 500??C do matrix pyrite-pyrrhotite pairs with polygonal or aligned granoblastic microstructures approach isotopic equilibrium at millimeter to centimeter scales, suggesting that the process that favoured equilibration was recrystallization accompanying metamorphism and deformation. This disequilibrium may be a function of preferential interaction of one of the phases with an infiltrating fluid, but the lack of any systematic trends in the data, particularly with both negative and positive ??34Spy-po at some outcrops, does not permit ready identification of fluid sources, fluxes, or compositions. By combining published fluid fluxes for the area and a knowledge of the mass of sulfur contained in the rocks and the inferred infiltrating fluid, it appears that sulfur should have been homogenized over at least 10's to 1000's of meters, if equilibrium had been attained between rock sulfides and an infiltrating fluid of constant composition. That this did not occur was probably due to lack of equilibration between sulfides and the fluid but may also have arisen because of channelling of fluid flow along rather than across layers, or a lack of fluid infiltration through this unit. ?? 1992.

Re-assessing the Molybdenum Isotope Composition of Pre-GOE Seawater: Evidence for Dynamic Ocean Redox

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Kendall, B.; Roy, M.; Romaniello, S. J.; Nunn, S. J.; Gordon, G. W.; Olson, S. L.; Lyons, T. W.; Zheng, W.; Anbar, A. D.

2016-12-01

Molybdenum (Mo) isotope compositions of Archean shales can provide important insights into ocean and atmosphere redox dynamics prior to the Great Oxidation Event (GOE). Unfortunately, the relatively limited Mo isotope database and small number of sample sets for Archean shales do not allow for in-depth reconstructions and specifically make it difficult to differentiate global from local effects. To accurately estimate the Mo isotope composition of Archean seawater and better investigate the systematics of local and global redox, more complete sample sets are needed. We carried out a Mo isotope analysis of the euxinic 2.65 Ga Roy Hill Shale sampled in two stratigraphically correlated cores, and revisited the well-studied euxinic 2.5 Ga Mt. McRae Shale in higher resolution. Our data show contrasting Mo isotope values in the 2.65 Ga Roy Hill Shale between near- and offshore depositional environments, with systematically heavier isotope values in the near-shore environment. High-resolution analysis of the Mt. McRae Shale yields oscillating Mo concentrations and isotope values at the cm- to dm-scale during the well-characterized "whiff of O2" interval, with the heaviest isotope values measured during euxinic deposition. Variations in the measured isotope values within each section are primarily associated with redox changes in the local depositional environment and amount of detrital content. Both non-quantitative removal of Mo associated with incorporation into non-euxinic sediments and large detrital Mo contributions shift some measured isotopic compositions toward lighter values. This is readily apparent in the near-shore Roy Hill Shale section and the Mt. McRae Shale, but may not fully explain variations observed in the offshore Roy Hill Shale deposit. Here, euxinic deposition is not accompanied by Mo enrichments or isotopic compositions as heavy as the near-shore equivalent, even after detrital correction. This disparity between the near- and offshore environment could signify spatial variation in the Mo isotope composition of 2.65 Ga seawater and highlights the need for multi-site and high-resolution studies in order to best assess paleoenvironmental conditions.

Role of Secondary Particle Formation in the Persistence of Silver Nanoparticles in Humic Acid Containing Water under Light Irradiation.

PubMed

Zhang, Tuoya; Lu, Dawei; Zeng, Lixi; Yin, Yongguang; He, Yujian; Liu, Qian; Jiang, Guibin

2017-12-19

The wide use of silver nanoparticles (AgNPs) leads to the increasing release of AgNPs into the environment. Dissolved organic matter (DOM) is a key factor affecting the behaviors and fate of AgNPs in the aquatic environment. However, the mechanisms for the DOM-mediated transformations of AgNPs are still not fully understood. In this study, we investigated the persistence of AgNPs in the aquatic environment in the presence of different concentrations of humic acid (HA) over periods of time up to 14 days. The Ag species were monitored and characterized by absorption spectrometry, transmission electron microscopy (TEM), inductively coupled plasma mass spectrometry (ICP-MS), and multicollector ICP-MS (MC-ICP-MS). Results showed that the long-term persistence of AgNPs in HA-containing water was determined by two critical concentrations of HA. When the HA concentration exceeded a lower critical value, AgNPs could be persistent in the solution, and a large number of AgNPs were formed secondarily from the HA-induced reduction of the Ag + ions released from the primary AgNPs, causing a redistribution of the particle size. With the HA concentration above a higher critical value, AgNPs could persist in the solution without a significant change in particle size. Notably, we used Ag isotope fractionation to investigate the transformation mechanism of AgNPs. The natural isotopic analysis by MC-ICP-MS revealed that the size redistribution of AgNPs caused significant Ag isotope fractionation, which gave additional evidence for the proposed mechanisms. This study provides new insights into the environmental fate of engineered AgNPs and highlights the usefulness of stable isotope fractionation in environmental nanotechnology.

Establishment of a National Accelerator Facility: Design and construction phase

NASA Astrophysics Data System (ADS)

1981-06-01

The main components of an accelerator facility for nuclear physics, isotope production, and radiotherapy in South Africa are in 8-MeV solid pole injector cyclotron and a separated sector cyclotron with a k-value of 200 MeV. Progress made in the development of the light ion injector and in the design of the control and beam transport systems is described. Mechanical and engineering tasks associated with component manufacture are discussed as well as the construction of the building to house the facility and the installation of necessary services.

Diverse origins of Arctic and Subarctic methane point source emissions identified with multiply-substituted isotopologues

NASA Astrophysics Data System (ADS)

Douglas, P. M. J.; Stolper, D. A.; Smith, D. A.; Walter Anthony, K. M.; Paull, C. K.; Dallimore, S.; Wik, M.; Crill, P. M.; Winterdahl, M.; Eiler, J. M.; Sessions, A. L.

2016-09-01

Methane is a potent greenhouse gas, and there are concerns that its natural emissions from the Arctic could act as a substantial positive feedback to anthropogenic global warming. Determining the sources of methane emissions and the biogeochemical processes controlling them is important for understanding present and future Arctic contributions to atmospheric methane budgets. Here we apply measurements of multiply-substituted isotopologues, or clumped isotopes, of methane as a new tool to identify the origins of ebullitive fluxes in Alaska, Sweden and the Arctic Ocean. When methane forms in isotopic equilibrium, clumped isotope measurements indicate the formation temperature. In some microbial methane, however, non-equilibrium isotope effects, probably related to the kinetics of methanogenesis, lead to low clumped isotope values. We identify four categories of emissions in the studied samples: thermogenic methane, deep subsurface or marine microbial methane formed in isotopic equilibrium, freshwater microbial methane with non-equilibrium clumped isotope values, and mixtures of deep and shallow methane (i.e., combinations of the first three end members). Mixing between deep and shallow methane sources produces a non-linear variation in clumped isotope values with mixing proportion that provides new constraints for the formation environment of the mixing end-members. Analyses of microbial methane emitted from lakes, as well as a methanol-consuming methanogen pure culture, support the hypothesis that non-equilibrium clumped isotope values are controlled, in part, by kinetic isotope effects induced during enzymatic reactions involved in methanogenesis. Our results indicate that these kinetic isotope effects vary widely in microbial methane produced in Arctic lake sediments, with non-equilibrium Δ18 values spanning a range of more than 5‰.

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

USGS Publications Warehouse

Ellis, A.S.; Johnson, T.M.; Bullen, T.D.

2004-01-01

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto ??-Al2O3 and goethite is less than 0.04???. (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO42- was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in ??53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Does a Heavy Fe-Isotope Composition of Akilia Quartz-Amphibole-Pyroxene Rocks Necessitate a BIF Origin?

PubMed

Whitehouse, M J; Schoenberg, R; Fedo, C M; Kamber, B S

2015-10-01

The age and origin of the quartz-amphibole-pyroxene (qap) gneiss from the island of Akilia, southern West Greenland, have been the subject of intense debate since the light C-isotope composition of graphite inclusions in apatite was interpreted to indicate the presence of Earth's earliest biological activity. Although this claim for biogenic relicts has been vigorously challenged, the possibility that the rocks might represent some of Earth's earliest water-lain sediments and, hence, a suitable repository for life remains an open question. While some workers have suggested that the entire sequence represents an originally mafic-ultramafic igneous precursor subsequently modified by metasomatism, quartz injection, high-grade metamorphism, and extreme ductile deformation, others maintain that at least a small part of the sequence retains geochemical characteristics indicative of a chemical sedimentary origin. Fractionated Fe isotopes with δ(56)Fe values similar to those observed in Isua BIF have been reported from high-SiO2 units of qap and used to support a chemical sedimentary protolith for the qap unit. Here, we present new Fe isotope data from all lithologic variants in the qap gneiss on Akilia, including layers of undisputed ultramafic igneous origin. Since the latter require introduction of fractionated Fe into at least part of the qap unit, we argue that Fe isotopes must therefore be treated with considerable caution when used to infer BIF for part or all of the qap protolith.

Implications for chloro- and pheopigment synthesis and preservation from combined compound-specific δ13C, δ15N, and Δ14C analysis

NASA Astrophysics Data System (ADS)

Kusch, S.; Kashiyama, Y.; Ogawa, N. O.; Altabet, M.; Butzin, M.; Friedrich, J.; Ohkouchi, N.; Mollenhauer, G.

2010-08-01

Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotopic analysis to examine the timescales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 132,173-cyclopheophorbide-a-enol until burial in Black Sea surface sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment δ15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates contribution from N2-fixation. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. However, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotopic analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and assess their precise timescales.

Nuclear transition matrix elements for neutrinoless double-β decay of 76Ge and 82Se isotopes

NASA Astrophysics Data System (ADS)

Rath, P. K.

2017-10-01

Within mechanisms involving light and heavy Majorana neutrinos, the nuclear transition matrix elements (NTMEs) for the neutrinoless double-β decay of 76Ge and 82Se isotopes are calculated. Uncertainties in the average NTMEs M¯ (0 v ) and M¯ (0 N ) due to the exchange of light and heavy Majorana neutrinos, respectively, turn out to be about 10% and 37%, respectively. Limits on the effective mass of light Majorana neutrino , heavy Majorana neutrino and Majoron-neutrino coupling constant of classical Majoron model are extracted.

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.

Silicon Isotope Fractionation by Banana Under Continuous Nutrient and Silica Flux

NASA Astrophysics Data System (ADS)

Opfergelt, S.; Cardinal, D.; Henriet, C.; Delvaux, B.; André, L.

2004-12-01

Silicon is absorbed by plants as aqueous H4SiO4 with other essential nutrients, and precipitates in aerial parts of the plant as phytolith, a biogenic opal. Phytoliths are restored to the soil by decomposition of organic debris from plant material. The role of higher plants in the biogeochemical cycle of silicon is therefore major although it is still poorly studied. Biomineralization processes are known to fractionate the three stable silicon isotopes with a preferential uptake of light isotopes. Therefore, following some preliminary results from Douthitt (1982), and studies presented in recent conferences (Ziegler et al., 2002; Ding et al., 2003), we suspect that phytolith production by plants could also fractionate the silicon isotopes. Inversely, intensity of phytolith-related isotopic fractionations might contribute to a better understanding of the soil-plant silicon cycle. Our study focused on banana, a silicon accumulating plant (>1% Si, dry weight).Musa acuminata cv Grande Naine has been grown in hydroponics under controlled conditions (light, temperature, humidity, nutrients) during six weeks. The nutrient supply was kept constant: three batches of five plants were grown with a continuous nutrient solution flow of 5, 50 and 100 ppm SiO2 respectively. Si isotopic compositions were measured in the source solution, and in silica extracted from the various parts of banana (roots, pseudostems, midribs and petioles, leaves), using a Nu Plasma multicollector mass spectrometer (MC-ICP-MS) operating in dry plasma mode. The results are expressed as δ 29Si relatively to the NBS28 standard, with an average precision of ± 0.03‰ . Silicon contents and morphological studies of phytoliths were also achieved. Banana δ 29Si varied between -0.18 and -0.76‰ with a source solution at -0.02‰ . Values of δ 29Si were less fractionated, relatively to the nutrient solution, in roots, where no phytoliths have been observed until now, than in upper parts of banana where phytoliths were clearly abundant as long chain of typical cone shaped morphotypes truncated saddle-like. The bulk isotopic composition of the leaves in the five plants grown at 100 ppm SiO2 displayed a homogeneous negative signature (-0.44 ± 0.08‰ ) indicating a small inter-specimen variability. The difference between δ 29Si in roots and in upper parts of the plant was much larger with a silica offer of 100 ppm SiO2 (0.58‰ ) than with 50 ppm SiO2 (0.08‰ ). However, silicon isotope fractionation in leaves was not affected by a change in Si supply. Our preliminary results show that biomineralization of silica in bananas fractionates silicon isotopes in a similar extent as marine diatoms.

Orbitally Tuned C and N Isotopic Records of Aptian Oceanic Anoxic Event1a in Northeastern Mexico and Deep Sea Drilling Project Site 398, North Atlantic Ocean

NASA Astrophysics Data System (ADS)

Montanez, I. P.; Li, Y.; Osleger, D. A.; Bralower, T. J.

2006-12-01

High-resolution and expanded records of early Aptian Oceanic Anoxic Event (OAE) 1a (120 Ma) were recovered from outer shelf and slope deposits from the Sierra Madre Oriental of northeast Mexico and from hemipelagic deposits at Deep Sea Drilling Project Site 398 on Vigo Seamount in the North Atlantic Ocean. OAE1a is recognized in these deposits by minor increases in organic carbon content (up to 2 wt%) and widely-recognized, characteristic δ13Corg and δ13Ccarb variations that record significant changes in global carbon cycling. Here we present continuous dm-scale records of grain size distributions, wt% TOC and carbonate, C/N ratios, and C and N isotopes for these stratigraphically-expanded sections. Our high-resolution rock magnetic study of the same stratigraphic intervals establishes orbital timescales for OAE1a at these sites. The highly expanded records reveal significantly more structure in isotopic and TOC variation throughout OAE1a than contemporaneous condensed deep-sea records. Our data define an initial prominent negative excursion followed by repeated and short-lived (103 to 104 yr) fluctuations and a final interval of near invariant δ13Ccarb and δ13Corg values. Elevated TOC, a significant increase in C/N ratios from background marine values, rapid shifts in C and N isotopic compositions and sustained decoupling of δ13Corg and δ15Norg occur throughout the interval of short- lived isotopic fluctuations. Anhysteretic remanent magnetization (ARM) measurements were used as proxies for terrigenous influx during OAE1a. Spectral analyses of ARM depth series reveal dominant cycles with wavelength ratios resembling those of modern orbital periodicities, implying that orbital variations may have modulated depositional processes. These orbitally tuned geochemical proxy records indicate that the Aptian deposits from northeastern Mexican and Site 398 on Vigo Seamount hold promise for refining phase relationships between geochemical and isotopic proxies throughout OAE1a, and, in turn, constraining the mechanics of addition of light carbon to the ocean-atmosphere system.

Characterization of wines according the geographical origin by analysis of isotopes and minerals and the influence of harvest on the isotope values.

PubMed

Dutra, S V; Adami, L; Marcon, A R; Carnieli, G J; Roani, C A; Spinelli, F R; Leonardelli, S; Vanderlinde, R

2013-12-01

We studied Brazilian wines produced by microvinification from Cabernet Sauvignon and Merlot grapes, vintages 2007 and 2008, from the Serra Gaúcha, Campanha and Serra do Sudeste regions, in order to differentiate them according to geographical origin by using isotope and mineral element analyses. In addition, the influence of vintage production in isotope values was verified. Isotope analysis was performed by isotope ratio mass spectrometry (IRMS), and the determination of minerals was by flame atomic absorption (FAA). The best parameters to classify the wines in the 2008 vintage were Rb and Li. The results of the δ(13)C of wine ethanol, Rb and Li showed a significant difference between the varieties regardless of the region studied. The δ(18)O values of water and δ(13)C of ethanol showed significant differences, regardless of the variety. Discriminant analysis of isotope and minerals values allowed to classify approximately 80% of the wines from the three regions studied. Copyright © 2013 Elsevier Ltd. All rights reserved.

Weathering and vegetation controls on nickel isotope fractionation in surface ultramafic environments (Albania)

NASA Astrophysics Data System (ADS)

Estrade, Nicolas; Cloquet, Christophe; Echevarria, Guillaume; Sterckeman, Thibault; Deng, Tenghaobo; Tang, YeTao; Morel, Jean-Louis

2015-08-01

The dissolved nickel (Ni) isotopic composition of rivers and oceans presents an apparent paradox. Even though rivers represent a major source of Ni in the oceans, seawater is more enriched in the heavier isotopes than river-water. Additional sources or processes must therefore be invoked to account for the isotopic budget of dissolved Ni in seawater. Weathering of continental rocks is thought to play a major role in determining the magnitude and sign of isotopic fractionation of metals between a rock and the dissolved product. We present a study of Ni isotopes in the rock-soil-plant systems of several ultramafic environments. The results reveal key insights into the magnitude and the control of isotopic fractionation during the weathering of continental ultramafic rocks. This study introduces new constraints on the influence of vegetation during the weathering process, which should be taken into account in interpretations of the variability of Ni isotopes in rivers. The study area is located in a temperate climate zone within the ophiolitic belt area of Albania. The serpentinized peridotites sampled present a narrow range of heavy Ni isotopic compositions (δ60Ni = 0.25 ± 0.16 ‰, 2SD n = 2). At two locations, horizons within two soil profiles affected by different degrees of weathering all presented light isotopic compositions compared to the parent rock (Δ60Nisoil-rock up to - 0.63 ‰). This suggests that the soil pool takes up the light isotopes, while the heavier isotopes remain in the dissolved phase. By combining elemental and mineralogical analyses with the isotope compositions determined for the soils, the extent of fractionation was found to be controlled by the secondary minerals formed in the soil. The types of vegetation growing on ultramafic-derived soils are highly adapted and include both Ni-hyperaccumulating species, which can accumulate several percent per weight of Ni, and non-accumulating species. Whole-plant isotopic compositions were found to be isotopically heavier than the soil (Δ60Niwhole plant-soil up to 0.40‰). Fractions of Ni extracted by DTPA (diethylenetriaminepentaacetic acid) presented isotopically heavy compositions compared to the soil (Δ60NiDTPA-soil up to 0.89‰), supporting the hypothesis that the dissolved Ni fraction controlled by weathering has a heavy isotope signature. The non-hyperaccumulators (n = 2) were inclined to take up and translocate light Ni isotopes with a large degree of fractionation (Δ60Nileaves-roots up to - 0.60 ‰). For Ni-hyperaccumulators (n = 7), significant isotopic fractionation was observed in the plants in their early growth stages, while no fractionation occurred during later growth stages, when plants are fully loaded with Ni. This suggests that (i) the high-efficiency translocation process involved in hyperaccumulators does not fractionate Ni isotopes, and (ii) the root uptake process mainly controls the isotopic composition of the plant. In ultramafic contexts, vegetation composed of hyperaccumulators can significantly influence isotopic compositions through its remobilization in the upper soil horizon, thereby influencing the isotopic balance of Ni exported to rivers.

Intra-event isotope and raindrop size data of tropical rain reveal effects concealed by event averaged data

NASA Astrophysics Data System (ADS)

Managave, S. R.; Jani, R. A.; Narayana Rao, T.; Sunilkumar, K.; Satheeshkumar, S.; Ramesh, R.

2016-08-01

Evaporation of rain is known to contribute water vapor, a potent greenhouse gas, to the atmosphere. Stable oxygen and hydrogen isotopic compositions (δ18O and, δD, respectively) of precipitation, usually measured/presented as values integrated over rain events or monthly mean values, are important tools for detecting evaporation effects. The slope ~8 of the linear relationship between such time-averaged values of δD and δ18O (called the meteoric water line) is widely accepted as a proof of condensation under isotopic equilibrium and absence of evaporation of rain during atmospheric fall. Here, through a simultaneous investigation of the isotopic and drop size distributions of seventeen rain events sampled on an intra-event scale at Gadanki (13.5°N, 79.2°E), southern India, we demonstrate that the evaporation effects, not evident in the time-averaged data, are significantly manifested in the sub-samples of individual rain events. We detect this through (1) slopes significantly less than 8 for the δD-δ18O relation on intra-event scale and (2) significant positive correlations between deuterium excess ( d-excess = δD - 8*δ18O; lower values in rain indicate evaporation) and the mass-weighted mean diameter of the raindrops ( D m ). An estimated ~44 % of rain is influenced by evaporation. This study also reveals a signature of isotopic equilibration of rain with the cloud base vapor, the processes important for modeling isotopic composition of precipitation. d-excess values of rain are modified by the post-condensation processes and the present approach offers a way to identify the d-excess values least affected by such processes. Isotope-enabled global circulation models could be improved by incorporating intra-event isotopic data and raindrop size dependent isotopic effects.

Observations of geomagnetically trapped light isotopes by NINA

NASA Astrophysics Data System (ADS)

Bakaldin, A.; Galper, A.; Koldashov, S.; Korotkov, M.; Leonov, A.; Mikhailov, V.; Murashov, A.; Voronov, S.; Bidoli, V.; Casolino, M.; De Pascale, M.; Furano, G.; Iannucci, A.; Morselli, A.; Picozza, P.; Sparvoli, R.; Boezio, M.; Bonvicini, V.; Cirami, R.; Vacci, A.; Zampa, N.; Ambriola, M.; Bellotti, R.; sCafagna, F.; Ciacio, F.; Circella, M.; De Marzo, C.; Adriani, O.; Papini, P.; Spillantini, P.; Straulino, S.; Vannuccini, E.; Bartalucci, S.; Ricci, M.; Castellini, G.; Wizard-NINA Collaboration

2001-08-01

The detector NINA aboard the satellite Resurs-01N4 detected hydrogen and helium isotopes geomagnetically trapped, while crossing the South Atlantic Anomaly. Deuterium and tritium at L-shell<1.2 were unambiguously recognized. The 3 He and 4 He power-law spectra, reconstructed at L-shell=1.2 and B<0.22 G, have indices equal to 2.30±0.08 in the energy range 12-50 MeV/n, and 3.4±0.2 in 10-40 MeV/n respectively. The measured 3 He/4 He ratio bring to the conclusion that the main source of radiation belt light isotopes is the interaction of trapped protons with residual atmospheric helium.

ICC-CLASS: isotopically-coded cleavable crosslinking analysis software suite

PubMed Central

2010-01-01

Background Successful application of crosslinking combined with mass spectrometry for studying proteins and protein complexes requires specifically-designed crosslinking reagents, experimental techniques, and data analysis software. Using isotopically-coded ("heavy and light") versions of the crosslinker and cleavable crosslinking reagents is analytically advantageous for mass spectrometric applications and provides a "handle" that can be used to distinguish crosslinked peptides of different types, and to increase the confidence of the identification of the crosslinks. Results Here, we describe a program suite designed for the analysis of mass spectrometric data obtained with isotopically-coded cleavable crosslinkers. The suite contains three programs called: DX, DXDX, and DXMSMS. DX searches the mass spectra for the presence of ion signal doublets resulting from the light and heavy isotopic forms of the isotopically-coded crosslinking reagent used. DXDX searches for possible mass matches between cleaved and uncleaved isotopically-coded crosslinks based on the established chemistry of the cleavage reaction for a given crosslinking reagent. DXMSMS assigns the crosslinks to the known protein sequences, based on the isotopically-coded and un-coded MS/MS fragmentation data of uncleaved and cleaved peptide crosslinks. Conclusion The combination of these three programs, which are tailored to the analytical features of the specific isotopically-coded cleavable crosslinking reagents used, represents a powerful software tool for automated high-accuracy peptide crosslink identification. See: http://www.creativemolecules.com/CM_Software.htm PMID:20109223

2007 California Aerosol Study: Evaluation of δ15N as a Tracer Of NOx Sources and Chemsitry

NASA Astrophysics Data System (ADS)

Katzman, T. L.

2017-12-01

Although stable isotopes of N are commonly used as a source tracer, how this tracer is applied is a point of contention. The "source" hypothesis argues that the δ15N value of NO3- reflects the δ15N value of NOx source inputs into the environment, and any observed variation is solely the result of differences in source contributions. Conversely, the "chemistry" hypothesis argues that N isotopes are influenced by chemical reactions, atmospheric or biologic processing, and post-depositional effects. Previous studies often apply the source hypothesis, writing off the chemistry hypothesis as "minor," but others have noted the impact chemistry should has on δ15N values. Given the known complications, this work seeks to assess the use of stable isotopes as tracers, specifically, the assumption that the δ15N value is a tracer of source alone without significant influence from chemical reactions. If the "source" hypothesis is correct, source emission data, known source δ15N values, and isotope mass balance should be able to approximate measured δ15NNO3 values and determine the δ15N value associated with wildfire derived NOx, which is currently unknown. Significant deviations from observed values would support the significance of equilibrium and kinetic isotope effects associated with chemical reactions and processing in the atmosphere. Aerosols collected in during 2007, emission data, and isotopic analysis were utilized to determine the utility of δ15N as tracer of NOx sources. San Diego, California is a coastal urban area influenced by sea salt aerosols, anthropogenic combustion emissions, and seasonal wildfires. Wildfires also have a significant influence on local atmospheric chemistry and 2007 was notable for being one of the worst fire seasons in the San Diego region on record. Isotopic analysis of collected NO3- has suggested that source δ15N values are likely not conserved as NOx is oxidized into NO3-. Given known source contributions and known δ15N values of NOx sources, isotope mass balance predicts that a NOx source with highly positive δ15N value must exist for the source hypothesis to be valid. Furthermore, isotopic analysis has also suggested that wildfire emissions may produce a depleted δ15N, disagreeing with previously predicted δ15N values.

Cenozoic marine geochemistry of thallium deduced from isotopic studies of ferromanganese crusts and pelagic sediments

USGS Publications Warehouse

Rehkamper, M.; Frank, M.; Hein, J.R.; Halliday, A.

2004-01-01

Cenozoic records of Tl isotope compositions recorded by ferromanganese (Fe-Mn) crusts have been obtained. Such records are of interest because recent growth surfaces of Fe-Mn crusts display a nearly constant Tl isotope fractionation relative to seawater. The time-series data are complemented by results for bulk samples and leachates of various marine sediments. Oxic pelagic sediments and anoxic marine deposits can be distinguished by their Tl isotope compositions. Both pelagic clays and biogenic oozes are typically characterized by ??205Tl greater than +2.5, whereas anoxic sediments have ??205Tl of less than -1.5 (??205Tl is the deviation of the 205Tl/203Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 104). Leaching experiments indicate that the high ??205Tl values of oxic sediments probably reflect authigenic Fe-Mn oxyhydroxides. Time-resolved Tl isotope compositions were obtained from six Fe-Mn crusts from the Atlantic, Indian, and Pacific oceans and a number of observations indicate that these records were not biased by diagenetic alteration. Over the last 25 Myr, the data do not show isotopic variations that significantly exceed the range of Tl isotope compositions observed for surface layers of Fe-Mn crusts distributed globally (??205 Tl=+12.8??1.2). This indicates that variations in deep-ocean temperature were not recorded by Tl isotopes. The results most likely reflect a constant Tl isotope composition for seawater. The growth layers of three Fe-Mn crusts that are older than 25 Ma show a systematic increase of ??205Tl with decreasing age, from about +6 at 60-50 Ma to about +12 at 25 Ma. These trends are thought to be due to variations in the Tl isotope composition of seawater, which requires that the oceans of the early Cenozoic either had smaller output fluxes or received larger input fluxes of Tl with low ??205Tl. Larger inputs of isotopically light Tl may have been supplied by benthic fluxes from reducing sediments, rivers, and/or volcanic emanations. Alternatively, the Tl isotope trends may reflect the increasing importance of Tl fluxes to altered ocean crust through time. ?? 2004 Elsevier B.V. All rights reserved.

The early bird gets the shrimp: Confronting assumptions of isotopic equilibrium and homogeneity in a wild bird population

USGS Publications Warehouse

Wunder, Michael B.; Jehl, Joseph R.; Stricker, Craig A.

2012-01-01

1. Because stable isotope distributions in organic material vary systematically across energy gradients that exist in ecosystems, community and population structures, and in individual physiological systems, isotope values in animal tissues have helped address a broad range of questions in animal ecology. It follows that every tissue sample provides an isotopic profile that can be used to study dietary or movement histories of individual animals. Interpretations of these profiles depend on the assumption that metabolic pools are isotopically well mixed and in equilibrium with dietary resources prior to tissue synthesis, and they extend to the population level by assuming isotope profiles are identically distributed for animals using the same proximal dietary resource. As these assumptions are never fully met, studying structure in the variance of tissue isotope values from wild populations is informative. 2. We studied variation in δ13C, δ15N, δ2H and δ18O data for feathers from a population of eared grebes (Podiceps nigricollis) that migrate to Great Salt Lake each fall to moult feathers. During this time, they cannot fly and feed almost exclusively on superabundant brine shrimp (Artemia franciscana). The ecological simplicity of this situation minimized the usual spatial and trophic complexities often present in natural studies of feather isotope values. 3. Ranges and variances of isotope values for the feathers were larger than those from previously published studies that report feather isotopic variance, but they were bimodally distributed in all isotope dimensions. Isotope values for proximal dietary resources and local surface water show that some of the feathers we assumed to have been grown locally must have been grown before birds reached isotopic equilibrium with local diet or immediately prior to arrival at Great Salt Lake. 4. Our study provides novel insights about resource use strategies in eared grebes during migration. More generally, it demonstrates the utility of studying variance structures and questioning assumptions implicit in the interpretation of stable isotope data from wild animals.

Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

USGS Publications Warehouse

Qi, Haiping; Lorenz, Jennifer M.; Coplen, Tyler B.; Tarbox, Lauren V.; Mayer, Bernhard; Taylor, Steve

2014-01-01

RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean).

PubMed

van Geldern, Robert; Kuhlemann, Joachim; Schiebel, Ralf; Taubald, Heinrich; Barth, Johannes A C

2014-06-01

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δP) with values of-8.6(± 0.2) ‰ for δ(18)O and-58(± 2) ‰ for δ(2)H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of-0.17(± 0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

Isotope-Encoded Carboxyl Group Footprinting for Mass Spectrometry-Based Protein Conformational Studies

NASA Astrophysics Data System (ADS)

Zhang, Hao; Liu, Haijun; Blankenship, Robert E.; Gross, Michael L.

