Nitrogen isotopic baselines and implications for estimating foraging habitat and trophic position of yellowfin tuna in the Indian and Pacific Oceans

NASA Astrophysics Data System (ADS)

Lorrain, Anne; Graham, Brittany S.; Popp, Brian N.; Allain, Valérie; Olson, Robert J.; Hunt, Brian P. V.; Potier, Michel; Fry, Brian; Galván-Magaña, Felipe; Menkes, Christophe E. R.; Kaehler, Sven; Ménard, Frédéric

2015-03-01

Assessment of isotopic compositions at the base of food webs is a prerequisite for using stable isotope analysis to assess foraging locations and trophic positions of marine organisms. Our study represents a unique application of stable-isotope analyses across multiple trophic levels (primary producer, primary consumer and tertiary consumer) and over a large spatial scale in two pelagic marine ecosystems. We found that δ15N values of particulate organic matter (POM), barnacles and phenylalanine from the muscle tissue of yellowfin tuna all showed similar spatial patterns. This consistency suggests that isotopic analysis of any of these can provide a reasonable proxy for isotopic variability at the base of the food web. Secondly, variations in the δ15N values of yellowfin tuna bulk-muscle tissues paralleled the spatial trends observed in all of these isotopic baseline proxies. Variation in isotopic composition at the base of the food web, rather than differences in tuna diet, explained the 11‰ variability observed in the bulk-tissue δ15N values of yellowfin tuna. Evaluating the trophic position of yellowfin tuna using amino-acid isotopic compositions across the western Indian and equatorial Pacific Oceans strongly suggests these tuna occupy similar trophic positions, albeit absolute trophic positions estimated by this method were lower than expected. This study reinforces the importance of considering isotopic baseline variability for diet studies, and provides new insights into methods that can be applied to generate nitrogen isoscapes for worldwide comparisons of top predators in marine ecosystems.

Silicon isotopes in angrites and volatile loss in planetesimals

PubMed Central

Moynier, Frédéric; Savage, Paul S.; Badro, James; Barrat, Jean-Alix

2014-01-01

Inner solar system bodies, including the Earth, Moon, and asteroids, are depleted in volatile elements relative to chondrites. Hypotheses for this volatile element depletion include incomplete condensation from the solar nebula and volatile loss during energetic impacts. These processes are expected to each produce characteristic stable isotope signatures. However, processes of planetary differentiation may also modify the isotopic composition of geochemical reservoirs. Angrites are rare meteorites that crystallized only a few million years after calcium–aluminum-rich inclusions and exhibit extreme depletions in volatile elements relative to chondrites, making them ideal samples with which to study volatile element depletion in the early solar system. Here we present high-precision Si isotope data that show angrites are enriched in the heavy isotopes of Si relative to chondritic meteorites by 50–100 ppm/amu. Silicon is sufficiently volatile such that it may be isotopically fractionated during incomplete condensation or evaporative mass loss, but theoretical calculations and experimental results also predict isotope fractionation under specific conditions of metal–silicate differentiation. We show that the Si isotope composition of angrites cannot be explained by any plausible core formation scenario, but rather reflects isotope fractionation during impact-induced evaporation. Our results indicate planetesimals initially formed from volatile-rich material and were subsequently depleted in volatile elements during accretion. PMID:25404309

Ti Isotopes: Echoes of Grain-Scale Heterogenaity in the Protoplanetary Disk

NASA Technical Reports Server (NTRS)

Jordan, M. K.; Kohl, I. E.; McCain, K. A.; Simon, J. I.; Young, E. D.

2017-01-01

Calcium-aluminum-rich inclusions (CAIs) are the oldest surviving solids to have formed in the Solar System. Their chemical and isotopic compositions provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of how solids formed in the solar nebula, an important step in the eventual process of planet building. The isotopic compositions of CAIs are primarily controlled by volatility. Evaporation/sublimation are well understood through both theory and experimental work to produce an enrichment in the heavy isotopes of an element, but less is understood about the effects of condensation. Mass-dependent fractionation can potentially provide a record of nebular condensation. Ti is not likely to experience evaporation due to its refractory nature, making it a useful tool for assessing the effects of condensation. We have undertaken a study of the stable isotope fractionation of Ti isotopes as a tracer of processes that predate the last evaporation events affecting CAIs. We compare the 49Ti/47Ti stable isotope ratio with excess 50Ti common in CAIs. We have collected Ti, Mg, Si, and Ca isotope data for a suite of CAIs in order to search for heterogeneity in each of these isotope systems, and for potential correlations among them. We compare our results to expectations for condensation.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Stable isotopic variations of water vapor on the winter coastal area in Korea

NASA Astrophysics Data System (ADS)

Lee, Jeonghoon; Lee, Songyi; Han, Yeongcheol; Do Hur, Soon

2017-04-01

Studies of isotopic compositions of precipitation in Korea have been conducted for groundwater mixing and sources and residence time of water. Unravelling of water vapor isotopes will be very helpful in explaining the sources of moisture. In this work, we first present isotopic compositions of water vapor over western part of Korea in winter between December 2015 and February 2016. We collected the samples of water vapor isotopes by a cryogenic method with impingers and liquid nitrogen. We captured the water vapor for 4 to 6 hours, depending on humidity and collected 54 samples in total. The samples were analyzed by a Picarro L2130-i and the precisions were 0.06‰ and 0.7‰ for oxygen and hydrogen, respectively. The isotopic compositions of water vapor ranged from -34.04‰ to -15.27‰ for oxygen and from -221.9‰ to -100.2‰ for hydrogen. The deuterium excess (d=δD-8*δ18O) was between 17.4 and 44.0 in permil. Both air temperature (T, δ18O=0.57*T-25.5, R2=0.46) and relative humidity (RH, δ18O=0.18*RH-35.9, R2=0.38) were positively correlated with the water vapor isotopes. This is not consistent with the fact that precipitation isotopes are correlated with only temperate in winter Eastern Asia. We expect that the water vapor isotopes will be an important role to understand the origin and pathway of moistures over the Eastern Asia.

Modeling the influence of a reduced equator-to-pole sea surface temperature gradient on the distribution of water isotopes in the Early/Middle Eocene

NASA Astrophysics Data System (ADS)

Speelman, Eveline N.; Sewall, Jacob O.; Noone, David; Huber, Matthew; von der Heydt, Anna; Damsté, Jaap Sinninghe; Reichart, Gert-Jan

2010-09-01

Proxy-based climate reconstructions suggest the existence of a strongly reduced equator-to-pole temperature gradient during the Azolla interval in the Early/Middle Eocene, compared to modern. Changes in the hydrological cycle, as a consequence of a reduced temperature gradient, are expected to be reflected in the isotopic composition of precipitation (δD, δ 18O). The interpretation of water isotopic records to quantitatively reconstruct past precipitation patterns is, however, hampered by a lack of detailed information on changes in their spatial and temporal distribution. Using the isotope-enabled version of the National Center for Atmospheric Research (NCAR) atmospheric general circulation model, Community Atmosphere Model v.3 (isoCAM3), relationships between water isotopes and past climates can be simulated. Here we examine the influence of an imposed reduced meridional sea surface temperature gradient on the spatial distribution of precipitation and its isotopic composition in an Early/Middle Eocene setting. As a result of the applied forcings, the Eocene simulation predicts the occurrence of less depleted high latitude precipitation, with δD values ranging only between 0 and -140‰ (compared to Present-day 0 to -300‰). Comparison with Early/Middle Eocene-age isotopic proxy data shows that the simulation accurately captures the main features of the spatial distribution of the isotopic composition of Early/Middle Eocene precipitation over land in conjunction with the aspects of the modeled Early/Middle Eocene climate. Hence, the included stable isotope module quantitatively supports the existence of a reduced meridional temperature gradient during this interval.

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-Carbon Isotopic Composition of Maple Sap and Foliage 1

PubMed Central

Leavitt, Steven W.; Long, Austin

1985-01-01

The 13C/12C ratios of Acer grandidentatum sap sugar collected during the dormant period are compared to those of buds, leaves, and wood developed over the following growing season. As the primary carbon source for cellulose manufacture at initiation of annual growth in deciduous trees, sap sucrose would be expected to have an isotopic composition similar to first-formed cellulose. Although constancy in concentration and 13C/12C ratios of the maple sap sugar suggests any gains or losses (e.g. to maintenance metabolism) do not appreciably alter composition, the 13C/12C ratios of cellulose of the enlarging buds in the spring are quite distinct from those of the sap sugar, seemingly precluding a simple direct biochemical pathway of sap sucrose→glucose→cellulose in favor of a more complex pathway with greater likelihood of isotopic fractionation. The 13C/12C ratios of the leaves and in the growth ring were initially similar to the sap sugar but decreased steadily over the growing season. PMID:16664259

Stable-carbon isotopic composition of maple sap and foliage.

PubMed

Leavitt, S W; Long, A

1985-06-01

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

Hydrologic and environmental controls on uranium-series and strontium isotope ratios in a natural weathering environment

NASA Astrophysics Data System (ADS)

White, A. M.; Ma, L.; Moravec, B. G.; McIntosh, J. C.; Chorover, J.

2017-12-01

In a remote, volcanic headwater catchment of the Jemez River Basin Critical Zone Observatory (JRB-CZO) in NM, stable water isotopes and solute chemistry have shown that snowmelt infiltrates and is stored before later discharging into springs and streams via subsurface flowpaths that vary seasonally. Therefore, water-rock reactions are also expected to change with season as hydrologic flowpaths transport water, gases and solutes through different biogeochemical conditions, rock types and fracture networks. Uranium-series isotopes have been shown to be a novel tracer of water-rock reactions and source water contributions while strontium isotopes are frequently used as indicators of chemical weathering and bedrock geology. This study combines both isotopes to understand how U and Sr isotope signatures evolve through the Critical Zone (CZ). More specifically, this work examines the relationship between seasonality, water transit time (WTT), and U-series and Sr isotopes in stream and spring waters from three catchments within the JRB-CZO, as well as lithology, rock type and CZ structure in solid phase cores. Samples from ten springs with known WTTs were analyzed for U and Sr isotopes to determine the effect of WTT on the isotopic composition of natural waters. Results suggest that WTT alone cannot explain the variability of U and Sr isotopes in JRB-CZO springs. Stream samples were also collected across two water years to establish how seasonality controls surface water isotopic composition. U and Sr isotope values vary with season, consistent with a previous study from the La Jara catchment; however, this study revealed that these changes do not show a systematic pattern among the three catchments suggesting that differences in the mineralogy and structure of the deep CZ in individual catchments, and partitioning of water along deep vs surficial and fracture vs matrix flow paths, likely also control isotopic variability. The distribution of U-series and Sr isotopes in core samples with depth shows distinct weathering profiles with variable 234U/238U activity and Sr isotope ratios. Comparison of the isotopic composition of cores and groundwaters from similar depths, as well as surface waters in the JRB-CZO will be vital for the characterization of hydrogeologic controls on isotopic composition in this complex terrain.

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

USGS Publications Warehouse

Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-01-01

Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

Copper and zinc isotopes have recently been shown to be variable in isotopic composi-tion among terrestrial and extraterrestrial materials [1-3]. For this study, we have se-lected samples (bulk meteorite and chondrule separates) from the CR meteorite clan: Bencubbin (CB), Renazzo (CR2), NWA 801 (CR2), and HaH237 (CH-like). These meteorites were selected because meteorites from this clan have experienced very little alteration since their initial formation [4] and for their extremely high refrac-tory/volatile element ratios. The latter characteristic may allow a test of the correlation observed by [2] between element ratios and Cu isotope composition. Measurements were performed on NHM/IC Micromass Isoprobe and Oxford Nu MC-ICP-MS using techniques described elsewhere [1,5]. Each of the meteorites measured so far for Cu and Zn are isotopically light compared to the terrestrial mantle. This suggests that the terrestrial value may have been altered from the pristine solar system value, or else there were multiple early solar system components. Zinc isotopic com-positions lie on a fractionation line and range from δ66ZnNIST = -1.4±0.1ppm (bulk NWA801) to -1.9±0.1ppm (separated chondrule, NWA 801). Copper isotope compositions vary from δ65CuNIST976 = -1.5±0.1ppm (bulk Renazzo) to -3.1±0.1ppm (separated chondrule, NWA 801). Two chondrules from NWA 801 have differing Cu isotope values (-3.1±0.1 and -2.0±0.1ppm) and both are lighter than the bulk meteorite (-1.9±0.1ppm), suggesting a lack of equilibration with respect to Cu in this meteorite. The light values for the two separated chondrules, compared the bulk meteorite, hints that chondrules may be isotopically lighter than co-existing matrix, metal and sulphides with respect to Cu. The copper isotope compositions are not as isotopically light as expected for the high refractory/volatile element ratio observed in these chondrites. Thus a model to account for the Cu isotopes in chondrites may require greater com-plexity than one involving simple mixing of two primordial components. References: [1] Zhu et al., Chem. Geol. 163,139-149 (2000). [2] Luck et al., GCA 67 143 (2002). [3] Luck et al., MAPS 35 A100 (2000) [4] Krot et al., MAPS 37 1451-1490 (2002) [5] Mason et al. EOS Trans. AGU abstract V21A-0966 82 (2001)

Stable isotopes and Digital Elevation Models to study nutrient inputs in high-Arctic lakes

NASA Astrophysics Data System (ADS)

Calizza, Edoardo; Rossi, David; Costantini, Maria Letizia; Careddu, Giulio; Rossi, Loreto

2016-04-01

Ice cover, run-off from the watershed, aquatic and terrestrial primary productivity, guano deposition from birds are key factors controlling nutrient and organic matter inputs in high-Arctic lakes. All these factors are expected to be significantly affected by climate change. Quantifying these controls is a key baseline step to understand what combination of factors subtends the biological productivity in Arctic lakes and will drive their ecological response to environmental change. Basing on Digital Elevation Models, drainage maps, and C and N elemental content and stable isotope analysis in sediments, aquatic vegetation and a dominant macroinvertebrate species (Lepidurus arcticus Pallas 1973) belonging to Tvillingvatnet, Storvatnet and Kolhamna, three lakes located in North Spitsbergen (Svalbard), we propose an integrated approach for the analysis of (i) nutrient and organic matter inputs in lakes; (ii) the role of catchment hydro-geomorphology in determining inter-lake differences in the isotopic composition of sediments; (iii) effects of diverse nutrient inputs on the isotopic niche of Lepidurus arcticus. Given its high run-off and large catchment, organic deposits in Tvillingvatnet where dominated by terrestrial inputs, whereas inputs were mainly of aquatic origin in Storvatnet, a lowland lake with low potential run-off. In Kolhamna, organic deposits seem to be dominated by inputs from birds, which actually colonise the area. Isotopic signatures were similar between samples within each lake, representing precise tracers for studies on the effect of climate change on biogeochemical cycles in lakes. The isotopic niche of L. aricticus reflected differences in sediments between lakes, suggesting a bottom-up effect of hydro-geomorphology characterizing each lake on nutrients assimilated by this species. The presented approach proven to be an effective research pathway for the identification of factors subtending to nutrient and organic matter inputs and transfer within each water body, as well as for the modelling of expected changes in nutrient content associated to changes in isotopic composition of sediments. Key words: nitrogen; carbon, sediment; biogeochemical cycle; climate change; hydro-ecology; isotopic niche; Svalbard

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

NASA Astrophysics Data System (ADS)

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

2013-08-01

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

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.

The fate of moderately volatile elements during planetary formation in the inner Solar System

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2017-12-01

Moderately volatile element abundances are variable among inner Solar System bodies, with differing degrees of depletion compared to chondrites. These variations are a consequence of the processes of planetary formation. The conditions and the specific mechanisms of planetary accretion and differentiation can be investigated by analyzing the stable isotope compositions of terrestrial and extraterrestrial samples. The moderately volatile lithophile elements are particularly useful to distinguish between the effects of accretion and those of core formation. Recent work has shown isotope variations in inner Solar System bodies for the moderately volatile elements Zn and K. The purely lithophile nature of Rb (in contrast to Zn) and the higher volatility of Rb compared to K make Rb an ideal element with which to further study moderately volatile element depletion. We have developed a new method for the high-precision measurement of Rb isotope ratios by MC-ICP-MS. Terrestrial rocks define a narrow range in Rb isotope composition, indicating that Rb isotope fractionation during igneous differentiation is limited (<30 ppm/amu). Larger Rb isotope variations are observed in extraterrestrial materials. Carbonaceous chondrites display a trend toward lighter Rb isotope composition coupled with decreasing Rb/Sr, opposite to the effect expected if their volatile element variations were caused by evaporative loss of Rb. This relationship indicates that the volatile element abundance variations in carbonaceous chondrites are not due to evaporation or condensation, but rather are due to the mixing of chemically and isotopically distinct primordial reservoirs. In contrast, there is a clear signature of Rb loss during evaporation in volatile-depleted achondrites and lunar rocks. Significant heavy isotope enrichments (up to several per mil for 87Rb/85Rb) are found for volatile-depleted planetesimals, including eucrites. In addition, lunar rocks also display heavy Rb isotope enrichments compared to the BSE. The most likely cause of these variations is Rb isotope fractionation due to evaporation during accretion.

A Noninvasive Isotopic Approach to Estimate the Bone Lead Contribution to Blood in Children: Implications for Assessing the Efficacy of Lead Abatement

PubMed Central

Gwiazda, Roberto; Campbell, Carla; Smith, Donald

2005-01-01

Lead hazard control measures to reduce children’s exposure to household lead sources often result in only limited reductions in blood lead levels. This may be due to incomplete remediation of lead sources and/or to the remobilization of lead stores from bone, which may act as an endogenous lead source that buffers reductions in blood lead levels. Here we present a noninvasive isotopic approach to estimate the magnitude of the bone lead contribution to blood in children following household lead remediation. In this approach, lead isotopic ratios of a child’s blood and 5-day fecal samples are determined before and after a household intervention aimed at reducing the child’s lead intake. The bone lead contribution to blood is estimated from a system of mass balance equations of lead concentrations and isotopic compositions in blood at the different times of sample collection. The utility of this method is illustrated with three cases of children with blood lead levels in the range of 18–29 μg/dL. In all three cases, the release of lead from bone supported a substantial fraction of the measured blood lead level postintervention, up to 96% in one case. In general, the lead isotopic compositions of feces matched or were within the range of the lead isotopic compositions of the household dusts with lead loadings exceeding U.S. Environmental Protection Agency action levels. This isotopic agreement underscores the utility of lead isotopic measurements of feces to identify household sources of lead exposure. Results from this limited number of cases support the hypothesis that the release of bone lead into blood may substantially buffer the decrease in blood lead levels expected from the reduction in lead intake. PMID:15626656

Isotopic fingerprints of the Lake Żabińskie (NE Poland) hydrological system on contemporary carbonates precipitated in the lake.