2016-01-01

We report an isotope-encoding method coupled with carboxyl-group footprinting to monitor protein conformational changes. The carboxyl groups of aspartic/glutamic acids and of the C-terminus of proteins can serve as reporters for protein conformational changes when labeled with glycine ethyl ester (GEE) mediated by carbodiimide. In the new development, isotope-encoded "heavy" and "light" GEE are used to label separately the two states of the orange carotenoid protein (OCP) from cyanobacteria. Two samples are mixed (1:1 ratio) and analyzed by a single LC-MS/MS experiment. The differences in labeling extent between the two states are represented by the ratio of the "heavy" and "light" peptides, providing information about protein conformational changes. Combining isotope-encoded MS quantitative analysis and carboxyl-group footprinting reduces the time of MS analysis and improves the sensitivity of GEE and other footprinting.

Dual carbon isotopes (14C and 13C) and optical properties of WSOC and HULIS-C during winter in Guangzhou, China.

PubMed

Liu, Junwen; Mo, Yangzhi; Ding, Ping; Li, Jun; Shen, Chengde; Zhang, Gan

2018-08-15

Water-soluble brown carbon (ws-BrC) exerts an important influence on climate change, but its emission sources and optical properties remain poorly understood. In this study, we isolated two ws-BrC proxies, water-soluble organic carbon (WSOC) and humic-like substance carbon (HULIS-C), from particulate matter collected in Guangzhou, China, during December 2012 for the measurement of dual carbon isotopes ( 14 C and 13 C) and light absorption. The mass absorption efficiencies of WSOC and HULIS-C at 365nm were 0.81±0.16 and 1.33±0.21m 2 g -1 C, respectively. The 14 C results showed that two-thirds of WSOC and HULIS-C were derived from non-fossil sources (e.g., biomass burning and biogenic emission), and the remaining third was derived from fossil sources. The δ 13 C values of WSOC and HULIS-C were -23.7±1.2‰ and -24.2±0.9‰, respectively, underlining the limited influences of C4 plants and natural gas on ws-BrC. Fitting the data to a multiple linear regression, we further concluded that approximately 80% and 10% of the light absorption at 365nm was due to non-fossil and fossil carbon, respectively. Non-fossil sources of ws-BrC, such as the burning of agricultural residue, were responsible for the light absorption recorded in Guangzhou. Copyright © 2018 Elsevier B.V. All rights reserved.

Hydrogen sensor

DOEpatents

Duan, Yixiang; Jia, Quanxi; Cao, Wenqing

2010-11-23

A hydrogen sensor for detecting/quantitating hydrogen and hydrogen isotopes includes a sampling line and a microplasma generator that excites hydrogen from a gas sample and produces light emission from excited hydrogen. A power supply provides power to the microplasma generator, and a spectrometer generates an emission spectrum from the light emission. A programmable computer is adapted for determining whether or not the gas sample includes hydrogen, and for quantitating the amount of hydrogen and/or hydrogen isotopes are present in the gas sample.

Stable Ca Isotopes in Tamarix aphylla Tree Rings, Death Valley, California

NASA Astrophysics Data System (ADS)

Yang, W.; Depaolo, D. J.; Ingram, B. L.; Owens, T. L.

2008-12-01

As a dune stabilizer and windbreak, Tamarix aphylla is an exotic perennial and evergreen tree in Death Valley. Its tap roots can reach down to 30 m depth and sub-superficial side roots may reach 50 m horizontally. The species can store large amounts of water in its roots and undergoes high evapotranspiration. Since Tamarix aphylla is a perennial tree growing in desert environments and its roots reach deep to the water table, it could be a proxy for desert ecological and hydrologic systems through time. We measured Ca isotopes in the soluble fraction of 8 tree ring samples from a 50-year-old specimen growing on an alluvial fan in Death Valley near Furnace Creek. Previous studies (Yang et al, GCA 60, 1996) indicate that this tree's rings contain high sulfur concentrations (4-6% expressed as sulfate) with chemical composition of CaSO4 (0.15-0.62 H2O). The δ34S values of soluble sulfate increase from +13.5 to +18 permil VCDT from the core to the bark, which are interpreted as reflecting deeper sulfate sources as the tree grew. The δ13C variations of the tree-ring cellulose (-27.6 to -24.0 permil VPDB) reflect changes in the local precipitation and show that Tamarix aphylla undergoes C3 photosynthesis. The δ44Ca for the soluble sulfate Ca through the tree-ring section, which covers a time period from 1945 to 1993, have an average value -2.52 permil (-3.4 permil relative to seawater). Only small variations are observed, from -2.69 to -2.28; the highest value (for 1990) occurs near the end of an extended drought. These are the first measurements of tree rings, but the low δ44Ca values are consistent with previous measurements of beech roots and stems from a temperate forest (Page et al., Biogeochem. 88, 2008). In our case, the tree has only one Ca source, which is expected to be isotopically uniform and similar to both local rainfall and limestones (δ44Ca ~ -0.6 permil), and with the minimal vegetation and extensive deep root system it is unlikely that there is a significant depletion of soil Ca due to plant uptake. Thus the Ca isotopic fractionation between trunk and source (ΔCa = -2 permil) is clearly defined by the data. By analogy to the results of Page et al., the Ca fractionation between root and source may be larger (ΔCa ~ -3 permil). This biological Ca isotope fractionation is no doubt due to transport processes during root uptake of Ca, but the magnitude is significantly larger than that observed for inorganic processes such as mineral precipitation or aqueous diffusion. The slight increase in δ44Ca in drought conditions suggests that when the tree is stressed there may be less Ca isotope fractionation, either because the Ca is held more tightly in small pores in the soil, or because the available Ca pool shrinks such that the soil Ca starts to shift to more positive δ44Ca values due to depletion of light Ca by the plant. The slowly accumulating database on Ca isotopes in plants continues to suggest that systematic Ca isotope studies may be fruitful for understanding cation transport in plants, and soil ecological conditions in general.

The application of carbon isotope discrimination of charred wheat grains to reconstruct Late Holocene climate change and identify water management strategy in northwest China

NASA Astrophysics Data System (ADS)

Wang, W.; An, C.; Duan, F.; Zhao, Y.; Cao, Z.

2017-12-01

The AMS 14C dating and corresponding carbon stable isotope datum of charred wheat grains from archaeological sites in northwest China especially Hexi Corridor and Xinjiang have been collected widely to study its potential roles in reconstructing past climate change and identifying water management strategies through comparison with integrated regional humidity index, carbon isotope data of wheat grown under modern irrigation environment from study area and Mediterranean charred wheat carbon isotope data. The results suggest (1) carbon isotope discrimination values of charred wheat both in Hexi corridor and Xinjiang could respond well to regional moisture change, and there are also good positive correlation relationship between them (2) in contrast to consistent relationship between decreased carbon isotope discrimination values of charred wheat and dry climate condition, increased carbon isotope discrimination values does not represent wetter regional climate completely and may also reveal effects of human irrigation activities. The higher carbon isotope discrimination value of charred wheat which occurred in the Hexi Corridor from 4000 to 3850 a BP, 2100 a BP and 550 a BP and in Tianshan area of Xinjiang from 3730 a BP could be likely to be related with human activities (3) the carbon isotope discrimination value of charred wheat may have a certain limit which is generally not beyond 19‰. And this upper limit could influence its availability in reflecting abrupt change of precipitation/humidity especially rapid wetter trend. We conclude that carbon isotope analysis of charred wheat grains could be a good tool for reconstructing past climate change and identifying ancient irrigation practices.

Discrimination factors of carbon and nitrogen stable isotopes from diet to hair and scat in captive tigers (Panthera tigris) and snow leopards (Uncia uncia).

PubMed

Montanari, Shaena; Amato, George

2015-06-15

In order to use stable isotope ratio values obtained from wild animal tissues, we must accurately calculate the differences in isotope ratios between diet and consumer (δtissue - δdiet). These values, called trophic discrimination factors (TDFs, denoted with ∆), are necessary for stable isotope ecology studies and are best calculated in controlled environments. Scat, hair, and diet samples were collected from captive tigers (n = 8) and snow leopards (n = 10) at the Bronx Zoo. The isotope ratios of carbon and nitrogen, the two most commonly used in ecological studies, of the samples were measured by continuous-flow isotope ratio mass spectrometry. The trophic discrimination factors were calculated for both carbon (δ(13)C values) and nitrogen (δ(15)N values). It was found that the only significant TDFs in this study were diet-hair, ∆(13)CHair, for snow leopards (5.97 ± 1.25‰) and tigers (6.45 ± 0.54‰), and diet-scat, ∆(15)NScat, in snow leopards (2.49 ± 1.30‰). The other mean isotope ratios were not significantly different from that of the premixed feline diet. The ∆(15)NHair values for both species were unusually low, potentially due to the protein content and quality of the feline diet. The discrimination factors of the stable isotopes of carbon and nitrogen calculated in this study can be applied to ecological studies of wild, non-captive terrestrial mammals. The effect of protein quality in isotope discrimination is also worthy of further investigation to better understand variation in TDFs. Carnivore scat is shown to be a valuable material for isotopic analysis. Copyright © 2015 John Wiley & Sons, Ltd.

The Cadmium Isotope Record of the Great Oxidation Event from the Turee Creek Group, Hamersley Basin, Australia

NASA Astrophysics Data System (ADS)

Abouchami, W.; Busigny, V.; Philippot, P.; Galer, S. J. G.; Cheng, C.; Pecoits, E.

2016-12-01

The evolution of the ocean, atmosphere and biosphere throughout Earth's history has impacted on the biogeochemistry of some key trace metals that are of particular importance in regulating the exchange between Earth's reservoirs. Several geochemical proxies exhibit isotopic shifts that have been linked to major changes in the oxygenation levels of the ancient oceans during the Great Oxygenation Event (GOE) between 2.45 and 2.2 Ga and the Neoproterozoic Oxygenation Event at ca. 0.6 Ga. Studies of the modern marine biogeochemical cycle of the transition metal Cadmium have shown that stable Cd isotope fractionation is mainly driven by biological uptake of light Cd into marine phytoplankton in surface waters leaving behind the seawater enriched in the heavy Cd isotopes. Here we use of the potential of this novel proxy to trace ancient biological productivity which remains an enigma, particularly during the early stages of Earth history. The Turee Creek Group in the Hamersley Basin, Australia, provides a continuous stratigraphic sedimentary section covering the GOE and at least two glacial events, offering a unique opportunity to examine the changes that took place during these periods and possibly constrain the evolution, timing and onset of oxygenic photosynthesis. Stable Cd isotope data were obtained on samples from the Boolgeeda Iron Fm. (BIFs), the siliciclastic and carbonate successions of Kungara (including the Meteorite Bore Member) and the Kazputt Fm., using a double spike technique by TIMS (ThermoFisher Triton) and Cd concentrations were determined by isotope dilution. The Boolgeeda BIFs have generally low Cd concentrations varying between 8 and 50ppb, with two major excursions marked by an increase in Cd content, reaching similar levels to those in the overlying Kungarra Fm. (≥150 ppb). These variations are associated with a large range in ɛ112/110Cd values (-2 to +2), with the most negative values typically found in the organic and Cd-rich shales and siltstones of the Kungara and Kazput formations. This suggests that a significant portion of the Cd present is organically bound, as also supported by the relationship with δ13Corg and TOC. These data will serve to assess the size of the ancient biomass during the GOE in view of our understanding of the modern Cd isotope biogeochemical cycling in the oceans.

Effects of acidification, lipid removal and mathematical normalization on carbon and nitrogen stable isotope compositions in beaked whale (Ziphiidae) bone.

PubMed

Tatsch, Ana Carolina C; Secchi, Eduardo R; Botta, Silvina

2016-02-15

The analysis of stable isotopes in tissues such as teeth and bones has been used to study long-term trophic ecology and habitat use in marine mammals. However, carbon isotope ratios (δ(13) C values) can be altered by the presence of (12) C-rich lipids and carbonates. Lipid extraction and acidification are common treatments used to remove these compounds. The impact of lipids and carbonates on carbon and nitrogen isotope ratios (δ(15) N values), however, varies among tissues and/or species, requiring taxon-specific protocols to be developed. The effects of lipid extraction and acidification and their interaction on carbon and nitrogen isotope values were studied for beaked whale (Ziphiidae) bone samples. δ(13) C and δ(15) N values were determined in quadruplicate samples: control, lipid-extracted, acidified and lipid-extracted followed by acidification. Samples were analyzed by means of elemental analysis isotope ratio mass spectrometry. Furthermore, the efficiency of five mathematical models developed for estimating lipid-normalized δ(13) C values from untreated δ(13) C values was tested. Significant increases in δ(13) C values were observed after lipid extraction. No significant changes in δ(13) C values were found in acidified samples. An interaction between both treatments was demonstrated for δ(13) C but not for δ(15) N values. No change was observed in δ(15) N values for lipid-extracted and/or acidified samples. Although all tested models presented good predictive power to estimate lipid-free δ(13) C values, linear models performed best. Given the observed changes in δ(13) C values after lipid extraction, we recommend a priori lipid extraction or a posteriori lipid normalization, through simple linear models, for beaked whale bones. Furthermore, acidification seems to be an unnecessary step before stable isotope analysis, at least for bone samples of ziphiids. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Scale of human mobility in the southern Andes (Argentina and Chile): A new framework based on strontium isotopes.

PubMed

Barberena, Ramiro; Durán, Víctor A; Novellino, Paula; Winocur, Diego; Benítez, Anahí; Tessone, Augusto; Quiroga, María N; Marsh, Erik J; Gasco, Alejandra; Cortegoso, Valeria; Lucero, Gustavo; Llano, Carina; Knudson, Kelly J

2017-10-01

The goal of this article is to assess the scale of human paleomobility and ecological complementarity between the lowlands and highlands in the southern Andes during the last 2,300 years. By providing isotope results for human bone and teeth samples, we assess a hypothesis of "high residential mobility" suggested on the basis of oxygen isotopes from human remains. We develop an isotopic assessment of human mobility in a mountain landscape combining strontium and oxygen isotopes. We analyze bone and teeth samples as an approach to life-history changes in spatial residence. Human samples from the main geological units and periods within the last two millennia are selected. We present a framework for the analysis of bioavailable strontium based on the combination of the geological data with isotope results for rodent samples. The 87 Sr/ 86 Sr values from human samples indicate residential stability within geological regions along life history. When comparing strontium and oxygen values for the same human samples, we record a divergent pattern: while δ 18 O values for samples from distant regions overlap widely, there are important differences in 87 Sr/ 86 Sr values. Despite the large socio-economic changes recorded, 87 Sr/ 86 Sr values indicate a persisting scenario of low systematic mobility between the different geological regions. Our results suggest that strontium isotope values provide the most germane means to track patterns of human occupation of distinct regions in complex geological landscapes, offering a much higher spatial resolution than oxygen isotopes in the southern Andes. © 2017 Wiley Periodicals, Inc.

Nitrogen cycling in the deep sedimentary biosphere: nitrate isotopes in porewaters underlying the oligotrophic North Atlantic

NASA Astrophysics Data System (ADS)

Wankel, S. D.; Buchwald, C.; Ziebis, W.; Wenk, C. B.; Lehmann, M. F.

2015-12-01

Nitrogen (N) is a key component of fundamental biomolecules. Hence, its cycling and availability are central factors governing the extent of ecosystems across the Earth. In the organic-lean sediment porewaters underlying the oligotrophic ocean, where low levels of microbial activity persist despite limited organic matter delivery from overlying water, the extent and modes of nitrogen transformations have not been widely investigated. Here we use the N and oxygen (O) isotopic composition of porewater nitrate (NO3-) from a site in the oligotrophic North Atlantic (Integrated Ocean Drilling Program - IODP) to determine the extent and magnitude of microbial nitrate production (via nitrification) and consumption (via denitrification). We find that NO3- accumulates far above bottom seawater concentrations (~ 21 μM) throughout the sediment column (up to ~ 50 μM) down to the oceanic basement as deep as 90 m b.s.f. (below sea floor), reflecting the predominance of aerobic nitrification/remineralization within the deep marine sediments. Large changes in the δ15N and δ18O of nitrate, however, reveal variable influence of nitrate respiration across the three sites. We use an inverse porewater diffusion-reaction model, constrained by the N and O isotope systematics of nitrification and denitrification and the porewater NO3- isotopic composition, to estimate rates of nitrification and denitrification throughout the sediment column. Results indicate variability of reaction rates across and within the three boreholes that are generally consistent with the differential distribution of dissolved oxygen at this site, though not necessarily with the canonical view of how redox thresholds separate nitrate regeneration from dissimilative consumption spatially. That is, we provide stable isotopic evidence for expanded zones of co-occurring nitrification and denitrification. The isotope biogeochemical modeling also yielded estimates for the δ15N and δ18O of newly produced nitrate (δ15NNTR (NTR, referring to nitrification) and δ18ONTR), as well as the isotope effect for denitrification (15ϵDNF) (DNF, referring to denitrification), parameters with high relevance to global ocean models of N cycling. Estimated values of δ15NNTR were generally lower than previously reported δ15N values for sinking particulate organic nitrogen in this region. We suggest that these values may be, in part, related to sedimentary N2 fixation and remineralization of the newly fixed organic N. Values of δ18ONTR generally ranged between -2.8 and 0.0 ‰, consistent with recent estimates based on lab cultures of nitrifying bacteria. Notably, some δ18ONTR values were elevated, suggesting incorporation of 18O-enriched dissolved oxygen during nitrification, and possibly indicating a tight coupling of NH4+ and NO2- oxidation in this metabolically sluggish environment. Our findings indicate that the production of organic matter by in situ autotrophy (e.g., nitrification, nitrogen fixation) supplies a large fraction of the biomass and organic substrate for heterotrophy in these sediments, supplementing the small organic-matter pool derived from the overlying euphotic zone. This work sheds new light on an active nitrogen cycle operating, despite exceedingly low carbon inputs, in the deep sedimentary biosphere.

Nitrogen cycling in the subsurface biosphere: nitrate isotopes in porewaters underlying the oligotrophic North Atlantic

NASA Astrophysics Data System (ADS)

Wankel, S. D.; Buchwald, C.; Ziebis, W.; Wenk, C. B.; Lehmann, M. F.

2015-08-01

Nitrogen (N) is a key component of fundamental biomolecules. Hence, the cycling and availability of N is a central factor governing the extent of ecosystems across the Earth. In the organic-lean sediment porewaters underlying the oligotrophic ocean, where low levels of microbial activity persist despite limited organic matter delivery from overlying water, the extent and modes of nitrogen transformations have not been widely investigated. Here we use the N and oxygen (O) isotopic composition of porewater nitrate (NO3-) from a site in the oligotrophic North Atlantic (IODP) to determine the extent and magnitude of microbial nitrate production (via nitrification) and consumption (via denitrification). We find that NO3- accumulates far above bottom seawater concentrations (∼ 21 μM) throughout the sediment column (up to ∼ 50 μM) down to the oceanic basement as deep as 90 mbsf, reflecting the predominance of aerobic nitrification/remineralization within the deep marine sediments. Large changes in the δ15N and δ18O of nitrate, however, reveal variable influence of nitrate respiration across the three sites. We use an inverse porewater diffusion-reaction model, constrained by the N and O isotope systematics of nitrification and denitrification and the porewater NO3- isotopic composition, to estimate rates of nitrification and denitrification throughout the sediment column. Results indicate variability of reaction rates across and within the three boreholes that are generally consistent with the differential distribution of dissolved oxygen at this site, though not necessarily with the canonical view of how redox thresholds separate nitrate regeneration from dissimilative consumption spatially. That is, we provide isotope evidence for expanded zones of co-ocurring nitrification and denitrification. The isotope biogeochemical modeling also yielded estimates for the δ15N and δ18O of newly produced nitrate (δ15NNTR and δ18ONTR), as well as the isotope effect for denitrification (15ϵDNF), parameters with high relevance to global ocean models of N cycling. Estimated values of δ15NNTR were generally lower than previously reported δ15N values for sinking PON in this region. We suggest that these values can be related to sedimentary N-fixation and remineralization of the newly fixed organic N. Values of δ18ONTR generally ranged between -2.8 and 0.0 ‰, consistent with recent estimates based on lab cultures of nitrifying bacteria. Notably, some δ18ONTR values were elevated, suggesting incorporation of 18O-enriched dissolved oxygen during nitrification, and possibly indicating a tight coupling of NH4+ and NO2- oxidation in this metabolically sluggish environment. Our findings indicate that the production of organic matter by in situ autotrophy (e.g., nitrification, nitrogen fixation) supply a large fraction of the biomass and organic substrate for heterotrophy in these sediments, supplementing the small organic matter pool derived from the overlying euphotic zone. This work sheds new light on an active nitrogen cycle operating, despite exceedingly low carbon inputs, in the deep sedimentary biosphere.

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 mechanisms have been invoked to explain this phenomenon: 1) addition of metals by aerial dust and wet deposition or 2) absorption of metals from the soil by organisms that develop on the litter. Our vertical profiles of isotopic compositions in the O horizons show that the first hypothesis is unlikely. Instead, they suggest a downward transfer of isotopically light metals from the fresh litter to the base of the O horizon. In addition, the assumption of an upward transfer of isopically heavy Cu and Zn from the upper soil horizon to the Of horizon is needed to fully explain the profiles we observed. 1 Lomander and Johansson (2001) Water, Air, and Soil Pollut. 132, 165-184 2 Scheid et al. (2009) Eur. J. Soil Sci. 60, 613-621

Relation of compositions of deep fluids in geothermal activity of Pleistocene-Holocene volcanic fields of Lesser Caucasus

NASA Astrophysics Data System (ADS)

Meliksetian, Khachatur; Lavrushin, Vassily; Shahinyan, Hrach; Aidarkozhina, Altin; Navasardyan, Gevorg; Ermakov, Alexander; Zakaryan, Shushan; Prasolov, Edward; Manucharyan, Davit; Gyulnazaryan, Shushan; Grigoryan, Edmond

2017-04-01

It is widely accepted, that geothermal activity in the conductive heat flow processes, such as volcanism and hydrothermal activity, is manifestation of the thermal mass transfer process in the Earth's crust, where geothermal and geochemical processes are closely connected. Therefore, geochemistry and isotope compositions of thermal mineral waters within and on periphery of volcanic clusters may represent key indicators for better understanding of geothermal activity in geodynamically active zones. Geochemical features of heat and mass transport in hydrothermal systems related to active volcanic and fault systems in continental collision related orogenic elevated plateaus such as Anatolian-Armenian-Iranian highlands are still poorly understood. In this contribution we attempt to fill these gaps in our knowledge of relations of geochemical and geothermal processes in collision zones. We present new data on chemical compositions, trace element geochemistry of thermal waters of Lesser Caucasus, (Armenia) as well as isotope analysis of free gases such as {}3He/{}4He, {}40Ar/{}36Ar, δ{}13?(CO{}2), nitrogen δ{}15N(N{}2) and oxygen and hydrogen isotopes in water phases (δD, δ{}18O). To reveal some specific features of formation of fluid systems related to thermal activity in the areas of collision related active volcanism and active geodynamics a complex geochemical (SiO{}2, K-Na, Na-Li, Li-Mg) and isotope geothermometers (δ{}18O(CaCO{}3) - δ{}18O(H{}2O)) were applied. The distribution of δ{}13?(??{}2) values in free gases of mineral waters of Armenia demonstrates that gases related to Quaternary volcanic fields are characterized by relatively light δ{}13?(CO{}2) values close to mantle derived gases, while on periphery of volcanic systems relatively heavy values of δ{}13?(CO{}2) indicate strong influence of metamorphic and sedimentary derived carbon dioxide. Distribution of nitrogen isotopes δ{}15N(N{}2) demonstrate an inverse correlation with δ{}13?(CO{}2) values and similarly to carbon dioxide indicate presence of metamorphic nitrogen on the periphery and strong influence of atmospheric (and mantle derived) nitrogen within volcanic fields. Results of geochemical and isotope investigations, as well as estimated temperatures of the formation of the mineral compositions of thermal waters demonstrate, that these studied hydrothermal systems originated within thermal anomaly fields associated with young (Pleistocene-Holocene) volcanic fields in Armenia. Basing on geochemical and isotope data, as well as on estimations of temperatures of water formation, calculated using various geothermometers, thermal anomaly fields, related to young volcanic activity and faults, within Armenian and neighboring areas of Lesser Caucasus are outlined. These results are used to reveal potential and promising areas for geothermal energy exploration in Armenia. This research is completed in framework of joint Armenian-Russian research grant funded by State Committee of Science of Armenia (grant #15RF-076) and Russian Foundation for Basic Research (grant#15-55-05069).

Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH.

PubMed

Xie, Hong; Huang, Zhi-Yong; Cao, Ying-Lan; Cai, Chao; Zeng, Xiang-Cheng; Li, Jian

2012-08-01

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p < 0.05) than the values estimated with L values, single chemical extractants and the Σ(BCR) values obtained with the BCR approach, respectively. A strong negative correlation (R(2) = 0.984) between E(24 h) values and soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted with EDTA and the Σ(BCR) values extracted with the modified BCR approach are helpful to detect the labile pools of Pb in soils. In addition, the negative correlation between soil pH and the labile pools of Pb in soils may be useful for further remediation to reduce the bioavailability of Pb in contaminated soils.

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.

Isotopic ratios D/H and 15N/14N in giant planets

NASA Astrophysics Data System (ADS)

Marboeuf, Ulysse; Thiabaud, Amaury; Alibert, Yann; Benz, Willy

2018-04-01

The determination of isotopic ratios in planets is important since it allows us to investigate the origins and initial composition of materials. The present work aims to determine the possible range of values for isotopic ratios D/H and 15N/14N in giant planets. The main objective is to provide valuable theoretical assumptions on the isotopic composition of giant planets, their internal structure, and the main reservoirs of species. We use models of ice formation and planet formation that compute the composition of ices and gas accreted in the core and the envelope of planets. Assuming a single initial value for isotopic ratios in volatile species, and disruption of planetesimals in the envelope of gaseous planets, we obtain a wide variety of D/H and 15N/14N ratios in low-mass planets (≤100 Mearth) due to the migration pathway of planets, the accretion time of gas species whose relative abundance evolves with time, and isotope exchanges among species. If giant planets with mass greater than 100 Mearth have solar isotopic ratios such as Jupiter and Saturn due to their higher envelope mass, Neptune-type planets present values ranging between one and three times the solar value. It seems therefore difficult to use isotopic ratios in the envelope of these planets to get information about their formation in the disc. For giant planets, the ratios allow us to constrain the mass fraction of volatile species in the envelope needed to reproduce the observational data by assuming initial values for isotopic ratios in volatile species.

Ni Isotope Signatures in Banded Iron Formations Before, During, and After the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Wasylenki, L.; Wang, S.

2016-12-01

We have measured the Ni isotope compositions of banded iron formations (BIF) in an effort to test the hypothesis of Konhauser et al. that a decrease in supply of Ni to the Late Archean oceans may have triggered a decline in methanogen productivity [1,2]. These microorganisms are critically dependent on Ni, and their decline may have triggered a drop in atmospheric CH4 that allowed the first sustained rise of free O2 in the atmosphere at 2.4 Ga. While simultaneously considering other processes that may have controlled the Ni isotope composition of Precambrian seawater, and in turn the BIF, we are looking for a shift in δ60/58Ni over time that correlates with the decrease in BIF Ni/Fe ratios documented previously [1,2] and that possibly reflects a dramatic change in methanogen Ni status over that same time interval (2.7-2.4 Ga). Our preliminary results indicate that the ocean's Ni isotope composition has varied considerably over geologic time. Using results from an accompanying experimental study of Ni fractionation during incorporation into ferric oxyhydroxides/oxides, we can reconstruct the Ni isotope compositions of seawater from which BIF precipitated. We observe that Precambrian seawater was generally considerably enriched in light isotopes of Ni relative to modern seawater. So far we observe the widest range of δ60/58Ni values in those BIF samples aged 2.7-2.4 Ga, implying significant changes in the controls on δ60/58Ni in the Late Archean Eon and possibly much greater sensitivity of the biogeochemical cycle of Ni to perturbations in Ni sources, such as oxidative weathering of sulfides, input/output fluxes, or biological uptake. [1] Konhauser et al. (2009) Nature 458,750; [2] Konhauser et al. (2015) Astrobiology 15,804.

Benthic nitrogen turnover processes in coastal sediments at the Danube Delta

NASA Astrophysics Data System (ADS)

Bratek, Alexander; Dähnke, Kirstin; Neumann, Andreas; Möbius, Jürgen; Graff, Florian

2017-04-01

The Black Sea Shelf has been exposed to strong anthropogenic pressures from intense fisheries and high nutrient inputs and eutrophication over the past decades. In the light of decreasing riverine nutrient loads and improving nutrient status in the water column, nutrient regeneration in sediments and biological N-turnover in the Danube Delta Front have an important effect on nutrient loads in the shelf region. In May 2016 we determined pore water nutrient profiles in the Danube River Delta-Black Sea transition zone, aiming to assess N-regeneration and elimination based on nutrient profiles and stable N- isotope changes (nitrate and ammonium) in surface water masses and in pore water. We aimed to investigate the magnitude and isotope values of sedimentary NH4+ and NO3- and their impact on the current N-budget in Black Sea Shelf water. Based on changes in the stable isotope ratios of NO3- and NH4+, we aimed to differentiate diffusion and active processing of ammonium as well as nitrate sources and sinks in bottom water. First results show that the concentration of NH4+ in pore water increases with depth, reaching up to 1500 µM in deeper sediment layers. We find indications for high fluxes of ammonium to the overlying water, while stable isotope profiles of ammonium suggest that further processing, apart from mere diffusion, acts on the pore water ammonium pool. Nitrate concentration and stable isotope profiles show rapid consumption in deeper anoxic sediment layers, but also suggest that nitrate regeneration in bottom water increases the dissolved nitrate pool. Overall, the isotope and concentration data of pore water ammonium clearly mirror a combination of turnover processes and diffusion.

Diet-tissue discrimination factors and turnover of carbon and nitrogen stable isotopes in tissues of an adult predatory coral reef fish, Plectropomus leopardus.

PubMed

Matley, J K; Fisk, A T; Tobin, A J; Heupel, M R; Simpfendorfer, C A

2016-01-15

Stable isotope ratios (δ(13)C and δ(15)N values) provide a unique perspective into the ecology of animals because the isotope ratio values of consumers reflect the values in food. Despite the value of stable isotopes in ecological studies, the lack of species-specific experimentally derived diet-tissue discrimination factors (DTDFs) and turnover rates limits their application at a broad scale. Furthermore, most aquatic feeding experiments use temperate, fast-growing fish species and few have considered medium- to large-sized adults with low growth rates from tropical ecosystems. A controlled-diet stable isotope feeding trial was conducted over a 196-day period for the adult predatory reef fish leopard coralgrouper (Plectropomus leopardus). This study calculated δ(13)C and δ(15)N DTDFs and turnover rates in five tissues (liver, plasma, red blood cells (RBC), fin, and muscle) using a continuous flow isotope ratio mass spectrometer equipped with an elemental analyzer. In addition, the effect of chemical lipid extraction (LE) on stable isotope values was examined for each tissue. Turnover was mainly influenced by metabolism (as opposed to growth) with LE δ(15)N half-life values lowest in fin (37 days) and plasma (66 days), and highest in RBC (88 days) and muscle (126 days). The diet-tissue discrimination factors for δ(15)N values in all tissues (Δ(15)N: -0.15 to 1.84‰) were typically lower than commonly reported literature values. Lipid extraction altered both δ(15) N and δ(13)C values compared with untreated samples; however, for the δ(15)N values, the differences were small (mean δ(15)N(LE-Bulk) <0.46‰ in all tissues). This study informs future interpretation of stable isotope data for medium- to large-sized fish and demonstrates that DTDFs developed for temperate fish species, particularly for δ(15)N values, may not apply to tropical species. Sampling of muscle and/or RBC is recommended for a relatively long-term representation of feeding habits, while plasma and/or fin should be used for a more recent indication of diet. Copyright © 2015 John Wiley & Sons, Ltd.

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--discrimination of ammonium nitrate sources.

PubMed

Benson, Sarah J; Lennard, Christopher J; Maynard, Philip; Hill, David M; Andrew, Anita S; Roux, Claude

2009-06-01

An evaluation was undertaken to determine if isotope ratio mass spectrometry (IRMS) could assist in the investigation of complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. The focus of the research was on ammonium nitrate (AN), a common oxidiser used in improvised explosive mixtures. The potential value of IRMS to attribute Australian AN samples to the manufacturing source was demonstrated through the development of a preliminary AN classification scheme based on nitrogen isotopes. Although the discrimination utilising nitrogen isotopes alone was limited and only relevant to samples from the three Australian manufacturers during the evaluated time period, the classification scheme has potential as an investigative aid. Combining oxygen and hydrogen stable isotope values permitted the differentiation of AN prills from three different Australian manufacturers. Samples from five different overseas sources could be differentiated utilising a combination of the nitrogen, oxygen and hydrogen isotope values. Limited differentiation between Australian and overseas prills was achieved for the samples analysed. The comparison of nitrogen isotope values from intact AN prill samples with those from post-blast AN prill residues highlighted that the nitrogen isotopic composition of the prills was not maintained post-blast; hence, limiting the technique to analysis of un-reacted explosive material.

Coordinated Isotopic and TEM Studies of Presolar Graphites from Murchison

NASA Astrophysics Data System (ADS)

Croat, T. K.; Stadermann, F. J.; Zinner, E.; Bernatowicz, T. J.

2004-03-01

TEM and NanoSIMS investigations of the same presolar Murchison KFC graphites revealed high Zr, Mo, and Ru content in refractory carbides within the graphites. Along with isotopically light carbon, these suggest a low-metallicity AGB source.

Geochemistry of the Neoproterozoic metabasic rocks from the Negele area, southern Ethiopia: Tectonomagmatic implications

NASA Astrophysics Data System (ADS)

Yihunie, Tadesse; Adachi, Mamoru; Yamamoto, Koshi

2006-03-01

Neoproterozoic metabasic rocks along with metasediments and ultramafic rocks constitute the Kenticha and Bulbul lithotectonic domains in the Negele area. They occur as amphibolite and amphibole schist in the Kenticha, and amphibole schist and metabasalt in the Bulbul domains. These rocks are dominantly basaltic in composition and exhibit low-K tholeiitic characteristics. They are slightly enriched in large ion lithophile (LIL) and light rare earth (LRE) elements and depleted in high field strength (HFS) and heavy rare earth (HRE) elements. They exhibit chemical characteristics similar to back-arc basin and island-arc basalts, but include a few samples with slightly higher Y, Zr and Nb contents. Initial Sr isotopic ratios and ɛNd values for the Kenticha metabasic rocks range from 0.7048 to 0.7051 and from 4.7 to 9.6 whereas for the Bulbul metabasic rocks they range from 0.7032 to 0.7055 and from -0.1 to 5.5, respectively. The trace elements and Sr-Nd isotope compositions of samples from the Kenticha and Bulbul domains suggest similar, but isotopically heterogeneous magma sources. The magma is inferred to have derived from depleted source with a contribution from an enriched mantle source component.

Isotopy of the hydrosphere

NASA Astrophysics Data System (ADS)

Ferronskii, V. I.; Poliakov, V. A.

This book is concerned with the natural relations regarding the distribution of the stable isotopes of hydrogen and oxygen in the hydrosphere, taking into account the most important problems with respect to the dynamics and the origin of waters. The solution of these problems on an isotopic basis is considered. The physicochemical principles of isotope separation are discussed along with the isotopic composition of atmospheric moisture, the isotopic composition of surface continental waters, the hydrogen and oxygen isotopic composition of minerals of magmatic and metamorphic rocks and fluid inclusions, the isotopic composition of groundwaters of modern volcanic regions, and the origin of the earth's hydrosphere in the light of isotopic, cosmochemical, and theoretical studies. Attention is also given to the separation of hydrogen and oxygen isotopes of waters in the underground cycle, the isotopic composition of the deep-formation waters of sedimentary basins, the relationship between surface and ground waters, and the groundwater residence time in an aquifer.

Iron isotope fractionation in marine invertebrates in near shore environments

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Schuessler, J. A.; Vinther, J.; Matthews, A.; von Blanckenburg, F.

2014-04-01

Chitons (Mollusca) are marine invertebrates that produce radula (teeth or rasping tongue) containing high concentrations of biomineralized magnetite and other iron bearing minerals. As Fe isotope signatures are influenced by redox processes and biological fractionation, Fe isotopes in chiton radula might be expected to provide an effective tracer of ambient oceanic conditions and biogeochemical cycling. Here, in a pilot study to measure Fe isotopes in marine invertebrates, we examine Fe isotopes in modern marine chiton radula collected from different locations in the Atlantic and Pacific oceans to assess the range of isotopic values, and to test whether or not the isotopic signatures reflect seawater values. Furthermore, by comparing two species that have very different feeding habits but collected from the same location, we infer a possible link between diet and Fe isotopic signatures. Values of δ56Fe (relative to IRMM-014) in chiton teeth range from -1.90 to 0.00‰ (±0.05‰ (2σ) uncertainty in δ56Fe), probably reflecting a combination of geographical control and biological fractionation processes. Comparison with published local surface seawater Fe isotope data shows a consistent negative offset of chiton teeth Fe isotope compositions relative to seawater. Strikingly, two different species from the same locality in the North Pacific (Puget Sound, Washington, USA) have distinct isotopic signatures. Tonicella lineata, which feeds on red algae, has a mean δ56Fe of -0.65 ± 0.26‰ (2σ, 3 specimens), while Mopalia muscosa, which feeds primarily on green algae, shows lighter isotopic values with a mean δ56Fe of -1.47 ± 0.98‰ (2σ, 5 specimens). Although chitons are not simple recorders of the ambient seawater Fe isotopic signature, these preliminary results suggest that Fe isotopes provide information concerning Fe biogeochemical cycling in near shore environments, and might be used to probe sources of Fe in the diets of different organisms.

Multiple sources of selenium in ancient seafloor hydrothermal systems: Compositional and Se, S, and Pb isotopic evidence from volcanic-hosted and volcanic-sediment-hosted massive sulfide deposits of the Finlayson Lake District, Yukon, Canada

NASA Astrophysics Data System (ADS)

Layton-Matthews, Daniel; Leybourne, Matthew I.; Peter, Jan M.; Scott, Steven D.; Cousens, Brian; Eglington, Bruce M.

2013-09-01

Volcanic-hosted massive sulfide (VHMS) and volcanic-sediment-hosted massive sulfide (VSHMS; i.e., hosted by both volcanic and sedimentary rocks) deposits in the Finlayson Lake District, Yukon, Canada, provide a unique opportunity to study the influence of seafloor and sub-seafloor hydrothermal processes on the formation of Se-poor (GP4F VHMS deposit; 7 ppm Se average), intermediate (Kudz Ze Kayah—KZK VHMS deposit; 200 ppm Se average), and Se-enriched (Wolverine VSHMS deposit; 1100 ppm Se average) mineralization. All three deposits are hosted by mid-Paleozoic (˜360-346 Ma) felsic volcanic rocks, but only the Wolverine deposit has voluminous coeval carbonaceous argillites (black shales) in the host rock package. Here we report the first application of Se isotope analyses to ancient seafloor mineralization and use these data, in conjunction with Pb and S isotope analyses, to better understand the source(s) and depositional process(es) of Se within VHMS and VSHMS systems. The wide range of δ82Se (-10.2‰ to 1.3‰, relative to NIST 3149), δ34S (+2.0‰ to +12.8‰ CDT), and elevated Se contents (up to 5865 ppm) within the Wolverine deposit contrast with the narrower range of δ82Se (-3.8‰ to -0.5‰), δ34S (9.8‰ to 13.0‰), and lower Se contents (200 ppm average) of the KZK deposit. The Wolverine and KZK deposits have similar sulfide depositional histories (i.e., deposition at the seafloor, with concomitant zone refining). The Se in the KZK deposit is magmatic (leaching or degassing) in origin, whereas the Wolverine deposit requires an additional large isotopically negative Se source (i.e. ˜-15‰ δ82Se). The negative δ82Se values for the Wolverine deposit are at the extreme light end for measured terrestrial samples, and the lightest observed for hypogene sulfide minerals, but are within calculated equilibrium values of δ82Se relative to NIST 3149 (˜30‰ at 25 °C between SeO4 and Se2-). We propose that the most negative Se isotope values at the Wolverine deposit record the δ82Se of the Se-source, and that the wide range in δ82Se values results from the combined effects of thermal and chemical degradation and Se-loss from the carbonaceous argillite source to a hydrothermal fluid (including magmatic Se i.e., leached and/or magmatic-hydrothermal) with deposition at or near the paleoseafloor. Pristine unaltered black shales show little variation in δ82Se relative to bulk earth; Se accumulation and fractionation to more negative isotopic values is interpreted to have been produced by post-sediment deposition, but pre-ore stage, reduction of seawater Se within the black shales.

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry.

PubMed

Wassenaar, L I; Terzer-Wassmuth, S; Douence, C; Araguas-Araguas, L; Aggarwal, P K; Coplen, T B

2018-03-15

Water stable isotope ratios (δ 2 H and δ 18 O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test. Eight test water samples were distributed by the IAEA to international stable isotope laboratories. These consisted of a core set of five samples spanning the common δ-range of natural waters, and three optional samples (highly depleted, enriched, and saline). The fifth core sample contained unrevealed trace methanol to assess analyst vigilance to the impact of organic contamination on water isotopic measurements made by all instrument technologies. For the core and optional samples ~73 % of laboratories gave acceptable results within 0.2 ‰ and 1.5 ‰ of the reference values for δ 18 O and δ 2 H, respectively; ~27 % produced unacceptable results. Top performance for δ 18 O values was dominated by dual-inlet IRMS laboratories; top performance for δ 2 H values was led by laser spectrometer laboratories. Continuous-flow instruments yielded comparatively intermediate results. Trace methanol contamination of water resulted in extreme outlier δ-values for laser instruments, but also affected reactor-based continuous-flow IRMS systems; however, dual-inlet IRMS δ-values were unaffected. Analysis of the laboratory results and their metadata suggested inaccurate or imprecise performance stemmed mainly from skill- and knowledge-based errors including: calculation mistakes, inappropriate or compromised laboratory calibration standards, poorly performing instrumentation, lack of vigilance to contamination, or inattention to unreasonable isotopic outcomes. To counteract common errors, we recommend that laboratories include 1-2 'known' control standards in all autoruns; laser laboratories should screen each autorun for spectral contamination; and all laboratories should evaluate whether derived d-excess values are realistic when both isotope ratios are measured. Combined, these data evaluation strategies should immediately inform the laboratory about fundamental mistakes or compromised samples. Copyright © 2018 John Wiley & Sons, Ltd.

Diffusion coefficients of Mg isotopes in enstatite and forsterite melts calculated by first-principles molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Huang, F.; Qi, Y.; Liu, X.; He, L.

2016-12-01

Stable isotopes can be fractionated by kinetic chemical diffusion because diffusion coefficients (D) of isotopes are mass-dependent. Diffusive isotopic fractionation recorded in rocks and minerals provide unique temporal constrains on geological processes. The mass dependence of D can be described in the form of Di/Dj= (mj/mi)β, where m denotes masses of isotope i and j, and β is an emperical parameter used to quantify the diffusive transport of isotopes [1]. β values can be estimated by experimental calibration and observation of natural samples, which are still rarely reported because it is challenging to precisely quantify the boundary conditions of diffusion processes [2,3,4]. Recent advances in computation technique provide a new way to theoretically calculate β values. For instance, classical molecular dynamics with empirical potential have been used to simulate interactions between atoms and estimate β of Mg isotopes in MgSiO3 melt [3]. Here, to further consider the effect of bonding and electron properties on β values, we apply first-principles Born-Oppenheimer Molecular Dynamics and pseudo-isotope methods (assuming mj/mi = 1/24, 1/4, 2, and 5) to estimate β for MgSiO3 and Mg2SiO4 melts. Our calculation shows that β of Mg isotopes with pseudo-mass ratios are consistent, indicating the reliability of the pseudo-isotope method. For MgSiO3 melt, β is 0.18 at 4000K and 0 GPa, higher than the value calculatedusing molecular dynamics simulations (0.135) [3]. For Mg2SiO4 melt at 0 GPa, β values are: 0.23 ± 0.04 at 2300K, 0.24 ± 0.07 at 3000K, and 0.24 ± 0.01 at 4000K. Notably, β of MgSiO3 and Mg2SiO4 melts are significantly higher than the value determined by diffusion experiments (0.05) [2]. These results indicate that β values are not sensitive to temperature, but dependent on melt composition.

Estimating the Seasonal Importance of Precipitation to Plant Source Water over Time and Space with Water Isotopes

NASA Astrophysics Data System (ADS)

Nelson, D. B.; Kahmen, A.

2017-12-01

The stable isotopic composition of hydrogen and oxygen are physical properties of water molecules that can carry information on their sources or transport histories. This provides a useful tool for assessing the importance of rainfall at different times of the year for plant growth, provided that rainwater values vary over time and that waters do not partially evaporate after deposition. We tested the viability of this approach using data from samples collected at nineteen sites throughout Europe at monthly intervals over two consecutive growing seasons in 2014 and 2015. We compared isotope measurements of plant xylem water with soil water from multiple depths, and measured and modeled precipitation isotope values. Paired analyses of oxygen and hydrogen isotope values were used to screen out a limited number of water samples that were influenced by evaporation, with the majority of all water samples indicating meteoric sources. The isotopic composition of soil and xylem waters varied over the course of an individual growing season, with many trending towards more enriched values, suggesting integration of the plant-relevant water pool at a timescale shorter than the annual mean. We then quantified how soil water residence times varied at each site by calculating the interval between measured xylem water and the most recently preceding match in modeled precipitation isotope values. Results suggest a generally increasing interval between rainfall and plant uptake throughout each year, with source water corresponding to dates in the spring, likely reflecting a combination of spring rain, and mixing with winter and summer precipitation. The seasonally evolving spatial distribution of source water-precipitation lag values was then modeled as a function of location and climatology to develop continental-scale predictions. This spatial portrait of the average date for filling the plant source water pool provides insights on the seasonal importance of rainfall for plant growth. It also permits continental scale predictions of monthly plant source water isotope values, with applications to improving isotopic paleoclimate proxies from plants such as tree rings or sedimentary leaf waxes, and for using oxygen and hydrogen isotopes to track the origins of agricultural products.

Seeking excellence: An evaluation of 235 international laboratories conducting water isotope analyses by isotope-ratio and laser-absorption spectrometry

USGS Publications Warehouse

Wassenaar, L. I.; Terzer-Wassmuth, S.; Douence, C.; Araguas-Araguas, L.; Aggarwal, P. K.; Coplen, Tyler B.

2018-01-01

RationaleWater stable isotope ratios (δ2H and δ18O values) are widely used tracers in environmental studies; hence, accurate and precise assays are required for providing sound scientific information. We tested the analytical performance of 235 international laboratories conducting water isotope analyses using dual-inlet and continuous-flow isotope ratio mass spectrometers and laser spectrometers through a water isotope inter-comparison test.MethodsEight test water samples were distributed by the IAEA to international stable isotope laboratories. These consisted of a core set of five samples spanning the common δ-range of natural waters, and three optional samples (highly depleted, enriched, and saline). The fifth core sample contained unrevealed trace methanol to assess analyst vigilance to the impact of organic contamination on water isotopic measurements made by all instrument technologies.ResultsFor the core and optional samples ~73 % of laboratories gave acceptable results within 0.2 ‰ and 1.5 ‰ of the reference values for δ18O and δ2H, respectively; ~27 % produced unacceptable results. Top performance for δ18O values was dominated by dual-inlet IRMS laboratories; top performance for δ2H values was led by laser spectrometer laboratories. Continuous-flow instruments yielded comparatively intermediate results. Trace methanol contamination of water resulted in extreme outlier δ-values for laser instruments, but also affected reactor-based continuous-flow IRMS systems; however, dual-inlet IRMS δ-values were unaffected.ConclusionsAnalysis of the laboratory results and their metadata suggested inaccurate or imprecise performance stemmed mainly from skill- and knowledge-based errors including: calculation mistakes, inappropriate or compromised laboratory calibration standards, poorly performing instrumentation, lack of vigilance to contamination, or inattention to unreasonable isotopic outcomes. To counteract common errors, we recommend that laboratories include 1–2 'known' control standards in all autoruns; laser laboratories should screen each autorun for spectral contamination; and all laboratories should evaluate whether derived d-excess values are realistic when both isotope ratios are measured. Combined, these data evaluation strategies should immediately inform the laboratory about fundamental mistakes or compromised samples.

Open system sulphate reduction in a diagenetic environment - Isotopic analysis of barite (δ34S and δ18O) and pyrite (δ34S) from the Tom and Jason Late Devonian Zn-Pb-Ba deposits, Selwyn Basin, Canada

NASA Astrophysics Data System (ADS)

Magnall, J. M.; Gleeson, S. A.; Stern, R. A.; Newton, R. J.; Poulton, S. W.; Paradis, S.

2016-05-01

Highly positive δ34S values in sulphide minerals are a common feature of shale hosted massive sulphide deposits (SHMS). Often this is attributed to near quantitative consumption of seawater sulphate, and for Paleozoic strata of the Selwyn Basin (Canada), this is thought to occur during bacterial sulphate reduction (BSR) in a restricted, euxinic water column. In this study, we focus on drill-core samples of sulphide and barite mineralisation from two Late Devonian SHMS deposits (Tom and Jason, Macmillan Pass, Selwyn Basin), to evaluate this euxinic basin model. The paragenetic relationship between barite, pyrite and hydrothermal base metal sulphides has been determined using transmitted and reflected light microscopy, and backscatter electron imaging. This petrographic framework provides the context for in-situ isotopic microanalysis (secondary ion mass spectrometry; SIMS) of barite and pyrite. These data are supplemented by analyses of δ34S values for bulk rock pyrite (n = 37) from drill-core samples of un-mineralised (barren), siliceous mudstone, to provide a means by which to evaluate the mass balance of sulphur in the host rock. Three generations of barite have been identified, all of which pre-date hydrothermal input. Isotopically, the three generations of barite have overlapping distributions of δ34S and δ18O values (+22.5‰ to +33.0‰ and +16.4‰ to +18.3‰, respectively) and are consistent with an origin from modified Late Devonian seawater. Radiolarian tests, enriched in barium, are abundant within the siliceous mudstones, providing evidence that primary barium enrichment was associated with biologic activity. We therefore propose that barite formed following remobilisation of productivity-derived barium within the sediment, and precipitated within diagenetic pore fluids close to the sediment water interface. Two generations of pyrite are texturally associated with barite: framboidal pyrite (py-I), which has negative δ34S values (-23‰ to -28‰; n = 9), and euhedral pyrite (py-II), which has markedly more positive δ34S values (+8‰ to +26‰; n = 86). We argue that stratiform pyrite and barite developed along diagenetic redox fronts, where the isotopic relationships (δ34Spyrite ≈ δ34Sbarite) are explained by anaerobic oxidation of methane coupled to sulphate reduction (AOM-SR). Furthermore, the relatively narrow distribution of δ34Sbarite values is consistent with an open system model of sulphate reduction, in which reduced sulphur generation occurred with a reduced isotopic fractionation (ε34S = <15‰) linked to higher rates of sulphate reduction and AOM-SR. Importantly, hydrothermal sulphides (pyrite, sphalerite and galena) all post-date this diagenetic barite-pyrite assemblage, and textural and mineralogical evidence indicates barite replacement to be an important process during hydrothermal mineralisation. Neither the textures nor the documented isotopic relationships can be produced by processes operating in a euxinic water column, which represents a major departure from the conventional model for SHMS formation at Macmillan Pass. We suggest that positive δ34S values in sulphides, a common feature of SHMS systems both in the Selwyn Basin and throughout the geologic record, could be linked to AOM-SR. At Macmillan Pass, positive δ34Spyrite values developed during open system diagenesis, which was critical for rapid sulphur cycling and the development of an effective metal trap.

Nitrogen isotopic components in the early solar system

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1994-01-01

It is quite common to take the terrestrial atmospheric value of (15)N/(14)N (0.00366) as typical of nitrogen in the early solar system, but in fact there is little reason to suppose that this value had a nebula-wide significance. Indeed, it is not clear that there was a unique solar-system-wide (15)N/(14)N ratio, of whatever value. Here we review what is known about the distribution of the nitrogen isotopes among those solar-system objects that have been sampled so far and conclude that those isotopes reveal widespread inhomogeneity in the early solar system. Whether the isotopically distinct primordial components implied by this analysis were solid or gaseous or a mixture of both is not known. The isotopic composition of N in the Earth's mantle is controversial: estimates range from a 1.1 percent depletion in (15)N to a 1.4 percent enrichment. (Isotopic compositions will be expressed throughout as percent deviations from the terrestrial atmospheric value.) The present-day Martian atmosphere is characterized by a value of plus 62 percent but this enrichment in (15)N is attributed to selective loss of (14)N from the Martian exosphere. Modelling of this fractionation leads to an estimated primordial composition similar to the terrestrial atmospheric value, through the precision of this model-dependent result is unclear.

Sulfur record of rising and falling marine oxygen and sulfate levels during the Lomagundi event.

PubMed

Planavsky, Noah J; Bekker, Andrey; Hofmann, Axel; Owens, Jeremy D; Lyons, Timothy W

2012-11-06

Carbonates from approximately 2.3-2.1 billion years ago show markedly positive δ(13)C values commonly reaching and sometimes exceeding +10‰. Traditional interpretation of these positive δ(13)C values favors greatly enhanced organic carbon burial on a global scale, although other researchers have invoked widespread methanogenesis within the sediments. To resolve between these competing models and, more generally, among the mechanisms behind Earth's most dramatic carbon isotope event, we obtained coupled stable isotope data for carbonate carbon and carbonate-associated sulfate (CAS). CAS from the Lomagundi interval shows a narrow range of δ(34)S values and concentrations much like those of Phanerozoic and modern marine carbonate rocks. The δ(34)S values are a close match to those of coeval sulfate evaporites and likely reflect seawater composition. These observations are inconsistent with the idea of diagenetic carbonate formation in the methanic zone. Toward the end of the carbon isotope excursion there is an increase in the δ(34)S values of CAS. We propose that these trends in C and S isotope values track the isotopic evolution of seawater sulfate and reflect an increase in pyrite burial and a crash in the marine sulfate reservoir during ocean deoxygenation in the waning stages of the positive carbon isotope excursion.

Disequilibrium δ18O values in microbial carbonates as a tracer of metabolic production of dissolved inorganic carbon

NASA Astrophysics Data System (ADS)

Thaler, Caroline; Millo, Christian; Ader, Magali; Chaduteau, Carine; Guyot, François; Ménez, Bénédicte

2017-02-01

Carbon and oxygen stable isotope compositions of carbonates are widely used to retrieve paleoenvironmental information. However, bias may exist in such reconstructions as carbonate precipitation is often associated with biological activity. Several skeleton-forming eukaryotes have been shown to precipitate carbonates with significant offsets from isotopic equilibrium with water. Although poorly understood, the origin of these biologically-induced isotopic shifts in biogenic carbonates, commonly referred to as "vital effects", could be related to metabolic effects that may not be restricted to mineralizing eukaryotes. The aim of our study was to determine whether microbially-mediated carbonate precipitation can also produce offsets from equilibrium for oxygen isotopes. We present here δ18O values of calcium carbonates formed by the activity of Sporosarcina pasteurii, a carbonatogenic bacterium whose ureolytic activity produces ammonia (thus increasing pH) and dissolved inorganic carbon (DIC) that precipitates as solid carbonates in the presence of Ca2+. We show that the 1000 lnαCaCO3-H2O values for these bacterially-precipitated carbonates are up to 24.7‰ smaller than those expected for precipitation at isotopic equilibrium. A similar experiment run in the presence of carbonic anhydrase (an enzyme able to accelerate oxygen isotope equilibration between DIC and water) resulted in δ18O values of microbial carbonates in line with values expected at isotopic equilibrium with water. These results demonstrate for the first time that bacteria can induce calcium carbonate precipitation in strong oxygen isotope disequilibrium with water, similarly to what is observed for eukaryotes. This disequilibrium effect can be unambiguously ascribed to oxygen isotope disequilibrium between DIC and water inherited from the oxygen isotope composition of the ureolytically produced CO2, probably combined with a kinetic isotope effect during CO2 hydration/hydroxylation. The fact that both disequilibrium effects are triggered by the metabolic production of CO2, which is common in many microbially-mediated carbonation processes, leads us to propose that metabolically-induced offsets from isotopic equilibrium in microbial carbonates may be more common than previously considered. Therefore, precaution should be taken when using the oxygen isotope signature of microbial carbonates for diagenetic and paleoenvironmental reconstructions.

Stable-isotope fingerprints of biological agents as forensic tools.

PubMed

Horita, Juske; Vass, Arpad A

2003-01-01

Naturally occurring stable isotopes of light elements in chemical and biological agents may possess unique "stable-isotope fingerprints" depending on their sources and manufacturing processes. To test this hypothesis, two strains of bacteria (Bacillus globigii and Erwinia agglomerans) were grown under controlled laboratory conditions. We observed that cultured bacteria cells faithfully inherited the isotopic composition (hydrogen, carbon, and nitrogen) of media waters and substrates in predictable manners in terms of bacterial metabolism and that even bacterial cells of the same strain, which grew in media water and substrates of different isotopic compositions, have readily distinguishable isotopic signatures. These "stable-isotopic fingerprints" of chemical and biological agents can be used as forensic tools in the event of biochemical terrorist attacks.

δ15N values of atmospheric N species simultaneously collected using sector-based samplers distant from sources - Isotopic inheritance and fractionation

NASA Astrophysics Data System (ADS)

Savard, Martine M.; Cole, Amanda; Smirnoff, Anna; Vet, Robert

2017-08-01

The nitrogen isotope ratios (δ15N) of atmospheric N species are commonly suggested as indicators of N emission sources. Therefore, numerous research studies have developed analytical methodologies and characterized primary (gases) and secondary emission products (mostly precipitation and aerosols) from various emitters. These previous studies have generally collected either reduced or oxidized N forms, and sampled them separately prior to determining their δ15N values. Distinctive isotopic signals have been reported for emissions from various sources, and seasonality of the δ15N values has been frequently attributed to shifts in relative contributions from sources with different isotopic signals. However, theoretical concepts suggest that temperature effects on isotopic fractionation may also affect the δ15N values of atmospheric reaction products. Here we use a sector-based multi-stage filter system to simultaneously collect seven reduced and oxidized N species downwind from five different source types in Alberta, Canada. We report δ15N values obtained with a state-of-the-art gold-furnace pre-concentrator online with an isotope ratio mass spectrometer (IRMS) to provide representative results even for oxidized-N forms. We find that equilibrium isotope effects and their temperature dependence play significant roles in determining the δ15N values of the secondary emission products. In the end, seasonal δ15N changes here are mainly caused by temperature effects on fractionation, and the δ15N values of only two N species from one source type can be retained as potential fingerprints of emissions.

Relative quantification of enantiomers of chiral amines by high-throughput LC-ESI-MS/MS using isotopic variants of light and heavy L-pyroglutamic acids as the derivatization reagents.

PubMed

Mochizuki, Toshiki; Taniguchi, Sayuri; Tsutsui, Haruhito; Min, Jun Zhe; Inoue, Koichi; Todoroki, Kenichiro; Toyo'oka, Toshimasa

2013-04-22

L-Pyroglutamic acid (L-PGA) was evaluated as a chiral labeling reagent for the enantioseparation of chiral amines in terms of separation efficiency by reversed-phase chromatography and detection sensitivity by ESI-MS/MS. Several amines and amino acid methyl esters were used as typical representatives of the chiral amines. Both enantiomers of the chiral amines were easily labeled with L-PGAS at room temperature for 60 min in the presence of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1-hydroxy-1H-benzotriazole as the activation reagents. The resulting diastereomers were completely separated by reversed-phase chromatography using the small particle (1.7 μm) ODS column (Rs=1.6-6.8). A highly sensitive detection at a low-fmol level (1-4 fmol) was also obtained from the multiple reaction monitoring (MRM) chromatograms. Therefore, a high-throughput determination was achieved by the present UPLC-ESI-MS/MS method. An isotope labeling strategy using light and heavy L-PGAs for the differential analysis of chiral amines in different sample groups was also proposed in this paper. As a model study, the differential analysis of the R and S ratio of 1-phenylethylamine (PEA) was performed according to the proposed procedure using light and heavy reagents, i.e., L-PGA and L-PGA-d5. The R/S ratio of PEA, spiked at the different concentrations in rat plasma, was almost similar to the theoretical values. Consequently, the proposed strategy using light and heavy chiral labeling reagents seems to be applicable for the differential analysis of chiral amine enantiomers in different sample groups, such as healthy persons and disease patients. Copyright © 2013 Elsevier B.V. All rights reserved.