PubMed

Ustrzycka, Alicja; Piotrowska, Natalia; Bonk, Alicja; Filipiak, Janusz; Tylmann, Wojciech

2018-06-01

An isotopic monitoring was undertaken in 2012-2014 at Lake Żabińskie (Mazurian Lakeland, NE Poland). The aim was to identify the factors and processes controlling an isotopic composition of the lake water and to explore the mechanism responsible for recording the climatic signal in stable isotope composition of deposited carbonates. δ 18 O and δ 2 H in the precipitation, lake water column, inflows and outflow, δ 18 O and δ 13 C in the carbonate fraction of sediments trapped in the water column were recorded with monthly resolution. A relationship between δ 18 O and δ 2 H in local precipitation was used to estimate the local meteoric water line. The dataset obtained for the water enabled to identify the modification of the water's isotopic composition due to evaporation, connected with seasonal lake water stratification and mixing patterns. Statistically significant correlation coefficients suggest that the δ 18 O of the carbonate fraction in the sediment traps depends on the δ 18 O of rainfall water and on air temperature. The fractionation coefficient α shows that in summer months the carbonate precipitation process is closest to equilibrium. As expected for an exorheic lake, no significant correlation was observed between δ 18 O and δ 13 C in precipitated carbonate.

Anthropogenic osmium in rain and snow reveals global-scale atmospheric contamination.

PubMed

Chen, Cynthia; Sedwick, Peter N; Sharma, Mukul

2009-05-12

Osmium is one of the rarer elements in seawater, with typical concentration of approximately 10 x 10(-15) g g(-1) (5.3 x 10(-14) mol kg(-1)). The osmium isotope composition ((187)Os/(188)Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (approximately 1.3) and mantle/cosmic dust (approximately 0.13). Here, we show that the (187)Os/(188)Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (approximately 0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower (187)Os/(188)Os ratio (approximately 0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts.

Altitude effect on leaf wax carbon isotopic composition in humid tropical forests

NASA Astrophysics Data System (ADS)

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

2017-06-01

The carbon isotopic composition of plant leaf wax biomarkers is commonly used to reconstruct paleoenvironmental conditions. Adding to the limited calibration information available for modern tropical forests, we analyzed plant leaf and leaf wax carbon isotopic compositions in forest canopy trees across a highly biodiverse, 3.3 km elevation gradient on the eastern flank of the Andes Mountains. We sampled the dominant tree species and assessed their relative abundance in each tree community. In total, 405 sunlit canopy leaves were sampled across 129 species and nine forest plots along the elevation profile for bulk leaf and leaf wax n-alkane (C27-C33) concentration and carbon isotopic analyses (δ13C); a subset (76 individuals, 29 species, five forest plots) were additionally analyzed for n-alkanoic acid (C22-C32) concentrations and δ13C. δ13C values display trends of +0.87 ± 0.16‰ km-1 (95% CI, r2 = 0.96, p < 0.01) for bulk leaves and +1.45 ± 0.33‰ km-1 (95% CI, r2 = 0.94, p < 0.01) for C29n-alkane, the dominant chain length. These carbon isotopic gradients are defined in multi-species sample sets and corroborated in a widespread genus and several families, suggesting the biochemical response to environment is robust to taxonomic turnover. We calculate fractionations and compare to adiabatic gradients, environmental variables, leaf wax n-alkane concentrations, and sun/shade position to assess factors influencing foliar chemical response. For the 4 km forested elevation range of the Andes, 4-6‰ higher δ13C values are expected for upland versus lowland C3 plant bulk leaves and their n-alkyl lipids, and we expect this pattern to be a systematic feature of very wet tropical montane environments. This elevation dependency of δ13C values should inform interpretations of sedimentary archives, as 13C-enriched values may derive from C4 grasses, petrogenic inputs or upland C3 plants. Finally, we outline the potential for leaf wax carbon isotopes to trace biomarker sourcing within catchments and for paleoaltimetry.

Pb isotope geochemistry of Piton de la Fournaise historical lavas

NASA Astrophysics Data System (ADS)

Vlastélic, Ivan; Deniel, Catherine; Bosq, Chantal; Télouk, Philippe; Boivin, Pierre; Bachèlery, Patrick; Famin, Vincent; Staudacher, Thomas

2009-07-01

Variations of Pb isotopes in historical lavas (1927-2007) from Piton de la Fournaise are investigated based on new (116 samples) and published (127 samples) data. Lead isotopic signal exhibits smooth fluctuations (18.87 < 206Pb/ 204Pb < 18.94) on which superimpose unradiogenic spikes ( 206Pb/ 204Pb down to 18.70). Lead isotopes are decoupled from 87Sr/ 86Sr and 143Nd/ 144Nd, which display small and barely significant variations, respectively. No significant change of Pb isotope composition occurred during the longest (> 3 years) periods of inactivity of the volcano (1939-1942, 1966-1972, 1992-1998), supporting previous inferences that Pb isotopic variations occur mostly during and not between eruptions. Intermediate compositions (18.904 < 206Pb/ 204Pb < 18.917) bracket the longest periods of quiescence. In this respect, the highly frequent occurrence of an intermediate composition (18.90 < 206Pb/ 204Pb < 18.91), which clearly defines an isotopic baseline during the most recent densely sampled period (1975-2007), either suggests direct sampling of plume melts or sampling of a voluminous magma reservoir that buffers Pb isotopic composition. Deviations from this prevalent composition occurred during well-defined time periods, namely 1977-1986 (radiogenic signature), 1986-1990 and 1998-2005 (unradiogenic signatures). The three periods display a progressive isotopic drift ending by a rapid return (mostly during a single eruption) to the isotopic baseline. The isotopic gradients could reflect progressive emptying of small magma reservoirs or magma conduits, which are expected to be more sensitive to wall-rock interactions than the main magma chamber. These gradients provide a lower bound ranging from 0.1 to 0.17 km 3 for the size of the shallow magma storage system. The isotopic shifts (March 1986, January 1990 and February 2005) are interpreted as refilling the plumbing system with deep melts that have not interacted with crustal components. The volume of magma erupted between the two major refilling events of March 1986 and February 2005 (0.28 km 3) could provide a realistic estimate of the magma reservoir size. Unradiogenic anomalies appear to be linked, more or less directly, to the eruption of olivine-rich lavas. The related samples have low 206Pb/ 204Pb and 208Pb/ 204Pb but normal 207Pb/ 204Pb, suggesting a recent decrease of U/Pb and Th/Pb, for instance through sequestration of Pb into sulfides. Olivine and sulfides, which are both denser than silicate melts, could be entrained with magma pulses, which give rise to high-flux oceanite eruptions.

Moss stable isotopes (carbon-13, oxygen-18) and testate amoebae reflect environmental inputs and microclimate along a latitudinal gradient on the Antarctic Peninsula.

PubMed

Royles, Jessica; Amesbury, Matthew J; Roland, Thomas P; Jones, Glyn D; Convey, Peter; Griffiths, Howard; Hodgson, Dominic A; Charman, Dan J

2016-07-01

The stable isotope compositions of moss tissue water (δ(2)H and δ(18)O) and cellulose (δ(13)C and δ(18)O), and testate amoebae populations were sampled from 61 contemporary surface samples along a 600-km latitudinal gradient of the Antarctic Peninsula (AP) to provide a spatial record of environmental change. The isotopic composition of moss tissue water represented an annually integrated precipitation signal with the expected isotopic depletion with increasing latitude. There was a weak, but significant, relationship between cellulose δ(18)O and latitude, with predicted source water inputs isotopically enriched compared to measured precipitation. Cellulose δ(13)C values were dependent on moss species and water content, and may reflect site exposure to strong winds. Testate amoebae assemblages were characterised by low concentrations and taxonomic diversity, with Corythion dubium and Microcorycia radiata types the most cosmopolitan taxa. The similarity between the intra- and inter-site ranges measured in all proxies suggests that microclimate and micro-topographical conditions around the moss surface were important determinants of proxy values. Isotope and testate amoebae analyses have proven value as palaeoclimatic, temporal proxies of climate change, whereas this study demonstrates that variations in isotopic and amoeboid proxies between microsites can be beyond the bounds of the current spatial variability in AP climate.

Stable isotopes of pedogenic carbonates from the Somma-Vesuvius area, southern Italy, over the past 18 kyr: palaeoclimatic implications

NASA Astrophysics Data System (ADS)

Zanchetta, G.; di Vito, M.; Fallick, A. E.; Sulpizio, R.

2000-12-01

Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma-Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in 18O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1 in 18O of pedogenic carbonate recorded after this eruption. The 13C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO2, and the pedogenic carbonate. Carbon isotopes suggest prevailing C3 vegetation and negligible mixing with volcanogenic or atmospheric CO2.

Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

USDA-ARS?s Scientific Manuscript database

Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understanding feedbacks in the cl...

The isotope mass effect on chlorine diffusion in dacite melt, with implications for fractionation during bubble growth

NASA Astrophysics Data System (ADS)

Fortin, Marc-Antoine; Watson, E. Bruce; Stern, Richard

2017-12-01

Previous experimental studies have revealed that the difference in diffusivity of two isotopes can be significant in some media and can lead to an observable fractionation effect in silicate melts based on isotope mass. Here, we report the first characterization of the difference in diffusivities of stable isotopes of Cl (35Cl and 37Cl). Using a piston-cylinder apparatus, we generated quenched melts of dacitic composition enriched in Cl; from these we fabricated diffusion couples in which Cl atoms were induced to diffuse in a chemical gradient at 1200 to 1350 °C and 1 GPa. We analyzed the run products by secondary ion mass spectrometry (SIMS) for their isotopic compositions along the diffusion profiles, and we report a diffusivity ratio for 37Cl/35Cl of 0.995 ± 0.001 (β = 0.09 ± 0.02). No significant effect of temperature on the diffusivity ratio was discernable over the 150 °C range covered by our experiments. The observed 0.5% difference in diffusivity of the two isotopes could affect our interpretation of isotopic measurements of Cl isotopes in bubble-bearing or degassed magmas, because bubble growth is regulated in part by the diffusive supply of volatiles to the bubble from the surrounding melt. Through numerical simulations, we constrain the extent of Cl isotopic fractionation between bubble and host melt during this process. Bubble growth rates vary widely in nature-which implies a substantial range in the expected magnitude of isotopic fractionation-but plausible growth scenarios lead to Cl isotopic fractionations up to about 5‰ enrichment of 35Cl relative to 37Cl in the bubble. This effect should be considered when interpreting Cl isotopic measurements of systems that have experienced vapor exsolution.

The effect of fusion-relevant helium levels on the mechanical properties of isotopically tailored ferritic alloys

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

Hankin, G.L.; Hamilton, M.L.; Gelles, D.S.

1997-04-01

The yield and maximum strengths of an irradiated series of isotopically tailored ferritic alloys were evaluated using the shear punch test. The composition of three of the alloys was Fe-12Cr-1.5Ni. Different balances of nickel isotopes were used in each alloy in order to produce different helium levels. A fourth alloy, which contained no nickel, was also irradiated. The addition of nickel at any isotopic balance to the Fe-12Cr base alloy significantly increased the shear yield and maximum strengths of the alloys, and as expected, the strength of the alloys decreased with increasing irradiation temperature. Helium itself, up to 75 appmmore » over 7 dpa appears to have little effect on the mechanical properties of the alloys.« less

Stable Chlorine Isotope Study: Application to Early Solar System Materials

NASA Technical Reports Server (NTRS)

Mala,ira. M/; Nyquist, L. E.; Reese, Y.; Shih, C-Y; Fujitani, T.; Okano, O.

2010-01-01

A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the Cl-37/Cl-35 ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For example, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. A significantly large mass fractionation between two stable chlorine isotopes is expected during planetary processes In addition, in view of the isotopic heterogeneity of other light elements, the chlorine isotopes can potentially be used as a tracer for the origins and evolutionary processes of early solar system materials. Due to analytical difficulties, however, current chlorine isotope studies on planetary materials are quite controversial among IRMS (gas source mass spectrometry) and/or TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1-3]. Although a cross-calibration of IRMS and TIMS indicates that both techniques are sufficiently consistent with each other [4], some authors have claimed that the 37Cl/35Cl ratio of geological samples obtained by TIMS technique are, in general, misleadingly too high and variable compared to those of IRMS [3]. For eample, almost no differences of Cl isotope composition were observed among mantle materials and carbonaceous meteorites by [3]. On the other hand, according to more recent IRMS work [2], significant Cl isotope variations are confirmed for mantle materials. Therefore, additional careful investigation of Cl isotope analyses are now required to confirm real chlorine isotope variations for planetary materials including carbonaceous chondrites [5]. In order to clarify the stable chlorine isotope features of early solar system materials, we have initiated development of the TIMS technique at NASA JSC applicable to analysis of small amounts of meteoritic and planetary materials. We report here the current status of chlorine isotope analysis at NASA JSC.

Solvent isotope-induced equilibrium perturbation for isocitrate lyase.

PubMed

Quartararo, Christine E; Hadi, Timin; Cahill, Sean M; Blanchard, John S

2013-12-23

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacterium's life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage ((D₂O)V = 2.0 ± 0.1, and (D₂O)[V/K(isocitrate)] = 2.2 ± 0.3) arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of the succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate, and succinate prepared in D₂O would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by ¹H NMR spectroscopy shows a clear equilibrium perturbation in D₂O. The final equilibrium isotopic composition of reactants in D₂O revealed dideuterated succinate, protiated glyoxylate, and monodeuterated isocitrate, with the transient appearance and disappearance of monodeuterated succinate. A model for the equilibrium perturbation of substrate species and their time-dependent isotopic composition is presented.

Isotopic composition (oxygen and hydrogen) of groundwater in Norway - a review of current knowledge and future perspectives

NASA Astrophysics Data System (ADS)

Kracht, O.

2012-04-01

A review of current knowledge and available data covering the stable isotope composition of groundwater in Norway is presented. Furthermore, the future challenge of obtaining systematic background datasets and of integrating isotopes into the mainstream of hydrogeological observation programmes is discussed. I will summarize our experiences gained from different preliminary studies and will try to identify relationships to existing datasets, historical registrations, and networks on precipitation data. The study of transient effects in hydrological cycles is highly topical as these are supposed to provide means for investigating the effects of climate change and increasing human activities. From a hydrogeological point of view, is critical to establish suitable tools for the large scale observation of changes in groundwater recharge and depletion, their likely controls, and the expected nature of responses to changing climate, urbanization and other human activities. In this context, stable isotopes (δ18O and δ2H of water) can provide an expedient instrument to investigate the general hydrological setting, connections, and pathways of various scale aquifer systems. However, we are up to now missing an expedient background dataset on hydrogeological and hydrological stable isotopes observations for mainland Norway. Against this background, during years 2010 and 2011 the Geological Survey of Norway (NGU) organized two nation-wide sampling campaigns on the stable isotope composition of modern groundwater. These pilot studies aimed to obtain a first overview about the data ranges and natural variations to be expected. We used stations from the existing Norwegian Groundwater Monitoring Network (Landsomfattende Grunnvannsnett, LGN) to collect samples of groundwater at 55 different locations throughout Norway. As a main characteristic of these two datasets, all δ18O and δ2H values of the "LGN series" were well correlated and plotted close to the global meteoric water line. This essentially documents the in principal exclusively meteoric origin of these waters, and indicates that the LGN groundwaters investigated shared the same type of origin: (i) evaporation from the ocean, and (ii) isotopic enrichment by rainout (continental effect). Conversely this also indicates that other processes (re-evaporation, admixture of water with a different genesis, etc.) did not have significant influence in this dataset. In parallel, two more detailed local application studies have been conducted in unconsolidated glaciofluvial aquifers in S-Norway (eastern part of the Gardermoen / Øvre Romerike Aquifer in Akershus county, and glaciofluvial deposits at the Granli waterworks of Kongsvinger in Hedmark county). In these investigations, detailed vertical profiles obtained with multi level sampling devices displayed systematic vertical evolution of groundwater isotopic composition, and it is demonstrated how an extended local dataset can enable to discuss the discrimination between different groundwater / surface water influences, and supports the planning of groundwater exploitations and groundwater water resources management.

Carbon isotope effects associated with autotrophic acetogenesis

NASA Technical Reports Server (NTRS)

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

1989-01-01

The carbon kinetic isotope effects associated with synthesis of acetate from CO2 and H2 during autotrophic growth of Acetobacterium woodii at 30 degrees C have been measured by isotopic analyses of CO2, methyl-carbon, and total acetate. Closed systems allowing construction of complete mass balances at varying stages of growth were utilized, and the effects of the partitioning of carbon between CO2 and HCO3- were taken account. For the overall reaction, total carbonate --> total acetate, isotope effects measured in replicate experiments ranged from -59.0 +/- 0.9% to -57.2 +/- 2.3%. Taking into account all measurements, the weighted mean and standard deviation are -58.6 +/- 0.7%. There is no evidence for intramolecular ordering in the acetate. The carbon isotopic composition of sedimentary acetate, otherwise expected to be near that of sedimentary organic carbon, is likely to be depleted in environments in which autotrophic acetogenesis is occurring.

Potassium isotopic evidence for a high-energy giant impact origin of the Moon.

PubMed

Wang, Kun; Jacobsen, Stein B

2016-10-27

The Earth-Moon system has unique chemical and isotopic signatures compared with other planetary bodies; any successful model for the origin of this system therefore has to satisfy these chemical and isotopic constraints. The Moon is substantially depleted in volatile elements such as potassium compared with the Earth and the bulk solar composition, and it has long been thought to be the result of a catastrophic Moon-forming giant impact event. Volatile-element-depleted bodies such as the Moon were expected to be enriched in heavy potassium isotopes during the loss of volatiles; however such enrichment was never found. Here we report new high-precision potassium isotope data for the Earth, the Moon and chondritic meteorites. We found that the lunar rocks are significantly (>2σ) enriched in the heavy isotopes of potassium compared to the Earth and chondrites (by around 0.4 parts per thousand). The enrichment of the heavy isotope of potassium in lunar rocks compared with those of the Earth and chondrites can be best explained as the result of the incomplete condensation of a bulk silicate Earth vapour at an ambient pressure that is higher than 10 bar. We used these coupled constraints of the chemical loss and isotopic fractionation of K to compare two recent dynamic models that were used to explain the identical non-mass-dependent isotope composition of the Earth and the Moon. Our K isotope result is inconsistent with the low-energy disk equilibration model, but supports the high-energy, high-angular-momentum giant impact model for the origin of the Moon. High-precision potassium isotope data can also be used as a 'palaeo-barometer' to reveal the physical conditions during the Moon-forming event.

Lead isotopic fingerprinting of aerosols to characterize the sources of atmospheric lead in an industrial city of India

NASA Astrophysics Data System (ADS)

Sen, Indra S.; Bizimis, Michael; Tripathi, Sachchida Nand; Paul, Debajyoti

2016-03-01

Anthropogenic Pb in the environment is primarily sourced from combustion of fossil fuel and high-temperature industries such as smelters. Identifying the sources and pathways of anthropogenic Pb in the environment is important because Pb toxicity is known to have adverse effects on human health. Pb pollution sources for America, Europe, and China are well documented. However, sources of atmospheric Pb are unknown in India, particularly after leaded gasoline was phased out in 2000. India has a developing economy with a rapidly emerging automobile and high temperature industry, and anthropogenic Pb emission is expected to rise in the next decade. In this study, we report on the Pb-isotope compositions and trace metal ratios of airborne particulates collected in Kanpur, a large city in northern part of India. The study shows that the PM10 aerosols had elevated concentration of Cd, Pb, Zn, As, and Cu in the Kanpur area, however their concentrations are well below the United States Environmental Protection Agency chronic exposure limit. Lead isotopic and trace metal data reveal industrial emission as the plausible source of anthropogenic Pb in the atmosphere in Kanpur. However, Pb isotopic compositions of potential source end-members are required to fully evaluate Pb contamination in India over time. This is the first study that characterizes the isotopic composition of atmospheric Pb in an Indian city after leaded gasoline was phased out by 2000.

SULFUR ISOTOPIC COMPOSITIONS OF SUBMICROMETER SiC GRAINS FROM THE MURCHISON METEORITE

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

Xu, Yuchen; Zinner, Ernst; Gallino, Roberto

2015-02-01

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

Uranium Isotopic Ratio Measurements of U3O8 Reference Materials by Atom Probe Tomography

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

Fahey, Albert J.; Perea, Daniel E.; Bartrand, Jonah AG

2016-01-01

We report results of measurements of isotopic ratios obtained with atom probe tomography on U3O8 reference materials certified for their isotopic abundances of uranium. The results show good agreement with the certified values. High backgrounds due to tails from adjacent peaks complicate the measurement of the integrated peak areas as well as the fact that only oxides of uranium appear in the spectrum, the most intense of which is doubly charged. In addition, lack of knowledge of other instrumental parameters, such as the dead time, may bias the results. Isotopic ratio measurements can be performed at the nanometer-scale with themore » expectation of sensible results. The abundance sensitivity and mass resolving power of the mass spectrometer are not sufficient to compete with magnetic-sector instruments but are not far from measurements made by ToF-SIMS of other isotopic systems. The agreement of the major isotope ratios is more than sufficient to distinguish most anthropogenic compositions from natural.« less

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis

NASA Astrophysics Data System (ADS)

VanStone, Nancy; Przepiora, Andrzej; Vogan, John; Lacrampe-Couloume, Georges; Powers, Brian; Perez, Ernesto; Mabury, Scott; Sherwood Lollar, Barbara

2005-08-01

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. > 9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and δ13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched δ13C values compared to the upgradient mean. In addition, δ13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis.

PubMed

VanStone, Nancy; Przepiora, Andrzej; Vogan, John; Lacrampe-Couloume, Georges; Powers, Brian; Perez, Ernesto; Mabury, Scott; Sherwood Lollar, Barbara

2005-08-01

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals within and immediately downgradient of the PRB, concentrations remained higher than expected at wells further downgradient (i.e. >9 m) of the PRB. At two wells downgradient of the PRB, TCE concentrations were comparable to upgradient values, and delta13C values of TCE at these wells were not significantly different than upgradient values. Since the process of sorption/desorption does not significantly fractionate carbon isotope values, this suggests that the TCE observed at these wells is desorbing from local aquifer materials and was present before the PRB was installed. In contrast, three other downgradient wells show significantly more enriched delta13C values compared to the upgradient mean. In addition, delta13C values for the degradation products of TCE, cis-dichloroethene and vinyl chloride, show fractionation patterns expected for the products of the reductive dechlorination of TCE. Since concentrations of both TCE and degradation products drop to below detection limit in wells within the PRB and directly below it, these downgradient chlorinated hydrocarbon concentrations are attributed to desorption from local aquifer material. The carbon isotope values indicate that this dissolved contaminant is subject to local degradation, likely due to in situ microbial activity.

Pb isotope constaints on the extent of crustal recycling into a steady state mantle

NASA Technical Reports Server (NTRS)

Galer, S. J. G.; Goldstein, S. L.; Onions, R. K.

1988-01-01

Isotopic and geochemical evidence was discussed against recycling of continental crust into the mantle. Element ratios such as Sm/Nd, Th/Sc, and U/Pb in sedimentary masses have remained relatively constant throughout Earth history, and this can only be reconciled with steady state recycling models if new crustal materials added from the mantle have had similar ratios. Such recycling models would also require shorter processing times for U, Th, and Pb through the mantle than are geodynamically reasonable. Models favoring subduction of pelagic sediments as the only recycling mechanism fail to account for the Pb isotopic signature of the mantle. Recycling of bulk crust with Pb isotopic compositions similar to those expected for primitive mantle would be permissable with available data, but there appear to be no plausible tectonic mechanisms to carry this out.

Rapid passage of a small-scale mantle heterogeneity through the melting regions of Kilauea and Mauna Loa Volcanoes

NASA Astrophysics Data System (ADS)

Marske, Jared P.; Pietruszka, Aaron J.; Weis, Dominique; Garcia, Michael O.; Rhodes, J. Michael

2007-07-01

Recent Kilauea and Mauna Loa lavas provide a snapshot of the size, shape, and distribution of compositional heterogeneities within the Hawaiian mantle plume. Here we present a study of the Pb, Sr, and Nd isotope ratios of two suites of young prehistoric lavas from these volcanoes: (1) Kilauea summit lavas erupted from AD 900 to 1400, and (2) 14C-dated Mauna Loa flows erupted from ˜ 2580-140 yr before present (relative to AD 1950). These lavas display systematic isotopic fluctuations, and the Kilauea lavas span the Pb isotopic divide that was previously thought to exist between these two volcanoes. For a brief period from AD 250 to 1400, the 206Pb/ 204Pb and 87Sr/ 86Sr isotope ratios and ɛNd values of Kilauea and Mauna Loa lavas departed from values typical for each volcano (based on historical and other young prehistoric lavas), moved towards an intermediate composition, and subsequently returned to typical values. This is the only known period in the eruptive history of these volcanoes when such a simultaneous convergence of Pb, Sr, and Nd isotope ratios has occurred. The common isotopic composition of lavas erupted from both Kilauea and Mauna Loa during this transient magmatic event was probably caused by the rapid passage of a small-scale compositional heterogeneity through the melting regions of both volcanoes. This heterogeneity is thought to have been either a single body (˜ 35 km long based on the distance between the summits of these volcanoes) or the plume matrix itself (which would be expected to be present beneath both volcanoes). The time scale of this event (centuries) is much shorter than previously noted for variations in the isotopic composition of Hawaiian lavas due to the upwelling of heterogeneities within the plume (thousands to tens of thousands of years). Calculations based on the timing of the isotopic convergence suggest a maximum thickness for the melting region (and thus, the heterogeneity) of ˜ 5-10 km. The small size of the heterogeneity indicates that melt can be extracted from small regions within the Hawaiian plume with minimal subsequent chemical modification (beyond the effects of crystal fractionation). This would be most effective if melt transport in the mantle beneath Hawaiian shield volcanoes occurs mostly in chemically isolated channels.

Biological forcing controls the chemistry of the coral exoskeleton

NASA Astrophysics Data System (ADS)

Meibom, A.; Mostefaoui, S.; Cuif, J.; Yurimoto, H.; Dauphin, Y.; Houlbreque, F.; Dunbar, R.; Constantz, B.

2006-12-01

A multitude of marine organisms produce calcium carbonate skeletons that are used extensively to reconstruct water temperature variability of the tropical and subtropical oceans - a key parameter in global climate-change models. Such paleo-climate reconstructions are based on the notion that skeletal oxygen isotopic composition and certain trace-element abundances (e.g., Sr/Ca and Mg/Ca ratios) vary in response to changes in the water temperature. However, it is a fundamental problem that poorly understood biological processes introduce large compositional deviations from thermodynamic equilibrium and hinder precise calibrations of many paleo-climate proxies. Indeed, the role of water temperature in controlling the composition of the skeleton is far from understood. We have studied trace-element abundances as well as oxygen and carbon isotopic compositions of individual skeletal components in the zooxanthellate and non-zooxanthellate corals at ultra-structural, i.e. micrometer to sub-micrometer length scales. From this body of work we draw the following, generalized conclusions: 1) Centers of calcification (COC) are not in equilibrium with seawater. Notably, the Sr/Ca ratio is higher than expected for aragonite equilibrium with seawater at the temperature at which the skeleton was formed. Furthermore, the COC are further away from equilibrium with seawater than fibrous skeleton in terms of stable isotope composition. 2) COC are dramatically different from the fibrous aragonite skeleton in terms of trace element composition. 3) Neither trace element nor stable isotope variations in the fibrous (bulk) part of the skeleton are directly related to changes in SST. In fact, changes in SST can have very little to do with the observed compositional variations. 4) Trace element variations in the fibrous (bulk) part of the skeleton are not related to the activity of zooxanthellae. These observations are directly relevant to the issue of biological versus non-biological control over skeleton composition and will be discussed.

Anthropogenic osmium in rain and snow reveals global-scale atmospheric contamination

PubMed Central

Chen, Cynthia; Sedwick, Peter N.; Sharma, Mukul

2009-01-01

Osmium is one of the rarer elements in seawater, with typical concentration of ≈10 × 10−15 g g−1 (5.3 × 10−14 mol kg−1). The osmium isotope composition (187Os/188Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (≈1.3) and mantle/cosmic dust (≈0.13). Here, we show that the 187Os/188Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (≈0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower 187Os/188Os ratio (≈0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts. PMID:19416862

Evaporation induced 18O and 13C enrichment in lake systems: A global perspective on hydrologic balance effects

NASA Astrophysics Data System (ADS)

Horton, Travis W.; Defliese, William F.; Tripati, Aradhna K.; Oze, Christopher

2016-01-01

Growing pressure on sustainable water resource allocation in the context of global development and rapid environmental change demands rigorous knowledge of how regional water cycles change through time. One of the most attractive and widely utilized approaches for gaining this knowledge is the analysis of lake carbonate stable isotopic compositions. However, endogenic carbonate archives are sensitive to a variety of natural processes and conditions leaving isotopic datasets largely underdetermined. As a consequence, isotopic researchers are often required to assume values for multiple parameters, including temperature of carbonate formation or lake water δ18O, in order to interpret changes in hydrologic conditions. Here, we review and analyze a global compilation of 57 lacustrine dual carbon and oxygen stable isotope records with a topical focus on the effects of shifting hydrologic balance on endogenic carbonate isotopic compositions. Through integration of multiple large datasets we show that lake carbonate δ18O values and the lake waters from which they are derived are often shifted by >+10‰ relative to source waters discharging into the lake. The global pattern of δ18O and δ13C covariation observed in >70% of the records studied and in several evaporation experiments demonstrates that isotopic fractionations associated with lake water evaporation cause the heavy carbon and oxygen isotope enrichments observed in most lakes and lake carbonate records. Modeled endogenic calcite compositions in isotopic equilibrium with lake source waters further demonstrate that evaporation effects can be extreme even in lake records where δ18O and δ13C covariation is absent. Aridisol pedogenic carbonates show similar isotopic responses to evaporation, and the relevance of evaporative modification to paleoclimatic and paleotopographic research using endogenic carbonate proxies are discussed. Recent advances in stable isotope research techniques present unprecedented opportunities to overcome the underdetermined nature of stable isotopic data through integration of multiple isotopic proxies, including dual element 13C-excess values and clumped isotope temperature estimates. We demonstrate the utility of applying these multi-proxy approaches to the interpretation of paleohydroclimatic conditions in ancient lake systems. Understanding past, present, and future hydroclimatic systems is a global imperative. Significant progress should be expected as these modern research techniques become more widely applied and integrated with traditional stable isotopic proxies.

The potential source of lead in the Permian Kupferschiefer bed of Europe and some selected Paleozoic mineral deposits in the Federal Republic of Germany

USGS Publications Warehouse

Wedepohl, K.H.; Delevaux, M.H.; Doe, B.R.

1978-01-01

New lead isotopic compositions have been measured for Paleozoic bedded and vein ore deposits of Europe by the high precision thermal emission (triple filament) technique. Eleven samples have been analyzed from the Upper Permian Kupferschiefer bed with representatives from Poland to England, three samples from the Middle Devonian Rammelsberg deposit and one from the Middle Devonian Meggen deposit, both of which are conformable ore lenses and are in the Federal Republic of Germany (FRG); and also two vein deposits from the FRG were analyzed, from Ramsbeck in Devonian host rocks and from Grund in Carboniferous host rocks. For Kupferschiefer bed samples from Germany, the mineralization is of variable lead isotopic composition and appears to have been derived about 250 m.y. ago from 1700 m.y. old sources, or detritus of this age, in Paleozoic sedimentary rocks. Samples from England, Holland, and Poland have different isotopic characteristics from the German samples, indicative of significantly different source material (perhaps older). The isotopic variability of the samples from the Kupferschiefer bed in Germany probably favors the lead containing waters coming from shoreward (where poor mixing is to be expected) rather than basinward (where better mixing is likely) directions. The data thus support the interpretation of the metal source already given by Wedepohl in 1964. Data on samples from Rammelsberg and Meggen tend to be slightly less radiogenic than for the Kupferschiefer, about the amount expected if the leads were all derived from the same source material but 100 to 150 m.y. apart in time. The vein galena from Ramsbeck is similar to that from Rammelsberg conformable ore lenses, both in rocks of Devonian age; vein galena from Grund in Upper Carboniferous country rocks is similar to some bedded Kupferschiefer mineralization in Permian rocks, as if the lead composition was formed at about the same time and from similar source material as the bedded deposits. Although heat has played a more significant role in the formation of some of these deposits (veins and Rammelsberg-Meggen) than in others (Kupferschiefer), there is no indication of radically different sources for the lead, all apparently coming from sedimentary source material containing Precambrian detritus. One feldspar lead sample from the Brocken-Oker Granite is not the same in isotopic composition as any of the ores analyzed. ?? 1978 Springer-Verlag.

Solvent Isotope-induced Equilibrium Perturbation for Isocitrate Lyase

PubMed Central

Quartararo, Christine E.; Hadi, Timin; Cahill, Sean M.; Blanchard, John S.

2014-01-01

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacteria’s life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage of D2OV = 2.0 ± 0.1 and D2O[V/Kisocitrate] = 2.2 ± 0.3 arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate and succinate prepared in D2O, would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of NMR spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by 1H NMR spectroscopy shows a clear equilibrium perturbation in D2O. The final equilibrium isotopic composition of reactants in D2O revealed di-deuterated succinate, protiated glyoxylate, and mono-deuterated isocitrate, with the transient appearance and disappearance of mono-deuterated succinate. A model for the equilibrium perturbation of substrate species, and their time-dependent isotopic composition is presented. PMID:24261638

Oxygen isotopic composition of chondritic interplanetary dust particles: A genetic link between carbonaceous chondrites and comets

NASA Astrophysics Data System (ADS)

Aléon, J.; Engrand, C.; Leshin, L. A.; McKeegan, K. D.

2009-08-01

Oxygen isotopes were measured in four chondritic hydrated interplanetary dust particles (IDPs) and five chondritic anhydrous IDPs including two GEMS-rich particles (Glass embedded with metal and sulfides) by a combination of high precision and high lateral resolution ion microprobe techniques. All IDPs have isotopic compositions tightly clustered around that of solar system planetary materials. Hydrated IDPs have mass-fractionated oxygen isotopic compositions similar to those of CI and CM carbonaceous chondrites, consistent with hydration of initially anhydrous protosolar dust. Anhydrous IDPs have small 16O excesses and depletions similar to those of carbonaceous chondrites, the largest 16O variations being hosted by the two GEMS-rich IDPs. Coarse-grained forsteritic olivine and enstatite in anhydrous IDPs are isotopically similar to their counterparts in comet Wild 2 and in chondrules suggesting a high temperature inner solar system origin. The small variations in the 16O content of GEMS-rich IDPs suggest that most GEMS either do not preserve a record of interstellar processes or the initial interstellar dust is not 16O-rich as expected by self-shielding models, although a larger dataset is required to verify these conclusions. Together with other chemical and mineralogical indicators, O isotopes show that the parent-bodies of carbonaceous chondrites, of chondritic IDPs, of most Antarctic micrometeorites, and comet Wild 2 belong to a single family of objects of carbonaceous chondrite chemical affinity as distinct from ordinary, enstatite, K- and R-chondrites. Comparison with astronomical observations thus suggests a chemical continuum of objects including main belt and outer solar system asteroids such as C-type, P-type and D-type asteroids, Trojans and Centaurs as well as short-period comets and other Kuiper Belt Objects.

Os isotopes in SNC meteorites and their implications to the early evolution of Mars and Earth

NASA Technical Reports Server (NTRS)

Jagoutz, E.; Luck, J. M.; Othman, D. Ben; Wanke, H.

1993-01-01

A new development on the measurement of the Os isotopic composition by mass spectrometry using negative ions opened a new field of applications. The Re-Os systematic provides time information on the differentiation of the nobel metals. The nobel metals are strongly partitioned into metal and sulphide phases, but also the generation of silicate melts might fractionate the Re-Os system. Compared to the other isotopic systems which are mainly dating the fractionation of the alkalis and alkali-earth elements, the Re-Os system is expected to disclose entirely new information about the geochemistry. Especially the differentiation and early evolution of the planets such as the formation of the core will be elucidated with this method.

The Isotopologue Record of Repeat Vital Effect Offenders: Tracking (Dis)equilibrium Effects in Sea Urchins and Nannofossil Using Clumped Isotopes

NASA Astrophysics Data System (ADS)

John, C. M.; Davies, A.; Drury, A. J.

2016-12-01

Vital effects vary between species and affect various isotopic systems in unequal proportion. The magnitude of the response of different isotopic systems might thus be key in understanding biologically-mediated disequilibrium, especially in groups that show a tendency to be "repeat offenders" with regards to vital effects. Here we present carbon, oxygen, and clumped isotope data from echinoderm calcite and nannofossil ooze, both of which exhibit strong vital effects in bulk isotopes. Our study is the first to investigate the clumped isotope (dis)equilibrium of echinoids. Results from two echinoids, three marine gastropods and a bivalve mollusk from modern beach deposits of Bali, Indonesia, highlight a significant offset in clumped isotopes of a regular echinoid test from expected values, interpreted as evidence of a similar "vital effect" as observed in surface corals. This is in contrast to the test of an irregular "sand dollar" echinoid, with clumped isotope values within error of expected sea surface temperature. Furthermore, data on the inter-skeletal variability in the clumped isotopic composition of two regular echinoid species shows that the spines of the echinoids are in equilibrium with seawater with respect to clumped isotopes, but the test is not. For the nannofossil material, no clumped isotope vital effects are observed, consistent with previously published studies but at odds with strong vital effects in carbon and oxygen isotopes, often correlated with cell-size. In addition, we reveal that the <63 micron fraction of deep-sea ooze could constitute useful material for clumped isotope studies. An intriguing result of our study is that vital effects are mostly absent in clumped isotopes, even in phylums known for important isotopic effects. It remains to be explained why some parts of the echinoids show clear vital effects, notably enrichment in clumped isotopes of urchin tests. Mechanisms that could explain this include pH effects during calcification. Rapid precipitation of calcite is however not considered as a likely mechanism as skeletal components with the largest growth rates show no clear clumped isotope vital effects.