Tooth enamel stable isotopes of Holocene and Pleistocene fossil fauna reveal glacial and interglacial paleoenvironments of hominins in Indonesia

NASA Astrophysics Data System (ADS)

Janssen, Renée; Joordens, Josephine C. A.; Koutamanis, Dafne S.; Puspaningrum, Mika R.; de Vos, John; van der Lubbe, Jeroen H. J. L.; Reijmer, John J. G.; Hampe, Oliver; Vonhof, Hubert B.

2016-07-01

The carbon (δ13C) and oxygen (δ18O) isotope compositions of fossilized animal tissues have become important proxies of paleodiet and paleoenvironment, but such stable isotope studies have not yet been extensively applied to the fossil assemblages of Sundaland (the biogeographical region comprising most of the Indonesian Archipelago). Here, we use the isotope composition of tooth enamel to investigate the diet and habitat of bovids, cervids, and suids from several Holocene and Pleistocene sites on Java and Sumatra. Our carbon isotope results indicate that individual sites are strongly dominated by either C3-browsers or C4-grazers. Herbivores from the Padang Highlands (Sumatra) and Hoekgrot (Java) cave faunas were mainly C3-browsers, while herbivores from Homo erectus-bearing sites Trinil and Sangiran (Java) utilized an almost exclusive C4 diet. The suids from all sites show a wide range of δ13C values, corroborating their omnivorous diet. For the dataset as a whole, oxygen and carbon isotope values are positively correlated. This suggests that isotopic enrichment of rainwater and vegetation δ18O values coincides with an increase of C4-grasslands. We interpret this pattern to mainly reflect the environmental contrast between glacial (drier, more C4) and interglacial (wetter, more C3) conditions. Intermediate herbivore δ13C values indicating mixed C3/C4 feeding is relatively rare, which we believe to reflect the abruptness of the transition between glacial and interglacial precipitation regimes in Sundaland. For seven Homo erectus bone samples we were not able distinguish between diagenetic overprint and original isotope values, underlining the need to apply this isotopic approach to Homo erectus tooth enamel instead of bone. Importantly, our present results on herbivore and omnivore faunas provide the isotopic framework that will allow interpretation of such Homo erectus enamel isotope data.

Magnesium isotope systematics in Martian meteorites

NASA Astrophysics Data System (ADS)

Magna, Tomáš; Hu, Yan; Teng, Fang-Zhen; Mezger, Klaus

2017-09-01

Magnesium isotope compositions are reported for a suite of Martian meteorites that span the range of petrological and geochemical types recognized to date for Mars, including crustal breccia Northwest Africa (NWA) 7034. The δ26Mg values (per mil units relative to DSM-3 reference material) range from -0.32 to -0.11‰; basaltic shergottites and nakhlites lie to the heavier end of the Mg isotope range whereas olivine-phyric, olivine-orthopyroxene-phyric and lherzolitic shergottites, and chassignites have slightly lighter Mg isotope compositions, attesting to modest correlation of Mg isotopes and petrology of the samples. Slightly heavier Mg isotope compositions found for surface-related materials (NWA 7034, black glass fraction of the Tissint shergottite fall; δ26Mg > -0.17‰) indicate measurable Mg isotope difference between the Martian mantle and crust but the true extent of Mg isotope fractionation for Martian surface materials remains unconstrained. The range of δ26Mg values from -0.19 to -0.11‰ in nakhlites is most likely due to accumulation of clinopyroxene during petrogenesis rather than garnet fractionation in the source or assimilation of surface material modified at low temperatures. The rather restricted range in Mg isotope compositions between spatially and temporally distinct mantle-derived samples supports the idea of inefficient/absent major tectonic cycles on Mars, which would include plate tectonics and large-scale recycling of isotopically fractionated surface materials back into the Martian mantle. The cumulative δ26Mg value of Martian samples, which are not influenced by late-stage alteration processes and/or crust-mantle interactions, is - 0.271 ± 0.040 ‰ (2SD) and is considered to reflect δ26Mg value of the Bulk Silicate Mars. This value is robust taking into account the range of lithologies involved in this estimate. It also attests to the lack of the Mg isotope variability reported for the inner Solar System bodies at current analytical precision, also noted for several other major elements.

Stable Isotope Analysis Reveals Detrital Resource Base Sources of the Tree Hole Mosquito, Aedes triseriatus

PubMed Central

Kaufman, Michael G.; Pelz-Stelinski, Kirsten S.; Yee, Donald A.; Juliano, Steven A.; Ostrom, Peggy H.; Walker, Edward D.

2010-01-01

1. Detritus that forms the basis for mosquito production in tree hole ecosystems can vary in type and timing of input. We investigated the contributions of plant- and animal-derived detritus to the biomass of Aedes triseriatus (Say) pupae and adults by using stable isotope (15N and 13C) techniques in lab experiments and field collections. 2. Lab-reared mosquito isotope values reflected their detrital resource base, providing a clear distinction between mosquitoes reared on plant or animal detritus. 3. Isotope values from field-collected pupae were intermediate between what would be expected if a single (either plant or animal) detrital source dominated the resource base. However, mosquito isotope values clustered most closely with plant-derived values, and a mixed feeding model analysis indicated tree floral parts contributed approximately 80% of mosquito biomass. The mixed model also indicated that animal detritus contributed approximately 30% of mosquito tissue nitrogen. 4. Pupae collected later in the season generally had isotope values that were consistent with an increased contribution from animal detritus, suggesting this resource became more nutritionally important for mosquitoes as plant inputs declined over the summer. PMID:21132121

Light-Shifts of an Integrated Filter-Cell Rubidium Atomic Clock

DTIC Science & Technology

2015-05-25

the light-shift coefficient for two different rf- discharge lamps (i.e., a pure 87Rb lamp and a lamp filled with the natural Rb isotope abundance...for the Galileo Rb clock under the assumption of a natural (or 85Rb isotopically enriched) rf- discharge lamp for the Galileo clock. I...satellites [14]. 6.8347… GHz 85Rb Filter Cell Cell Resonance Photodiode Microwave Cavity 87Rb Discharge Lamp 87Rb & N2 Rb & Xe, Kr Optical Pumping 87Rb

A Coast Mountains provenance for the Valdez and Orca groups, southern Alaska, based on Nd, Sr, and Pb isotopic evidence

USGS Publications Warehouse

Farmer, G.L.; Ayuso, R.; Plafker, G.

1993-01-01

Nd, Sr, and Pb isotopic data were obtained for fourteen fine- to coarse-grained samples of accreted flysch of the Late Cretaceous and early Tertiary Valdez and Orca Groups in southern Alaska to determine the flysch provenance. Argillites and greywackes from the Orca Group, as well as compositionally similar but higher metamorphic grade rocks from the Valdez Group, show a restricted range of correlated ??{lunate}Nd ( -0.6 to -3.8) and 87Sr 86Sr (0.7060-0.7080) at the time of sediment deposition ( ??? 50 Ma). Pb isotopic compositions also vary over a narrow range ( 206Pb 204Pb = 19.138-19.395, 207Pb 204Pb = 15.593-15.703, 208Pb 204Pb = 38.677-39.209), and in the Orca Group the samples generally become more radiogenic with decreasing ??{lunate}Nd and increasing 87Sr 86Sr. All samples have similar trace element compositions characterized by moderate light rare earth element enrichments, and low ratios of high field strength elements to large ion lithophile elements. Based on petrographic, geochemical, and isotopic data the sedimentary rocks are interpreted to have been derived largely from a Phanerozoic continental margin arc complex characterized by igneous rocks with ??{lunate}Nd values between 0 and -5. The latter conclusion is supported by the ??{lunate}Nd values of a tonalite clast and a rhyodacite clast in the Orca Group (??{lunate}Nd = -4.9 and -0.9, respectively). However, trondjemitic clasts in the Orca Group have significantly lower ??{lunate}Nd ( ??? -10) and require a derivation of a portion of the flysch from Precambrian crustal sources. The Nd, Sr, and Pb isotopic compositions of both the Valdez and Orca Groups overlap the values determined for intrusive igneous rocks exposed within the northern portion of the Late Cretaceous to early Tertiary Coast Mountains Plutonic Complex in western British Columbia and equivalent rocks in southeastern Alaska. The isotopic data support previous conclusions based on geologic studies which suggest that the flysch was shed from this portion of the batholith, and from overlying continental margin arc-related volcanic rocks, following its rapid uplift in the Late Cretaceous and early Tertiary. The Precambrian crustal material present in the flysch may have been derived from Late Proterozoic or older metasedimentary and metaigneous rocks now exposed along the western margin of the Coast Mountains Plutonic Complex. ?? 1993.

Coupling experimental and field-based approaches to decipher carbon sources in the shell of the great scallop, Pecten maximus (L.)

NASA Astrophysics Data System (ADS)

Marchais, V.; Richard, J.; Jolivet, A.; Flye-Sainte-Marie, J.; Thébault, J.; Jean, F.; Richard, P.; Paulet, Y.-M.; Clavier, J.; Chauvaud, L.

2015-11-01

This research investigated how the carbon isotopic composition of food source (δ13Cfood) and dissolved inorganic carbon (δ13CDIC) influences the carbon isotopic composition of Pecten maximus shells (δ13Cshell) under both experimental and natural conditions. The objectives are to better understand the relationship between P. maximus and its environment, and to specifically distinguish conditions under which calcification is influenced by respired CO2 derived from food sources versus conditions in which calcification uses inorganic carbon from seawater. Laboratory experiment investigated carbon incorporation into shell carbonates by maintaining scallops under conditions where the stable carbon isotopic composition of food sources was considerably depleted (-54‰), relative to values observed in the natural environment (-21‰). Laboratory experiment ran for 78 days under three temperature conditions, 15 °C, 21 °C and 25 °C. A survey of the environmental parameters and stable carbon isotopic composition into shell carbonate of natural population of P. maximus was also realized during the same year in the Bay of Brest, France. Data collected from both laboratory experiment and the natural environment confirmed that both δ13CDIC and δ13Cfood influence δ13Cshell values and that organic carbon incorporation (CM) averages about 10% (4.3-6.8% under experimental conditions and 1.9-16.6% in the natural environment). The shift in stable carbon isotopic composition from the uptake of depleted food sources under experimental conditions realized a marked divergence in the predicted equilibrium between calcium carbonate and ambient bicarbonate, relative to the natural environment. This offset was 1.7 ± 0.6‰ for scallops in their natural environment and 2.5 ± 0.5 and 3.2 ± 0.9‰ for scallops under experimental conditions at water temperatures of 15 °C and 21 °C, respectively. The offset of 3‰ for scallops subjected to laboratory experiment could not be explained in light of growth rate but may be related to food supply and/or temperature. Food source and temperature effects may also explain the annual variation observed in CM values measured from scallops in their natural environment. CM estimation from the natural population of P. maximus varied seasonally from around 2% at the end of winter, to 12% in summer. The seasonal variation resembles variability in the carbon isotopic composition of the food sources throughout the year with an exception at the end of winter.

Constraints on nitrogen cycling at the subtropical North Pacific Station ALOHA from isotopic measurements of nitrate and particulate nitrogen

NASA Astrophysics Data System (ADS)

Casciotti, K. L.; Trull, T. W.; Glover, D. M.; Davies, D.

2008-07-01

Nitrogen supply to surface waters can play an important role in the productivity and ecology of subtropical ecosystems. As part of the Vertical Transport in the Global Ocean (VERTIGO) program, we examined the fluxes of nitrogen into and out of the euphotic zone at station ALOHA in the North Pacific Subtropical Gyre using natural abundance stable isotopic measurements of nitrate ( δN and δO), as well as sinking and suspended particulate nitrogen (δ 15N PN). Paralleling the steep gradient in nitrate concentration in the upper thermocline at ALOHA, we observed a steep gradient in δN, decreasing from a maximum of +7.1‰ at 500 meters (m) to +1.5-2.4‰ at 150 m. δO values also decreased from +3.0‰ at 300 m to +0.7-0.9‰ at 150 m. The decreases in both δN and δO require inputs of isotopically "light" nitrate to balance the upward flux of nitrate with high δN (and δO). We conclude that both nitrogen fixation and diagenetic alteration of the sinking flux contribute to the decrease in δN and δO in the upper thermocline at station ALOHA. While nitrogen fixation is required to explain the nitrogen isotope patterns, the rates of nitrogen fixation may be lower than previously estimated. By including high-resolution nitrate isotope measurements in the nitrogen isotope budget for the euphotic zone at ALOHA, we estimate that approximately 25%, rather than 50%, of export production was fueled by N 2 fixation during our study. On the other hand, this input of N 2-derived production accumulates in the upper thermocline over time, playing a significant role in subtropical nutrient cycling through maintenance of the subsurface nitrate pool. An increase in sinking δ 15N PN between 150 and 300 m, also suggests that fractionation during remineralization contributed to the low δN values observed in this depth range by introducing a subsurface nitrate source that is 0.5‰ lower in δ 15N than the particle flux exported from the euphotic zone. While the time scale of these observations are currently limited, they highlight the need for inclusion of δN measurements in a time series program to allow a broader assessment of the variations in subsurface δN values and the links between subsurface nitrate and export flux at station ALOHA.

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 predictive algorithms for metal lability in the contaminated catchment based on simple soil properties (such as pH, organic matter (LOI), and total metal content). Examine the incidence of non-isotopically-exchangeable metal held within suspended colloidal particles (SCP-metal) in filtered soil solutions (<0.22 μm) by comparing E-values from isotopic abundance in solutions equilibrated with soil and in a resin phase equilibrated with the separated solution. Assess the ability of a geochemical speciation model, WHAM(VII), to predict metal solubility using isotopically exchangeable metal as an input variable.

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. (Goldschmidt abstract, 2005), but distinctly lower than altered dolostones (δ57Fe = 0.10 - 1.02‰) in a Jurassic, organic-rich mudstone (Matthews et al., GCA, 2004). It is difficult to conclude at this time whether or not the relatively low δ57Fe composition of the cap dolostones is consistent with the Beard et al. (Geology, 2003) hypothesis due to large uncertainties in the solution-mineral fractionation factors for carbonates, the potential effects of diagenesis and biological influences on dolomite precipitation, and the possibility that the Marinoan deep ocean was euxinic.

CO2-dependent carbon isotope fractionation in the dinoflagellate Alexandrium tamarense

NASA Astrophysics Data System (ADS)

Wilkes, Elise B.; Carter, Susan J.; Pearson, Ann

2017-09-01

The carbon isotopic composition of marine sedimentary organic matter is used to resolve long-term histories of pCO2 based on studies indicating a CO2-dependence of photosynthetic carbon isotope fractionation (εP). It recently was proposed that the δ13C values of dinoflagellates, as recorded in fossil dinocysts, might be used as a proxy for pCO2. However, significant questions remain regarding carbon isotope fractionation in dinoflagellates and how such fractionation may impact sedimentary records throughout the Phanerozoic. Here we investigate εP as a function of CO2 concentration and growth rate in the dinoflagellate Alexandrium tamarense. Experiments were conducted in nitrate-limited chemostat cultures. Values of εP were measured on cells having growth rates (μ) of 0.14-0.35 d-1 and aqueous carbon dioxide concentrations of 10.2-63 μmol kg-1 and were found to correlate linearly with μ/[CO2(aq)] (r2 = 0.94) in accord with prior, analogous chemostat investigations with eukaryotic phytoplankton. A maximum fractionation (εf) value of 27‰ was characterized from the intercept of the experiments, representing the first value of εf determined for an algal species employing Form II RubisCO-a structurally and catalytically distinct form of the carbon-fixing enzyme. This value is larger than theoretical predictions for Form II RubisCO and not significantly different from the ∼25‰ εf values observed for taxa employing Form ID RubisCO. We also measured the carbon isotope contents of dinosterol, hexadecanoic acid, and phytol from each experiment, finding that each class of biomarker exhibits different isotopic behavior. The apparent CO2-dependence of εP values in our experiments strengthens the proposal to use dinocyst δ13C values as a pCO2 proxy. Moreover, the similarity between the εf value for A. tamarense and the consensus value of ∼25‰ indicates that the CO2-sensitivity of carbon isotope fractionation saturates at similar CO2 levels across all three ecologically prominent clades of eukaryotic phytoplankton. This continuity of εf across taxa may help to explain why there is no coherent signature of phytoplankton evolutionary succession in Phanerozoic carbon isotope records.

Using Natural Stable Calcium Isotopes to Rapidly Assess Changes in Bone Mineral Balance Using a Bed Rest Model to Induce Bone Loss

NASA Technical Reports Server (NTRS)

Morgan, J. L. L.; Skulan, J. L.; Gordon, G. E.; Smith, Scott M.; Romaniello, S. J.; Anbar, A. D.

2012-01-01

Metabolic bone diseases like osteoporosis result from the disruption of normal bone mineral balance (BMB) resulting in bone loss. During spaceflight astronauts lose substantial bone. Bed rest provides an analog to simulate some of the effects of spaceflight; including bone and calcium loss and provides the opportunity to evaluate new methods to monitor BMB in healthy individuals undergoing environmentally induced-bone loss. Previous research showed that natural variations in the Ca isotope ratio occur because bone formation depletes soft tissue of light Ca isotopes while bone resorption releases that isotopically light Ca back into soft tissue (Skulan et al, 2007). Using a bed rest model, we demonstrate that the Ca isotope ratio of urine shifts in a direction consistent with bone loss after just 7 days of bed rest, long before detectable changes in bone mineral density (BMD) occur. The Ca isotope variations tracks changes observed in urinary N-teleopeptide, a bone resorption biomarker. Bone specific alkaline phosphatase, a bone formation biomarker, is unchanged. The established relationship between Ca isotopes and BMB can be used to quantitatively translate the changes in the Ca isotope ratio to changes in BMD using a simple mathematical model. This model predicts that subjects lost 0.25 0.07% ( SD) of their bone mass from day 7 to day 30 of bed rest. Given the rapid signal observed using Ca isotope measurements and the potential to quantitatively assess bone loss; this technique is well suited to study the short-term dynamics of bone metabolism.

Dual temperature effects on oxygen isotopic ratio of shallow-water coral skeleton: Consequences on seasonal and interannual records

NASA Astrophysics Data System (ADS)

Juillet-Leclerc, A.; Reynaud, S.

2009-04-01

Oxygen isotopic ratio from coral skeleton is regarded for a long time as promising climate archives at seasonal scale. Although in isotopic disequilibrium relative to seawater, it is supposed to obey to the isotope thermometer. Indeed, coral oxygen isotopic records are strongly temperature dependent, but d18O-temperature calibrations derived from different corals are highly variable. The isotope thermometer assumption does not take into account vital effects due to biogenic origin of the mineral. Corals are animals living in symbiosis with algae (zooxanthellae). Interactions between symbiont photosynthesis and coral skeleton carbonation have been abundantly observed but they remain poorly understood and the effects of photosynthesis on coral growth and skeleton oxygen ratio are ignored. Coral cultured under two light conditions enabled to relate metabolic parameters and oxygen isotopic variability with photosynthetic activity. By examining responses provided by each colony they revealed that photosynthesis significantly affected d18O, by an opposite sense compared with the sole temperature influence. Since temperature and light changes are associated during seasonal variations, this complicates the interpretation of seasonal record. Additionally, this complexity is amplified because photosynthetic activity is also directly impacted by temperature variability. Thus, the annual isotopic amplitude due to the "physical" temperature influence is partly compensated through photosynthesis. Similar opposite effect is also shown by extension rate of the cultured colonies. First, we will examine and quantify consequences of photosynthesis on growth rate and oxygen isotopic signature, from cultured corals. Second, we will consider the consequences of this vital effect on data series, at seasonal and interannual time scales.

Understanding Potassium Isotope Fractionation During Authigenic Clay Formation in Pore-fluid Systems: Implications for the δ41K of Seawater

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2015-12-01

Improvements in analytical precision on the latest generation multi-collector inductively coupled plasma mass spectrometers (MC-ICP-MS) have revealed a ~2‰ range in the ratios of stable potassium isotopes (41K/39K) in terrestrial materials (Morgan et al., in prep). Preliminary measurements of δ41K values indicate that seawater and silicate rocks are isotopically distinct reservoirs, with seawater having a δ41K value that is ~0.5‰ heavier than the silicate average (-0.5‰; Morgan et al., in prep). The heavy δ41K character of seawater might be related to 1) an isotopically enriched input flux (rivers and high-temperature hydrothermal reactions); or 2) a 41K-depleted sink associated with authigenic clay formation during low-temperature alteration of volcanic rocks. Here we present measurements of the δ41K values of pore-fluids from ODP site 1052 in order to constrain potassium isotope fractionation during secondary clay formation. We find that δ41K values and K concentrations both decline systematically with depth. Results from 1-D diffusion-advection-reaction modeling of potassium concentrations and isotopic compositions indicate that fractionation of K isotopes during diffusion (Bourg et al., 2010) can explain all of the change in δ41K values of the pore-fluid with depth. Although the size of the K sink at site 1052 is a trivial fraction of the global K sink in clay minerals, our results suggest that diffusive fractionation of K isotopes in shallow pore-fluids may be, in part, responsible for the elevated δ41K value of seawater.

Studies On Particle-Accompanied Fission Of 252Cf(sf) And 235U(nth,f)

NASA Astrophysics Data System (ADS)

Kopatch, Yu N.; Tishchenko, V.; Speransky, M.; Mutterer, M.; Gönnenwein, F.; Jesinger, P.; Gagarski, A. M.; von Kalben, J.; Kojouharov, I.; Lubkiewics, E.; Mezentseva, Z.; Nezvishevsky, V.; Petrov, G. A.; Schaffner, H.; Scharma, H.; Trzaska, W. H.; Wollersheim, H.-J.

2005-11-01

In recent multi-parameter studies of spontaneous and thermal neutron induced fission, 252Cf(sf) and 235U(nth,f) respectively, the energies and emission angles of fission fragments and light charged particles were measured. Fragments were detected by an energy and angle sensitive twin ionization chamber while the light charged particles were identified by a series of ΔE-Erest telescopes. Up to Be the light particle isotopes could be disentangled. In addition, in the 252Cf(sf) experiment, gammas emitted by the fragments were analyzed by a pair of large-volume segmented clover Ge detectors. Here the main interest is to study the γ-decay and the anisotropy of gammas emitted by fragments and light particles. On the other hand, the high count rates achieved in the U-experiment performed at the high flux reactor of the ILL, Grenoble, should allow to explore fragment-particle correlations in very rare events like quaternary fission. At the present stage of data evaluation, yields and energy distributions of light particles are available. For the present contribution in particular the yields of Be-isotopes for the two reactions studied are compared and discussed. For 252Cf(sf) these isotopic yields were hitherto not known.

'Trophic' and 'source' amino acids in trophic estimation: a likely metabolic explanation.

PubMed

O'Connell, T C

2017-06-01

Amino acid nitrogen isotopic analysis is a relatively new method for estimating trophic position. It uses the isotopic difference between an individual's 'trophic' and 'source' amino acids to determine its trophic position. So far, there is no accepted explanation for the mechanism by which the isotopic signals in 'trophic' and 'source' amino acids arise. Yet without a metabolic understanding, the utility of nitrogen isotopic analyses as a method for probing trophic relations, at either bulk tissue or amino acid level, is limited. I draw on isotopic tracer studies of protein metabolism, together with a consideration of amino acid metabolic pathways, to suggest that the 'trophic'/'source' groupings have a fundamental metabolic origin, to do with the cycling of amino-nitrogen between amino acids. 'Trophic' amino acids are those whose amino-nitrogens are interchangeable, part of a metabolic amino-nitrogen pool, and 'source' amino acids are those whose amino-nitrogens are not interchangeable with the metabolic pool. Nitrogen isotopic values of 'trophic' amino acids will reflect an averaged isotopic signal of all such dietary amino acids, offset by the integrated effect of isotopic fractionation from nitrogen cycling, and modulated by metabolic and physiological effects. Isotopic values of 'source' amino acids will be more closely linked to those of equivalent dietary amino acids, but also modulated by metabolism and physiology. The complexity of nitrogen cycling suggests that a single identifiable value for 'trophic discrimination factors' is unlikely to exist. Greater consideration of physiology and metabolism should help in better understanding observed patterns in nitrogen isotopic values.

Food-web structure of seep sediment macrobenthos from the Gulf of Mexico

USGS Publications Warehouse

Demopoulos, Amanda W.J.; Gualtieri, Daniel; Kovacs, Kaitlin

2010-01-01

The slope environment of the Gulf of Mexico (GOM) supports dense communities of seep megafaunal invertebrates that rely on endosymbiotic bacteria for nutrition. Seep sediments also contain smaller macrofaunal invertebrates whose nutritional pathways are not well understood. Using stable-isotope analysis, we investigate the utilization of chemosynthetically fixed and methane-derived organic matter by macrofauna. Biological sampling was conducted in three lower-slope GOM seep environs: Green Canyon (GC852, 1428 m), Atwater Valley (AT340, 2230 m), and Alaminos Canyon (AC601, 2384 m). Infaunal delta13C and delta15N exhibited a broad range of values; most infauna appeared to be heterotrophic, although several taxa had very light delta15N and delta13C values, indicating possible reliance on chemoautotrophic symbioses. The lightest delta13C and delta15N values were observed in nematodes (delta13C=-54.6 + or - 0.1 per mil, delta15N=-6.1 + or - 0.2 per mil) and one gastropod (delta13C=-54.1 per mil, delta15N=-1.1 per mil) from Green Canyon. Mixing-model results indicated that sulfur-oxidizing Beggiatoa may be an important food source for seep infauna; the rate of utilization ranged from 60% to 100% at Green Canyon and Atwater Valley. The overall range in isotope values was similar across the three sites, suggesting that biogeochemical processes may be very similar in these geographically distinct areas.

Titanium stable isotope investigation of magmatic processes on the Earth and Moon

NASA Astrophysics Data System (ADS)

Millet, Marc-Alban; Dauphas, Nicolas; Greber, Nicolas D.; Burton, Kevin W.; Dale, Chris W.; Debret, Baptiste; Macpherson, Colin G.; Nowell, Geoffrey M.; Williams, Helen M.

2016-09-01

We present titanium stable isotope measurements of terrestrial magmatic samples and lunar mare basalts with the aims of constraining the composition of the lunar and terrestrial mantles and evaluating the potential of Ti stable isotopes for understanding magmatic processes. Relative to the OL-Ti isotope standard, the δ49Ti values of terrestrial samples vary from -0.05 to +0.55‰, whereas those of lunar mare basalts vary from -0.01 to +0.03‰ (the precisions of the double spike Ti isotope measurements are ca. ±0.02‰ at 95% confidence). The Ti stable isotope compositions of differentiated terrestrial magmas define a well-defined positive correlation with SiO2 content, which appears to result from the fractional crystallisation of Ti-bearing oxides with an inferred isotope fractionation factor of ΔTi49oxide-melt = - 0.23 ‰ ×106 /T2. Primitive terrestrial basalts show no resolvable Ti isotope variations and display similar values to mantle-derived samples (peridotite and serpentinites), indicating that partial melting does not fractionate Ti stable isotopes and that the Earth's mantle has a homogeneous δ49Ti composition of +0.005 ± 0.005 (95% c.i., n = 29). Eclogites also display similar Ti stable isotope compositions, suggesting that Ti is immobile during dehydration of subducted oceanic lithosphere. Lunar basalts have variable δ49Ti values; low-Ti mare basalts have δ49Ti values similar to that of the bulk silicate Earth (BSE) while high-Ti lunar basalts display small enrichment in the heavy Ti isotopes. This is best interpreted in terms of source heterogeneity resulting from Ti stable isotope fractionation associated with ilmenite-melt equilibrium during the generation of the mantle source of high-Ti lunar mare basalts. The similarity in δ49Ti between terrestrial samples and low-Ti lunar basalts provides strong evidence that the Earth and Moon have identical stable Ti isotope compositions.

Biscayne aquifer drinking water (USGS45): a new isotopic reference material for δ2H and δ18O measurements of water

USGS Publications Warehouse

Lorenz, Jennifer M.; Tarbox, Lauren V.; Buck, Bryan; Qi, Haiping; Coplen, Tyler B.

2014-01-01

RATIONALE As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from drinking water collected from the Biscayne aquifer in Ft. Lauderdale, Florida. METHODS This isotopic reference water was filtered, homogenized, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This reference material is available by the case of 144 glass ampoules containing either 4 mL or 5 mL of water in each ampoule. RESULTS The δ2H and δ18O values of this reference material are –10.3 ± 0.4 ‰ and –2.238 ± 0.011 ‰, respectively, relative to VSMOW, on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. CONCLUSIONS This isotopic reference material, designated as USGS45, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer. 

Antarctic ice-core water (USGS49) – A new isotopic reference material for δ2H and δ18O measurements of water

USGS Publications Warehouse

Lorenz, Jennifer M.; Qi, Haiping; Coplen, Tyler B.

2017-01-01

As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice-core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual-inlet isotope-ratio mass spectrometry. The δ2H and δ18O values of USGS49 are −394.7 ± 0.4 and −50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), respectively, relative to VSMOW, on scales normalised such that the δ2H and δ18O values of SLAP reference water are, respectively, −428 and −55.5 mUr. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95% probability of encompassing the true value. This isotopic reference material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.

Carbonate stable isotope constraints on sources of arsenic contamination in Neogene tufas and travertines of Attica, Greece

NASA Astrophysics Data System (ADS)

Kampouroglou, Evdokia E.; Tsikos, Harilaos; Economou-Eliopoulos, Maria

2017-11-01

We presented new C and O isotope data of rockforming calcite in terrestrial carbonate deposits from Neogene basins of Attica (Greece), coupled with standard mineralogical and bulk geochemical results. Whereas both isotope datasets [δ18O from -8.99 to -3.20‰(VPDB); δ13C from -8.17 to +1.40‰(VPDB)] could be interpreted in principle as indicative of a meteoric origin, the clear lack of a statistical correlation between them suggests diverse sources for the isotopic variation of the two elements. On the basis of broad correlations between lower carbon isotope data with increasing Fe and bulk organic carbon, we interpreted the light carbon isotope signatures and As enrichments as both derived mainly from a depositional process involving increased supply of metals and organic carbon to the original basins. Periodically augmented biological production and aerobic cycling of organic matter in the ambient lake waters, would have led to the precipitation of isotopically light calcite in concert with elevated fluxes of As-bearing iron oxy-hydroxide and organic matter to the initial terrestrial carbonate sediment. The terrestrial carbonate deposits of Attica therefore represented effective secondary storage reservoirs of elevated As from the adjacent mineralized hinterland; hence these and similar deposits in the region ought to be regarded as key geological candidates for anomalous supply of As to local soils, groundwater and related human activities.

Isotope effect in heavy/light water suspensions of optically active gold nanoparticles

NASA Astrophysics Data System (ADS)

Kutsenko, V. Y.; Artykulnyi, O. P.; Petrenko, V. I.; Avdeev, M. V.; Marchenko, O. A.; Bulavin, L. A.; Snegir, S. V.

2018-04-01

Aqueous suspensions of optically active gold nanoparticles coated with trisodium citrate were synthesized in light (H2O) water and mixture of light and heavy (H2O/D2O) water using the modified Turkevich protocol. The objective of the paper was to verify sensitivity of neutron scattering methods (in particular, neutron reflectometry) to the potential isotope H/D substitution in the stabilizing organic shell around particles in colloidal solutions. First, the isotope effect was studied with respect to the changes in the structural properties of metal particles (size, shape, crystalline morphology) in solutions by electron microscopy including high-resolution transmission electron microscopy from dried systems. The structural factors determining the variation in the adsorption spectra in addition to the change in the optical properties of surrounding medium were discussed. Then, neutron reflectometry was applied to the layered nanoparticles anchored on a silicon wafer via 3-aminopropyltriethoxysilane molecules to reveal the presence of deuterated water molecules in the shell presumably formed by citrate molecules around the metallic core.

The light curve of SN 1987A revisited: constraining production masses of radioactive nuclides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seitenzahl, Ivo R.; Timmes, F. X.; Magkotsios, Georgios, E-mail: ivo.seitenzahl@anu.edu.au

2014-09-01

We revisit the evidence for the contribution of the long-lived radioactive nuclides {sup 44}Ti, {sup 55}Fe, {sup 56}Co, {sup 57}Co, and {sup 60}Co to the UVOIR light curve of SN 1987A. We show that the V-band luminosity constitutes a roughly constant fraction of the bolometric luminosity between 900 and 1900 days, and we obtain an approximate bolometric light curve out to 4334 days by scaling the late time V-band data by a constant factor where no bolometric light curve data is available. Considering the five most relevant decay chains starting at {sup 44}Ti, {sup 55}Co, {sup 56}Ni, {sup 57}Ni, andmore » {sup 60}Co, we perform a least squares fit to the constructed composite bolometric light curve. For the nickel isotopes, we obtain best fit values of M({sup 56}Ni) = (7.1 ± 0.3) × 10{sup –2} M {sub ☉} and M({sup 57}Ni) = (4.1 ± 1.8) × 10{sup –3} M {sub ☉}. Our best fit {sup 44}Ti mass is M({sup 44}Ti) = (0.55 ± 0.17) × 10{sup –4} M {sub ☉}, which is in disagreement with the much higher (3.1 ± 0.8) × 10{sup –4} M {sub ☉} recently derived from INTEGRAL observations. The associated uncertainties far exceed the best fit values for {sup 55}Co and {sup 60}Co and, as a result, we only give upper limits on the production masses of M({sup 55}Co) < 7.2 × 10{sup –3} M {sub ☉} and M({sup 60}Co) < 1.7 × 10{sup –4} M {sub ☉}. Furthermore, we find that the leptonic channels in the decay of {sup 57}Co (internal conversion and Auger electrons) are a significant contribution and constitute up to 15.5% of the total luminosity. Consideration of the kinetic energy of these electrons is essential in lowering our best fit nickel isotope production ratio to [{sup 57}Ni/{sup 56}Ni] = 2.5 ± 1.1, which is still somewhat high but is in agreement with gamma-ray observations and model predictions.« less

Hg-201 (+) CO-Magnetometer for HG-199(+) Trapped Ion Space Atomic Clocks

NASA Technical Reports Server (NTRS)

Burt, Eric A. (Inventor); Taghavi, Shervin (Inventor); Tjoelker, Robert L. (Inventor)

2011-01-01

Local magnetic field strength in a trapped ion atomic clock is measured in real time, with high accuracy and without degrading clock performance, and the measurement is used to compensate for ambient magnetic field perturbations. First and second isotopes of an element are co-located within the linear ion trap. The first isotope has a resonant microwave transition between two hyperfine energy states, and the second isotope has a resonant Zeeman transition. Optical sources emit ultraviolet light that optically pump both isotopes. A microwave radiation source simultaneously emits microwave fields resonant with the first isotope's clock transition and the second isotope's Zeeman transition, and an optical detector measures the fluorescence from optically pumping both isotopes. The second isotope's Zeeman transition provides the measure of magnetic field strength, and the measurement is used to compensate the first isotope's clock transition or to adjust the applied C-field to reduce the effects of ambient magnetic field perturbations.

A model for osmium isotopic evolution of metallic solids at the core-mantle boundary

NASA Astrophysics Data System (ADS)

Humayun, Munir

2011-03-01

Some plumes are thought to originate at the core-mantle boundary, but geochemical evidence of core-mantle interaction is limited to Os isotopes in samples from Hawaii, Gorgona (89 Ma), and Kostomuksha (2.7 Ga). The Os isotopes have been explained by physical entrainment of Earth's liquid outer core into mantle plumes. This model has come into conflict with geophysical estimates of the timing of core formation, high-pressure experimental determinations of the solid metal-liquid metal partition coefficients (D), and the absence of expected 182W anomalies. A new model is proposed where metallic liquid from the outer core is partially trapped in a compacting cumulate pile of Fe-rich nonmetallic precipitates (FeO, FeS, Fe3Si, etc.) at the top of the core and undergoes fractional crystallization precipitating solid metal grains, followed by expulsion of the residual metallic liquid back to the outer core. The Os isotopic composition of the solids and liquids in the cumulate pile is modeled as a function of the residual liquid remaining and the emplacement age using 1 bar D values, with variable amounts of oxygen (0-10 wt %) as the light element. The precipitated solids evolve Os isotope compositions that match the trends for Hawaii (at an emplacement age of 3.5-4.5 Ga; 5%-10% oxygen) and Gorgona (emplacement age < 1.5 Ga; 0%-5% oxygen). The Fe-rich matrix of the cumulate pile dilutes the precipitated solid metal decoupling the Fe/Mn ratio from Os and W isotopes. The advantages to using precipitated solid metal as the Os host include a lower platinum group element and Ni content to the mantle source region relative to excess iron, miniscule anomalies in 182W (<0.1 ɛ), and no effects for Pb isotopes, etc. A gradual thermomechanical erosion of the cumulate pile results in incorporation of this material into the base of the mantle, where mantle plumes subsequently entrain it. Fractional crystallization of metallic liquids within the CMB provides a consistent explanation of both Os isotope correlations, Os-W isotope systematics, and Fe/Mn evidence for core-mantle interaction over the entire Hawaiian source.

Isotopic Measurements of Organic Sulfonates From The Murchison Meteorite

NASA Technical Reports Server (NTRS)

Cooper, G. W.; Chang, S.; DeVincenzi, Donald L. (Technical Monitor)

1995-01-01

Organic sulfonates and phosphonates have been extracted from the Murchison meteorite for stable isotope measurements. Preliminary stable isotope measurements of individual alkyl sulfonates, R-SO3H (R=C(sub n)H(sub 2n+l)), are shown. These compounds were found in aqueous extracts of Murchison. Both groups show trends similar to other homologous series of organic compounds indigenous to Murchison. Molecular abundances decrease with increasing carbon number, and all possible isomers at each carbon number (through C-4) are present. Carbon isotope measurements of the sulfonates show a decrease in the C-13/C-12 ratio with increasing carbon number. The overall objectives of this project are to obtain dime element carbon, hydrogen, and sulfur - intramolecular isotopic analyses of individual sulfonates, and isotopic measurement of carbon and hydrogen of the phosphonates as a group. The Murchison meteorite is the best characterized carbonaceous chondrite with respect to organic chemistry. The finding of organic sulfonates and phosphonates in Murchison is of interest because they are the first well-characterized series of sulfur and phosphorus containing organic compounds found in meteorites. Also, meteorites, comets, and interplanetary dust particles may have been involved in chemical evolution on the early Earth. Because of the critical role of organic phosphorus and sulfur in all living systems, it is particularly interesting to see examples of abiotic syntheses of these classes of compounds. The study of the isotopic composition of the sulfonates and phosphonates can yield insight into their possible interstellar origin as well as their mechanisms of synthesis in the early solar system. Previous isotopic analyses of other classes of organic compounds indigenous to meteorites, e.g., amino acids, carboxylic acids, and hydrocarbons indicate the possibility that interstellar molecules were incorporated into meteorite parent bodies. In these compounds the ratios of heavy to light isotopes of hydrogen (D/H), carbon (C-13/C-12), and nitrogen (N-15/N-14), are anomalous relative to bulk terrestrial and meteoritic values. In some cases, the D/H ratios approach those observed for molecules in interstellar clouds.

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

NASA Astrophysics Data System (ADS)

Immenhauser, A.; Buhl, D.; Richter, D.; Niedermayr, A.; Riechelmann, D.; Dietzel, M.; Schulte, U.

2010-08-01

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ 26Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ 26Mg values of loess-derived soil above the cave (-1.0 ± 0.5‰), soil water (-1.2 ± 0.5‰), the carbonate hostrock (-3.8 ± 0.5‰), dripwater in the cave (-1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; -4.3 ± 0.6‰), cave loam (-0.6 ± 0.1‰) and runoff water (-1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000ln αMg-cc-Mg(aq) = -2.4‰. A similar Mg-isotope fractionation (1000ln αMg-cc-Mg(aq) ≈ -2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, 26Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg 2+ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.

Human Provenancing: It's Elemental…

NASA Astrophysics Data System (ADS)

Meier-Augenstein, Wolfram; Kemp

2009-04-01

Forensic science already uses a variety of methods often in combination to determine a deceased person's identity if neither personal effects nor next of kin (or close friends) can positively identify the victim. While disciplines such as forensic anthropology are able to work from a blank canvass as it were and can provide information on age, gender and ethnical grouping, techniques such as DNA profiling do rely on finding a match either in a database or a comparative sample presumed to be an ante-mortem sample of the victim or from a putative relation. Chances for either to succeed would be greatly enhanced if information gained from a forensic anthropological examination and, circumstances permitting a facial reconstruction could be linked to another technique that can work from a blank canvass or at least does not require comparison to a subject specific database. With the help of isotope ratio mass spectrometry even the very atoms from which a body is made can be used to say something about a person that will help to focus human identification using traditional techniques such as DNA, fingerprints and odontology. Stable isotope fingerprinting works on the basis that almost all chemical elements and in particular the so-called light elements such as carbon (C) that comprise most of the human body occur naturally in different forms, namely isotopes. 2H isotope abundance values recorded by the human body through food and drink ultimately reflect averaged isotopic composition of precipitation or ground water. Stable isotope analysis of 2H isotopic composition in different human tissue such as hair, nails, bone and teeth enables us to construct a time resolved isotopic profile or ‘fingerprint' that may not necessarily permit direct identification of a murder victim or mass disaster victim but in conjunction with forensic anthropological information will provide sufficient intelligence to construct a profile for intelligence lead identification stating where a victim was from (point of origin), how old they were, what their ‘life style' was and even if and where they had recently travelled. Data from several criminal investigations are presented to illustrate potential and limitation of stable isotope analysis of human tissue in aid of victim identification.

Sulfur cycling in wetland peat of the New Jersey Pinelands and its effect on stream water chemistry

NASA Astrophysics Data System (ADS)

Mandernack, Kevin W.; Lynch, L.; Krouse, H. R.; Morgan, M. D.

2000-12-01

The dynamics of sulfur cycling in wetland peat along an elevational transect at high, intermediate, and low locations (MS, NW, and LB sites, respectively) was investigated in the watershed of McDonalds Branch within the New Jersey Pinelands, by utilizing both soil incubation experiments (with 35SO 42- as a radiotracer) and stable isotope (δ 34S and δ 18O) analyses of soil, rain, and streamwater. The results indicate that sulfur cycling can vary greatly among different portions of the watershed and this can have large effects on streamwater chemistry and δ 34S values over distances as short as 1 km. Laboratory incubations of peat samples collected in July 1993 revealed the co-occurrence of dissimilatory sulfate reduction (DSR; rates ranging from 0.2 to 22.1 nmol/wet g/day) and net generation of sulfate (NaH 2PO 4 extractable) in the porewater. Generation of sulfate, which was most pronounced at the LB site, may involve oxidation of reduced sulfur in the peat and/or hydrolysis of ester sulfates (ES). Seasonal changes in streamwater SO 42-/Cl - molar ratios were similar at LB and NW, being low during the summer and high in the winter, probably a result of higher rates of DSR within the peat during the summer. Consistent with this, higher δ 34S values of sulfate in streamwater at NW during the summer are attributable to kinetic isotope effects associated with DSR. In contrast to NW, δ 34S values of streamwater sulfate at LB were consistently lower, fluctuated little throughout the year, and were most negative during the summer (as much as 9‰ lower than streamwater at NW 1 km upstream). In comparison to NW, SO 42-/Cl - ratios were lower in streamwater at LB throughout most of the year except for reversals during the summer, which coincided with the lowest δ 34S values. In addition, there was a marked difference in the relationship of δ 18O vs. δ 34S of sulfate in LB and NW streamwater, further suggesting that sulfur cycling varies greatly over relatively short distances within this watershed. In order to explain some of these site-specific differences in streamwater SO 42-/Cl - ratios, δ 34S, and δ 18O values, we hypothesize that the ES pool at LB may, by means of hydrolysis or isotopic exchange with streamwater sulfate, serve as an additional source of isotopically light sulfate to streamwater throughout most of the year. During the summer, drier conditions lower the water table at LB and enhance oxidation of reduced sulfur which releases a pulse of even isotopically lighter sulfate to the stream.

Iron and oxygen isotope signatures of the Pea Ridge and Pilot Knob magnetite-apatite deposits, southeast Missouri, USA

USGS Publications Warehouse

Childress, Tristan; Simon, Adam C.; Day, Warren C.; Lundstrom, Craig C.; Bindeman, Ilya N.

2016-01-01

New O and Fe stable isotope ratios are reported for magnetite samples from high-grade massive magnetite of the Mesoproterozoic Pea Ridge and Pilot Knob magnetite-apatite ore deposits and these results are compared with data for other iron oxide-apatite deposits to shed light on the origin of the southeast Missouri deposits. The δ18O values of magnetite from Pea Ridge (n = 12) and Pilot Knob (n = 3) range from 1.0 to 7.0 and 3.3 to 6.7‰, respectively. The δ56Fe values of magnetite from Pea Ridge (n = 10) and Pilot Knob (n = 6) are 0.03 to 0.35 and 0.06 to 0.27‰, respectively. These δ18O and the δ56Fe values suggest that magnetite crystallized from a silicate melt (typical igneous δ56Fe ranges 0.06–0.49‰) and grew in equilibrium with a magmatic-hydrothermal aqueous fluid. We propose that the δ18O and δ56Fe data for the Pea Ridge and Pilot Knob magnetite-apatite deposits are consistent with the flotation model recently proposed by Knipping et al. (2015a), which invokes flotation of a magmatic magnetite-fluid suspension and offers a plausible explanation for the igneous (i.e., up to ~15.9 wt % TiO2 in magnetite) and hydrothermal features of the deposits.

Anomalous δ13C in POC at the chemoautotrophy maximum in the Cariaco Basin

NASA Astrophysics Data System (ADS)

Scranton, M. I.; Taylor, G. T.; Thunell, R.; Tappa, E.; benitez-Nelson, C. R.; Muller-Karger, F. E.; Lorenzoni, L.; Astor, Y. M.

2016-02-01

The Cariaco Basin is the world's largest truly marine, permanently anoxic basin and is located on the continental shelf of Venezuela which experiences strong seasonal upwelling. The CARIACO program has been studying the hydrography, biogeochemistry and properties of sinking flux of the Cariaco Basin since 1995. One of the major puzzles of CARIACO has been the nature of the chemoautotrophic maximum which is seen at depths just below the appearance of hydrogen sulfide ( 250-300 m). The identity and sources of oxidants and reductants to this active microbial community, and the identity of the chemoautotrophic organisms themselves, are still only partially known. Below about 50m (the euphotic zone), δ13C values of suspended particulates range from -23 to -26‰, typical of marine phytoplankton. However we have observed both enrichments (values of up to -16‰) and depletions (values of -28‰) near the redox interface. We had expected to see isotopically light POC in the chemoautotrophy maximum, since DIC δ13C should decrease with depth as organic carbon is remineralized. However both positive and negative isotopic excursions in POC occur at depths where dark carbon fixation is at a maximum, and at or near the transition from micro-oxic to sulfidic water. We postulate that this signal may help to define carbon fixation pathways (and dominant chemoautotrophic populations) in the oxic/sulfidic transition region.

What Drives Hydrogen Isotopic Variability Recorded by Biomarkers in Sediments of Lake Karakul, Pamir?

NASA Astrophysics Data System (ADS)

Aichner, B.; Mischke, S.; Pausata, F. S. R.; Werner, M.; Zhang, Q.; Heinecke, L.; Feakins, S. J.; Sachse, D.; Mahmoudov, Z.; Rajabov, I.

2017-12-01

Central Asia is a climate sensitive region located at the boundary of large scale atmospheric circulation systems. To examine glacial to interglacial hydrological changes in the region, we analysed the hydrogen isotopic composition (δD values) of n-alkanes in a 30-ka record from Lake Karakul, eastern Pamir (altitude: 3,915m, MAT: -3.9 °C, MAP: 82 mm). δD values of both aquatic and terrestrial compounds showed distinct trends throughout the studied time interval, with generally higher values during the glacial and lower values during the Holocene, and variability of up to 60‰. In particular shifts towards higher δD values were observed for aquatic biomarkers at ca. 30, 27, and 15 ka BP. Temperature and precipitation effects alone cannot explain the higher δD values during the glacial and the large isotopic amplitudes. To explain these observations we conducted a set of experiments using atmospheric models with embedded isotope modules (CAM3iso- and ECHAM5-wiso). We assume that terrestrial n-alkanes mainly record the isotopic signature of summer precipitation within the lower elevated parts of the Karakul Basin. Based on the model output we hypothesize that shifts between local and more distant vapour sources are the reason behind the trends within isotopic data. Data derived from aquatic biomarkers are more difficult to explain due to multiple influencing factors on δD of the lake water. Assuming that the lake water integrates an annual isotopic signal from the whole lake catchment, we suggest that a change in precipitation seasonality drives the large variability of hydrogen isotopic values. This is in agreement with the models, which suggest reduced winter (more negative δD) and slightly higher summer precipitation (more positive δD) during the glacial compared to the Holocene. Consequently, a net-increase of isotopically enriched inflow into the lake could explain the three distinct shifts towards higher δD values. Expansion of terrestrial vegetation, indicated by increasing biomarker concentrations, during these periods is another indicator for wetter summers in an arid environment. We conclude that δD values of terrestrial compounds reflect major shifts of vapour sources which are driven by insolation, while aquatic biomarkers are additionally influenced by changes of precipitation seasonality.

Lipid Extraction and the Fugacity of Stable Isotope Values

NASA Astrophysics Data System (ADS)

Padula, V.; Causey, D.; Wolf, N.; Welker, J. M.

2013-12-01

Stable isotope analysis of blood, feathers, and other tissues are often used to infer migration patterns, diet composition and trophic status of seabirds. Tissues contain variable amounts of lipids that are depleted in the heavy carbon isotope (13C) and may introduce a bias in these values. There is evidence that lipid extraction may affect other stable isotope ratios, such as δ15N. Consequently, correction factors need to be applied to appropriately interpret δ13C and δ15N values for individual species and tissue type. In this study, we collected seven species of seabirds from the Near Islands, the western most group of islands in the Aleutian Island archipelago. We sampled kidney, liver, heart and muscle samples from each bird and after freeze drying, individual tissue samples were divided into two subsamples. We left one subsample unaltered and extracted lipids from the other subsample using a 2:1 chloroform-methanol solution. We found that the change in δ13C values after lipid extraction (Δδ13C) varied widely among categories (eg., species, tissue type) from 0 - 4 ‰, while Δδ15N values ranged from 0 to 2‰. Notably, within category variation was nonsignificant and the Δδ values were linear against the covariant C:N ratio of the isotopic data, which allows us to use arithmetic corrections for categorical values. Our data strongly indicate that the effects of lipid extraction on stable isotopic values, while linear within category, vary widely by species, tissue, geographic area, year of collection, and isotope. Fugacity is usually employed as a thermodynamic quantity related to the chemical potential or activity that characterizes the escaping tendency from a phase (eg. Mackay & Paterson 1982). Here we use fugacity in the earlier, broader sense of fleeting, transitory, or instable states (eg., S. Johnson 1751), and its measure may be approximated by the higher order variance of Δδ13C and Δδ15N among data categories. Clearly, understanding the nature of variation and the physiological processes responsible for stable isotope values from biological tissues are critical for their interpretation. Change in carbon and nitrogen stable isotopes (ΔδC13, Δδ15N) after lipid extraction for Tufted Puffins (Fratercula cirrhata) collected July 2010 at Attu Island, Aleutians.

Experimentally determined isotope effect during Mg-Fe interdiffusion in olivine

NASA Astrophysics Data System (ADS)

Sio, C. K. I.; Roskosz, M.; Dauphas, N.; Bennett, N.; Mock, T. D.; Shahar, A.

2017-12-01

Isotopic fractionation provides the most direct means to investigate the nature of chemical zoning in minerals, which can be produced by either diffusive transport or crystal growth. Misinterpreting the nature of chemical zoning can result in erroneous conclusions regarding magmatic cooling rates and diffusion timescales. Isotopes are useful in this regard because the light isotopes diffuse faster than their heavier counterparts. As a result, isotopic fractionations should be associated with chemical zoning profiles if they are diffusion-driven. In contrast, little isotopic fractionation is associated with crystal growth during slow cooling at magmatic temperatures. The isotope effect for diffusion is described by β and is related to the mass (m) and diffusivity (D) of isotopes i and j of an element via: Di/Dj = (mj/mi)β. To model isotopic profiles, knowledge of β is required. Several estimates of β for Mg and Fe diffusion in olivine have been reported using natural samples but these estimates are uncertain because they depend on the choice of modeling parameters (Sio et al., 2013; Oeser et al., 2015; Collinet et al., 2017). We have experimentally determined β for Fe (βFe) in olivine as a function of crystallographic orientation, composition, and temperature. Thirty experiments have been conducted by juxtaposing crystallographically oriented olivine crystals to make Fo83.4-Fo88.8 and Fo88.8-Fo100 diffusion couples. These diffusion couples were annealed in a 1 atm gas mixing furnace at 1200 °C, 1300 °C or 1400 °C at QFM - 1.5 for up to 15 days. Chemical profiles were characterized using an electron microprobe and isotopic analyses were done using laser ablation MC-ICPMS. We found a crystallographic dependence of βFe for the Fo88.8-Fo100 couple where βFe [100] ≈ βFe [010] > βFe [001]. For the Fo83.4-Fo88.8 couple, βFe is 0.16 ± 0.09 (2σ) for all 3 major crystallographic axes. A temperature dependence of βFe could not be resolved. These experimentally determined β-values can be used in conjunction with the Mg-Fe diffusivities given in Dohmen and Chakraborty (2007) to simultaneously model the chemical-isotopic profiles of olivine to retrieve cooling and crystallization histories of magmatic rocks.

Isotopic ecology of coyotes from scat and road kill carcasses: A complementary approach to feeding experiments

PubMed Central

Koch, Paul L.

2017-01-01

Scat is frequently used to study animal diets because it is easy to find and collect, but one concern is that gross fecal analysis (GFA) techniques exaggerate the importance of small-bodied prey to mammalian mesopredator diets. To capitalize on the benefits of scat, we suggest the analysis of scat carbon and nitrogen isotope values (δ13C and δ15N). This technique offers researchers a non-invasive method to gather short-term dietary information. We conducted three interrelated studies to validate the use of isotopic values from coyote scat: 1) we determined tissue-to-tissue apparent C and N isotope enrichment factors (ε13* and ε15*) for coyotes from road kill animals (n = 4); 2) we derived diet-to-scat isotope discrimination factors for coyotes; and 3) we used field collected coyote scats (n = 12) to compare estimates of coyote dietary proportions from stable isotope mixing models with estimates from two GFA techniques. Scat consistently had the lowest δ13C and δ15N values among the tissues sampled. We derived a diet-to-scat Δ13C value of -1.5‰ ± 1.6‰ and Δ15N value of 2.3‰ ± 1.3‰ for coyotes. Coyote scat δ13C and δ15N values adjusted for discrimination consistently plot within the isotopic mixing space created by known dietary items. In comparison with GFA results, we found that mixing model estimates of coyote dietary proportions de-emphasize the importance of small-bodied prey. Coyote scat δ13C and δ15N values therefore offer a relatively quick and non-invasive way to gain accurate dietary information. PMID:28369133

Isotopic ecology of coyotes from scat and road kill carcasses: A complementary approach to feeding experiments.

PubMed

Reid, Rachel E B; Koch, Paul L

2017-01-01

Scat is frequently used to study animal diets because it is easy to find and collect, but one concern is that gross fecal analysis (GFA) techniques exaggerate the importance of small-bodied prey to mammalian mesopredator diets. To capitalize on the benefits of scat, we suggest the analysis of scat carbon and nitrogen isotope values (δ13C and δ15N). This technique offers researchers a non-invasive method to gather short-term dietary information. We conducted three interrelated studies to validate the use of isotopic values from coyote scat: 1) we determined tissue-to-tissue apparent C and N isotope enrichment factors (ε13* and ε15*) for coyotes from road kill animals (n = 4); 2) we derived diet-to-scat isotope discrimination factors for coyotes; and 3) we used field collected coyote scats (n = 12) to compare estimates of coyote dietary proportions from stable isotope mixing models with estimates from two GFA techniques. Scat consistently had the lowest δ13C and δ15N values among the tissues sampled. We derived a diet-to-scat Δ13C value of -1.5‰ ± 1.6‰ and Δ15N value of 2.3‰ ± 1.3‰ for coyotes. Coyote scat δ13C and δ15N values adjusted for discrimination consistently plot within the isotopic mixing space created by known dietary items. In comparison with GFA results, we found that mixing model estimates of coyote dietary proportions de-emphasize the importance of small-bodied prey. Coyote scat δ13C and δ15N values therefore offer a relatively quick and non-invasive way to gain accurate dietary information.

Isotopic discrimination of stable isotopes of nitrogen (δ15N) and carbon (δ13C) in a host-specific holocephalan tapeworm.

PubMed

Navarro, J; Albo-Puigserver, M; Coll, M; Saez, R; Forero, M G; Kutcha, R

2014-09-01

During the past decade, parasites have been considered important components of their ecosystems since they can modify food-web structures and functioning. One constraint to the inclusion of parasites in food-web models is the scarcity of available information on their feeding habits and host-parasite relationships. The stable isotope approach is suggested as a useful methodology to determine the trophic position and feeding habits of parasites. However, the isotopic approach is limited by the lack of information on the isotopic discrimination (ID) values of parasites, which is pivotal to avoiding the biased interpretation of isotopic results. In the present study we aimed to provide the first ID values of δ(15)N and δ(13)C between the gyrocotylidean tapeworm Gyrocotyle urna and its definitive host, the holocephalan Chimaera monstrosa. We also test the effect of host body size (body length and body mass) and sex of the host on the ID values. Finally, we illustrate how the trophic relationships of the fish host C. monstrosa and the tapeworm G. urna could vary relative to ID values. Similar to other studies with parasites, the ID values of the parasite-host system were negative for both isotopic values of N (Δδ(15)N = - 3.33 ± 0.63‰) and C (Δδ(13)C = - 1.32 ± 0.65‰), independent of the sex and size of the host. By comparing the specific ID obtained here with ID from other studies, we illustrate the importance of using specific ID in parasite-host systems to avoid potential errors in the interpretation of the results when surrogate values from similar systems or organisms are used.

Stable isotopes (carbon, nitrogen, sulfur), diet, and anthropometry in urban Colombian women: investigating socioeconomic differences.

PubMed

Bender, Richard L; Dufour, Darna L; Valenzuela, Luciano O; Cerling, Thure E; Sponheimer, Matt; Reina, Julio C; Ehleringer, James R

2015-01-01

We conducted stable isotope and dietary analyses of women from higher and lower socioeconomic status (SES) groups in Cali, Colombia. The objectives were to test between-group differences in stable isotope, dietary, and anthropometric characteristics, and to evaluate relationships between diet and stable isotope values. Hair samples from 38 women (mean age 33.4) from higher and lower SES groups were analyzed for δ(13) C, δ(15) N, and δ(34) S values. Dietary intake was assessed via 24-h recalls. Anthropometric variables measured were body mass index, five body circumferences, and six skinfold thicknesses. Mean δ(13) C and δ(15) N values of the higher SES group (-16.4 and 10.3‰) were significantly greater than those of the lower SES group (-17.2 and 9.6‰; P < 0.01), but mean δ(34) S values did not differ significantly between groups (higher SES: 4.6‰; lower SES: 5.1‰). The higher SES group consumed a greater percentage of protein than the lower SES group (14% vs. 12% of energy; P = 0.03), but the groups did not differ in other dietary characteristics or in anthropometric characteristics. δ(13) C, δ(15) N, and δ(34) S values were not correlated with intake of the dietary items predicted (sugars, animal-source protein, and marine foods, respectively). The lower SES group was more variable in all three stable isotope values (P < 0.05), mirroring a trend toward greater dietary variability in this group. Stable isotope values revealed a difference between SES groups that was not explained by the dietary data. The relationship between diet and stable isotope composition is complex. © 2014 Wiley Periodicals, Inc.