Regulation of Isotopic Composition of Water - way of Improvement of Cosmonauts Drinking Water Functional Properties

NASA Astrophysics Data System (ADS)

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

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

Multi-isotope tracers to investigate processes in the Elbe, Weser and Ems river catchment using B, Mo, Sr, and Pb isotope ratios assessed by MC ICP-MS

NASA Astrophysics Data System (ADS)

Irrgeher, Johanna; Reese, Anna; Zimmermann, Tristan; Prohaska, Thomas; Retzmann, Anika; Wieser, Michael E.; Zitek, Andreas; Proefrock, Daniel

2017-04-01

Environmental monitoring of complex ecosystems requires reliable sensitive techniques based on sound analytical strategies to identify the source, fate and sink of elements and matter. Isotopic signatures can serve to trace pathways by making use of specific isotopic fingermarks or to distinguish between natural and anthropogenic sources. The presented work shows the potential of using the isotopic variation of Sr, Pb (as well-established isotopic systems), Mo and B (as novel isotopic system) assessed by MC ICP-MS in water and sediment samples to study aquatic ecosystem transport processes. The isotopic variation of Sr, Pb, Mo and B was determined in different marine and estuarine compartments covering the catchment of the German Wadden Sea and its main tributaries, the Elbe, Weser and Ems River. The varying elemental concentrations, the complex matrix and the expected small variations in the isotopic composition required the development and application of reliable analytical measurement approaches as well as suited metrological data evaluation strategies. Aquatic isoscapes were created using ArcGIS® by relating spatial isotopic data with geographical and geological maps. The elemental and isotopic distribution maps show large variation for different parameters and also reflect the numerous impact factors (e.g. geology, anthropogenic sources) influencing the catchment area.

Mass Dependency of Isotope Fractionation of Gases Under Thermal Gradient and Its Possible Implications for Planetary Atmosphere Escaping Process

NASA Technical Reports Server (NTRS)

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard

2014-01-01

Physical processes that unmix elements/isotopes of gas molecules involve phase changes, diffusion (chemical or thermal), effusion and gravitational settling. Some of those play significant roles for the evolution of chemical and isotopic compositions of gases in planetary bodies which lead to better understanding of surface paleoclimatic conditions, e.g. gas bubbles in Antarctic ice, and planetary evolution, e.g. the solar-wind erosion induced gas escaping from exosphere on terrestrial planets.. A mass dependent relationship is always expected for the kinetic isotope fractionations during these simple physical processes, according to the kinetic theory of gases by Chapman, Enskog and others [3-5]. For O-bearing (O16, -O17, -O18) molecules the alpha O-17/ alpha O-18 is expected at 0.5 to 0.515, and for S-bearing (S32,-S33. -S34, -S36) molecules, the alpha S-33/ alpha S-34 is expected at 0.5 to 0.508, where alpha is the isotope fractionation factor associated with unmixing processes. Thus, one isotope pair is generally proxied to yield all the information for the physical history of the gases. However, we recently] reported the violation of mass law for isotope fractionation among isotope pairs of multiple isotope system during gas diffusion or convection under thermal gradient (Thermal Gradient Induced Non-Mass Dependent effect, TGI-NMD). The mechanism(s) that is responsible to such striking observation remains unanswered. In our past studies, we investigated polyatomic molecules, O2 and SF6, and we suggested that nuclear spin effect could be responsible to the observed NMD effect in a way of changing diffusion coefficients of certain molecules, owing to the fact of negligible delta S-36 anomaly for SF6.. On the other hand, our results also showed that for both diffusion and convection under thermal gradient, this NMD effect is increased by lower gas pressure, bigger temperature gradient and lower average temperature, which indicate that the nuclear spin effect may not be the significant contributor as the energies involved in the hyperfine effect are much smaller than those with molecular collisions, especially under convective conditions.

High-Resolution Spectroscopy of Mars: Recent Results and Implications for Atmospheric Evolution

NASA Technical Reports Server (NTRS)

Krasnopolsky, V. A.; Owen, T. C.; Maillard, J. P.

1999-01-01

It is believed that Earth, Venus, and Mars were formed by the same rocky and icy planetesimals, which resembled meteorites and comets in their composition, respectively. These planets are thus expected to have initially had the same chemical and isotope composition. Scaling the mass of the terrestrial ocean by the planetary mass ratio, the expected initial H2O abundance on Mars is a layer of about 1 km thick. Scaling the abundance of CO2 on Venus, the expected initial CO2 abundance on Mars is 15 bars. Evidently, significant parts of the initial H2O and CO2 abundances have been lost. Intense meteorite impact erosion and hydrodynamic escape of hydrogen (which could drag to escape more heavy species) were dominant loss processes in the first 0.8 Byr. Later, atmospheric sputtering by O+ ions resulted in the dissociation of CO2 and massive losses of O, C, and H. Formation of carbonates also reduced CO2 to its present abundance which currently exists in the atmosphere, on the polar caps, and is absorbed by regolith. Water loss is currently due to thermal escape of H and nonthermal escape of O, both formed by photodissociation of H2O. All loss processes resulted in fractionation of the H, O, and C isotopes. Therefore, the current isotope ratios in H2O and CO2 are clues to the history of volatiles on Mars. There are three tools to study H2O and CO2 isotopes in the martian atmosphere: (i) mass spectrometry from landing probes, (ii) analyses of Mars' gases trapped in the SNC meteorites which were ejected from Mars, and (iii) high-resolution spectroscopy of the H2O andCO2 bands. Method (i) is the best but is the most expensive. Mass spectrometers to be used should be designed for high-precision isotope measurements. Method (ii) makes it possible to reach an uncertainty +/- 0.1%. However, the obtained results are affected by some uncontrolled interactions: isotope fractionations of (1) trapped gases and (2) those released in pyrolysis, (3) contribution of the impactor, isotope exchanges (4) in the terrestrial environment and (5) with the host rock during pyrolysis. Therefore, the spectroscopic data are of great interest, though their formal accuracy is lower. High-resolution spectroscopy is also a tool to study the current atmosphere of Mars by mapping of some photochemically important species and searching for some minor constituents and their variations. Additional information is contained in the original extended abstract.

Can Transport of Saharan Dust Explain Extensive Clay Deposits in the Amazon Basin? A Test Using Radiogenic Isotopes

NASA Astrophysics Data System (ADS)

Andreae, M. O.; Abouchami, W.; Näthe, K.; Kumar, A.; Galer, S. J.; Jochum, K. P.; Williams, E.; Horbe, A. M.; Rosa, J. W.; Adams, D. K.; Balsam, W. R.

2012-12-01

The Bodélé Depression, located in the Southern Sahara, is a huge source of atmospheric dust and thus an important element in biogeochemical cycles and the radiative budget of Earth's atmosphere. Previous studies have shown that Saharan dust transport across the Atlantic acts as an important source of mineral nutrients to the Amazon rainforest. The Belterra Clay, which outcrops extensively across the Amazon Basin in Brazil, has been proposed to result from dry deposition of African dusts. We have investigated this hypothesis by measuring the radiogenic isotopic composition (Sr, Nd and Pb) of a suite of samples from the Belterra Clay, the Bodélé Depression, dusts deposits collected at various locations along the airmass transport trajectory, as well as loess from the Cape Verde Islands. Radiogenic isotope systems are powerful tracers of provenance and can be used to fingerprint dust sources and atmospheric transport patterns. Our results identify distinct isotopic signatures in the Belterra Clay samples and the African sources. The Belterra Clay display radiogenic Sr and Pb isotope ratios associated with non-radiogenic Nd isotope signatures. In contrast, Bodélé samples and dusts deposits show lower Pb isotope ratios, variable 87Sr/86Sr, and relatively homogeneous Nd isotopic compositions, albeit more radiogenic than those of the Belterra Clay. Our data show unambiguously that the Belterra Clay is not derived from African dust deposition, nor from the Andean chain, as originally suggested by W. Sombroek. Rather, isotopic compositions and Nd model ages are consistent with simple mixing of Archean and younger Proterozoic terranes within the Amazon Basin as a result of weathering and erosion under humid tropical conditions. Whether Saharan dusts contribute to the fertilization in the Amazon Basin cannot be ruled out, however, since the African dust isotopic signature is expected to be entirely overprinted by local sources. Radiogenic isotope data obtained on aerosol filters collected in the US Virgin Islands and Tobago are similar to those of aerosols from Mali, demonstrating that the African dust isotope signal is detectable and transported as far as Central and South America. Thus, while it appears undeniable that Saharan dust reaches the Amazon Basin, its importance for overall soil fertility requires a careful assessment of the dust budget versus bedrock weathering rates for key nutrient elements.

Determination of the isotopic composition of atmospheric methane and its application in the Antarctic

NASA Technical Reports Server (NTRS)

Lowe, David C.; Brenninkmeijer, Carl A. M.; Tyler, Stanley C.; Dlugkencky, Edward J.

1991-01-01

A procedure for establishing the C-13/C-12 ratio and the C-14 abundance in the atmospheric methane is discussed. The method involves air sample collection, measurement of the methane mixing ratio by gas chromotography followed by quantitative conversion of the methane in the air samples to CO2 and H2O, and analysis of the resulting CO2 for the C-13/C-12 ratio by stable isotope ratio mass spectrometry and measurement of C-14 content by accelerator mass spectrometry. The carbon isotropic composition of methane in air collected at Baring Head, New Zealand, and in air collected on aircraft flights between New Zealand and Antarctica is determined by the method, and no gradient in the composition between Baring Head and the South Pole station is found. As the technique is refined, and more data is gathered, small seasonal and long-term variations in C-13 are expected to be resolved.

Ion microprobe analysis of {sup 18}O/{sup 16}O in authigenic and detrital quartz in the St. Peter Sandstone, Michigan Basin and Wisconsin Arch, USA: Contrasting diagenetic histories

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

Graham, C.M.; Valley, J.W.; Winter, B.L.

1996-12-01

The oxygen isotopic compositions of authigenic quartz cements in sandstones provide a monitor of the temperatures, compositions, and origins of pore-occluding fluids during diagenesis, but quartz overgrowths are too fine-grained to be amenable to conventional isotopic analysis. We have used a Cameca ims-4f ion microprobe to determine oxygen isotopic variations in authigenic and detrital quartz in four samples of the Ordovician St. Peter Sandstone from the Michigan Basin and Wisconsin Arch, midwestern USA. Ion microprobe isotopic analyses have been successfully accomplished with an internal precision of {+-}1{per_thousand} (1{sigma}) and a spatial resolution of 20-30 {mu}m at low mass resolution usingmore » a high voltage offset technique. Repeated analyses of the quartz standard demonstrate a reproducibility of close to {+-}1{per_thousand} (1 sd) in good agreement with that expected from counting statistics. Conventional and ion microprobe analyses are mutually consistent, supporting the accuracy of the ion microprobe analyses. Within-sample isotopic variations of up to 13{per_thousand} and micro-scale isotopic variations of at least 4{per_thousand} over a distance of 100 {mu}m have been measured within quartz overgrowths in a sandstone from the Wisconsin Arch. Overgrowths are uniformly higher in {delta}{sup 18}O than detrital grains, and gradients of up to 25% exist across a few microns. {sup 18}O-enriched quartz overgrowths in sandstones from the Wisconsin Arch show complex CL zonation and reflect one of two possible processes: (1) low-temperature quartz precipitation during mixing of meteoric waters with upwelling basinal fluids; (2) higher temperature quartz precipitation during episodic gravity-driven upwelling of warm basinal fluids (of comparable isotopic composition to Michigan Basin fluids) from the Illinois Basin, related to evolution of Mississippi Valley type Pb-Zn ore-forming fluids. 59 refs., 7 figs., 4 tabs.« less

Stable isotopic compositions of carbon in vegetation and soil organic matter along the bioclimatic transect, North Caucasus

NASA Astrophysics Data System (ADS)

Kovda, Irina; Morgun, Evgeny; Golubeva, Natalia

2010-05-01

Stable isotopic composition of carbon in plant species and soil organic matter was investigated along the bioclimatic transect in the North Caucasus. The aim of this research was to find the possible shift of stable isotopic composition of carbon reflecting the gradual successive changes of landscapes connected with the changes of climatic conditions (temperature, precipitation, air humidity) at a various absolute heights above sea level i.e. along the vertical zonation. The study site was located in the North Caucasus near Arkhiz, Big Zelentchuk valley (43o33-40'N; 41o16-27'E). Soil and vegetation samples were collected along Precaucasus and Caucasus slopes at an absolute heights interval of 1280 - 2065 m. Soils are formed at eluvo-deluvium of noncarbonated silicate massive rocks under warm temperate climate with MAT 4-5oC and MAP ~ 860 mm and more. Samples of vegetation (whole grasses and tree leaves) represented several altitudinal vegetation belts including forest and subalpine belts with coniferous (pine, spruce, fir), mixed coniferous-deciduous (fir + beech), broad-leaved (beech, maple), small-leaved (birch, aspen) forests, elfin birch wood and subalpine meadows. Stable isotope composition of carbon was determined using IRMS Finnigan Delta V+. Stable isotopic composition of vegetal species ranges from -33.04 to -27.29 o/oo with the general trend of lighter δ13С with the decreasing of absolute heights. The most heavier δ13С = ~ -27o/oo were found in subalpine meadow plants, while at a smaller altitudes in the forest belt δ13С shifts to ~ 30-31, and up to ~ - 32-33o/oo. More clear regularities were found for vegetation specimens grouped into three categories such as "trees", "grasses" and "litter". δ13С of each category clearly shifts to the lighter values with the decrease of absolute heights i.e from subalpine meadows to spruce-broad-leaved forests. δ13С shift is about 2,49o/oo for trees, 1,75-4,92 o/oo for grasses and ~ 1,8 o/oo for the litter. The complimentary determination of δ15N have shown large variability from -3,59 to + 18,24o/oo which corresponds with the expected large variation of δ15N of plant debris and general trend of lighter δ15N during the decomposition. δ13С of soil organic matter varies from -28.92 to -24.99 o/oo. The similar trend for lighter stable isotopic composition of carbon at a lower absolute heights i.e. in forest belt was found for soil organic matter. The whole picture of δ13С values in soil samples is quite complicated and needs further investigation. As a result, the isotopic characteristic of carbon and nitrogen in vegetal specimens, and carbon in soil organic matter were obtained along a bioclimatic topocatena. The general trend of lighter C isotopic composition was found. It is known that lighter isotopic composition correlates with cooler and/or wetter climate. While the temperature gradually decreases upward, the changes of precipitation are not linear. Further research is needed to better explain the variation of stable isotopic compositions in dependence of those climatic factors. This research was supported by the Presidium of Russian Academy of Sciences, Program 14

In Situ Mo Isotope Fractionation in the Water Columns of Euxinic Basins

NASA Astrophysics Data System (ADS)

Neubert, N.; Nägler, T. F.; Böttcher, M. E.

2007-12-01

The present study investigates for the first time the overall process of molybdenum (Mo) scavenging in modern euxinic systems using Mo concentration and stable isotope measurements. We analyzed samples from three different sites: The Black Sea, the largest permanently euxinic basin, and two anoxic basins of the Baltic Sea, the Gotland Deep and the Landsort Deep which have maximum water depths of 247 m and 459 m, respectively. Water column profiles, as well as surface sediment samples, were recovered from different water depths. Mo is a redox-sensitive trace metal which is soluble as the molybdate oxyanion in oxic seawater with a residence time of about 800 ka. The isotope signature of Mo is a relatively new proxy used to reconstruct the paleo-redox conditions of the Earth's atmosphere and the oceanic system. The Mo isotope composition in seawater is homogeneous (Siebert et al. 2003). Scavenging of Mo under euxinic conditions is related to the amount of free sulfide in the water column. Near total removal of Mo from the water column is reached at aquatic sulfide concentration of c. 11 μM (Erickson and Helz 2000). In the Black Sea this corresponds to a water depth of about 400 m. Sediment samples of the Black Sea from more then 400 m water depth show seawater isotopic composition, in line with the assumption of bulk Mo removal. However, shallower sediments deposited under lower aquatic sulfide concentrations show significant Mo isotope fractionation. The Baltic Sea oceanographic conditions, including temporary bottom water oxygenation due to sporadic North Sea water inflows, are more complex than in the Black Sea. The aquatic sulfide concentration in the water column is less than 5 μM in the two anoxic troughs. As expected from this lower sulfidity, the surface sediments show Mo fractionation similar to the oxic to slightly euxinic sediments of the Black Sea. Our new results on the Mo isotopic composition in euxinic water columns clearly indicate in situ fractionation of Mo isotopes. All euxinic water samples from the three settings are shifted towards heavier Mo isotope signatures, thus complementing the lighter values in the surface sediments (Nagler et al. 2005).

Characterization of frictional melting processes in subduction zone faults by trace element and isotope analyses

NASA Astrophysics Data System (ADS)

Ishikawa, T.; Ujiie, K.

2017-12-01

Pseudotachylytes found in exhumed accretionary complexes, which are considered to be formed originally at seismogenic depths, are of great importance for elucidating frictional melting and concomitant dynamic weakening of the fault during earthquake in subduction zones. However, fluid-rich environment of the subduction zone faults tends to cause extensive alteration of the pseudotachylyte glass matrix in later stages, and thus it has been controversial that pseudotachylytes are rarely formed or rarely preserved. Chemical analysis of the fault rocks, especially on fluid-immobile trace elements and isotopes, can be a useful means to identify and quantify the frictional melting occurred in subduction zone faults. In this paper, we report major and trace element and Sr isotope compositions for pseudotachylyte-bearing dark veins and surrounding host rocks from the Mugi area of the Shimanto accretionary complex (Ujiie et al., J. Struct. Geol. 2007). Samples were collected from a rock chip along the microstructure using a micro-drilling technique, and then analyzed by ICP-MS and TIMS. Major element compositions of the dark veins showed a clear shift from the host rock composition toward the illite composition. The dark veins, either unaltered or completely altered, were also characterized by extreme enrichment in some of the trace elements such as Ti, Zr, Nb and Th. These results are consistent with disequilibrium melting of the fault zone. Model calculations revealed that the compositions of the dark veins can be produced by total melting of clay-rich matrix in the source rock, leaving plagioclase and quartz grains almost unmolten. The calculations also showed that the dark veins are far more enriched in melt component than that expected from the source rock compositions, suggesting migration and concentration of frictional melt during the earthquake faulting. Furthermore, Sr isotope data of the dark veins implied the occurrence of frictional melting in multiple stages. These results demonstrate that trace element and isotope analyses are useful not only to detect preexistence of pseudotachylytes but also to evaluate the frictional melting in subduction zone faults quantitatively.

Non-zero Δ33S preserved in rocks from the Basal Ultramafic Sequence indicate crustal contamination in the most primitive magma of the Rustenburg Layered Suite (Bushveld Complex, South Africa)

NASA Astrophysics Data System (ADS)

Magalhaes, N.; Wilson, A.; Penniston-Dorland, S.; Farquhar, J.