Using n-alkane records to constrain carbon cycle - hydrological cycle coupling: Case study from the Northern Hemisphere mid-latitudes during the PETM

NASA Astrophysics Data System (ADS)

Krishnan, S.; Pagani, M.; Tipple, B. J.

2010-12-01

The early Eocene was a warmer world compared to the present and is characterized by rising temperatures interspersed with rapid hyperthermal events. During the largest of these rapid warming events; the Paleocene-Eocene Thermal Maximum (PETM), proxy records suggest that sea surface temperatures (SST) rose by 3-5 deg. C in the tropics (Zachos et al., 2003, Tripati and Elderfield, 2004), >5 deg. C in the Arctic (Sluijs et al., 2006) and perhaps has high as 9 deg. C in some sub-Antarctic regions (Kennett and Stott, 1991; Thomas et al., 1999). This warming is believed to be the result of massive input of 13C-depleted carbon into the ocean-atmosphere system, evidenced by the large negative carbon isotope excursion (CIE) and carbonate dissolution associated with the event. However, there are several questions regarding the exact mechanism of warming and feedbacks between the carbon cycle and climate. Did climate shift prior to the main event that led to the release of isotopically light carbon? Do we observe consistent leads or lags between changes in carbon isotopes and hydrological conditions during warm intervals? This study aims to reconstruct hydrological changes in the in the Northern Hemisphere mid-latitudes during the PETM using terrestrial biomarkers. Terrestrial biomarkers, such leaf-wax lipids stored in sediments, have the unique advantage of recording carbon and hydrogen isotopic compositions of atmospheric CO2 (modified by plant fractionation) and precipitation (modified by plant fractionation and evapotranspiration), allowing evaluation of the relative timing of carbon and hydrogen isotopic (i.e., climate) shifts. In this study, we compile and present three mid-latitude PETM records from the Northern Hemisphere, i.e. Alamedilla (Spain), Cicogna and Forada (Italy). The Cicogna and Forada sections are located in the Belluno basin (~12 km apart). Preliminary results do not indicate any significant pre-excursion hydrogen isotope changes at Cicogna, while at Forada we observe a pre-excursion shift toward more positive values. Comparison of the mean-weighted isotopic trends (to account for vegetation changes) indicates that the carbon and hydrogen isotopic compositions shift simultaneously at the start of the CIE at Cicogna and Forada and remain coupled during the latter part of the recovery. However, the most depleted values in δD do not coincide with the most negative δ13C values, suggesting that the response time of the hydrological cycle was slower than the carbon isotopic excursion. The δD trends appear to diverge from δ13C records during the initial recovery period. This difference in response and response times between the initial perturbation and recovery enable us to constrain the timing and mechanism of feedbacks. A third section (Alamedilla), located at lower latitude, will be used to test these hypotheses. The timing and average magnitudes of δD changes at these three sites will be extrapolated to infer precipitation trends during the late Paleocene, peak PETM, and early Eocene for this region and will be useful for future data-model comparisons.

Sulfur record of rising and falling marine oxygen and sulfate levels during the Lomagundi event

PubMed Central

Planavsky, Noah J.; Bekker, Andrey; Hofmann, Axel; Owens, Jeremy D.; Lyons, Timothy W.

2012-01-01

Carbonates from approximately 2.3–2.1 billion years ago show markedly positive δ13C values commonly reaching and sometimes exceeding +10‰. Traditional interpretation of these positive δ13C values favors greatly enhanced organic carbon burial on a global scale, although other researchers have invoked widespread methanogenesis within the sediments. To resolve between these competing models and, more generally, among the mechanisms behind Earth’s most dramatic carbon isotope event, we obtained coupled stable isotope data for carbonate carbon and carbonate-associated sulfate (CAS). CAS from the Lomagundi interval shows a narrow range of δ34S values and concentrations much like those of Phanerozoic and modern marine carbonate rocks. The δ34S values are a close match to those of coeval sulfate evaporites and likely reflect seawater composition. These observations are inconsistent with the idea of diagenetic carbonate formation in the methanic zone. Toward the end of the carbon isotope excursion there is an increase in the δ34S values of CAS. We propose that these trends in C and S isotope values track the isotopic evolution of seawater sulfate and reflect an increase in pyrite burial and a crash in the marine sulfate reservoir during ocean deoxygenation in the waning stages of the positive carbon isotope excursion. PMID:23090989

THEORETICAL AND EXPERIMENTAL ASPECTS OF ISOTOPIC FRACTIONATION.

USGS Publications Warehouse

O'Neil, James R.

1986-01-01

Essential to the interpretation of natural variations of light stable isotope ratios is knowledge of the magnitude and temperature dependence of isotopic fractionation factors between the common minerals and fluids. These fractionation factors are obtained in three ways: (1) Semi-empirical calculations using spectroscopic data and the methods of statistical mechanics. (2) Laboratory calibration studies. (3) Measurements of natural samples whose formation conditions are well-known or highly constrained. In this chapter methods (1) and (2) are evaluated and a review is given of the present state of knowledge of the theory of isotopic fractionation and the fraction that influence the isotopic properties of minerals.

Sr and Nd isotopes of suspended sediments from rivers of the Amazon basin

NASA Astrophysics Data System (ADS)

Hatting, Karina; Santos, Roberto V.; Sondag, Francis

2014-05-01

The Rb-Sr and Sm-Nd isotopic systems are important tools to constrain the provenance of sediment load in river systems. This study presents the isotopic composition of Sr and Nd isotopes and major and minor elements in suspended sediments from the Marañón-Solimões, Amazonas and Beni-Madeira rivers. The data were used to constrain the source region of the sediments and to better understand the main seasonal and spatial transport processes within the basin based on the variations of the chemical and isotopic signals. They also allow establishing a relationship between sediment concentrations and flow rate values. The study presents data collected during a hydrological year between 2009 and 2010. The Marañón-Solimões River presents low Sr isotopic values (0.7090-0.7186), broad EpslonNd(0) range (-15.17 to -8.09) and Nd model (TDM) ages varying from 0.99 to 1.81 Ga. Sources of sediments to the Marañón-Solimões River include recent volcanic rocks in northern Peru and Ecuador, as well as rocks with long crustal residence time and carbonates from the Marañón Basin, Peru. The Beni-Madeira River has more radiogenic Sr isotope values (0.7255-0.7403), more negative EpslonNd(0) values (-20.46 to -10.47), and older Nd isotope model ages (from 1.40 to 2.35 Ga) when compared to the Marañón-Solimões River. These isotope data were related to the erosion of Paleozoic and Cenozoic foreland basins that are filled with Precambrian sediments derived from the Amazonian Craton. These basins are located in Bolivian Subandina Zone. The Amazon River presents intermediate isotopic values when compared to those found in the Marañón-Solimões and Beni-Madeira rivers. Its Sr isotope ratios range between 0.7193 and 0.7290, and its EpslonNd(0) values varies between -11.09 and -9.51. The Nd isotope model ages of the suspended sediments vary between 1.28 and 1.77 Ga. Concentrations of soluble and insoluble elements indicate a more intense weathering activity in sediments of the Beni-Madeira River. This river has a larger difference in the Sr isotopic composition between the diluted and solid phases, which has been assigned to the high level of weathering of its sediment source area. In the Beni-Madeira River sub-basin dominates weathering of silicate rocks, while in the Marañón-Solimões River sub-basin there also weathering of carbonate and evaporitic rocks.

Isotope Label-Aided Mass Spectrometry Reveals the Influence of Environmental Factors on Metabolism in Single Eggs of Fruit Fly

PubMed Central

Tseng, Te-Wei; Wu, June-Tai; Chen, Yu-Chie; Urban, Pawel L.

2012-01-01

In order to investigate the influence of light/dark cycle on the biosynthesis of metabolites during oogenesis, here we demonstrate a simple experimental protocol which combines in-vivo isotopic labeling of primary metabolites with mass spectrometric analysis of single eggs of fruit fly (Drosophila melanogaster). First, fruit flies were adapted to light/dark cycle using artificial white light. Second, female flies were incubated with an isotopically labeled sugar (13C6-glucose) for 12 h – either during the circadian day or the circadian night, at light or at dark. Third, eggs were obtained from the incubated female flies, and analyzed individually by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS): this yielded information about the extent of labeling with carbon-13. Since the incorporation of carbon-13 to uridine diphosphate glucose (UDP-glucose) in fruit fly eggs is very fast, the labeling of this metabolite was used as an indicator of the biosynthesis of metabolites flies/eggs during 12-h periods, which correspond to circadian day or circadian night. The results reveal that once the flies adapted to the 12-h-light/12-h-dark cycle, the incorporation of carbon-13 to UDP-glucose present in fruit fly eggs was not markedly altered by an acute perturbation to this cycle. This effect may be due to a relationship between biosynthesis of primary metabolites in developing eggs and an alteration to the intake of the labeled substrate – possibly related to the change of the feeding habit. Overall, the study shows the possibility of using MALDI-MS in conjunction with isotopic labeling of small metazoans to unravel the influence of environmental cues on primary metabolism. PMID:23185587

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Stable isotopes confirm a coastal diet for critically endangered Mediterranean monk seals.

PubMed

Karamanlidis, Alexandros A; Curtis, P Jeff; Hirons, Amy C; Psaradellis, Marianna; Dendrinos, Panagiotis; Hopkins, John B

2014-01-01

Understanding the ecology and behaviour of endangered species is essential for developing effective management and conservation strategies. We used stable isotope analysis to investigate the foraging behaviour of critically endangered Mediterranean monk seals (Monachus monachus) in Greece. We measured carbon and nitrogen isotope ratios (expressed as δ(13)C and δ(15)N values, respectively) derived from the hair of deceased adult and juvenile seals and the muscle of their known prey to quantify their diets. We tested the hypothesis that monk seals primarily foraged for prey that occupy coastal habitats in Greece. We compared isotope values from seal hair to their coastal and pelagic prey (after correcting all prey for isotopic discrimination) and used these isotopic data and a stable isotope mixing model to estimate the proportion of coastal and pelagic resources consumed by seals. As predicted, we found that seals had similar δ(13)C values as many coastal prey species and higher δ(13)C values than pelagic species; these results, in conjunction with mean dietary estimates (coastal=61 % vs. pelagic=39 %), suggest that seals have a diverse diet comprising prey from multiple trophic levels that primarily occupy the coast. Marine resource managers should consider using the results from this study to inform the future management of coastal habitats in Greece to protect Mediterranean monk seals.

a Dual Proxy of Oceanic Weathering Inputs: Rare Earth Element Patterns and nd Isotopes from Metalliferous Sediment Cores

NASA Astrophysics Data System (ADS)

Sherrell, R. M.; Wright, J. D.; Hamelin, B.; Michard, A.

2002-12-01

Recent interest in reconstructing Nd isotopic distributions in the past ocean using Fe-Mn crusts, oxide coatings on sediment particles, foraminifera shells and fish teeth has raised questions about relative influence of water mass mixing vs. variations in weathering input. We have explored the utility of hydrothermal metalliferous sediments for generating high-resolution records of both Nd isotopes and rare earth element (REE) patterns in deepwater. We present a 135kyr record of high precision REE data, preliminary Nd isotope ratios, and δ18O from a 2.3 m core collected at 3180m at 11S on the East Pacific Rise (EPR). REEs are dominated (\\>96%) by seawater REEs adsorbed to Fe particles in these metalliferous carbonates; the hydrothermal REE source itself is negligible. Downcore variations in Nd/Er (proxy for light/heavy pattern fractionation) are not large (10%) but are easily quantified by our ICP-MS method (precision 1%), and reproducibly correspond to δ18O shifts. The largest Nd/Er excusions occur during deglaciations, e.g. Nd/Er=5.1 to 4.4 mol/mol between glacial MIS 6 and interglacial MIS 5e. If these variations reflect composition of ambient deepwater, then the results are opposite those expected by reduced influence of Atlantic component water (high Nd/Er) during glacials. Prelimininary ɛNd values for samples taken at Nd/Er extrema in MIS 1, 2, 5e and 6 are nearly invarient at -3.5+/-0.4, in excellent agreement with modern water column ɛNd for Pacific deepwater at this depth. Thus, while paleo-ɛNd shows virtually no change over 135kyr, REE pattern does carry information, but not, we believe, about water mass mixing changes. We suggest instead that Nd/Er reflects climatically-influenced weathering inputs to the Pacific REE pool. We propose a sea-level-driven mechanism: glacial low sea-stand reduces the extent of estuarine environments in which the light-REE-depleted seawater pattern is imparted, causing 1) more direct input of unfractionated crustal REE sources, and 2) release of REEs during erosion of high Nd/Er shelf sediments. This mechanism, unlike tectonically-driven shifts in weathering sources, can occur on glacial/interglacial timescales, and is expected to result in negligible change in Nd isotopic input, consistent with observations. Alternative mechanisms could involve temporal variations in the flux and composition of water column particles. In a first application to longer timescales, a low-resolution Cenozoic record from DSDP Leg 92, shows much larger but smooth variation of 50% in Nd/Er between 28 and 1.5 Ma, with high values from 28 to 20 Ma, decreasing during the mid-Miocene to values similar to modern at <8 Ma. ɛNd varies from -3 (near present deepwater value) to ~-6, but does not co-vary simply with Nd/Er. The combination of Nd/Er and ɛNd constitutes a new tandem proxy that may reveal changes in the style and/or source of weathering inputs to the past ocean, not interpretable from ɛNd alone. The results may have implications for climate-linked changes in the oceanic supply of biogeochemically important elements such as Fe and P.

A New Dual Proxy of Oceanic Weathering Inputs: Rare Earth Element Patterns and Nd Isotopes From Metalliferous Sediment Cores

NASA Astrophysics Data System (ADS)

Sherrell, R.; Wright, J.; Michard, A.; Hamelin, B.

Recent interest in reconstructing Nd isotopic distributions in the past ocean using Fe- Mn crusts, oxide coatings on sediment particles, foraminifera shells and fish teeth has raised questions about relative influence of water mass mixing vs. variations in weath- ering input. We have explored the utility of hydrothermal metalliferous sediments for generating high-resolution records of both Nd isotopes and rare earth element (REE) patterns in deepwater. We present a 135kyr record of high precision REE data, pre- liminary Nd isotope ratios, and 18O from a 2.3 m core collected at 3180m at 11S on the East Pacific Rise (EPR). REEs are dominated ( 96%) by seawater REEs adsorbed to Fe particles in these metalliferous carbonates; the hydrothermal REE source itself is negligible. Downcore variations in Nd/Er (proxy for light/heavy pattern fractiona- tion) are not large (10%) but are easily quantified by our ICP-MS method (precision 1%), and reproducibly correspond to 18O shifts. The largest Nd/Er excusions occur during deglaciations, e.g. Nd/Er=5.1 to 4.4 mol/mol between glacial MIS 6 and inter- glacial MIS 5e. If these variations reflect composition of ambient deepwater, then the results are opposite those expected by reduced influence of Atlantic component water (high Nd/Er) during glacials. Prelimininary Nd values for samples taken at Nd/Er ex- trema in MIS 1, 2, 5e and 6 are nearly invarient at -3.5+/-0.4, in excellent agreement with modern water column Nd for Pacific deepwater at this depth. Thus, while paleo- Nd shows virtually no change over 135kyr, REE pattern does carry information, but not, we believe, about water mass mixing changes. We suggest instead that Nd/Er re- flects climatically-influenced weathering inputs to the Pacific REE pool. We propose a sea-level-driven mechanism: glacial low sea-stand reduces the extent of estuarine environments in which the light-REE-depleted seawater pattern is imparted, causing 1) more direct input of unfractionated crustal REE sources, and 2) release of REEs during erosion of high Nd/Er shelf sediments. This mechanism, unlike tectonically- driven shifts in weathering sources, can occur on glacial/interglacial timescales, and is expected to result in negligible change in Nd isotopic input, consistent with ob- servations. Alternative mechanisms could involve temporal variations in the flux and composition of water column particles. In a first application to longer timescales, a low-resolution Cenozoic record from DSDP Leg 92, shows much larger but smooth variation of 50% in Nd/Er between 28 and 1.5 Ma, with high values from 28 to 20 Ma, decreasing during the mid-Miocene to values similar to modern at <8 Ma. Nd varies from -3 (near present deepwater value) to -6, but does not co-vary simply with Nd/Er. The combination of Nd/Er and Nd constitutes a new tandem proxy that may reveal changes in the style and/or source of weathering inputs to the past ocean, not interpretable from Nd alone. The results may have implications for climate-linked changes in the oceanic supply of biogeochemically important elements such as Fe and P.

Estimating blue whale skin isotopic incorporation rates and baleen growth rates: Implications for assessing diet and movement patterns in mysticetes

PubMed Central

Busquets-Vass, Geraldine; Newsome, Seth D.; Calambokidis, John; Serra-Valente, Gabriela; Jacobsen, Jeff K.; Aguíñiga-García, Sergio; Gendron, Diane

2017-01-01

Stable isotope analysis in mysticete skin and baleen plates has been repeatedly used to assess diet and movement patterns. Accurate interpretation of isotope data depends on understanding isotopic incorporation rates for metabolically active tissues and growth rates for metabolically inert tissues. The aim of this research was to estimate isotopic incorporation rates in blue whale skin and baleen growth rates by using natural gradients in baseline isotope values between oceanic regions. Nitrogen (δ15N) and carbon (δ13C) isotope values of blue whale skin and potential prey were analyzed from three foraging zones (Gulf of California, California Current System, and Costa Rica Dome) in the northeast Pacific from 1996–2015. We also measured δ15N and δ13C values along the lengths of baleen plates collected from six blue whales stranded in the 1980s and 2000s. Skin was separated into three strata: basale, externum, and sloughed skin. A mean (±SD) skin isotopic incorporation rate of 163±91 days was estimated by fitting a generalized additive model of the seasonal trend in δ15N values of skin strata collected in the Gulf of California and the California Current System. A mean (±SD) baleen growth rate of 15.5±2.2 cm y-1 was estimated by using seasonal oscillations in δ15N values from three whales. These oscillations also showed that individual whales have a high fidelity to distinct foraging zones in the northeast Pacific across years. The absence of oscillations in δ15N values of baleen sub-samples from three male whales suggests these individuals remained within a specific zone for several years prior to death. δ13C values of both whale tissues (skin and baleen) and potential prey were not distinct among foraging zones. Our results highlight the importance of considering tissue isotopic incorporation and growth rates when studying migratory mysticetes and provide new insights into the individual movement strategies of blue whales. PMID:28562625

An interlaboratory study to test instrument performance of hydrogen dual-inlet isotope-ratio mass spectrometers

USGS Publications Warehouse

Brand, Willi A.; Coplen, T.B.

2001-01-01

An interlaboratory comparison of forty isotope-ratio mass spectrometers of different ages from several vendors has been performed to test 2H/1H performance with hydrogen gases of three different isotopic compositions. The isotope-ratio results (unsufficiently corrected for H3+ contribution to the m/z = 3 collector, uncorrected for valve leakage in the change-over valves, etc.) expressed relative to one of these three gases covered a wide range of values: -630??? to -790??? for the second gas and -368??? to -462??? for the third gas. After normalizing the isotopic abundances of these test gases (linearly adjusting the ?? values so that the gases with the lowest and highest 2H content were identical for all laboratories), the standard deviation of the 40 measurements of the intermediate gas was a remarkably low 0.85???. It is concluded that the use of scaling factors is mandatory for providing accurate internationally comparable isotope-abundance values. Linear scaling for the isotope-ratio scales of gaseous hydrogen mass spectrometers is completely adequate. ?? Springer-Verlag 2001.

Geographical patterns of human diet derived from stable-isotope analysis of fingernails

USGS Publications Warehouse

Nardoto, G.B.; Silva, S.; Kendall, C.; Ehleringer, J.R.; Chesson, L.A.; Ferraz, E.S.B.; Moreira, M.Z.; Ometto, Jean P. H. B.; Martinelli, L.A.

2006-01-01

Carbon and nitrogen isotope ratios of human fingernails were measured in 490 individuals in the western US and 273 individuals in southeastern Brazil living in urban areas, and 53 individuals living in a moderately isolated area in the central Amazon region of Brazil and consuming mostly locally grown foods. In addition, we measured the carbon and nitrogen isotope ratios of common food items to assess the extent to which these isotopic signatures remain distinct for people eating both omnivorous and vegetarian diets and living in different parts of the world, and the extent to which dietary information can be interpreted from these analyses. Fingernail ??13C values (mean ?? standard deviation) were -15.4 ?? 1.0 and -18.8 ?? 0.8??? and ??15N values were 10.4 ?? 0.7 and 9.4 ?? 0.6??? for southeastern Brazil and western US populations, respectively. Despite opportunities for a "global supermarket" effect to swamp out carbon and nitrogen isotope ratios in these two urbanized regions of the world, differences in the fingernail isotope ratios between southeastern Brazil and western US populations persisted, and appeared to be more associated with regional agricultural and animal production practices. Omnivores and vegetarians from Brazil and the US were isotopically distinct, both within and between regions. In a comparison of fingernails of individuals from an urban city and isolated communities in the Amazonian region, the urban region was similar to southeastern Brazil, whereas individuals from isolated nonurban communities showed distinctive isotopic values consistent with their diets and with the isotopic values of local foods. Although there is a tendency for a "global supermarket" diet, carbon and nitrogen isotopes of human fingernails hold dietary information directly related to both food sources and dietary practices in a region. ?? 2006 Wiley-Liss, Inc.

Geographical patterns of human diet derived from stable-isotope analysis of fingernails.

PubMed

Nardoto, Gabriela B; Silva, Steven; Kendall, Carol; Ehleringer, James R; Chesson, Lesley A; Ferraz, Epaminondas S B; Moreira, Marcelo Z; Ometto, Jean P H B; Martinelli, Luiz A

2006-09-01

Carbon and nitrogen isotope ratios of human fingernails were measured in 490 individuals in the western US and 273 individuals in southeastern Brazil living in urban areas, and 53 individuals living in a moderately isolated area in the central Amazon region of Brazil and consuming mostly locally grown foods. In addition, we measured the carbon and nitrogen isotope ratios of common food items to assess the extent to which these isotopic signatures remain distinct for people eating both omnivorous and vegetarian diets and living in different parts of the world, and the extent to which dietary information can be interpreted from these analyses. Fingernail delta13C values (mean +/- standard deviation) were -15.4 +/- 1.0 and -18.8 +/- 0.8 per thousand and delta15N values were 10.4 +/- 0.7 and 9.4 +/- 0.6 per thousand for southeastern Brazil and western US populations, respectively. Despite opportunities for a "global supermarket" effect to swamp out carbon and nitrogen isotope ratios in these two urbanized regions of the world, differences in the fingernail isotope ratios between southeastern Brazil and western US populations persisted, and appeared to be more associated with regional agricultural and animal production practices. Omnivores and vegetarians from Brazil and the US were isotopically distinct, both within and between regions. In a comparison of fingernails of individuals from an urban city and isolated communities in the Amazonian region, the urban region was similar to southeastern Brazil, whereas individuals from isolated nonurban communities showed distinctive isotopic values consistent with their diets and with the isotopic values of local foods. Although there is a tendency for a "global supermarket" diet, carbon and nitrogen isotopes of human fingernails hold dietary information directly related to both food sources and dietary practices in a region. 2006 Wiley-Liss, Inc.

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

USGS Publications Warehouse

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

2009-01-01

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N values. Comparative ??13C and ??15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials.

Hydrogen and oxygen stable isotope ratios of milk in the United States.

PubMed

Chesson, Lesley A; Valenzuela, Luciano O; O'Grady, Shannon P; Cerling, Thure E; Ehleringer, James R

2010-02-24

Models of hydrogen and oxygen incorporation in human tissues recognize the impact of geographic location on the isotopic composition of fluid intake, but inputs can include nonlocal beverages, such as milk. Milk and cow drinking water were collected from dairies, and commercially available milk was purchased from supermarkets and fast food restaurants. It was hypothesized that milk water delta(2)H and delta(18)O values record geographic location information. Correlations between milk water isotope ratios and purchase location tap water were significant. However, the amount of variation in milk delta(2)H and delta(18)O values explained by tap water was low, suggesting a single estimation of fluid input isotope ratios may not always be adequate in studies. The delta(2)H and delta(18)O values of paired milk and cow drinking water were related, suggesting potential for geographical origin assignment using stable isotope analysis. As an application example, milk water delta(18)O values were used to predict possible regions of origin for restaurant samples.

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.

Relationship between microbial sulfate reduction rates and sulfur isotopic fractionation

NASA Astrophysics Data System (ADS)

Matsu'Ura, F.

2009-12-01

Sulfate reduction is one of the common processes to obtain energy for certain types of microorganisms.They use hydrogen gas or organic substrates as electron donor and sulfates as electron acceptor, and reduce sulfates to sulfides. Sulfate reducing microbes extend across domains Archea and Bacteria, and are believed to be one of the earliest forms of terrestrial life (Shen 2004). The origin of 34S-depleted (light) sulfide sulfur, especially δ34S < -30 ‰, around hydrothermal vents or beneath the sea-floor is speculated to be the products of sulfate reducers. But laboratory experiments using sulfate reducers fail to produce such light sulfur, and many models were proposed to explain the discrepancy. Canfield et al. (2006) proposed so-called "standard model" based on previous studies. The standard model explained the reason for the large fractionation by temperature dependence of sulfur isotopic fractionation factor and rate of sulfate reduction, which indicated the growth conditions of microbes. However, they failed to prove their model by their other experiments (Canfield et al., 2006). In this study, I performed laboratory culture experiment of sulfate reducing bacteria (SRB) to explain the 34S-depleted sulfide sulfur. [Experiments] To compare the result with Canfield et al. (2006), I used Desulfovibrio desulfuricans for my laboratory culture experiment. D. desulfuricans was inoculated into glass vials, which contain 40ml of liquid culture media slightly modified from DSMZ #63 medium.Excess amount of Fe (II) is added to the DSMZ#63 medium to precipitate sulfide as iron sulfide. The vials were incubated at 25°C, 30°C, and 37°C, respectively. 21 vials were used for one temperature and sulfide and sulfate was collected from each three glass vials at every 12 hours from 72 hours to 144 hours after start of incubation. The sulfide was precipitated as iron sulfide and the sulfate was precipitated as barite. Sulfur isotope compositions of sulfate and sulfide were measured by standard method using Delta Plus mass-spectrometer. [Results and Discussion] The fractionation between sulfide and sulfate ranged from 2.7 to 11.0. The fractionation values varied among the different incubation temperature and growth phase of D. desulfuricans. The maximum fractionation values of three incubation temperatures were 9.9, 11.0, and 9.7, for 25 °C, 30°C, and 37°C, respectively. These results were different from standard model and Canfield et al. (2006). I could not find the clear correlation between ∂34S values and incubation temperatures in this experiment. The measured fractionation values during the incubation varied with incubation stage. The fractionation values clearly increased with incubation time at every temperature, and at 25°C ∂34S value was 3.6 at the 72h and it increased to 7.9 at 144 hours. This indicated the difference of sulfate reduction rate due to the growth phase of SRB. In the early logarithmic growth phase, metabolic activity of SRB is high and sulfate reduction rate is fast. In contrast at the stationary phase, SRB stop growing and sulfate reduction rate get slower. My result suggested that the sulfur isotopic fractionation is controlled by growth phase of SRB and lighter sulfide would be produced by the stationary phase or half-dormant SRB in natural environment.

High-Precision Measurement of 13C/12C Isotopic Ratio Using Gas Chromatography-Combustion-Cavity Ring-Down Spectroscopy

NASA Astrophysics Data System (ADS)

Saad, N.; Kuramoto, D. S.; Haase, C.; Crosson, E.; Tan, S.; Zare, R. N.

2009-12-01

Light stable isotope analysis, and in particular, compound specific isotopic analysis (CSIA), is a valuable tool to elucidate pathways and provide a better insight into biological, ecological, and geological systems. We present here the results of compound-specific isotopic carbon analysis of short chain hydrocarbons using the world’s first combination of gas chromatography, combustion interface, and cavity ring-down spectroscopy (GC-C-CRDS). Cavity ring-down spectroscopy (CRDS) is a highly sensitive optical spectroscopy, one application of which is to measure the stable isotopic ratios in small molecules. Because it uses a highly reflective optical cavity with many kilometers effective path length, CRDS provides some of the most sensitive and precise optical absorption measurements. Most optical spectroscopy isotopic analysis measures the quantities of each isotopologue independently using their distinct ro-vibrational spectra. The most common isotopes measured with optical spectroscopy are 13C and 12C in carbon dioxide. However, the isotopes of hydrogen, oxygen, and sulfur have also been measured. Unlike isotope ratio mass spectrometry (IRMS), optical spectroscopy can distinguish among isobars, which have essentially identical m/z ratios. The combination of chemical separation, chemical conversion, and CRDS makes a nearly universal tool for isotopic analysis of mixtures. In addition, CRDS can tolerate a variety of compounds mixed with the target. For example, CRDS can measure carbon dioxide and its isotopic 13C/12C ratio in the presence of oxygen. Using the novel GC-C-CRDS system, we injected a 75-microliter mixture of approximately equal quantities of methane, ethane, and propane into a gas chromatograph using helium as carrier gas. The methane, ethane, and propane were separated in time by 100 to 200 seconds after the chromatograph. Oxygen gas was added, and the hydrocarbons were combusted in a catalytic combustor with platinum and nickel, held at 1150oC. The combusted products were combined with dry nitrogen gas to provide sufficient gas flow for the CRDS analyzer, which measured the 13C/12C isotopic ratio of the separated methane, ethane, and propane, obtaining a precision of 0.95 permil or better. The calibration accuracy was within 3 permil of the values determined using IRMS. The current CRDS-based system is less expensive, does not require highly trained personnel to operate, and is portable, compared with IRMS. We anticipate that advances in spectroscopic analysis will improve the precision and accuracy of the CRDS isotopic measurement, making it comparable with IRMS.

Benthic iron cycling in a high-oxygen environment: Implications for interpreting the Archean sedimentary iron isotope record.

PubMed

McCoy, V E; Asael, D; Planavsky, N

2017-09-01

The most notable trend in the sedimentary iron isotope record is a shift at the end of the Archean from highly variable δ 56 Fe values with large negative excursions to less variable δ 56 Fe values with more limited negative values. The mechanistic explanation behind this trend has been extensively debated, with two main competing hypotheses: (i) a shift in marine redox conditions and the transition to quantitative iron oxidation; and (ii) a decrease in the signature of microbial iron reduction in the sedimentary record because of increased bacterial sulfate reduction (BSR). Here, we provide new insights into this debate and attempt to assess these two hypotheses by analyzing the iron isotope composition of siderite concretions from the Carboniferous Mazon Creek fossil site. These concretions precipitated in an environment with water column oxygenation, extensive sediment pile dissimilatory iron reduction (DIR) but limited bacterial sulfate reduction (BSR). Most of the concretions have slightly positive iron isotope values, with a mean of 0.15‰ and limited iron isotope variability compared to the Archean sedimentary record. This limited variability in an environment with high DIR and low BSR suggests that these conditions alone are insufficient to explain Archean iron isotope compositions. Therefore, these results support the idea that the unusually variable and negative iron isotope values in the Archean are due to dissimilatory iron reduction (DIR) coupled with extensive water column iron cycling. © 2017 John Wiley & Sons Ltd.

Calibration strategies for the determination of stable carbon absolute isotope ratios in a glycine candidate reference material by elemental analyser-isotope ratio mass spectrometry.

PubMed

Dunn, Philip J H; Malinovsky, Dmitry; Goenaga-Infante, Heidi

2015-04-01

We report a methodology for the determination of the stable carbon absolute isotope ratio of a glycine candidate reference material with natural carbon isotopic composition using EA-IRMS. For the first time, stable carbon absolute isotope ratios have been reported using continuous flow rather than dual inlet isotope ratio mass spectrometry. Also for the first time, a calibration strategy based on the use of synthetic mixtures gravimetrically prepared from well characterised, highly (13)C-enriched and (13)C-depleted glycines was developed for EA-IRMS calibration and generation of absolute carbon isotope ratio values traceable to the SI through calibration standards of known purity. A second calibration strategy based on converting the more typically determined delta values on the Vienna PeeDee Belemnite (VPDB) scale using literature values for the absolute carbon isotope ratio of VPDB itself was used for comparison. Both calibration approaches provided results consistent with those previously reported for the same natural glycine using MC-ICP-MS; absolute carbon ratios of 10,649 × 10(-6) with an expanded uncertainty (k = 2) of 24 × 10(-6) and 10,646 × 10(-6) with an expanded uncertainty (k = 2) of 88 × 10(-6) were obtained, respectively. The absolute carbon isotope ratio of the VPDB standard was found to be 11,115 × 10(-6) with an expanded uncertainty (k = 2) of 27 × 10(-6), which is in excellent agreement with previously published values.

A City-wide Investigation of the Isotopic Distribution and Source of Tap Waters for Forensic Human Geolocation Ground-truthing.

PubMed

Ueda, Momoko; Bell, Lynne S

2017-05-01

Human geolocation is prefaced on the accuracy of the geographic precision of mapped isotopic values for drinking water. As most people live in cities, it becomes important to understand city water supplies and how the isotopic values uniquely reflect that city. This study investigated the isotopic distribution of δ 2 H and δ 18 O from sourced tap waters that were collected from across the Metro Vancouver (MV) area (n = 135). The results revealed that the isotopic values reflect their water sources with a range of 5.3‰ for δ 18 O tap and 29.3‰ for δ 2 H tap for MV. The results indicate that individual cities need higher resolution studies to determine their tap water isotopic ranges, and a good understanding of the water supply network itself for human geolocation work. With an extended high-resolution understanding of each city, human tissue may be compared with more certainty for geolocation. © 2016 American Academy of Forensic Sciences.

Stable isotope discrimination factors and between-tissue isotope comparisons for bone and skin from captive and wild green sea turtles (Chelonia mydas).

PubMed

Turner Tomaszewicz, Calandra N; Seminoff, Jeffrey A; Price, Mike; Kurle, Carolyn M

2017-11-30

The ecological application of stable isotope analysis (SIA) relies on taxa- and tissue-specific stable carbon (Δ 13 C) and nitrogen (Δ 15 N) isotope discrimination factors, determined with captive animals reared on known diets for sufficient time to reflect dietary isotope ratios. However, captive studies often prohibit lethal sampling, are difficult with endangered species, and reflect conditions not experienced in the wild. We overcame these constraints and determined the Δ 13 C and Δ 15 N values for skin and cortical bone from green sea turtles (Chelonia mydas) that died in captivity and evaluated the utility of a mathematical approach to predict discrimination factors. Using stable carbon (δ 13 C values) and nitrogen (δ 15 N values) isotope ratios from captive and wild turtles, we established relationships between bone stable isotope (SI) ratios and those from skin, a non-lethally sampled tissue, to facilitate comparisons of SI ratios among studies using multiple tissues. The mean (±SD) Δ 13 C and Δ 15 N values (‰) between skin and bone from captive turtles and their diet (non-lipid-extracted) were 2.3 ± 0.3 and 4.1 ± 0.4 and 2.1 ± 0.6 and 5.1 ± 1.1, respectively. The mathematically predicted Δ 13 C and Δ 15 N values were similar (to within 1‰) to the experimentally derived values. The mean δ 15 N values from bone were higher than those from skin for captive (+1.0 ± 0.9‰) and wild (+0.8 ± 1.0‰) turtles; the mean δ 13 C values from bone were lower than those from skin for wild turtles (-0.6 ± 0.9‰), but the same as for captive turtles. We used linear regression equations to describe bone vs skin relationships and create bone-to-skin isotope conversion equations. For sea turtles, we provide the first (a) bone-diet SI discrimination factors, (b) comparison of SI ratios from individual-specific bone and skin, and (c) evaluation of the application of a mathematical approach to predict stable isotope discrimination factors. Our approach opens the door for future studies comparing different tissues, and relating SI ratios of captive to wild animals. Copyright © 2017 John Wiley & Sons, Ltd.

Using the Abitibi Greenstone Belt to Understand Martian Hydrothermal Systems and the Potential for Biosignature Preservation in High Temperature Aqueous Environments

NASA Technical Reports Server (NTRS)

Hurowitz, J.; Abelson, J.; Allwood, A.; Anderson, R.; Atkinson, B.; Beaty, D.; Bristow, T.; Ehlmann, B.; Eigenbrode, J.; Grotzinger, J.;

Stable carbon isotope ratios of intact GDGTs indicate heterogeneous sources to marine sediments

NASA Astrophysics Data System (ADS)

Pearson, Ann; Hurley, Sarah J.; Walter, Sunita R. Shah; Kusch, Stephanie; Lichtin, Samantha; Zhang, Yi Ge

2016-05-01

Thaumarchaeota, the major sources of marine glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), are believed to fix the majority of their carbon directly from dissolved inorganic carbon (DIC). The δ13C values of GDGTs (δ13CGDGT) may be powerful tools for reconstructing variations in the ocean carbon cycle, including paleoproductivity and water mass circulation, if they can be related to values of δ13CDIC. To date, isotope measurements primarily are made on the C40 biphytane skeletons of GDGTs, rather than on complete tetraether structures. This approach erases information revealed by the isotopic heterogeneity of GDGTs within a sample and may impart an isotopic fractionation associated with the ether cleavage. To circumvent these issues, we present δ13C values for GDGTs from twelve recent sediments representing ten continental margin locations. Samples are purified by orthogonal dimensions of HPLC, followed by measurement of δ13C values by Spooling Wire Microcombustion (SWiM)-isotope ratio mass spectrometry (IRMS) with 1σ precision and accuracy of ±0.25‰. Using this approach, we confirm that GDGTs, generally around -19‰, are isotopically ;heavy; compared to other marine lipids. However, measured δ13CGDGT values are inconsistent with predicted values based on the 13C content of DIC in the overlying water column and the previously-published biosynthetic isotope fractionation for a pure culture of an autotrophic marine thaumarchaeon. In some sediments, the isotopic composition of individual GDGTs differs, indicating multiple source inputs. The data appear to confirm that crenarchaeol primarily is a biomarker for Thaumarchaeota, but its δ13C values still cannot be explained solely by autotrophic carbon fixation. Overall the complexity of the results suggests that both organic carbon assimilation (ca. 25% of total carbon) and multiple source(s) of exogenous GDGTs (contributing generally <30% of input to sediments) are necessary to explain the observed δ13CGDGT values. The results suggest caution when interpreting the total inputs of GDGTs to sedimentary records. Biogenic or open-slope sediments, rather than clastic basinal or shallow shelf sediments, are preferred locations for generating minimally-biased GDGT proxy records.

Effects of geothermal activity and primary production on molybdenum isotopes: Lake Mývatn, Iceland

NASA Astrophysics Data System (ADS)

Neely, R.; Gíslason, S. R.; Ólafsson, M.; Pearce, C. R.; Torssander, P.; Eiríksdóttir, E. S.; Burton, K. W.

2016-12-01

Molybdenum (Mo) is highly sensitive to oxidation state and its isotopes are used as a proxy for redox conditions in the palaeoenvironent, particularly in the oceans. Geothermal systems play an important role in element cycles, comprising 10% of the Mo flux to the oceans and the dominant mechanism for Mo ore formation in porphyry deposits. Currently, little is known about Mo isotopes in either geothermal or groundwaters or how these systems may affect global mass balance. This study takes the Lake Mývatn area as a natural laboratory to study both geothermally affected and unaffected groundwaters, along with seasonal variations in a lacustrine environment. We present a comprehensive elemental and Mo isotope study of two groundwater systems from a basaltic terrain in North Iceland. The waters are of meteoric origin, range in sampling temperature from 2-93°C and in Mo isotope composition (δ98MoNIST) from -0.40 to 1.81‰. The Mo isotopic signature of the waters is largely controlled by mixing between cold groundwaters (isotopically light) and a geothermal end member (isotopically heavy). One of these groundwater systems forms the only input into Lake Mývatn: one of the most productive lakes in the northern hemisphere. Here we also present a time series from the Laxá River, which is the only outflow from the lake. Whilst seasonal variations in Mo isotopes are small (from δ98MoNIST 0.1 to 0.3‰) they positively correlate (R2 = 0.8) with variations in δ34S (from δ43S 1.7 to 4.6‰) with a shift to a heavier isotope peaks in late summer (September). This increase in δ98Mo coincides with a documented cyanobacteria bloom in late July to early September, known to preferentially use light isotopes.

Tracing fluid transfer across subduction zones using iron and zinc stable isotopes

NASA Astrophysics Data System (ADS)

Williams, H. M.; Debret, B.; Pons, M. L.; Bouilhol, P.

2016-12-01

In subduction zones, serpentinite devolatilization within the downgoing slab and the fluids released play a fundamental role in volatile transfer as well as the redox evolution of the sub-arc mantle. Constraining subduction-related serpentinite devolatilisation is essential in order to better understand of the nature and composition of slab-derived fluids and fluid/rock interactions. Fe and Zn stable isotopes can trace fluid composition and speciation as isotope partitioning is driven by changes in oxidation state, coordination, and bonding environment. In the case of serpentinite devolatilisation, Fe isotope fractionation should reflect changes in Fe redox state and the formation of Fe-Cl- and SO42- complexes (Hill et al., GCA 2010); Zn isotope fractionation should be sensitive to complexation with CO32-, HS- and SO42- anions (Fujii et al., GCA 2011). We targeted samples from Western Alps ophiolite complexes, interpreted as remnants of serpentinized oceanic lithosphere metamorphosed and devolatilized during subduction (Hattori and Guillot, G3 2007; Debret et al., Chem. Geol. 2013). A striking negative correlation is present between bulk serpentinite Fe isotope composition and Fe3+/Fetot, with the highest grade samples displaying the heaviest Fe isotope compositions and lowest Fe3+/Fetot (Debret et al., Geology, 2016). The same samples also display a corresponding variation in Zn isotopes, with the highest grade samples displaying isotopically light compositions (Pons et al., in revision). The negative correlation between Fe and Zn isotopes and decrease in Fe3+/Fetot can explained by serpentinite sulfide breakdown and the release of fluids enriched in isotopically light Fe and heavy Zn sulphate complexes. The migration of these SOX-bearing fluids from the slab to the slab-mantle interface or mantle wedge has important implications for the redox evolution of the sub-arc mantle and the transport of metals from the subducting slab.

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 heavy Zn from the soil to cell wall remains and release of light Zn to the soil. Overall, this study provides a complete overview of Zn cycling in an urban wetland soil-plant system, and describes several changes in Zn speciation with Zn isotopic fractionation processes in a complex system.

Sulfide in the core and the composition of the silicate Earth

NASA Astrophysics Data System (ADS)

Burton, K. W.

2015-12-01

The chemical composition of the Earth is traditionally explained in terms of evolution from a solar-like composition, similar to that found in primitive 'chondritic' meteorites. It now appears, however, that the silicate Earth is not 'chondritic', but depleted in incompatible elements, including refractory lithophile and heat-producing elements. Either Earth lost material during planet-building due to collisional erosion or else internal differentiation processes produced a hidden reservoir deep in the early Earth. Sulfide in the core may provide a reservoir capable of balancing the composition of the silicate Earth. Recent experimental work suggests that the core contains a significant proportion of sulfide, added during the final stages of accretion and new data suggests that at high pressures sulfide can incorporate a substantial amount of refractory lithophile and heat-producing elements [1]. Pioneering work using the short-lived 146Sm-142Nd system strongly suggests that Earth's silicate mantle is non-chondritic [e.g. 2]. The drawback of such radiogenic isotope systems is that it is not possible to distinguish the fractionation of Sm/Nd that occurs during silicate melting from that occurring during the segregation of a sulfide-melt to form the core. Neodymium stable isotopes have the potential to provide just such a tracer of sulfide segregation, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Preliminary data indicate that mantle rocks do indeed possess heavier 146Nd/144Nd values than chondritic meteorites, consistent with the removal of light Nd into sulfide in the core, driving the residual mantle to heavy values. Overall, our isotope and elemental data indicate that the rare earths and other incompatible elements are substantially incorporated into sulfide. While Nd Stable isotope data for chondritic meteorites and mantle rocks, are consistent with the segregation of sulfide to the core. [1] Wohlers &Wood, Nature 520, 337 (2015) [2] Boyet & Carlson, Science 309, 576 (2005)

Patterns in Stable Isotope Values of Nitrogen and Carbon in Particulate Matter from the Northwest Atlantic Continental Shelf, from the Gulf of Maine to Cape Hatteras

EPA Science Inventory

Stable isotope measurements of nitrogen and carbon (15N, 13ddC) are often used to characterize estuarine, nearshore, and open ocean ecosystems. Reliable information about the spatial distribution of base-level stable isotope values, often represented by primary producers, is crit...

Sulfide in the core and the Nd isotopic composition of the silicate Earth

NASA Astrophysics Data System (ADS)

McCoy-West, A.; Millet, M. A.; Nowell, G. M.; Wohlers, A.; Wood, B. J.; Burton, K. W.

2016-12-01

The chemical composition of the Earth is traditionally explained in terms of evolution from a solar-like composition, similar to that found in primitive chondritic meteorites. It now appears, however, that the silicate Earth is not chondritic, but depleted in incompatible elements and a resovable 20 ppm excess is observed in 142Nd relative to chondirtes [1, 2]. This anomaly requires a process that occurred within 30 Myr of solar system formation and has been variably ascribed to: a complementary enriched reservoir in the deep Earth [1]; loss to space through collisional erosion [3]; or the inhertence of nucleosynthetic anomalies [4]. Sulfide in the core may provide a reservoir capable of balancing the composition of the silicate Earth. Recent experimental work suggests that the core contains a significant proportion of sulfide, added during the final stages of accretion and new data suggests that at high pressures sulfide can incorporate a substantial amount of refractory lithophile and heat-producing elements [5]. The drawback of the short-lived 146Sm-142Nd radiogenic isotope system is that it is not possible to distinguish between fractionations of Sm/Nd that occurs during silicate melting or segregation of a sulfide-melt. Neodymium stable isotopes have the potential to provide just such a tracer of sulfide segregation, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Preliminary data indicate that mantle rocks do indeed possess heavier 146Nd/144Nd values than chondritic meteorites by 0.3 ‰, consistent with the removal of light Nd into sulfide in the core, driving the residual mantle to heavier values. Overall, our isotope and elemental data indicate that the rare earths and other incompatible elements are substantially incorporated into sulfide. While Nd stable isotope data for chondritic meteorites and mantle rocks, are consistent with the segregation of sulfide to the core. [1] Boyet & Carlson, Science 309, 576 (2005) [2] Carlson et al. Science 316, 1175 (2007) [3] Campbell& O'Neill Nature 483, 553 (2012) [4] Burkhardt Goldschmidt Ab. 429 (2015) [5] Wohlers &Wood, Nature 520, 337 (2015)

Diet analysis of Alaska Arctic snow crabs (Chionoecetes opilio) using stomach contents and δ13C and δ15N stable isotopes

NASA Astrophysics Data System (ADS)

Divine, Lauren M.; Bluhm, Bodil A.; Mueter, Franz J.; Iken, Katrin

2017-01-01

We used stomach content and stable δ13C and δ15N isotope analyses to investigate male and female snow crab diets over a range of body sizes (30-130 mm carapace width) in five regions of the Pacific Arctic (southern and northern Chukchi Sea, western, central, and Canadian Beaufort Sea). Snow crab stomach contents from the southern Chukchi Sea were also compared to available prey biomass and abundance. Snow crabs consumed four main prey taxa: polychaetes, decapod crustaceans (crabs, amphipods), echinoderms (mainly ophiuroids), and mollusks (bivalves, gastropods). Both approaches revealed regional differences. Crab diets in the two Chukchi regions were similar to those in the western Beaufort (highest bivalve, amphipod, and crustacean consumption). The Canadian Beaufort region was most unique in prey composition and in stable isotope values. We also observed a trend of decreasing carbon stable isotopes in crabs from the Chukchi to those in the Canadian Beaufort, likely reflecting the increasing use of terrestrial carbon sources towards the eastern regions of the Beaufort Sea from Mackenzie River influx. Cannibalism on snow crabs was higher in the Chukchi regions relative to the Beaufort regions. We suggest that cannibalism may have an impact on recruitment in the Chukchi Sea via reduction of cohort strength after settlement to the benthos, as known from the Canadian Atlantic. Prey composition varied with crab size only in some size classes in the southern Chukchi and central Beaufort, while stable isotope results showed no size-dependent differences. Slightly although significantly higher mean carbon isotope values for males in the southern Chukchi may not be reflective of a gender-specific pattern but rather be driven by low sample size. Finally, the lack of prey selection relative to availability in crabs in the southern Chukchi suggests that crabs consume individual prey taxa in relative proportions to prey field abundances. The present study is the first to provide a baseline of the omnivorous role of snow crabs across the entire Pacific Arctic, as well as evidence for cannibalism in the Chukchi Sea. In light of climate change predictions for the Alaska Arctic, and the potential for future fisheries harvest of snow crabs in this region, continued monitoring of snow crabs, including population and trophic dynamics, is increasingly important to assess snow crab impacts on benthic communities and vice versa.

Early Cretaceous bimodal volcanic rocks in the southern Lhasa terrane, south Tibet: Age, petrogenesis and tectonic implications

NASA Astrophysics Data System (ADS)

Wang, Chao; Ding, Lin; Liu, Zhi-Chao; Zhang, Li-Yun; Yue, Ya-Hui

2017-01-01

Limited geochronological and geochemical data from Early Cretaceous igneous rocks of the Gangdese Belt have resulted in a dispute regarding the subduction history of Neo-Tethyan Ocean. To approach this issue, we performed detailed in-situ zircon U-Pb and Hf isotopic, whole-rock elemental and Sr-Nd isotopic analyses on Late Mesozoic volcanic rocks exposed in the Liqiongda area, southern Lhasa terrane. These volcanic rocks are calc-alkaline series, dominated by basalts, basaltic andesites, and subordinate rhyolites, with a bimodal suite. The LA-ICPMS zircon U-Pb dating results of the basaltic andesites and rhyolites indicate that these volcanic rocks erupted during the Early Cretaceous (137-130 Ma). The basaltic rocks are high-alumina (average > 17 wt.%), enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depleted in high field strength elements (HFSEs), showing subduction-related characteristics. They display highly positive zircon εHf(t) values (+ 10.0 to + 16.3) and whole-rock εNd(t) values (+ 5.38 to + 7.47). The silicic suite is characterized by low Al2O3 (< 15.4 wt.%), Mg# (< 40), and TiO2 (< 0.3 wt.%) abundances; enriched and variable concentrations of LILEs and REEs; and strongly negative Eu anomalies (Eu/Eu* = 0.08-0.19), as well as depleted Hf isotopic compositions (εHf(t) = + 4.9 to + 16.4) and Nd isotopic compositions (εNd(t) = + 5.26 to + 6.71). Consequently, we envision a process of basaltic magmas similar to that of MORB extracted from a source metasomatized by slab-derived components for the petrogenesis of mafic rocks, whereas the subsequent mafic magma underplating triggered partial melting of the juvenile crust to generate acidic magma. Our results confirm the presence of Early Cretaceous volcanism in the southern Lhasa terrane. Combined with the distribution of the contemporary magmatism, deformation style, and sedimentary characteristics in the Lhasa terrane, we favor the suggestion that the Neo-Tethyan oceanic lithosphere was flat-lying beneath the Lhasa terrane during the Early Cretaceous. Appendix Table A2. LA-MC-ICPMS zircon Hf isotopes of volcanic rocks from Liqiongda area. Appendix Table A3. Whole-rock major, trace element and Sr-Nd isotope data of the volcanic rocks from the Liqiongda area.

Correlated carbon and oxygen isotope signatures in eclogitic diamonds with coesite inclusions: A SIMS investigation of diamonds from Guaniamo, Argyle and Orapa mines

NASA Astrophysics Data System (ADS)

Schulze, D. J.; Page, Z.; Harte, B.; Valley, J.; Channer, D.; Jaques, L.

2006-12-01

Using ion microprobes and secondary-ion mass spectrometry we have analyzed the carbon and oxygen isotopic composition of eclogite-suite diamonds and their coesite inclusions, respectively, from three suites of diamonds of Proterozoic age. Extremely high (for the mantle) oxygen isotope values (delta 18O of +10.2 to +16.9 per mil VSMOW) are preserved in coesites included in eclogitic diamonds from Guaniamo, Venezuela (Schulze et al., Nature, 2003), providing compelling evidence for an origin of their eclogite hosts by subduction of sea water altered ocean floor basalts. In situ SIMS analyses of their host diamonds yield carbon isotope values (delta 13C) of -12 to -18 per mil PDB. SIMS analyses of coesite inclusions from Argyle, Australia diamonds previously analyzed by combustion methods for d13C composition (Jaques et al., Proc. 4th Kimb. Conf, 1989), also yield anomalously high d18O values (+6.8 to +16.0 per mil VSMOW), that correlate with the anomalously low carbon isotope values (-10.3 to -14.1 per mil PDB). One coesite-bearing diamond from Orapa, Botswana analyzed in situ by SIMS has a d18O value of the coesite of +8.5 per mil VSMOW and a d13C value of the adjacent diamond host of -9.0 per mil PDB. A second Orapa stone has a SIMS carbon isotope compositional range of d13C = -14 to -16 per mil PDB, but the coesite is too small for ion probe analysis. At each of these localities, carbon isotope values of coesite-bearing diamonds that are lower than typical of mantle carbon are correlated with oxygen isotope compositions of included coesites that are substantially above the common mantle oxygen isotope range. Such results are not in accord with diamond genesis models involving formation of eclogitic diamonds from igneous melts undergoing fractionation in the mantle or by crystallization from primordial inhomogeneities in Earth's mantle. By analogy with the oxygen isotope compositions of altered ocean floor basalts and Alpine (subduction zone) eclogites they are, however, consistent with a subduction origin for these eclogite assemblages from altered ocean floor basaltic protoliths, and thus the simplest explanation for the source of the low carbon isotope values of these diamonds is formation from biogenic carbon accumulated on or near the ocean floor and subducted to the depths of eclogite and diamond stability with the altered basalts. Significantly these results, which were not predicted from studies of diamond-bearing eclogites, apply to the mantle beneath three different continental crustal blocks of both Proterozoic (Guaniamo and Argyle) and Archean/Proterozoic (Orapa) age.

Geochemical structure of the Hawaiian plume: Sr, Nd, and Os isotopes in the 2.8 km HSDP-2 section of Mauna Kea volcano

NASA Astrophysics Data System (ADS)

Bryce, Julia G.; Depaolo, Donald J.; Lassiter, John C.

2005-09-01

Sr, Nd, and Os isotopic measurements were made on 110 Mauna Kea lava and hyaloclastite samples from the drillcore retrieved from the second phase of the Hawaii Scientific Drilling Project (HSDP-2). The samples come from depths of 255 to 3098 meters below sea level, span an age range from 200 to about 550-600 kyr, and represent an ordered record of the lava output from Mauna Kea volcano as it drifted a distance of about 40 km over the magma-producing region of the Hawaiian hot spot. The deepest (oldest) samples represent the time when Mauna Kea was closest to the center of the melting region of the Hawaiian plume. The Sr and Os isotopic ratios in HSDP-2 lavas show only subtle isotopic shifts over the ˜400 kyr history represented by the core. Neodymium isotopes (ɛNd values) increase systematically with decreasing age from an average value of nearly +6.5 to an average value of +7.5. This small change corresponds to subtle shifts in 87Sr/86Sr and 187Os/188Os isotope ratios, with small shifts of ɛHf, a large shift in 208Pb/204Pb and 208Pb/207Pb values, and with a very large shift in He isotope ratios from R/RA values of about 7-8 to values as high as 25. When Mauna Kea was closest to the plume core, the magma source did not have primitive characteristics for Nd, Sr, Pb, Hf, and Os isotopes but did have variable amounts of "primitive" helium. The systematic shifts in Nd, Hf, Pb, and He isotopes are consistent with radial isotopic zoning within the melting region of the plume. The melting region constitutes only the innermost, highest-temperature part of the thermally anomalous plume mantle. The different ranges of values observed for each isotopic system, and comparison of Mauna Kea lavas with those of Mauna Loa, suggest that the axial region of the plume, which has a radius of ˜20 km, is a mixture of recycled subducted components and primitive lower mantle materials, recently combined during the formational stages of the plume at the base of the mantle. The proportions of recycled and primitive components are not constant, and this requires there be longitudinal (vertical) heterogeneity within the core of the plume. The remainder of the plume, outside this plume "core zone," is less heterogeneous but distinct from upper mantle as represented by mid-ocean ridge basalt (MORB). The plume structure may provide a detailed view of mantle isotopic composition near the core-mantle boundary.

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

NASA Astrophysics Data System (ADS)

Wieser, Michael Eugene

1998-09-01

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

Oxygen Isotope Records in Modern Oyster Shells from Chi Ku, Tainan and Their Implication of Seasonality

NASA Astrophysics Data System (ADS)

Chen, Y. C.; Mii, H. S.; Li, K. T.

2015-12-01

To exam whether oxygen isotope records of Crassostrea gigasoysters can be used as proxies of environment, 133 cultivated oysters and 21 water samples were collected from Chi Ku area, Tainan City, southern Taiwan in December of 2012, and from March, 2013 to July, 2014. Instrumental air and water temperatures and precipitation records were obtained from a nearest Central Weather Bureau (CWB) station roughly 16 km north of Chi Ku. The oxygen and carbon isotope values of the ligamental area of the modern oyster shells are from -6.92‰ to -0.08‰ (-3.05 ± 1.17‰, N = 2280; 1σ; VPDB) and from -5.57‰ to 0.63‰ (-1.88 ± 0.81‰), respectively. Oxygen isotope values of the water samples are mainly between -0.28‰ and 0.74‰ (0.18 ± 0.29‰, N = 20; 1σ; VSMOW). However, water oxygen isotope value of -2.75‰ was observed for the water sample collected immediately after a typhoon heavy rainfall. Seasonal temperature fluctuation pattern of estimated oxygen isotope temperatures from modern shells is similar to that of CWB instrumental records. However, the oxygen isotope temperatures are respectively about 3 °C and 10°C higher than those of instrumental records for winter and summer. Higher estimated oxygen isotope temperatures are most likely caused by underestimated fraction of freshwater. We analyzed 5 archaeological oyster shells of Siraya culture (500~250B.P.) collected from Wu Chien Tuso North (WCTN) archaeological site of Tainan branch of Southern Taiwan Science Park to infer the harvest season of mollusks. Oxygen isotope values of the ligamental area of the archaeological oyster shells are between -5.98‰ and -1.26‰ (-3.34 ± 1.37‰, N = 60; 1σ), and carbon isotope values are between -3.21‰ and 0.60‰ (-2.04‰ ± 0.55‰). The oxygen isotope records of archaeological oyster shells also showed clear seasonality. Most of the oysters were collected in autumn and winter. Oxygen isotope values of archaeological oyster shells was 1‰ greater than that of present for summer whereas was 1.2‰ less than that of present for wintwr. Assuming the temperature of 500-300 B.P. in Tainan was similar to that of present, it may indicate that the precipitation was weaker in summer but heavier in winter in southern Taiwan 500-300 B.P.

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

USGS Publications Warehouse

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

2014-01-01

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

Oxygen isotope ranking of late Eocene and Oligocene planktonic foraminifers: Implications for Oligocene sea-surface temperatures and global ice-volume

USGS Publications Warehouse

Poore, R.Z.; Matthews, R.K.

1984-01-01

Oxygen isotope analyses of late Eocene and Oligocene planktonic foraminifers from low and middle latitude sites in the Atlantic Basin show that different species from the same samples can yield significantly different isotopic values. The range of isotopic values observed between species is greatest at low-latitudes and declines poleward. Many planktonic foraminifers exhibit a systematic isotopic ranking with respect to each other and can therefore be grouped on the basis of their isotopic ranking. The isotopic ranking of some taxa, however, appears to vary geographically and/or through time. Isotopic and paleontologic data from DSDP Site 522 indicate that commonly used isotopic temperature scales underestimate Oligocene sea surface temperatures. We suggest these temperature scales require revision to reflect the presence of Oligocene glaciation. Comparison of isotopic and paleontologic data from Sites 522, 511 and 277 suggests cold, low-salinity surface waters were present in high southern latitudes during the early Oligocene. Lowsalinity, high latitude surface waters could be caused by Eocene/Oligocene paleogeography or by the production of warm saline bottom water. ?? 1984.