2017-12-01

The sulfur isotope composition of the Rustenburg Layered Suite (RLS) of the Bushveld Complex is different than expected from a magma sourced from the mantle (Δ33S=0), as measurements indicate the presence of an Archean surface-derived sulfur component. The Basal Ultramafic Sequence (BUS) is thought to be the most primitive magma of the RLS, as it is the lowest in the stratigraphy, has the highest Mg# (>0.92) for primary phases (olivine and orthopyroxene), and is in direct contact with the Magaliesberg quartzite of the Pretoria Group.We have measured the composition of sulfides in rocks from the Lower Zone, Marginal Zone, and the BUS, which were sampled in a 2300m drill core from the Clapham area, in the eastern Bushveld Complex. While the rocks of the Lower Zone have a relatively homogeneous non-zero Δ33S of 0.065‰, comparable to previous findings, there is an abrupt increase in the value of Δ33S (up to +0.301‰) in the Marginal Zone, which may be consistent with the observation in hand sample of assimilation of country rocks. The BUS also shows a surface-derived signal (average of 0.040‰), which is the lowest measured for any zone of the RLS.The non-zero Δ33S found in the Basal Ultramafic Sequence is evidence of the contamination of the magma with surface-derived material. In the upper parts of the intrusion, the Δ33S signature relates to whole-rock Sr and Nd isotopes, and their relationship suggests multiple sources of contamination. However, the relationship between sulfur and in-situ strontium isotope compositions (plagioclase) in this section of the RLS is not as clear as it is further up in the stratigraphy. This might reflect small-scale processes during the magmatic chamber stage, different compositions of local wall rock compared to deeper contaminants, or the presence of decoupled behavior between the isotope systems.These differences in the sulfur isotope composition between the different stratigraphic layers have been preserved regardless of any late magmatic processes that may have occurred, which further supports that the sulfur isotope composition of the RLS was not fully homogenized at a later stage by fluid migration.

Nitrogen isotopes suggest a change in nitrogen dynamics between the Late Pleistocene and modern time in Yukon, Canada

PubMed Central

Longstaffe, Fred J.; Zazula, Grant

2018-01-01

A magnificent repository of Late Pleistocene terrestrial megafauna fossils is contained in ice-rich loess deposits of Alaska and Yukon, collectively eastern Beringia. The stable carbon (δ13C) and nitrogen (δ15N) isotope compositions of bone collagen from these fossils are routinely used to determine paleodiet and reconstruct the paleoecosystem. This approach requires consideration of changes in C- and N-isotope dynamics over time and their effects on the terrestrial vegetation isotopic baseline. To test for such changes between the Late Pleistocene and modern time, we compared δ13C and δ15N for vegetation and bone collagen and structural carbonate of some modern, Yukon, arctic ground squirrels with vegetation and bones from Late Pleistocene fossil arctic ground squirrel nests preserved in Yukon loess deposits. The isotopic discrimination between arctic ground squirrel bone collagen and their diet was measured using modern samples, as were isotopic changes during plant decomposition; Over-wintering decomposition of typical vegetation following senescence resulted in a minor change (~0–1 ‰) in δ13C of modern Yukon grasses. A major change (~2–10 ‰) in δ15N was measured for decomposing Yukon grasses thinly covered by loess. As expected, the collagen-diet C-isotope discrimination measured for modern samples confirms that modern vegetation δ13C is a suitable proxy for the Late Pleistocene vegetation in Yukon Territory, after correction for the Suess effect. The N-isotope composition of vegetation from the fossil arctic ground squirrel nests, however, is determined to be ~2.8 ‰ higher than modern grasslands in the region, after correction for decomposition effects. This result suggests a change in N dynamics in this region between the Late Pleistocene and modern time. PMID:29447202

Compound-specific nitrogen isotope analysis of D-alanine, L-alanine, and valine: application of diastereomer separation to delta15N and microbial peptidoglycan studies.

PubMed

Takano, Yoshinori; Chikaraishi, Yoshito; Ogawa, Nanako O; Kitazato, Hiroshi; Ohkouchi, Naohiko

2009-01-01

We have developed an analytical method to determine the compound-specific nitrogen isotope compositions of individual amino acid enantiomers using gas chromatography/combustion/isotope ratio mass spectrometry. A novel derivatization of amino acid diastereomers by optically active (R)-(-)-2-butanol or (S)-(+)-2-butanol offers two advantages for nitrogen isotope analysis. First, chromatographic chiral separation can be achieved without the use of chiral stationary-phase columns. Second, the elution order of these compounds on the chromatogram can be switched by a designated esterification reaction. We applied the method to the compound-specific nitrogen isotope analysis of D- and L-alanine in a peptidoglycan derived from the cell walls of cultured bacteria (Firmicutes and Actinobacteria; Enterococcus faecalis, Staphylococcus aureus, Staphylococcus staphylolyticus, Lactobacillus acidophilus, Bacillus subtilis, Micrococcus luteus, and Streptomyces sp.), natural whole bacterial cells (Bacillus subtilis var. natto), (pseudo)-peptidoglycan from archaea (Methanobacterium sp.), and cell wall from eukaryota (Saccharomyces cerevisiae). We observed statistically significant differences in nitrogen isotopic compositions; e.g., delta15N ( per thousand vs air) in Staphylococcus staphylolyticus for d-alanine (19.2 +/- 0.5 per thousand, n = 4) and L-alanine (21.3 +/- 0.8 per thousand, n = 4) and in Bacillus subtilis for D-alanine (6.2 +/- 0.2 per thousand, n = 3) and L-alanine (8.2 +/- 0.4 per thousand, n = 3). These results suggest that enzymatic reaction pathways, including the alanine racemase reaction, produce a nitrogen isotopic difference in amino acid enantiomers, resulting in 15N-depleted D-alanine. This method is expected to facilitate compound-specific nitrogen isotope studies of amino acid stereoisomers.

Nitrogen isotopes suggest a change in nitrogen dynamics between the Late Pleistocene and modern time in Yukon, Canada.

PubMed

Tahmasebi, Farnoush; Longstaffe, Fred J; Zazula, Grant

2018-01-01

A magnificent repository of Late Pleistocene terrestrial megafauna fossils is contained in ice-rich loess deposits of Alaska and Yukon, collectively eastern Beringia. The stable carbon (δ13C) and nitrogen (δ15N) isotope compositions of bone collagen from these fossils are routinely used to determine paleodiet and reconstruct the paleoecosystem. This approach requires consideration of changes in C- and N-isotope dynamics over time and their effects on the terrestrial vegetation isotopic baseline. To test for such changes between the Late Pleistocene and modern time, we compared δ13C and δ15N for vegetation and bone collagen and structural carbonate of some modern, Yukon, arctic ground squirrels with vegetation and bones from Late Pleistocene fossil arctic ground squirrel nests preserved in Yukon loess deposits. The isotopic discrimination between arctic ground squirrel bone collagen and their diet was measured using modern samples, as were isotopic changes during plant decomposition; Over-wintering decomposition of typical vegetation following senescence resulted in a minor change (~0-1 ‰) in δ13C of modern Yukon grasses. A major change (~2-10 ‰) in δ15N was measured for decomposing Yukon grasses thinly covered by loess. As expected, the collagen-diet C-isotope discrimination measured for modern samples confirms that modern vegetation δ13C is a suitable proxy for the Late Pleistocene vegetation in Yukon Territory, after correction for the Suess effect. The N-isotope composition of vegetation from the fossil arctic ground squirrel nests, however, is determined to be ~2.8 ‰ higher than modern grasslands in the region, after correction for decomposition effects. This result suggests a change in N dynamics in this region between the Late Pleistocene and modern time.

Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

2017-10-01

Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

Impacts of changes in groundwater recharge on the isotopic composition and geochemistry of seasonally ice-covered lakes: insights for sustainable management

NASA Astrophysics Data System (ADS)

Arnoux, Marie; Barbecot, Florent; Gibert-Brunet, Elisabeth; Gibson, John; Noret, Aurélie

2017-11-01

Lakes are under increasing pressure due to widespread anthropogenic impacts related to rapid development and population growth. Accordingly, many lakes are currently undergoing a systematic decline in water quality. Recent studies have highlighted that global warming and the subsequent changes in water use may further exacerbate eutrophication in lakes. Lake evolution depends strongly on hydrologic balance, and therefore on groundwater connectivity. Groundwater also influences the sensitivity of lacustrine ecosystems to climate and environmental changes, and governs their resilience. Improved characterization of groundwater exchange with lakes is needed today for lake preservation, lake restoration, and sustainable management of lake water quality into the future. In this context, the aim of the present paper is to determine if the future evolution of the climate, the population, and the recharge could modify the geochemistry of lakes (mainly isotopic signature and quality via phosphorous load) and if the isotopic monitoring of lakes could be an efficient tool to highlight the variability of the water budget and quality. Small groundwater-connected lakes were chosen to simulate changes in water balance and water quality expected under future climate change scenarios, namely representative concentration pathways (RCPs) 4.5 and 8.5. Contemporary baseline conditions, including isotope mass balance and geochemical characteristics, were determined through an intensive field-based research program prior to the simulations. Results highlight that future lake geochemistry and isotopic composition trends will depend on four main parameters: location (and therefore climate conditions), lake catchment size (which impacts the intensity of the flux change), lake volume (which impacts the range of variation), and lake G index (i.e., the percentage of groundwater that makes up total lake inflows), the latter being the dominant control on water balance conditions, as revealed by the sensitivity of lake isotopic composition. Based on these model simulations, stable isotopes appear to be especially useful for detecting changes in recharge to lakes with a G index of between 50 and 80 %, but response is non-linear. Simulated monthly trends reveal that evolution of annual lake isotopic composition can be dampened by opposing monthly recharge fluctuations. It is also shown that changes in water quality in groundwater-connected lakes depend significantly on lake location and on the intensity of recharge change.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

Small-subunit ribosomal RNA (SSU rRNA) is a phylogenetically informative molecule found in all species. Because it is poorly preserved in most environments, it is a useful marker for active microbial populations. We are using the natural-abundance stable carbon isotopic composition of specific microbial groups to help identify the carbon substrates contributing to microbial biomass in a variety of marine environments. At Guaymas Basin, hydrothermal fluids interact with abundant sedimentary organic carbon to produce natural gas and petroleum. Where this reaches the sediment surface, it can support dense patches of seafloor life, including Beggiatoa mats. We report here on the stable carbon isotopic composition of SSU rRNA from a Beggiatoa mat transect, a cold background site, a warm site with high oil concentration, and a second Beggiatoa mat. The central part of the transect mat overlay the steepest temperature gradient, and was visually dominated by orange Beggiatoa. This was fringed by white Beggiatoa mat and bare, but still warm, sediment. Methane concentrations were saturating beneath the orange and white mats and at the oily site, lower beneath bare sediment, and below detection at the background site. Our initial hypotheses were that rRNA isotopic composition would be strongly influenced by methane supply, and that archaeal rRNA might be lighter than bacterial due to contributions from methanogens and anaerobic methane oxidizers. We used biotin-labeled oligonucleotides to capture Bacterial and Archaeal SSU rRNA for isotopic determination. Background-site rRNA was isotopically heaviest, and bacterial RNA from below 2 cm at the oily site was lightest, consistent with control by methane. Within the transect mat, however, the pattern was more complicated; at some sediment depths, rRNA from the mat periphery was isotopically lightest. Part of this may be due to the spatially and temporally variable paths followed by hydrothermal fluid, which can include horizontal flow. There was no consistent isotopic difference between rRNAs captured by the two probes, although RNA recoveries were too low for isotopic determinations at depths where methanogens and methane oxidizers are expected. Our prediction that rRNA stable carbon isotopic composition would correlate with methane supply was borne out by the comparison between background and mat sediments, but may be an oversimplification for sites within hydrothermal features. Future work will include the isotopic characterization of other potential carbon substrates, such as acetate. We are also investigating cold-seep sediments and brine pools in the Gulf of Mexico, where methane is significantly more 13C-depleted than at Guaymas Basin and may therefore leave a stronger imprint on microbial biomass.table carbon isotopes of rRNA captured with Bacterial and Archaeal probes at mat transect and background sites.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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.

The tungsten isotopic composition of the Earth's mantle before the terminal bombardment.

PubMed

Willbold, Matthias; Elliott, Tim; Moorbath, Stephen

2011-09-07

Many precious, 'iron-loving' metals, such as gold, are surprisingly abundant in the accessible parts of the Earth, given the efficiency with which core formation should have removed them to the planet's deep interior. One explanation of their over-abundance is a 'late veneer'--a flux of meteorites added to the Earth after core formation as a 'terminal' bombardment that culminated in the cratering of the Moon. Some 3.8 billion-year-old rocks from Isua, Greenland, are derived from sources that retain an isotopic memory of events pre-dating this cataclysmic meteorite shower. These Isua samples thus provide a window on the composition of the Earth before such a late veneer and allow a direct test of its importance in modifying the composition of the planet. Using high-precision (less than 6 parts per million, 2 standard deviations) tungsten isotope analyses of these rocks, here we show that they have a isotopic tungsten ratio (182)W/(184)W that is significantly higher (about 13 parts per million) than modern terrestrial samples. This finding is in good agreement with the expected influence of a late veneer. We also show that alternative interpretations, such as partial remixing of a deep-mantle reservoir formed in the Hadean eon (more than four billion years ago) or core-mantle interaction, do not explain the W isotope data well. The decrease in mantle (182)W/(184)W occurs during the Archean eon (about four to three billion years ago), potentially on the same timescale as a notable decrease in (142)Nd/(144)Nd (refs 3 and 6). We speculate that both observations can be explained if late meteorite bombardment triggered the onset of the current style of mantle convection.

Evidence of subduction and crust-mantle mixing from a single diamond

NASA Astrophysics Data System (ADS)

Schulze, Daniel J.; Harte, Ben; Valley, John W.; Channer, Dominic M. DeR.

2004-09-01

Cathodoluminescence (CL) imaging of polished sections of a diamond from the Guaniamo region of Venezuela suggests a history of the diamond involving two periods of growth separated by a period of resorption and possibly brittle deformation. In situ electron probe analysis of multiple eclogitic garnet inclusions reveals a correlation between garnet composition and location in the stone. An early-formed garnet in the diamond core has higher Ca/(Ca+Mg) and lower Mg/(Mg+Fe) values than later garnets associated with the second period of diamond growth. This variation conforms to an extensive trend of variation in the suite of eclogitic garnets extracted from Venezuelan diamonds. The diamond is zoned in carbon isotope composition (in situ secondary ion mass spectrometry, SIMS, data). The core compositions ( δ13C PDB), corresponding to the first stage of growth, average -17.7‰. The second period of growth is apparently in two sub-sets of CL zones with mean values of -13.0‰ and -7.9‰. Nitrogen contents of diamond are low (30-300 atomic ppm) and do not correlate with carbon isotope composition. Oxygen isotope ratios of the garnet inclusions are elevated substantially above those expected for "common mantle"; δ18O VSMOW of early garnet is approximately +10.5‰ and two late garnets average +8.8‰. The evolutionary trend of magnesium enrichment in garnet is unlikely to represent igneous fractionation. The stable isotope data are consistent with diamond formation in subducted meta-basic rocks that had interacted with sea water at low temperatures at or near the sea floor and contained a substantial biogenic carbon component. During or following subduction, diamonds continued to form in an evolving system that was progressively modified by interaction with mantle material.

Triple oxygen isotope systematics of structurally bonded water in gypsum

NASA Astrophysics Data System (ADS)

Herwartz, Daniel; Surma, Jakub; Voigt, Claudia; Assonov, Sergey; Staubwasser, Michael

2017-07-01

The triple oxygen isotopic composition of gypsum mother water (gmw) is recorded in structurally bonded water in gypsum (gsbw). Respective fractionation factors have been determined experimentally for 18O/16O and 17O/16O. By taking previous experiments into account we suggest using 18αgsbw-gmw = 1.0037; 17αgsbw-gmw = 1.00195 and θgsbw-gmw = 0.5285 as fractionation factors in triple oxygen isotope space. Recent gypsum was sampled from a series of 10 ponds located in the Salar de Llamara in the Atacama Desert, Chile. Total dissolved solids (TDS) in these ponds show a gradual increase from 23 g/l to 182 g/l that is accompanied by an increase in pond water 18O/16O. Gsbw falls on a parallel curve to the ambient water from the saline ponds. The offset is mainly due to the equilibrium fractionation between gsbw and gmw. However, gsbw represents a time integrated signal biased towards times of strong evaporation, hence the estimated gmw comprises elevated 18O/16O compositions when compared to pond water samples taken on site. Gypsum precipitation is associated with algae mats in the ponds with lower salinity. No evidence for respective vital effects on the triple oxygen isotopic composition of gypsum hydration water is observed, nor are such effects expected. In principle, the array of δ18Ogsbw vs. 17Oexcess can be used to: (1) provide information on the degree of evaporation during gypsum formation; (2) estimate pristine meteoric water compositions; and (3) estimate local relative humidity which is the controlling parameter of the slope of the array for simple hydrological situations. In our case study, local mining activities may have decreased deep groundwater recharge, causing a recent change of the local hydrology.

The oxygen isotope composition of Karoo and Etendeka picrites: High δ18O mantle or crustal contamination?

NASA Astrophysics Data System (ADS)

Harris, Chris; le Roux, Petrus; Cochrane, Ryan; Martin, Laure; Duncan, Andrew R.; Marsh, Julian S.; le Roex, Anton P.; Class, Cornelia

2015-07-01

Oxygen isotope compositions of Karoo and Etendeka large igneous province (LIP) picrites and picrite basalts are presented to constrain the effects of crustal contamination versus mantle source variation. Olivine and orthopyroxene phenocrysts from lavas and dykes (Mg# 64-80) from the Tuli and Mwenezi (Nuanetsi) regions of the ca 180 Ma Karoo LIP have δ18O values that range from 6.0 to 6.7 ‰. They appear to have crystallized from magmas having δ18O values about 1-1.5 ‰ higher than expected in an entirely mantle-derived magma. Olivines from picrite and picrite basalt dykes from the ca 135 Ma Etendeka LIP of Namibia and Karoo-age picrite dykes from Dronning Maud Land, Antarctica, do not have such elevated δ18O values. A range of δ18O values from 4.9 to 6.0 ‰, and good correlations between δ18O value and Sr, Nd and Pb isotope ratios for the Etendeka picrites are consistent with previously proposed models of crustal contamination. Explanations for the high δ18O values in Tuli/Mwenezi picrites are limited to (1) alteration, (2) crustal contamination, and (3) derivation from mantle with an abnormally high δ18O. Previously, a variety of models that range from crustal contamination to derivation from the `enriched' mantle lithosphere have been suggested to explain high concentrations of incompatible elements such as K, and average ɛNd and ɛSr values of -8 and +16 in Mwenezi (Nuanetsi) picrites. However, the primitive character of the magmas (Mg# 73), combined with the lack of correlation between δ18O values and radiogenic isotopic compositions, MgO content, or Mg# is inconsistent with crustal contamination. Thus, an 18O-enriched mantle source having high incompatible trace element concentration and enriched radiogenic isotope composition is indicated. High δ18O values are accompanied by negative Nb and Ta anomalies, consistent with the involvement of the mantle lithosphere, whereas the high δ18O themselves are consistent with an eclogitic source. Magma δ18O values about 1 ‰ higher than expected for mantle-derived magma are also a feature of the Bushveld mafic and ultramafic magmas, and the possibility exists that a long-lived 18O-enriched mantle source has existed beneath southern Africa. A mixed eclogite peridotite source could have developed by emplacement of oceanic lithosphere into the cratonic keel during Archaean subduction.

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

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

Formation and resulfidization of a South Texas roll-type uranium deposit

USGS Publications Warehouse

Goldhaber, Martin B.; Reynolds, Richard L.; Rye, Robert O.

1979-01-01

Core samples from a roll type uranium deposit in Live Oak County, south Texas have been studied and results are reported for Se, Mo, FeS2 and organic-carbon distribution, sulfide mineral petrology, and sulfur isotopic composition of iron-disulfide phases. In addition, sulfur isotopic compositions of dissolved sulfate and sulfide from the modern ground water within the ore bearing sand have been studied. The suite of elements in the ore sand and their geometric relationships throughout the deposit are those expected for typical roll-type deposits with well-developed oxidation-reduction interfaces. However, iron-disulfide minerals are abundant in the altered tongue, demonstrating that this interval has been sulfidized after mineralization (resulfidized or rereduced). Iron disulfide minerals in the rereduced interval differ mineralogically and isotopically from those throughout the remainder of the deposit. The resulfidized sand contains dominantly pyrite that is enriched in 34S, whereas the sand beyond the altered tongue contains abundant marcasite that is enriched in the light isotope, 32S. Textural relationships between pyrite and marcasite help to establish relative timing of iron disulfide formation. In reduced rock outside the altered tongue, three distinct generations of iron disulfide are present. The oldest of these generations consists largely of pyrite with lesser amounts of marcasite. A major episode of marcasite formation contemporaneous with ore genesis postdates the oldest pyrite generation but predates a younger pyrite generation. Resulfidization probably led to the final pyrite stage recognized beyond the altered tongue. Stable isotope data establish that the source of sulfur for the resulfidization was fault-leaked H2S probably derived from the Edwards Limestone of Cretaceous age which underlies the deposit. The deposit formed in at least two stages: (1) a pre-ore process of host rock sulfidization which produced disseminated pyrite as the dominant iron disulfide phase; and (2) an ore-stage process which led to the development of the uranium roll with emplacement of the characteristic suite of minor and accessory elements and which produced abundant isotopically light marcasite. The host rock was modified by a post-ore stage of resulfidization which precipitated isotopically heavy pyrite. Sulfur isotopic compositions of sulfide and sulfate present in modern ground water within the host sand differ greatly from sulfur isotopic composition of iron disulfides formed during the resulfidization episode. Iron disulfide minerals formed from the sulfur species of modern ground water have not been unequivocally identified.

Carbon and Oxygen Isotope Measurements of Ordinary Chondrite (OC) Meteorites from Antarctica Indicate Distinct Terrestrial Carbonate Species using a Stepped Acid Extraction Procedure Impacting Mars Carbonate Research

NASA Astrophysics Data System (ADS)

Evans, M. E.; Niles, P. B.; Locke, D.

2015-12-01

The purpose of this study is to characterize the stable isotope values of terrestrial, secondary carbonate minerals from five OC meteorites collected in Antarctica. These samples were selected for analysis based upon their size and collection proximity to known Martian meteorites. They were also selected based on petrologic type (3+) such that they were likely to be carbonate-free before falling to Earth. This study has two main tasks: 1) characterize the isotopic composition of terrestrial, secondary carbonate minerals formed on meteorites in Antarctica, and 2) study the mechanisms of carbonate formation in cold and arid environments with Antarctica as an analog for Mars. Two samples from each meteorite, each ~0.5g, was crushed and dissolved in pure phosphoric acid for 3 sequential reactions: a) Rx0 for 1 hour at 30°C, b) Rx1 for 18 hours at 30°C, and c) Rx2 for 3 hours at 150°C. CO2 was distilled by freezing with liquid nitrogen from each sample tube, then separated from organics and sulfides with a TRACE GC using a Restek HayeSep Q 80/100 6' 2mm stainless column, and then analyzed on a Thermo MAT 253 IRMS in Dual Inlet mode. This system was built at NASA/JSC over the past 3 years and proof tested with known carbonate standards to develop procedures, assess yield, and quantify expected uncertainties. Two distinct species of carbonates are found based on the stepped extraction technique: 1) Ca-rich carbonate released at low temperatures, and 2) Mg, or Fe-rich carbonate released at high temperatures. Preliminary results indicate that most of the carbonates present in the ordinary chondrites analyzed have δ13C=+5‰, which is consistent with formation from atmospheric CO2 δ13C=-7‰ at -20°C. The oxygen isotopic compositions of the carbonates vary between +4‰ and +34‰ with the Mg-rich and/or Fe-rich carbonates possessing the lowest δ18O values. This suggests that the carbonates formed under a wide range of temperatures. However, the carbonate oxygen isotope compositions are consistently heavier than what would be expected if the carbonates formed in equilibrium with melted ice in Antarctica.

Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients

NASA Astrophysics Data System (ADS)

Balter, Vincent; Nogueira da Costa, Andre; Paky Bondanese, Victor; Jaouen, Klervia; Lamboux, Aline; Sangrajrang, Suleeporn; Vincent, Nicolas; Fourel, François; Télouk, Philippe; Gigou, Michelle; Lécuyer, Christophe; Srivatanakul, Petcharin; Bréchot, Christian; Albarède, Francis; Hainaut, Pierre

2015-01-01

The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper (65Cu/63Cu) and sulfur (34S/32S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is 63Cu-enriched by ∼0.4‰ and sulfur is 32S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The 32S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.

Effects of drought and elevated atmospheric carbon dioxide on seed nutrition and 15N and 13C natural abundance isotopes in soybean cultivars under controlled environments

USDA-ARS?s Scientific Manuscript database

Climate change resulting from global warming is expected to affect crop production and seed quality. The objective of this research was to evaluate the response of soybean cultivars to the effect of drought and elevated temperature on seed composition and mineral nutrition. In a repeated growth cham...

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

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

Lithium elemental and isotopic disequilibrium in minerals from peridotite xenoliths from far-east Russia: Product of recent melt/fluid rock reaction

NASA Astrophysics Data System (ADS)

Rudnick, Roberta L.; Ionov, Dmitri A.

2007-04-01

Lithium concentrations and isotopic compositions of coexisting olivine and clinopyroxene (cpx) in well-characterized peridotite xenoliths from Tok (SE Siberian craton) and samples from two other far-east Russian localities reveal strong elemental and isotopic disequilibria, which correlates with bulk rock composition. Lithium concentrations in cpx from Tok (1-12 ppm) are equal to or significantly greater than those in coexisting olivines (1-5 ppm). The Li-rich cpx show core to rim zoning, indicative of Li infiltration from the grain boundaries. Olivines are generally unzoned, although Li concentrations can vary significantly from grain to grain. ol/cpxD varies from 0.2 to 1.0, which is lower than that expected for equilibrium partitioning ( ol/cpxDeq = 1.1 to 2.0), and reflects preferential Li enrichment in cpx. The Li isotopic compositions of both minerals range far beyond normal mantle δ7Li of ˜ + 4 ± 2. δ7Li cpx (- 0.8 to - 14.6) is systematically lighter than δ7Li of coexisting olivine (- 1.7 to + 11.9), and Δ 7Li ol-cpx varies from 2.8 to 22.9‰. The greatest elemental and isotopic disequilibria occur in the most fertile samples (lherzolites) and may reflect longer equilibration times and/or enhanced melt permeability in the more refractory samples. Collectively, these observations suggest that the peridotite minerals experienced Li addition via diffusion from a grain boundary melt or fluid shortly before or coincident with their entrainment into the host basalt (i.e., within tens of thousands of years, based on published diffusion coefficients for Li in cpx at the temperatures of equilibration). This diffusional ingress of Li generated large kinetic isotopic fractionation, leading to unusually light cpx and heavier olivines. Thus, low δ7Li cpx do not reflect the influence of an exotic mantle component related to crustal recycling.

A new method of tree xylem water extraction for isotopic analysis

NASA Astrophysics Data System (ADS)

Gierke, C.; Newton, B. T.

2011-12-01

The Sacramento Mountain Watershed Study in the southern Sacramento Mountains of New Mexico is designed to assess the forest restoration technique of tree thinning in mountain watersheds as an effective method of increasing local and regional groundwater recharge. The project is using a soil water balance approach to quantify the partitioning of local precipitation within this watershed before and after thinning trees. Understanding what sources trees extract their water from (e.g. shallow groundwater, unsaturated fractured bedrock, and soils) is difficult due to a complex hydrologic system and heterogeneous distribution of soil thicknesses. However, in order to accurately quantify the soil water balance and to assess how thinning trees will affect this water balance, it is important determine the sources from which trees extract their water. We plan to use oxygen and hydrogen stable isotopic analysis of various end member waters to identify these different sources. We are in the process of developing a new method of determining the isotopic composition of tree water that has several advantages over conventional methods. Within the tree there is the xylem which transports water from the roots to the leaves and the phloem which transports starches and sugars in a water media throughout the tree. Previous studies have shown that the isotopic composition of xylem water accurately reflects that of source water, while phloem water has undergone isotopic fractionation during photosynthesis and metabolism. The distillation of water from twigs, which is often used to extract tree water for isotopic analysis, is very labor intensive. Other disadvantages to distillation methods include possible fractionation due to phase changes and the possible extraction of fractionated phloem waters. Employing a new mixing method, the composition of the twig water (TW) can be determined by putting twigs of unknown isotopic water composition into waters of known compositions or initial waters (IW), allowing diffusive processes to proceed to equilibrium, measuring the composition of the resulting mixture or final water (FW) then, solving a simple mixing equation. To evaluate this method, we collected several twig samples from Douglas Firs in the Sacramento Mountains. Twig water was prepared for isotopic analysis both by cryogenic distillation and the mixing method. Soil in close proximity to these trees was also sampled and water was extracted by cryogenic distillation. Preliminary results show that the isotopic composition of distilled twig water and soil waters plot to the right of the local meteoric water line (LMWL) suggesting that trees are extracting shallow evaporated soil water. Twig water obtained from the mixing method plot near the LMWL within the range expected for local snow melt, suggesting a possibly deeper non-evaporated source. In general, distillation values are approximately 4% heavier with respect to delta 18O than waters obtained from the mixing method. It is possible that this difference is due to the contribution of the fractionated water of the twig phloem that is released during the distillation process. This difference is quite significant and can lead to very different interpretations. These results are being addressed with additional experiments.

Novel stable isotope laser spectrometry elucidates changing mechanisms of CH4 production and consumption across a climate change sequence in an arctic wetland

NASA Astrophysics Data System (ADS)

McCalley, C. K.; Wehr, R.; Crill, P. M.; Chanton, J.; Hodgkins, S. B.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Rich, V.; Tyson, G.; Mondav, R.; Frolking, S.; Li, C.; Saleska, S. R.

2011-12-01

Methane flux from high latitude wetlands is both a critical component of the global CH4 budget, and highly sensitive to global climate change, with expected increases in emissions as permafrost thaws. Gaps in our understanding of the mechanisms driving changing CH4 production and consumption dynamics under permafrost thaw, however, limit our ability to predict the magnitude of this response under future climate conditions. To address these gaps, we quantified the isotopic composition of carbon gas fluxes (δ13C of CH4 and CO2) from a high latitude (68° N) wetland in Sweden (Stordalen Mire) to partition net CH4 emissions into its component parts, methanogenesis (including both acetoclastic, and CO2-reductive pathways) and methanotrophy (which consumes CH4 primarily via aerobic metabolism). We used newly developed quantum cascade laser technology, linked to automated chambers, to quantify isotopes at high frequency. Our measurements across a permafrost thaw gradient, going from permafrost-dominated, well-drained palsas to intermediate permafrost sites dominated by Sphagnum spp. to wet sites with no underlying permafrost, dominated by Eriophorum angustifolium, show both large increases in productivity and CH4 emissions as well as shifts in the CH4 production pathway. Across this permafrost thaw gradient the isotopic composition of CH4 becomes 13C enriched, due to increased acetoclastic CH4 production. While the palsa sites have no detectable CH4 emissions, fluxes in the Sphagnum site have an average isotopic composition of -79%, a value indicative of CH4 production dominated by CO2 reduction, in contrast the isotopic composition of CH4 produced in the Eriophorum sites ranged from -71 to -57%, showing increased CH4 production via the acetate pathway. We also observed an increase in acetoclastic methanogenesis as the growing season progressed. Together, these initial results suggest that thaw induced changes in hydrology and plant community composition increase peat lability, stimulating acetate fermentation and yielding increased methane emissions. We conclude that the biological controls on metabolic pathways of methanogenesis, though poorly represented in most ecosystem models, may nonetheless be important, in interaction with permafrost thaw dynamics, in determining future CH4 emissions under changing climate.

Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zhang, Tongwei; Krooss, Bernhard M.

2001-08-01

Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the 12CH4 and 13CH4 species, respectively, have been calculated. Compared with the carbon isotopic composition of the source methane (δ13C1 = -39.1‰), a significant depletion of the heavier carbon isotope (13C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ13Cdiff -δ13Csource) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the 12CH4 and 13CH4 entities. No measurable solubility fractionation was observed. The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous ;semi-infinite; shale caprock over a period of 10 Ma. In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope fractionation effects. The examples demonstrate that methane losses by molecular diffusion are small in comparison with the contents of commercial size gas accumulations. The degree of isotopic fractionation is related inversely to the quantity of diffused gas so that strong fractionation effects are only observed for relatively small portions of gas. The experimental data can be readily used in numerical basin analysis to examine the effects of diffusion-related isotopic fractionation on the composition of natural gas reservoirs.

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.

Controls on the iron isotopic composition of global arc magmas

NASA Astrophysics Data System (ADS)

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

2018-07-01

We determined the iron isotope composition of 130 mafic lavas from 15 arcs worldwide with the hypothesis that the results would reflect the relatively high oxidation state of arc magmas. Although this expectation was not realized, this Fe isotope data set reveals important insights into the geodynamic controls and style of the melting regimes in the sub-arc mantle. Samples are from oceanic arcs from the circum-Pacific, the Indonesian Sunda-Banda islands, Scotia and the Lesser Antilles as well as from the eastern Pacific Cascades. Their mean δ57Fe value is +0.075 ± 0.05‰, significantly lighter than MORB (+0.15 ± 0.03‰). Western Pacific arcs extend to very light δ57Fe (Kamchatka = -0.11 ± 0.04‰). This is contrary to expectation, because Fe isotope fractionation factors (Sossi et al., 2016, 2012) and the incompatibility of ferric versus ferrous iron during mantle melting, predict that melts of more oxidized sources will be enriched in heavy Fe isotopes. Subducted oxidation capacity flux may correlate with hydrous fluid release from the slab. If so, a positive correlation between each arc's thermal parameter (ϕ) and δ57Fe is predicted. On the contrary, the sampled arcs mostly contribute to a negative array with the ϕ value. High ϕ arcs, largely in the western Pacific, have primary magmas with lower δ57Fe values than the low ϕ, eastern Pacific arcs. Arcs with MORB-like Sr-, Nd- and Pb-isotopes, show a large range of δ57Fe from heavy MORB-like values (Scotia or the Cascades) to very light values (Kamchatka, Tonga). Although all basalts with light δ57Fe values have MORB-like Pb-, Nd- and Sr-isotope ratios some, particularly those from eastern Indonesia, have heavier δ57Fe and higher Pb- and Sr- and lower Nd-isotope ratios reflecting sediment contamination of the mantle wedge. Because basalts with MORB-like radiogenic isotopes range all the way from heavy to light δ57Fe values this trend is process-, not source composition-driven. Neither the slab-derived influx of fluids with light iron or sediment-derived melts with heavier iron can drive the iron isotopic shifts. The trend to light iron isotopes is partly the result of repeated, hydrous flux-driven, fO2-buffered, melting of initially normal-DMM-like mantle. However the most negative δ57Fe must also reflect re-melting of sources that have experienced prior diffusive (disequilibrium) stripping of heavy Fe isotopes due to rapid melt extraction and metasomatism. Data from intra-arc to back-arc rifts in the western Pacific show that these arc signatures are rapidly dispersed by influx of DMM or OIB mantle once intra- and back-arc rifting and slab rollback gains momentum. We suggest that the characteristic light arc signatures only form when the source is lodged under arcs where sub-arc mantle undergoes corner flow forming an isolated roll. This process of heavy iron depletion is most efficient in the high ϕ arcs of the western Pacific and least prevalent in the low ϕ arcs of the eastern Pacific where δ57Fe values are MORB-like. This implies that there is a fundamental change in character of sub-arc mantle melting between east and west Pacific, percolative and fluid fluxed in the west and diapiric and decompressional in the east.

Asian dust input in the western Philippine Sea: Evidence from radiogenic Sr and Nd isotopes

NASA Astrophysics Data System (ADS)

Jiang, Fuqing; Frank, Martin; Li, Tiegang; Chen, Tian-Yu; Xu, Zhaokai; Li, Anchun

2013-05-01

The radiogenic strontium (Sr) and neodymium (Nd) isotope compositions of the detrital fraction of surface and subsurface sediments have been determined to trace sediment provenance and contributions from Asian dust off the east coast of Luzon Islands in the western Philippine Sea. The Sr and Nd isotope compositions have been very homogenous near the east coast of the Luzon Islands during the latest Quaternary yielding relatively least radiogenic Sr (87Sr/86Sr = 0.70453 to 0.70491) and more radiogenic Nd isotope compositions (ɛNd(0) = +5.3 to +5.5). These isotope compositions are similar to Luzon rocks and show that these sediments were mainly derived from the Luzon Islands. In contrast, the Sr and Nd isotope compositions of sediments on the Benham Rise and in the Philippine Basin are markedly different in that they are characterized by overall more variable and more radiogenic Sr isotope compositions (87Sr/86Sr = 0.70452 to 0.70723) and less radiogenic Nd isotope compositions (ɛNd(0) = -5.3 to +2.4). The Sr isotope composition in the Huatung Basin is intermediate between those of the east coast of Luzon and Benham Rise, but shows the least radiogenic Nd isotope compositions. The data are consistent with a two end-member mixing relationship between Luzon volcanic rocks and eolian dust from the Asian continent, which is characterized by highly radiogenic Sr and unradiogenic Nd isotope compositions. The results show that Asian continental dust contributes about 10-50% of the detrital fraction of the sediments on Benham Rise in the western Philippine Sea, which offers the potentials to reconstruct the climatic evolution of eastern Asia from these sediments and compare this information to the records from the central and northern Pacific.

Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

NASA Astrophysics Data System (ADS)

Lassiter, J. C.

2016-12-01

The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

Sulfur Isotope Composition of Putative Primary Troilite in Chondrules

NASA Technical Reports Server (NTRS)

Tachibana, Shogo; Huss, Gary R.

2002-01-01

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

Hydrogen Isotopic Composition of Apatite in Northwest Africa 7034: A Record of the "Intermediate" H-Isotopic Reservoir in the Martian Crust?