Online Compound-Specific δ13C and δD Determinations Using Laser Spectroscopy

NASA Astrophysics Data System (ADS)

Saad, N.; Hoffnagle, J.

2012-04-01

A unique laser spectroscopic approach for making online high-precision compound-specific isotope analysis (CSIA) of both δ13C and δD of the CO2 and H2O organic combustion products is described. The system consists of a gas chromatograph (GC) for the separation of an organic mixture coupled to a novel micro-fabricated microreactor (MFMR) for the complete combustion of each organic compound into CO2 and H2O and the precise measurements of δ13C in the CO2 gas and δ2H in the H2O vapor from the well established infrared spectrum of both gases, using an isotopic CO2 Cavity Ring-Down Spectroscopy (CRDS) analyzer and an isotopic H2O vapor CRDS analyzer, respectively. Light hydrocarbons are used as our test compounds in this study. The analyses of CH4, C2H6 and C3H8 for δ13C and δ2H values resulted in precisions of SD(δ13C)<1‰ and SD(δ2H)<2‰, respectively. These results were further compared to the gold standard method using Dual Inlet IRMS (DI-IRMS) and showed excellent agreements in isotopic measurements. The preliminary results presented here pave the way for a single CRDS analyzer-based system that simultaneously measures δ13C and δD, is field-deployable, less costly and necessitates less operator expertise than IRMS-based systems.

Experimental identification of mechanisms controlling calcium isotopic fractionations by the vegetation.

NASA Astrophysics Data System (ADS)

Cobert, Florian; Schimtt, Anne-Désirée.; Bourgeade, Pascale; Stille, Peter; Chabaux, François; Badot, Pierre-Marie; Jaegler, Thomas

2010-05-01

This study aims to better understand the role of vegetation on the Ca cycle at the level of the critical zone of the Earth, in order to specify the mechanisms controlling the Ca absorption by plants at the rock/plant interface. To do this, we performed experiments using hydroponic plant cultures in a way that we could control the co-occuring geochemical and physiological process and determine the impact of the nutritive solution on the Ca cycle within plants. A dicotyledon and calcicole plant with rapid growth, the French bean (Phaseolus vulgaris L.), has been chosen to have access to one complete growth cycle. Several experiments have been conducted with two Ca concentrations, 6 (L) and 60 (H) ppm and two pH values (4 and 6) in the nutritive solution, for which the Ca concentration was maintained constant, so its Ca content is considered as infinite. A second experiment (non infinite L6) allowed Ca depletion in the solution through time; therefore, response effects on the Ca isotopic signatures in the plant organs and in the nutritive solution were observed. We determined Ca concentrations and isotopic ratios in the nutritive solution and in different organs (main roots, secondary roots, old and young stems, old and young leaves and fruits) at two different growth stages (10 days and 6 weeks). Preliminary results show that: (1) the roots (main and secondary) were enriched in the light isotope (40Ca) compared to the nutritive solution, and leaves were enriched in the heavy isotope (44Ca) compared to stems. These results are in accord with previously published field studies (Wigand et al., 2005; Page et al., 2008; Cenki-Tok et al., 2009; Holmden and Bélanger, 2010). Leaves and secondary roots were however enriched in the heavy isotope (44Ca) compared to bean pods, stems and main roots. These results could be related to kinetic fractionation processes occurring either during the Ca root uptake, or during the Ca transport within the plant, or physiological mechanisms occurring first at the level of secondary roots, and second at the level of leaves. (2) No Ca isotope difference was observed neither between old and young organs, (except for H6 leaves), nor between the two growth stages (except for H6 roots). This suggest that the mechanisms controlling isotopic fractionations of Ca within common beans do not vary during growth, and that the nutrients stored in the cotyledons have only a minor effect on the Ca isotope fractionations of plants harvested after 10 days. (3) Strongest Ca isotope fractionations were observed at the nutritive solution/root interface. This implies that the mechanisms of light isotope enrichments in the plant are mainly due to transport processes taking place at this interface. (4) The non infinite L6 nutritive solution became enriched in 44Ca during the experiment compared to the infinite L6 nutritive solution and all the other solutions (L4, H4, and H6). This enrichment can be explained by Rayleigh fractionation or isotopic equilibrium. (5) Bean organs, from L4 and non infinite L6 experiment conditions, were enriched in 44Ca compared to stems and roots cultivated under H4, H6 and infinite L6 conditions. This might be due to the limited Ca in the nutritive solutions that cause smallest Ca isotope fractionations in the bean organs. All these results show that there is no simple correlation between Ca isotopic variations, Ca content and pH of the nutrient solution, and that physiological effects have also to be involved. They confirm the potential of the Ca isotopic system for tracing biological fractionations in natural ecosystems.

Palaeo-equatorial temperatures and carbon-cycle evolution at the Triassic- Jurassic boundary: A stable isotope perspective from shallow-water carbonates from the UAE

NASA Astrophysics Data System (ADS)

Honig, M. R.; John, C. M.

2013-12-01

The Triassic-Jurassic boundary was marked by global changes including carbon-cycle perturbations and the opening of the Atlantic Ocean. These changes were accompanied by one of the major extinction events of the Phanerozoic. The carbon-cycle perturbations have been recorded in carbon isotope curves from bulk carbonates, organic carbon and fossil wood in several Tethyan locations and have been used for chemostratigraphic purposes. Here we present data from shallow-marine carbonates deposited on a homoclinal Middle Eastern carbonate ramp (United Arab Emirates). Our site was located at the equator throughout the Late Triassic and the Early Jurassic, and this study provides the first constraints of environmental changes at the low-latitudes for the Triassic-Jurassic boundary. Shallow-marine carbonate depositional systems are extremely sensitive to palaeoenvironmental changes and their usefulness for chemostratigraphy is being debated. However, the palaeogeographic location of the studied carbonate ramp gives us a unique insight into a tropical carbonate factory at a time of severe global change. Stable isotope measurements (carbon and oxygen) are being carried out on micrite, ooids and shell material along the Triassic-Jurassic boundary. The stable isotope results on micrite show a prominent negative shift in carbon isotope values of approximately 2 ‰ just below the inferred position of the Triassic-Jurassic boundary. A similar isotopic trend is also observed across the Tethys but with a range of amplitudes (from ~2 ‰ to ~4 ‰). These results seem to indicate that the neritic carbonates from our studied section can be used for chemostratigraphic purposes, and the amplitudes of the carbon isotope shifts provide critical constraints on the magnitude of carbon-cycle perturbations at low latitudes across the Triassic-Jurassic boundary. Seawater temperatures across the Triassic-Jurassic boundary will be constrained using the clumped isotope palaeo-thermometer applied to blocky calcite, bulk carbonate, oyster shells and echinoids. Assuming a pristine depositional signal can be extracted from one of the components, clumped isotopes will either shed light on the palaeoenvironmental conditions and the isotopic composition of a tropical ocean during the Late Triassic / Early Jurassic, or on the diagenetic history of the platform. We gratefully acknowledge funding from Qatar Petroleum, Shell, and Qatar Science & Technology Park.

The Influence of Non-spectral Matrix Effects on the Accuracy of Isotope Ratio Measurement by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Barling, J.; Shiel, A.; Weis, D.

2006-12-01

Non-spectral interferences in ICP-MS are caused by matrix elements effecting the ionisation and transmission of analyte elements. They are difficult to identify in MC-ICP-MS isotopic data because affected analyses exhibit normal mass dependent isotope fractionation. We have therefore investigated a wide range of matrix elements for both stable and radiogenic isotope systems using a Nu Plasma MC-ICP-MS. Matrix elements commonly enhance analyte sensitivity and change the instrumental mass bias experienced by analyte elements. These responses vary with element and therefore have important ramifications for the correction of data for instrumental mass bias by use of an external element (e.g. Pb and many non-traditional stable isotope systems). For Pb isotope measurements (Tl as mass bias element), Mg, Al, Ca, and Fe were investigated as matrix elements. All produced signal enhancement in Pb and Tl. Signal enhancement varied from session to session but for Ca and Al enhancement in Pb was less than for Tl while for Mg and Fe enhancement levels for Pb and Tl were similar. After correction for instrumental mass fractionation using Tl, Mg effected Pb isotope ratios were heavy (e.g. ^{208}Pb/204Pbmatrix > ^{208}Pb/204Pbtrue) for both moderate and high [Mg] while Ca effected Pb showed little change at moderate [Ca] but were light at high [Ca]. ^{208}Pb/204Pbmatrix - ^{208}Pb/204Pbtrue for all elements ranged from +0.0122 to - 0.0177. Isotopic shifts of similar magnitude are observed between Pb analyses of samples that have seen either one or two passes through chemistry (Nobre Silva et al, 2005). The double pass purified aliquots always show better reproducibility. These studies show that the presence of matrix can have a significant effect on the accuracy and reproducibility of replicate Pb isotope analyses. For non-traditional stable isotope systems (e.g. Mo(Zr), Cd(Ag)), the different responses of analyte and mass bias elements to the presence of matrix can result in del/amu for measured & mass bias corrected data that disagree outside of error. Either or both values can be incorrect. For samples, unlike experiments, the correct del/amu is not known in advance. Therefore, for sample analyses to be considered accurate, both measured and exponentially corrected del/amu should agree.

Flotsam samples can help explain the δ13C and δ15N values of invertebrate resting stages in lake sediment

NASA Astrophysics Data System (ADS)

van Hardenbroek, Maarten; Rinta, Päivi; Wooller, Matthew J.; Schilder, Jos; Stötter, Tabea; Heiri, Oliver

2018-06-01

The stable isotopic composition of chitinous remains of Cladocera (water fleas) and freshwater Bryozoa (moss animals) preserved in lake sediment records can provide supporting insights into past environmental and ecosystem changes in lakes. Here we explore whether analyses of these remains isolated from lake flotsam can provide information on the driving variables affecting the isotopic composition of these remains. We collected flotsam in 53 lakes and found enough material in 33 lakes to measure the stable carbon and nitrogen isotope ratios (expressed as δ13C and δ15N values, respectively) of resting stages. These values were compared with lake characteristics, water chemistry measurements, and the isotopic composition of sedimentary organic matter (SOM) in the lakes. Mean δ13C values of cladoceran ephippia and SOM were correlated and both were also negatively correlated with deep water methane concentrations and indicators of lake stratification. This supports the findings of previous studies that methane-derived carbon can provide a significant proportion of carbon entering planktonic food webs. Mean δ15N values of bryozoan statoblasts and SOM were correlated, suggesting that both reflect the δ15N values of phytoplankton. Our results provide information on how environmental variables in lakes can influence the δ13C and δ15N values in resting stages, but flotsam samples can also potentially be used to assess seasonal stable isotope variability of resting stages. Both types of information are important to improve palaeoenvironmental interpretations of stable isotope records based on these remains in lake sediments.

Continuous and simultaneous measurements of precipitation and vapor isotopes over two monsoon seasons during 2016-2017 in Singapore

NASA Astrophysics Data System (ADS)

Jackisch, D.; He, S.; Ong, M. R.; Goodkin, N.

2017-12-01

Water isotopes are important tracers of climate dynamics and their measurement can provide valuable insights into the relationship between isotopes and atmospheric parameters and overall convective activities. While most studies provide data on daily or even monthly time scales, high-temporal in-situ stable isotope measurements are scarce, especially in the tropics. In this study, we presented δ18O and δ2H values in precipitation and vapor continuously and simultaneously measured using laser spectroscopy in Singapore during the 2016/2017 Northeast (NE) Asian monsoon and 2017 Southwest (SW) Asian monsoon. We found that δ-values of precipitation and vapor exhibit quite different patterns during individual events, although there is a significant correlation between the δ-values of precipitation and of vapor. δ-values in precipitation during individual precipitation events show a distinct V-shape pattern, with the lowest isotope values observed in the middle of the event. However, isotopes in water vapor mostly show an L-shape and are characterized by a gradual decrease with the onset of rainfall. The difference in δ-values of precipitation and vapor is generally constant during the early stage of the events but gradually increases near the end. It is likely that vapor and precipitation are closer to equilibrium at the early stage of a rain event, but diverge at the later stages. This divergence can be largely attributed to the evaporation of raindrops. We notice a frequent drop in d-excess of precipitation, whereas d-excess in vapor increases. In addition, a significant correlation exists between outgoing longwave radiation (OLR) and isotopes in both precipitation and vapor, suggesting an influence of regional convective activity.

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.

Periodicity analysis of δ18O in precipitation over Central Europe: Time-frequency considerations of the isotopic 'temperature' effect

NASA Astrophysics Data System (ADS)

Salamalikis, V.; Argiriou, A. A.; Dotsika, E.

2016-03-01

In this paper the periodic patterns of the isotopic composition of precipitation (δ18O) for 22 stations located around Central Europe are investigated through sinusoidal models and wavelet analysis over a 23 years period (1980/01-2002/12). The seasonal distribution of δ18O follows the temporal variability of air temperature providing seasonal amplitudes ranging from 0.94‰ to 4.47‰; the monthly isotopic maximum is observed in July. The isotopic amplitude reflects the geographical dependencies of the isotopic composition of precipitation providing higher values when moving inland. In order to describe the dominant oscillation modes included in δ18O time series, the Morlet Continuous Wavelet Transform is evaluated. The main periodicity is represented at 12-months (annual periodicity) where the wavelet power is mainly concentrated. Stations (i.e. Cuxhaven, Trier, etc.) with limited seasonal isotopic effect provide sparse wavelet power areas at the annual periodicity mode explaining the fact that precipitation has a complex isotopic fingerprint that cannot be examined solely by the seasonality effect. Since temperature is the main contributor of the isotopic variability in mid-latitudes, the isotope-temperature effect is also investigated. The isotope-temperature slope ranges from 0.11‰/°C to 0.47‰/°C with steeper values observed at the southernmost stations of the study area. Bivariate wavelet analysis is applied in order to determine the correlation and the slope of the δ18O - temperature relationship over the time-frequency plane. High coherencies are detected at the annual periodicity mode. The time-frequency slope is calculated at the annual periodicity mode ranging from 0.45‰/°C to 0.83‰/°C with higher values at stations that show a more distinguishable seasonal isotopic behavior. Generally the slope fluctuates around a mean value but in certain cases (sites with low seasonal effect) abrupt slope changes are derived and the slope becomes strongly unstable.

Are recycled carbonates essential to explain light Mg isotopes in magmatic rocks? Insights from Late Cenozoic mantle-derived magmas in Iran

NASA Astrophysics Data System (ADS)

Pang, K. N.; Teng, F. Z.; Sun, Y.; Chung, S. L.; Zarrinkoub, M. H.

2016-12-01

Mantle-derived magmas at continental collision zones represent probes into the mantle that might have been variably metasomatized prior to collision. To address how and to what extent mantle metasomatism occurred, particularly for the role of recycled carbonates, we conducted a Mg isotopic study of two suites of Late Cenozoic mantle-derived magmas in Iran, part of the Arabia-Eurasia collision zone preceded by the long-lasting Tethyan subduction. The Qal'eh Hasan Ali high-Mg ultrapotassic rocks, low-degree partial melts from the metasomatized lithospheric mantle, have mantle-like δ26Mg (-0.23 to -0.28 ‰) despite high CaO/Al2O3 and Zr/Hf, low Ti/Eu and Hf/Sm, and presence of carbonate globules in devitrified glass indicative of carbonate or carbonatite involvement in their genesis. The absence of light Mg isotopic composition of these rocks indicates that either the recycled carbonates were in the form of calcitic rather than dolomitic melts, or the amount of Mg from the carbonatite was too little to appear in these rocks. The Lut-Sistan alkali basalts, sodic magmas suggested to have derived from low-degree melting of the asthenosphere followed by variable differentiation, display a range of δ26Mg from -0.17 to -0.26 ‰ with three outlying data at -0.37‰, -0.39‰ and -0.56 ‰. The samples with light Mg isotopes do not show greater influence by carbonate or carbonatite in terms of the elemental indices noted above. Instead, they are characterized by lower light and middle REE abundances and slightly lower initial 143Nd/144Nd than the majority of samples. The covariations can be explained by minor incorporation of lower crustal garnet during magma ascent through local thickened crust in the collision zone. We propose that thickened crust where garnet pyroxenites exist is capable of imparting a light Mg isotopic signature to mantle-derived magmas, and that such signature is not unique to the involvement of carbonate or carbonatite in the mantle source.

Post‐mortem oxygen isotope exchange within cultured diatom silica

PubMed Central

Sloane, Hilary J.; Rickaby, Rosalind E.M.; Cox, Eileen J.; Leng, Melanie J.

2017-01-01

Rationale Potential post‐mortem alteration to the oxygen isotope composition of biogenic silica is critical to the validity of palaeoclimate reconstructions based on oxygen isotope ratios (δ18O values) from sedimentary silica. We calculate the degree of oxygen isotope alteration within freshly cultured diatom biogenic silica in response to heating and storing in the laboratory. Methods The experiments used freshly cultured diatom silica. Silica samples were either stored in water or dried at temperatures between 20 °C and 80 °C. The mass of affected oxygen and the associated silica‐water isotope fractionation during alteration were calculated by conducting parallel experiments using endmember waters with δ18O values of −6.3 to −5.9 ‰ and −36.3 to −35.0 ‰. Dehydroxylation and subsequent oxygen liberation were achieved by stepwise fluorination with BrF5. The 18O/16O ratios were measured using a ThermoFinnigan MAT 253 isotope ratio mass spectrometer. Results Significant alterations in silica δ18O values were observed, most notably an increase in the δ18O values following drying at 40–80 °C. Storage in water for 7 days between 20 and 80 °C also led to significant alteration in δ18O values. Mass balance calculations suggest that the amount of affected oxygen is positively correlated with temperature. The estimated oxygen isotope fractionation during alteration is an inverse function of temperature, consistent with the extrapolation of models for high‐temperature silica‐water oxygen isotope fractionation. Conclusions Routinely used preparatory methods may impart significant alterations to the δ18O values of biogenic silica, particularly when dealing with modern cultured or field‐collected material. The significance of such processes within natural aquatic environments is uncertain; however, there is potential that similar processes also affect sedimentary diatoms, with implications for the interpretation of biogenic silica‐hosted δ18O palaeoclimate records. PMID:28792631

Revisiting the Si Isotope Record of Precambrian Cherts and Banded Iron Formations Using New Experimental Results

NASA Astrophysics Data System (ADS)

Zheng, X. Y.; Satkoski, A.; Beard, B. L.; Reddy, T. R.; Beukes, N. J.; Johnson, C.

2017-12-01

Precambrian Banded iron formations (BIFs) and cherts provide a record of Fe and Si biogeochemical cycling in early Earth marine environments. Much of the focus on BIFs has been the origin and pathways for Fe, but Si is intimately tied to BIF genesis through its connection to Fe minerals, either through direct structural bonding or through sorption. In the Precambrian ocean, aqueous Si contents were high, and it is increasingly recognized that Fe(III)-Si gels were the most likely precursor to BIFs [1]. It is known that Fe-Si bonding affects stable Fe isotope fractionations [2], and our recent experimental work shows this to be true for stable Si isotope fractionations [3, 4]. Silicon isotope fractionations in the Fe-Si system vary from 0‰ to nearly 4‰ in 30Si/28Si ratios with the solid phase being isotopically light depending on Fe:Si ratio [3, 4, and this study], a range far larger than that of 56Fe/54Fe ratios, highlighting the fact that Si isotopes are a highly sensitive tracer of the Fe-Si cycle. This range in Si isotope fractionation factors for the Fe-Si system can explain the full range of δ30Si values measured in Precambrian BIFs, providing a new framework to interpret Precambrian δ30Si records. Our results provide strong support for a model where Fe(III)-Si gels are the precursor phase for BIFs, which in turn affects estimates for the aqueous Fe and Si contents of the Precambrian oceans through changes in Fe-Si gel solubility. Our experiments also showed that microbial dissimilatory iron reduction (DIR) of Fe(III)-Si gel can easily produce a solid with Fe(II)-Fe(III) stoichiometry equal to magnetite, in marked contrast to abiotic incorporation of Fe(II) into Fe(III)-Si gel that resulted in a solid with Fe(II)-Fe(III) stoichiometry much lower than magnetite. Moreover, this DIR process produces a unique, negative δ30Si signature that should be eventually preserved in quartz closely associated with magnetite upon phase transformation of Fe-Si gel, and serve as a bio-signature. This experimental finding well explains the tendency of magnetite-rich BIFs to have lower δ30Si values than hematite-rich BIFs. [1] Konhauser et al., Earth-Science Rev, 2017 [2] Wu et al., GCA, 2012 [3] Zheng et al., GCA, 2016 [4] Reddy et al., GCA, 2016

15N NATURAL ABUNDANCE AND 15N LABELLING STUDIES IN FOREST ECOSYSTEMS

EPA Science Inventory

The relative amounts of the two stable isotopes of Nitrogen (N), 15N, and N, vary predictably in soils and plant tissues of forests and other non-cultivated ecosystems. light fractionations, or discriminations against the heavier N isotope, that can occur as N cycles through vege...

Modes of planetary-scale Fe isotope fractionation

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; von Blanckenburg, Friedhelm

2006-12-01

A comprehensive set of high-precision Fe isotope data for the principle meteorite types and silicate reservoirs of the Earth is used to investigate iron isotope fractionation at inter- and intra-planetary scales. 14 chondrite analyses yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of - 0.015 ± 0.020‰ (2 SE) relative to the international iron standard IRMM-014. Eight non-cumulate and polymict eucrite meteorites that sample the silicate portion of the HED (howardite-eucrite-diogenite) parent body yield an average δ56Fe/ 54Fe value of - 0.001 ± 0.017‰, indistinguishable to the chondritic Fe isotope composition. Fe isotope ratios that are indistinguishable to the chondritic value have also been published for SNC meteorites. This inner-solar system homogeneity in Fe isotopes suggests that planetary accretion itself did not significantly fractionate iron. Nine mantle xenoliths yield a 2 σ envelope of - 0.13‰ to + 0.09‰ in δ56Fe/ 54Fe. Using this range as proxy for the bulk silicate Earth in a mass balance model places the Fe isotope composition of the outer liquid core that contains ca. 83% of Earth's total iron to within ± 0.020‰ of the chondritic δ56Fe/ 54Fe value. These calculations allow to interprete magmatic iron meteorites ( δ56Fe/ 54Fe = + 0.047 ± 0.016‰; N = 8) to be representative for the Earth's inner metallic core. Eight terrestrial basalt samples yield a homogeneous Fe isotope composition with an average δ56Fe/ 54Fe value of + 0.072 ± 0.016‰. The observation that terrestrial basalts appear to be slightly heavier than mantle xenoliths and that thus partial mantle melting preferentially transfers heavy iron into the melt [S. Weyer, A.D. Anbar, G.P. Brey, C. Munker, K. Mezger and A.B. Woodland, Iron isotope fractionation during planetary differentiation, Earth and Planetary Science Letters 240(2), 251-264, 2005.] is intriguing, but also raises some important questions: first it is questionable whether the Fe isotope composition of lithospheric mantle xenoliths are representative for an undisturbed melt source, and second, HED and SNC meteorites, representing melting products of 4Vesta and Mars silicate mantles would be expected to show a similar fractionation towards heavy isotope compositions. This is not observed. Four international granitoid standards with SiO 2 contents between 60 and 70 wt.% yield δ56Fe/ 54Fe values between 0.118‰ and 0.132‰. An investigation of the alpine Bergell igneous rock suite revealed a positive correlation between Fe isotope compositions and SiO 2 contents — from gabbros and tonalites ( δ56Fe/ 54Fe ≈ 0.03 to 0.09‰) to granodiorites and silicic dykes ( δ56Fe/ 54Fe ≈ 0.14 to 0.23‰). Although in this suite δ56Fe/ 54Fe correlates with δ18O values and radiogenic isotopes, open-system behavior to explain the heavy iron is not undisputed. This is because an obvious assimilant with the required heavy Fe isotope composition has so far not been identified. Alternatively, the relatively heavy granite compositions might be obtained by fractional crystallisation of the melt. Ultimately, further detailed studies on natural rocks and the experimental determination of mineral/melt fractionation factors at magmatic conditions are required to unravel whether or not iron isotope fractionation takes place during partial mantle melting and crystal fractionation.

Bonding of xenon to oxygen in magmas at depth

NASA Astrophysics Data System (ADS)

Leroy, Clémence; Sanloup, Chrystèle; Bureau, Hélène; Schmidt, Burkhard C.; Konôpková, Zuzana; Raepsaet, Caroline

2018-02-01

The field of noble gases chemistry has witnessed amazing advances in the last decade with over 100 compounds reported including Xe oxides and Xe-Fe alloys stable at the pressure-temperature conditions of planetary interiors. The chemistry of Xe with planetary materials is nonetheless still mostly ignored, while Xe isotopes are used to trace a variety of key planetary processes from atmosphere formation to underground nuclear tests. It is indeed difficult to incorporate the possibility of Xe reactivity at depth in isotopic geochemical models without a precise knowledge of its chemical environment. The structure of Xe doped hydrous silica-rich melts is investigated by in situ high energy synchrotron X-ray diffraction using resistive heating diamond anvil cells. Obtained pair distribution functions reveal the oxidation of Xe between 0.2 GPa and 4 GPa at high T up to 1000 K. In addition to the usual interatomic distances, a contribution at 2.05 ± 0.05 Å is observed. This contribution is not observed in the undoped melt, and is interpreted as the Xe-O bond, with a coordination number of about 12 consistent with Xe insertion in rings of the melt structure. Xe solubility measurements by electron microprobe and particle induced X-rays emission analysis confirm that Xe and Ar have similar solubility values in wt% in silicate melts. These values are nonetheless an order of magnitude higher than those theoretically calculated for Xe. The formation of Xe-O bonds explains the enhanced solubility of Xe in deep continental crust magmas, revealing a mechanism that could store Xe and fractionate its isotopes. Xenon is indeed atypical among noble gases, the atmosphere being notably depleted in elemental Xe, and very strongly depleted in Xe light isotopes. These observations are known as the 'missing' Xe paradox, and could be solved by the present findings.

Pressure-dependent boron isotopic fractionation observed by column chromatography

NASA Astrophysics Data System (ADS)

Musashi, M.; Oi, T.; Matsuo, M.; Nomura, M.

2007-12-01

Boron isotopic fractionation factor ( S ) between boron taken up in strongly basic anion exchange resin and boron in aqueous solution was determined by breakthrough column chromatography at 5 and 17 MPa at 25°C, using 0.1 mmol/L boric acid solution as feed solution. The S values obtained were 1.018 and 1.012, respectively, which were smaller than the value reported by using the same chromatographic method at atmospheric pressure at 25°C with the boron concentration of 10 mmol/L, but were larger than the values at the same condition with much higher concentration of 100 and 501 mmol/L, indicating that borate-polymerization reducing the isotopic fractionation was negligible. However, calculations based on the theory of isotope distribution between two phases estimated that 21% (5MPa) and 47% (17MPa) of boron taken up in the resin phase was in the three-coordinated B(OH)3-form, instead of in the four-coordinated B(OH)4--form, at high pressures even with the very diluted solution. We discussed this discrepancy by introducing (1) hydration or (2) a partial molar volume difference between isotopic molecules. It was inferred that borate ions were partially dehydrated upon transfer from the solution phase to the resin phase at high pressures, which resulted in smaller S values compared with those at the atmospheric pressure. Alternatively, it was likely that the S value decreased with increasing pressure, because the difference of the partial isotopic molar volumes between 10B(OH)3 and 11B(OH)3 was larger than that between 10B(OH)4- and 11B(OH)4-. If either will be the case, the influence of a pressure upon the isotope effect may not be negligible for boron isotopic exchange equilibrium. This knowledge is crucial for the principle of the boron isotopic pH-metry reconstructing a chemical variation at the paleo-deep oceanic environment where the early life may have been evolved.

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

PubMed

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

Study of yrast bands and electromagnetic properties in neutron-rich 114-128Cd isotopes

NASA Astrophysics Data System (ADS)

Chaudhary, Ritu; Pandit, Rakesh K.; Devi, Rani; Khosa, S. K.

2018-02-01

The projected shell model framework has been employed to carry out a systematic study on the deformation systematics of E (21+) and E (41+) / E (21+) values, BCS subshell occupation numbers, yrast spectra, backbending phenomena and electromagnetic quantities in 114-128Cd isotopes. Present calculations reproduce the observed systematics of the E (21+), R42 and B (E 2 ;2+ →0+) values for 114-128Cd isotopic mass chain and give the evidence that deformation increases as one moves from 114Cd to 118Cd, thereafter it decreases up to 126Cd. This in turn confirms 118Cd to be the most deformed nucleus in this set of isotopic mass chain. The emergence of backbending, decrease in B (E 2) values and change in g-factors in all these isotopes are intimately related to the crossing of g-band by 2-qp bands.

Identification of the geographical place of origin of an unidentified individual by multi-isotope analysis.

PubMed

Font, Laura; van der Peijl, Gerard; van Leuwen, Carina; van Wetten, Isis; Davies, Gareth R

2015-01-01

A multi-isotope investigation (Sr and Pb isotopes and δ18O, δ13C and δ15N) was applied to bone and teeth from an unidentified male found drowned in the"IJ" Ruyterkade in Amsterdam, The Netherlands in March of 1999. The individual remained unidentified until mid 2013, after the isotope study was completed. Coupled δ13C and δ15N values in bone collagen recovered from rib and femur are consistent with an omnivore living in a region where C3-type diet dominates (i.e. Europe). Integrated Sr and Pb isotopes and δ18O values in canine and third molar teeth and femur and rib bone data exclude extended residence in north-west Europe and particularly The Netherlands. Characteristic Pb isotope ratios coupled with inferred δ18O values of drinking water argue for a most probable place of origin for the unidentified individual in west and south Poland, south-east Slovakia and the region of Ukraine-Romania-Bulgaria, specifically the region associated with the Carpathian Mountains. Independent of the isotope study, the Cold Case Team made a positive identification with an individual from south-west Poland, validating the results of the multiple-isotopic approach. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.