NASA Technical Reports Server (NTRS)

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

2016-01-01

Northwest Africa (NWA) 7034 and its pairings comprise a regolith breccia with a basaltic bulk composition [1] that yields a better match than any other martian meteorite to visible-infrared reflectance spectra of the martian surface measured from orbit [2]. The composition of the fine-grained matrix within NWA 7034 bears a striking resemblance to the major element composition estimated for the martian crust, with several exceptions. The NWA 7034 matrix is depleted in Fe, Ti, and Cr and enriched in Al, Na, and P [3]. The differences in Al and Fe are the most substantial, but the Fe content of NWA 7034 matrix falls within the range reported for the southern highlands crust [6]. It was previously suggested by [4] that NWA 7034 was sourced from the southern highlands based on the ancient 4.4 Ga ages recorded in NWA 7034/7533 zircons [4, 5]. In addition, the NWA 7034 matrix material is enriched in incompatible trace elements by a factor of 1.2-1.5 [7] relative to estimates of the bulk martian crust. The La/Yb ratio of the bulk martian crust is estimated to be approximately 3 [7], and the La/Yb of the NWA 7034 matrix materials ranges from approximately 3.9 to 4.4 [3, 8], indicating a higher degree of LREE enrichment in the NWA 7034 matrix materials. This elevated La/Yb ratio and enrichment in incompatible lithophile trace elements is consistent with NWA 7034 representing a more geochemically enriched crustal terrain than is represented by the bulk martian crust, which would be expected if NWA 7034 represents the bulk crust from the southern highlands. Given the similarities between NWA 7034 and the martian crust, NWA 7034 may represent an important sample for constraining the composition of the martian crust, particularly the ancient highlands. In the present study, we seek to constrain the H isotopic composition of the martian crust using Cl-rich apatite in NWA 7034. Usui et al., [9] recently proposed that a H isotopic reservoir exists within the martian crust that has a H-isotopic composition that is intermediate (dD of 1000-2000per mille) between an isotopically light mantle (Delta D is less than 275per mille [10]) and an isotopically heavy atmosphere (dD of 2500-6100per mille [11, 12]). Apatites in NWA 7034 occur in a number of lithologic domains, however apatites across all lithologic domains have been affected by a Pb-loss event at about 1.5 Ga before present [5], so they are unlikely to have retained a primary composition and are more likely to have equilibrated with fluids within the martian crust that may or may not have exchanged with the martian atmosphere. Equilibration of apatite with crustal fluids is further supported by the chlorine-rich compositions exhibited by apatites in NWA 7034 in comparison to apatites from other martian meteorites (Figure 1; [13]). Cl is more hydrophilic than F, which promotes formation of Cl-rich apatite compositions in fluid-rich systems [e.g., 14, 15-17].

Isotopic signatures and distribution of nitrogen and trapped and radiogenic xenon in the Acapulco and FRO90011 meteorites

NASA Technical Reports Server (NTRS)

Kim, Y.; Marti, K.

1993-01-01

Acapulco metal and silicate show distinct N isotopic signatures. Trapped heavy noble gases are carried by 'magnetic' opx and radiogenic Xe-129 excesses are observed in phosphate and in minor surficial phases on metal grains. N and Xe isotopic signatures in FRO90011 do not agree with those observed in Acapulco. The Acapulco meteorite is unique in having achondritic texture and chondritic composition. Its mineralogical study shows the record of high temperature (1100 C) recrystallization. However, this meteorite shows abundances of volatile elements close to the levels observed in carbonaceous chondrites and concentrations of heavy noble gases comparable to those observed in type 4 ordinary chondrites, not expected for a presumed highly equilibrated object. Nitrogen measurements in bulk Acapulco revealed two different isotopic signatures, in apparent conflict with evidence for a high degree of recrystallization. N and Xe were studied in separated mineral phases to search for the carriers in order to better understand the formation and thermal history of the Acapulco parent body.

Variations in some environmental characteristics including C and N stable isotopic composition of suspended organic matter in the Mandovi estuary.

PubMed

Maya, M V; Soares, Melena A; Agnihotri, Rajesh; Pratihary, A K; Karapurkar, Supriya; Naik, Hema; Naqvi, S W A

2011-04-01

Chemical and isotopic (δ13C and δ15N) investigation of the Mandovi estuary along the Indian west coast affected strongly by the seasonal monsoon cycle was carried out. The Mandovi estuary is a major waterway for Goa and extensively used for transportation of iron and manganese ore. In addition, with large population centers as well as agricultural fields located on its shores, the estuary is assumed to have been influenced by human activities. Measurements of chemical and isotopic parameters made in the lower part of the estuary during the southwest (SW) monsoon and post-monsoon seasons reveal distinct changes, and it is observed that despite considerable enrichment of macronutrients during the SW monsoon, productivity of the estuary (phytoplankton biomass), as inferred from the chlorophyll-a content, is not as high as expected. This is due to occurrences of high turbidity and cloud cover that limits photosynthetic productivity. The isotopic characterization (C and N isotopes) of suspended organic matter produced/transported during the monsoon and post-monsoon seasons of year 2007 provides a baseline dataset for future isotopic studies in such type of tropical estuaries.

Atomic Weights and Isotopic Compositions

National Institute of Standards and Technology Data Gateway

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

Testing and Resilience of the Impact Origin of the Moon

NASA Technical Reports Server (NTRS)

Righter, K.; Canup, R. M.

2016-01-01

The leading hypothesis for the origin of the Moon is the giant impact model, which grew out of the post-Apollo science community. The hypothesis was able to explain the high E-M system angular momentum, the small lunar core, and consistent with the idea that the early Moon melted substantially. The standard hypothesis requires that the Moon be made entirely from the impactor, strangely at odds with the nearly identical oxygen isotopic composition of the Earth and Moon, compositions that might be expected to be different if Moon came from a distinct impactor. Subsequent geochemical research has highlighted the similarity of both geochemical and isotopic composition of the Earth and Moon, and measured small but significant amounts of volatiles in lunar glassy materials, both of which are seemingly at odds with the standard giant impact model. Here we focus on key geochemical measurements and spacecraft observations that have prompted a healthy re-evaluation of the giant impact model, provide an overview of physical models that are either newly proposed or slightly revised from previous ideas, to explain the new datasets.

Magnesium isotopic composition of the Earth and chondrites

NASA Astrophysics Data System (ADS)

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

2010-07-01

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

High-precision isotopic characterization of USGS reference materials by TIMS and MC-ICP-MS

NASA Astrophysics Data System (ADS)

Weis, Dominique; Kieffer, Bruno; Maerschalk, Claude; Barling, Jane; de Jong, Jeroen; Williams, Gwen A.; Hanano, Diane; Pretorius, Wilma; Mattielli, Nadine; Scoates, James S.; Goolaerts, Arnaud; Friedman, Richard M.; Mahoney, J. Brian

2006-08-01

The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR-1, 2; BHVO-1, 2), andesite (AGV-1, 2), rhyolite (RGM-1, 2), syenite (STM-1, 2), granodiorite (GSP-2), and granite (G-2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR-1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC-ICP-MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR-ICP-MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC-ICP-MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC-ICP-MS, respectively). Our results also show that the first- and second-generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC-ICP-MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC-ICP-MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first- and second-generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions, and concentrations, could be directly related to contamination by the steel (mortar/pestle) used to process the materials. Contamination also accounts for the high concentrations of certain other trace elements (e.g., Li, Mo, Cd, Sn, Sb, W) in various USGS reference materials.

Calcium Isotopes in Foraminifera Shells: Evaluation for Paleo-temperature Reconstruction

NASA Astrophysics Data System (ADS)

Paytan, A.; Revello, C. A.; Bullen, T. D.

2002-12-01

The Ca stable isotope ratio of foraminifera shells has been suggested as a potential paleo-temperature proxy and has recently been applied in several studies to reconstruct glacial interglacial fluctuations in seawater temperatures. The major advantage of using Ca isotopes for paleo-temperature reconstruction is the relatively long residence time of Ca in the ocean. Thus, no spatial or temporal change in the Ca isotopic composition of seawater is expected over time scales much shorter than a million years. Moreover, since Ca is a major constituent of carbonate, and an isotopic ratio rather than an element concentration or element-element ratio (e.g. Mg/Ca, Sr/Ca) is measured, the Ca isotope proxy is much less likely to be affected by post depositional diagenetic alteration. However, preliminary results indicate that kinetic effects might largely control the Ca isotope fractionation involved in calcite shell formation. Before this new and exciting proxy can be utilized routinely, a better understanding of the parameters controlling Ca isotope fractionation in carbonate minerals in general and in foraminifera and other carbonate-secreting organisms is required. We have measured the Ca stable isotope ratio of several foraminifera species from core top sediments from two well-studied sites to determine the inter-species and within-species variability in Ca isotopes. We assess the effects of water temperature, calcification rate, and vital effects on the Ca stable isotope ratio of modern foraminifera and evaluate the potential of this proxy for paleo-temperature reconstruction.

PALOMA : An instrument to measure the molecular, elemental and isotopic composition of Mars atmosphere from a landed platform (MSL 09, EXOMARS)

NASA Astrophysics Data System (ADS)

Chassefière, E.; Paloma Team

2003-04-01

An instrument to analyze the molecular, elemental and isotopic composition of Mars atmosphere from a landed platform is being developed under CNES funding. This instrument, called PALOMA (PAyload for Local Observation of Mars Atmosphere), will be proposed in response to the AO for the instrumentation of the NASA Mars Smart Lander mission, planned to be launched in 2009. It might be part as well of the EXOMARS mission presently studied at ESA in the frame of the Aurora program. Noble gases (He, Ne, Ar, Xr, Xe) and stable isotopes (C, H, O, N) will be analyzed by using a system of gas purification and separation, coupled with a mass spectrometer. The heaviest, radioactive, noble gas (Rn) and its short-lived daughters will be measured using a small additional device (alpha particle detector). Detailed search for trace constituents of astrobiological interest, like CH_4, H_2CO, N_2O, H_2S (abundances, isotopic ratios, time variability) will be done on a regular temporal basis during one Martian year. Isotopic ratios will be measured with an accuracy of about 1 ppm, or better, in order to provide a clear diagnosis of possible life signatures, to allow a detailed comparison of Earth and Mars atmospheric fractionation patterns and, finally, to accurately disentangle escape, climatic, geochemical and hypothesized biological effects. High sensitivity is required for elemental and isotopic compositions of trace gases of interest (a small fraction of ppbv). Such an accurate monitoring of Mars atmosphere volatile composition is expected to provide the necessary reference for future composition studies of minerals, soils, bio-markers, polar cap material, either by in-situ measurement, or from laboratory analyses of returned samples. The PALOMA instrument consists of : a gas purification and separation line, using techniques of chemical and cryogenic trapping, and possibly membrane permeation, a mass spectrometer working in static mode, a turbo-molecular pump that provides the required level of vacuum in the separation line and in the spectrometer, a small additional stand-alone sensor for radon and its short-lived daughters measurement. It is designed to work during one full Martian year, in order to perform accurate measurements of the atmospheric composition and its seasonal, and more generally temporal, variations. The gas is sampled directly from the ambient atmosphere, without need for an external sample distribution system. The main parameters of PALOMA are 6.5 kg, 20 W (peak value : 30 W), 4 kb/day (peak value : 15 kb/day).

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 ...

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

Zhang, Yuxuan; Bilheux, Jean -Christophe

ImagingReso is an open-source Python library that simulates the neutron resonance signal for neutron imaging measurements. By defining the sample information such as density, thickness in the neutron path, and isotopic ratios of the elemental composition of the material, this package plots the expected resonance peaks for a selected neutron energy range. Various sample types such as layers of single elements (Ag, Co, etc. in solid form), chemical compounds (UO 3, Gd 2O 3, etc.), or even multiple layers of both types can be plotted with this package. As a result, major plotting features include display of the transmission/attenuation inmore » wavelength, energy, and time scale, and show/hide elemental and isotopic contributions in the total resonance signal.« less

Industrially synthesized single-walled carbon nanotubes: compositional data for users, environmental risk assessments, and source apportionment

NASA Astrophysics Data System (ADS)

Plata, D. L.; Gschwend, P. M.; Reddy, C. M.

2008-05-01

Commercially available single-walled carbon nanotubes (SWCNTs) contain large percentages of metal and carbonaceous impurities. These fractions influence the SWCNT physical properties and performance, yet their chemical compositions are not well defined. This lack of information also precludes accurate environmental risk assessments for specific SWCNT stocks, which emerging local legislation requires of nanomaterial manufacturers. To address these needs, we measured the elemental, molecular, and stable carbon isotope compositions of commercially available SWCNTs. As expected, catalytic metals occurred at per cent levels (1.3-29%), but purified materials also contained unexpected metals (e.g., Cu, Pb at 0.1-0.3 ppt). Nitrogen contents (up to 0.48%) were typically greater in arc-produced SWCNTs than in those derived from chemical vapor deposition. Toluene-extractable materials contributed less than 5% of the total mass of the SWCNTs. Internal standard losses during dichloromethane extractions suggested that metals are available for reductive dehalogenation reactions, ultimately resulting in the degradation of aromatic internal standards. The carbon isotope content of the extracted material suggested that SWCNTs acquired much of their carbonaceous contamination from their storage environment. Some of the SWCNTs, themselves, were highly depleted in 13C relative to petroleum-derived chemicals. The distinct carbon isotopic signatures and unique metal 'fingerprints' may be useful as environmental tracers allowing assessment of SWCNT sources to the environment.

Flowsheets and source terms for radioactive waste projections

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

Forsberg, C.W.

1985-03-01

Flowsheets and source terms used to generate radioactive waste projections in the Integrated Data Base (IDB) Program are given. Volumes of each waste type generated per unit product throughput have been determined for the following facilities: uranium mining, UF/sub 6/ conversion, uranium enrichment, fuel fabrication, boiling-water reactors (BWRs), pressurized-water reactors (PWRs), and fuel reprocessing. Source terms for DOE/defense wastes have been developed. Expected wastes from typical decommissioning operations for each facility type have been determined. All wastes are also characterized by isotopic composition at time of generation and by general chemical composition. 70 references, 21 figures, 53 tables.

Modeling the carbon isotope composition of bivalve shells (Invited)

NASA Astrophysics Data System (ADS)

Romanek, C.

2010-12-01

The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., <10%) in shells from aquatic organism and high (>90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions, equilibrium carbon isotope fractionation relations dictate that shell carbonate should be preferentially enriched in C-13 by 3 to 5 per mill (from 30° to 0°C) compared to EPF at a pH of 7.5. Anomalous positive excursions are rarely, if ever, observed in shell carbonate and they have yet to be associated with growth cessation markers in bivalves. The most likely explanation for the lack of anomalous positive values is that the percentage of metabolic carbon increases in EPF when bivalves experience stressful condition. This influx of metabolic carbon is balanced to a measureable extent by the enhanced fractionation of carbon isotopes during shell deposition from EPF at relatively low pH. These two processes may be combined in a quantitative model to extract a historical record of metabolic activity from the carbon isotope profiles of bivalve shells.

Strontium and barium isotopes in presolar silicon carbide grains measured with CHILI-two types of X grains

NASA Astrophysics Data System (ADS)

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; Pellin, Michael J.; Rost, Detlef; Savina, Michael R.; Jadhav, Manavi; Kelly, Christopher H.; Gyngard, Frank; Hoppe, Peter; Dauphas, Nicolas

2018-01-01

We used CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis of small samples, to analyze strontium, zirconium, and barium isotopes in 22 presolar silicon carbide grains. Twenty of the grains showed detectable strontium and barium, but none of the grains had enough zirconium to be detected with CHILI. Nine grains were excluded from further consideration since they showed very little signals (<1000 counts) for strontium as well as for barium. Among the 11 remaining grains, we found three X grains. The discovery of three supernova grains among only 22 grains was fortuitous, because only ∼1% of presolar silicon carbide grains are type X, but was confirmed by silicon isotopic measurements of grain residues with NanoSIMS. While one of the X grains showed strontium and barium isotope patterns expected for supernova grains, the two other supernova grains have 87Sr/86Sr < 0.5, values never observed in any natural sample before. From their silicon isotope ratios, the latter two grains can be classified as X2 grains, while the former grain belongs to the more common X1 group. The differences of these grains in strontium and barium isotopic composition constrain their individual formation conditions in Type II supernovae.

Effect of trans-reservoir water supply on carbon and nitrogen stable isotope composition in hydrologically connected reservoirs in China

NASA Astrophysics Data System (ADS)

Zhang, Huajun; Peng, Liang; Gu, Binhe; Han, Bo-Ping

2017-09-01

Dajingshan, Fenghuangshan and Meixi reservoirs are located in Zhuhai, a coastal city in southern China, and they function to supply drinking water to Zhuhai and Macau. For effectively supplying waster, they are hydrologically connected and Dajingshan Reservoir first receives the water pumped from the river at Guangchang Pumping Station, and then feeds Fenghuangshan Reservoir, and the two well-connected reservoirs are mesotrophic. Meixi Reservoir is a small and oligotrophic water body and feeds Dajingshan Reservoir only in wet seasons when overflow occurs. Particulate organic matter (POM) was collected from three hydrologically connected water supply reservoirs, and seasonal variations of POM were ascertained from stable carbon and nitrogen isotopes in wet and dry seasons, and the effects of pumping water and reservoir connectivity on POM variations and composition were demonstrated by the relationships of the stable isotope ratios of POM. Seasonality and similarity of stable carbon and nitrogen isotopes of POM varied with hydrodynamics, connectivity and trophic states of the four studied water bodies. The two well-connected reservoirs displayed more similar seasonality for δ13CPOM than those between the river station and the two reservoirs. However, the opposite seasonality appeared for δ15NPOM between the above waters and indicates different processes affecting the stable carbon and nitrogen isotopes of POM. δ13CPOM and δ15NPOM changed little between wet and dry seasons in Meixi Reservoir-a low productive and rain-driven system, suggesting little POM response to environmental changes in that water system. As expected, connectivity enhanced the similarity of the stable isotope ratios of POM between the water bodies.

Paired N and O isotopic analysis of nitrate and nitrite in the Arabian Sea oxygen deficient zone

NASA Astrophysics Data System (ADS)

Martin, T. S.; Casciotti, K. L.

2017-03-01

The Arabian Sea is home to one of the three main oceanic oxygen deficient zones (ODZs). We present paired nitrogen (N) and oxygen (O) isotope measurements of nitrate (NO3-) and nitrite (NO2-) from the central Arabian Sea in order to understand the effects of N biogeochemistry on the distribution of these species in the low oxygen waters. Within the ODZ, NO2- accumulated in a secondary NO2- maximum (SNM), though the shape and magnitude of the SNM, along with the isotopic composition of NO3- and NO2-, were highly dependent on the location within the ODZ. We also explored water mass mixing within the Arabian Sea as an explanatory factor in the distribution of NO2- in the SNM. The intrusion of Persian Gulf Water at depth may influence the shape of the NO2- peak by introducing small amounts of dissolved oxygen (O2), favoring NO2- oxidation. There was also evidence that vertical mixing may play a role in shaping the top of the SNM peak. Finally, we present evidence for NO2- oxidation and NO2- reduction co-occurring within the ODZ, as has been previously suggested in the Arabian Sea, as well as in other ODZs. The decoupling of the N and O isotopes of NO3-, deviating from the expected 1:1 ratio for dissimilatory NO3- reduction, indicates that NO2- oxidation has a significant influence on the isotopic composition of NO3-. Additionally, the N isotopes of NO2- were generally fit well by Rayleigh curves for NO2- oxidation. However, the removal of dissolved inorganic nitrogen (DIN) within the domain reflects the importance of NO2- reduction to N2.

Variable sulfur isotope composition of sulfides provide evidence for multiple sources of contamination in the Rustenburg Layered Suite, Bushveld Complex

NASA Astrophysics Data System (ADS)

Magalhães, Nivea; Penniston-Dorland, Sarah; Farquhar, James; Mathez, Edmond A.

2018-06-01

The Rustenburg Layered Suite (RLS) of the Bushveld Complex (BC) is famous for its platinum group element (PGE) ore, which is hosted in sulfides. The source of sulfur necessary to generate this type of mineralization is inferred to be the host rock of the intrusion. The RLS has a sulfur isotopic signature that indicates the presence of Archean surface-derived material (Δ33 S ≠ 0) in the magma. This signature, with an average value of Δ33 S = 0.112 ± 0.024 ‰, deviates from the expected Δ33 S value of the mantle of 0 ± 0.008 ‰. Previous work suggested that this signature is uniform throughout the RLS, which contrasts with radiogenic isotopes which vary throughout the igneous stratigraphy of the RLS. In this study, samples from key intervals within the igneous stratigraphy were analyzed, showing that Δ33 S values vary in the same stratigraphic levels as Sr and Nd isotopes. However, the variation is not consistent; in some levels there is a positive correlation and in others a negative correlation. This observation suggests that in some cases distinct magma pulses contained assimilated sulfur from different sources. Textural analysis shows no evidence for late addition of sulfur. These results also suggest that it is unlikely that large-scale assimilation and/or efficient mixing of host rock material in a single magma chamber occurred during emplacement. The data do not uniquely identify the source of sulfur in the different layers of the RLS, but the variation in sulfur isotope composition and its relationship to radiogenic isotope data calls for a reevaluation of the models for the formation and evolution of the RLS, which has the potential to impact the knowledge of how PGE deposits form.

O and C stable isotopes in cryogenic cave calcite (CCC) - possible proxy for past climate changes

NASA Astrophysics Data System (ADS)

-Andreea, Badaluta Carmen; Ersek, Vasile; Piotrowska, Natalia; Persoiu, Aurel

2017-04-01

Perennial ice deposits in caves host various proxies of past climate variability, most notable, the isotopic composition of ice, which has been shown to reflect, generally, the temperature outside the cave during the formation of ice (usually, autumn though spring). This ice forms by the freezing of water, water that contains large amounts of dissolved calcium carbonate. The freezing is accompanied by degassing of CO2, and precipitation of cryogenic cave calcite (CCC) under strong kinetic conditions. These kinetic processes could lead to the alteration of the original putative climatic signal carried by the isotopic composition of CCC. Here, we present a possibly climatic explanation of the isotopic composition of CCC from a 1000 years old cave ice deposit from Scărișoara Ice Cave (SIC) in Romania, Eastern Europe. In a 7 m core from the Great Hall of SIC we have analyzed the isotopic composition of the water (oxygen and hydrogen) and CCC (oxygen and carbon) from individual ice layers in the core, as well as that of precipitation , outside the cave. The isotopic composition of precipitation from the cave area varies between -3.6 ‰ for δˡ⁸O and -22 ‰ for δ2H in summer, and -17.8 ‰ for δˡ⁸O and -22 ‰ for δ2H in winter, with mean values of -9.1 ‰ for δˡ⁸O and -62 ‰ for δ2H. A positive correlation between air temperature and the isotopic composition of precipitation, as well as drip water in the cave has been found. The mean values in the ice core during the past 1000 years are -10.3‰ for δ18O and -71 ‰ for δ2H. The water isotopic values in the ice core show low values up to 900 AD, higher values between 900 and 1300 AD (Medieval Warm Period, MWP), and again lower values after 1300 AD (Little Ice Age, LIA), reaching their minimum after 1800 AD. The isotopic composition of CCC shows slightly higher values in the MWP and lower in LIA, possibly suggesting a climatic influence. Modern observations are too short to be able to calibrate this putative signal. Further, clumped isotope thermometry has shown that the kinetic fractionation that dominates during the freezing of water leads to unusual reconstructed formative temperature: +20°C. However, δˡ3C and δˡ⁸O values in CCC have higher values for samples from the MWP than those from the LIA. CCC results from the deposition of CaCO3 from Ca(CO3)2. The main source of CO2 to form carbonic acid is soil CO2, produced by root respiration. Previous studies have shown that δˡ⁸O of this CO2 is in equilibrium with the δˡ⁸O of water, so that the higher (lower) δˡ⁸O values of CCC could reflect warmer (colder) conditions during the MPW (LIA). The interpretation of δˡ3C values of CCC is less straightforward. Higher δˡ3C values in soil CO2 are determined by moisture limitation on plants, either due to low moisture or higher evaporative conditions. While the MWP was warmer in the study area, conflicting data exists on precipitation, with studies suggesting both drier and wetter conditions, so that is difficult to interpret our carbon isotope data. Apart from the direct climatic influence, the depth of soil could have also played a part, as deeper soils, as expected under birch forests that dominated during the MWP, would have had more enrichment in the heavy isotopes with depth, than the thiner soils of the LIA (formed under mostly spruce forests). Further, drought/higher temperatures could also influence the kinetics of the reaction, which can be large enough to overprint any soil signal in δˡ3C.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

A new approach to aid the characterisation and identification of metabolites of a model drug; partial isotope enrichment combined with novel formula elucidation software.

PubMed

Hobby, Kirsten; Gallagher, Richard T; Caldwell, Patrick; Wilson, Ian D

2009-01-01

This work describes the identification of 'isotopically enriched' metabolites of 4-cyanoaniline using the unique features of the software package 'Spectral Simplicity'. The software is capable of creating the theoretical mass spectra for partially isotope-enriched compounds, and subsequently performing an elemental composition analysis to give the elemental formula for the 'isotopically enriched' metabolite. A novel mass spectral correlation method, called 'FuzzyFit', was employed. 'FuzzyFit' utilises the expected experimental distribution of errors in both mass accuracy and isotope pattern and enables discrimination between statistically probable and improbable candidate formulae. The software correctly determined the molecular formulae of ten previously described metabolites of 4-cyanoaniline confirming the technique of partial isotope enrichment can produce results analogous to standard methodologies. Six previously unknown species were also identified, based on the presence of the unique 'designer' isotope ratio. Three of the unknowns were tentatively identified as N-acetylglutamine, O-methyl-N acetylglucuronide and a putative fatty acid conjugate. The discovery of a significant number of unknown species of a model drug with a comprehensive history of investigation highlights the potential for enhancement to the analytical process by the use of 'designer' isotope ratio compounds. The 'FuzzyFit' methodology significantly aided the elucidation of candidate formulae, by provision of a vastly simplified candidate formula data set. Copyright (c) 2008 John Wiley & Sons, Ltd.

Steady state fractionation of heavy noble gas isotopes in a deep unsaturated zone

USGS Publications Warehouse

Seltzer, Alan M.; Severinghaus, Jeffrey P.; Andraski, Brian J.; Stonestrom, David A.

2017-01-01

To explore steady state fractionation processes in the unsaturated zone (UZ), we measured argon, krypton, and xenon isotope ratios throughout a ∼110 m deep UZ at the United States Geological Survey (USGS) Amargosa Desert Research Site (ADRS) in Nevada, USA. Prior work has suggested that gravitational settling should create a nearly linear increase in heavy-to-light isotope ratios toward the bottom of stagnant air columns in porous media. Our high-precision measurements revealed a binary mixture between (1) expected steady state isotopic compositions and (2) unfractionated atmospheric air. We hypothesize that the presence of an unsealed pipe connecting the surface to the water table allowed for direct inflow of surface air in response to extensive UZ gas sampling prior to our first (2015) measurements. Observed isotopic resettling in deep UZ samples collected a year later, after sealing the pipe, supports this interpretation. Data and modeling each suggest that the strong influence of gravitational settling and weaker influences of thermal diffusion and fluxes of CO2 and water vapor accurately describe steady state isotopic fractionation of argon, krypton, and xenon within the UZ. The data confirm that heavy noble gas isotopes are sensitive indicators of UZ depth. Based on this finding, we outline a potential inverse approach to quantify past water table depths from noble gas isotope measurements in paleogroundwater, after accounting for fractionation during dissolution of UZ air and bubbles.

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

NASA Astrophysics Data System (ADS)

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

2013-06-01

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

Archival processes of the water stable isotope signal in East Antarctic ice cores

NASA Astrophysics Data System (ADS)

Casado, Mathieu; Landais, Amaelle; Picard, Ghislain; Münch, Thomas; Laepple, Thomas; Stenni, Barbara; Dreossi, Giuliano; Ekaykin, Alexey; Arnaud, Laurent; Genthon, Christophe; Touzeau, Alexandra; Masson-Delmotte, Valerie; Jouzel, Jean

2018-05-01

The oldest ice core records are obtained from the East Antarctic Plateau. Water isotopes are key proxies to reconstructing past climatic conditions over the ice sheet and at the evaporation source. The accuracy of climate reconstructions depends on knowledge of all processes affecting water vapour, precipitation and snow isotopic compositions. Fractionation processes are well understood and can be integrated in trajectory-based Rayleigh distillation and isotope-enabled climate models. However, a quantitative understanding of processes potentially altering snow isotopic composition after deposition is still missing. In low-accumulation sites, such as those found in East Antarctica, these poorly constrained processes are likely to play a significant role and limit the interpretability of an ice core's isotopic composition. By combining observations of isotopic composition in vapour, precipitation, surface snow and buried snow from Dome C, a deep ice core site on the East Antarctic Plateau, we found indications of a seasonal impact of metamorphism on the surface snow isotopic signal when compared to the initial precipitation. Particularly in summer, exchanges of water molecules between vapour and snow are driven by the diurnal sublimation-condensation cycles. Overall, we observe in between precipitation events modification of the surface snow isotopic composition. Using high-resolution water isotopic composition profiles from snow pits at five Antarctic sites with different accumulation rates, we identified common patterns which cannot be attributed to the seasonal variability of precipitation. These differences in the precipitation, surface snow and buried snow isotopic composition provide evidence of post-deposition processes affecting ice core records in low-accumulation areas.

Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Freeman, K. H.; Popp, B. N.; Hoham, C. H.

1990-01-01

Patterns of isotopic fractionation in biogeochemical processes are reviewed and it is suggested that isotopic fractionations will be small when substrates are large. If so, isotopic compositions of biomarkers will reflect those of their biosynthetic precursors. This prediction is tested by consideration of results of analyses of geoporphyrins and geolipids from the Greenhorn Formation (Cretaceous, Western Interior Seaway of North America) and the Messel Shale (Eocene, lacustrine, southern Germany). It is shown (i) that isotopic compositions of porphyrins that are related to a common source, but which have been altered structurally, cluster tightly and (ii) that isotopic differences between geolipids and porphyrins related to a common source are equal to those observed in modern biosynthetic products. Both of these observations are consistent with preservation of biologically controlled isotopic compositions during diagenesis. Isotopic compositions of individual compounds can thus be interpreted in terms of biogeochemical processes in ancient depositional environments. In the Cretaceous samples, isotopic compositions of n-alkanes are covariant with those of total organic carbon, while delta values for pristane and phytane are covariant with those of porphyrins. In this unit representing an open marine environment, the preserved acyclic polyisoprenoids apparently derive mainly from primary material, while the extractable, n-alkanes derive mainly from lower levels of the food chain. In the Messel Shale, isotopic compositions of individual biomarkers range from -20.9 to -73.4% vs PDB. Isotopic compositions of specific compounds can be interpreted in terms of origin from methylotrophic, chemautotrophic, and chemolithotrophic microorganisms as well as from primary producers that lived in the water column and sediments of this ancient lake.

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.

ISOTOPE CONVERSION DEVICE

DOEpatents

Wigner, E.P.; Young, G.J.; Ohlinger, L.A.

1957-12-01

This patent relates to nuclear reactors of tbe type utilizing a liquid fuel and designed to convert a non-thermally fissionable isotope to a thermally fissionable isotope by neutron absorption. A tank containing a reactive composition of a thermally fissionable isotope dispersed in a liquid moderator is disposed within an outer tank containing a slurry of a non-thermally fissionable isotope convertible to a thermally fissionable isotope by neutron absorption. A control rod is used to control the chain reaction in the reactive composition and means are provided for circulating and cooling the reactive composition and slurry in separate circuits.

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Biogeochemical cycling in an organic-rich coastal marine basin. 8. A sulfur isotopic budget balanced by differential diffusion across the sediment-water interface

USGS Publications Warehouse

Chanton, J.P.; Martens, C.S.; Goldhaber, M.B.

1987-01-01

The sulfur isotopic composition of the sulfur fluxes occurring in the anoxic marine sediments of Cape Lookout Bight, N.C., U.S.A., was determined, and the result of isotopic mass balance was obtained via the differential diffusion model. Seasonal pore water sulfate ??34S measurements yielded a calculated sulfate input of 0.6%.. Sulfate transported into the sediments via diffusion appeared to be enriched in the lighter isotope because its concentration gradient was steeper, due to the increase in the measured isotopic composition of sulfate with depth. Similarly, the back diffusion of dissolved sulfide towards the sediment-water interface appeared enriched in the heavier isotope. The isotopic composition of this flux was calculated from measurements of the ??34S of dissolved sulfide and was determined to be 15.9%.. The isotopic composition of buried sulfide was determined to be -5.2%. and the detrital sulfur input was estimated to be -6.2%.. An isotope mass balance equation based upon the fluxes at the sediment-water interface successfully predicted the isotopic composition of the buried sulfur flux within 0.5%., thus confirming that isotopes diffuse in response to their individual concentration gradients. ?? 1987.

Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

NASA Technical Reports Server (NTRS)

Becker, H.; Walker, R. J.

2003-01-01

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

Nature of the impactor at the K/T boundary: clues from Os, W and Cr isotopes.

NASA Astrophysics Data System (ADS)

Quitté, G.; Robin, E.; Capmas, F.; Levasseur, S.; Rocchia, R.; Birck, J. L.; Allègre, C. J.

2003-04-01

We measured the isotope composition of Os, W and Cr in K/T boundary sediments of three marine sites (Stevns Klint, Caravaca and Bidart) to determine the nature of the bolid that impacted the Earth 65 Myrs ago. We also analysed Ni-rich cosmic spinels, because they are thought to keep the signature of the impactor. The low REE content in spinels precludes indeed the hypothesis of a mixing with more than 10% of terrestrial material. The Os and W enrichment at the K/T boundary could be explained by a scavenging of chalcophile elements at the time of sulfide precipitation. The 187Os/186Os ratio of the K/T sediments is higher than the ratio of any kind of meteorites. On top of a possible mixing with surrounding sediments, we suggest that the boundary contained more Re in the past (lost since that time by alteration and oxidation) and that the Os isotope ratio is in fact disturbed. On each of the three sites, the boundary itself does not present any tungsten isotopic anomaly. The most likely interpretation is that the extraterrestrial material is diluted enough into the sediments so that the isotopic signature has been erased. Spinels show a small deficit of (0.34±0.9) ɛ in 182W. The large error bar precludes any clear conclusion whether or not a meteoritic signature is really present. If the spinels really carry an extraterrestrial signature as expected, their W composition is in favour of an ordinary chondrite. All K/T samples (sediments and spinels) are apparently depleted in 53Cr by about 0.5 ɛ (after renormalization of 54Cr to the terrestrial value) whereas ordinary chondrites display an excess of about 0.5 ɛ. Among meteorites, only carbonaceous chondrites present a negative value for the 53Cr/52Cr ratio relative to the terrestrial value. As more than 90% of the Cr present in spinels is of extraterrestrial origin, the Cr isotopes unambiguously show that the K/T impactor was a carbonaceous chondrite. These isotopic results also confirm the extraterrestrial origin of spinels. The W isotope composition of the spinels does not fully agree with the conclusion of a carbonaceous chondrite, but a refined measurement is required to discuss this discrepancy in more details.

Lack of Correlated Isotopic and Compositional Variations in Mauna Loa Lavas: A Serious Problem for Pyroxenite/Eclogite Plume Source Models

NASA Astrophysics Data System (ADS)

Rhodes, J. M.; Weis, D.; Norman, M. D.; Garcia, M. O.

2007-12-01

The long held notion that basaltic magmas are produced by decompressional melting of peridotite is under challenge. Recent models for the Hawaiian and other plumes argue that they consist of a heterogeneous mix of peridotite and discrete eclogite blobs, the latter derived from recycled subducted crust. Eclogite melting produces relatively siliceous magmas (dacite to andesite) which either mix with picritic melts from the peridotite, or, more plausibly, react with the peridotite to produce pyroxenite. Melting of varying proportions of the peridotite/pyroxenite mix is thought to produce the correlated compositional and isotopic characteristics of Hawaiian volcanoes. Magmas from Mauna Loa and Koolau volcanoes are thought to contain more of the recycled component; those from Loihi and Kilauea volcanoes contain less. A simple test of these mixed source models examines whether isotopic changes within the long magmatic history of a single volcano are accompanied by corresponding changes in major and trace element characteristics. Mauna Loa, where we have sampled around 400 - 500 ka of the volcano's eruptive history, provides an excellent opportunity for such a test. During this time, Mauna Loa will have traversed almost half the Hawaiian plume. According to the models, it should have erupted magmas produced from a range of pyroxenite/peridotite mixes with corresponding differences in both isotopic ratios and major and trace elements. Our data show that there is only minor isotopic (Sr, Pb, Nd, Hf) diversity in young lavas (<100 ka), but older lavas are highly diverse, ranging from modern values to those that are close to, and overlap with, those of Loihi volcano. If this isotopic diversity is a consequence of different proportions of pyroxenite and peridotite in the plume source, as the new models predict, we should expect to see correlated changes in bulk composition, particularly. in normalized SiO2, CaO/Al2O3, FeO/MgO and Ni - MgO relationships, as well as changes in Ni - Sc - V relationships. We do not. These parameters remain remarkably uniform over the 400 to 500 ka magmatic history of the volcano, with no correlated variation with isotopic ratios. We conclude that the isotopic heterogeneity within the Hawaiian plume is intrinsic to the peridotite plume source and not dependent on variable contributions from entrained, lithologically-discrete units.

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.

The Origin of EM1 Signatures in Basalts From Tristan da Cunha and Gough

NASA Astrophysics Data System (ADS)

Stracke, A.; Willbold, M.; Hemond, C.

2004-12-01

A long-standing hypothesis is that enriched mantle 1 (EM-1)-type ocean island basalt (OIB) sources contain pelagic sediments. Pelagic sediments range in composition from clays to calcareous or siliceous oozes and encompass a wide range of chemical compositions [1]. For geochemical purposes the use of the term pelagic sediments is often restricted to a special group of pelagic sediments with distinctive enrichment of Rare Earth Elements (REE). The geochemical composition of such REE-enriched pelagic sediments, however, is by no means representative of the geochemical composition of pelagic sediments in general. The extremely high REE/non-REE element ratios in REE-enriched pelagic sediments (e.g. high Lu/Hf, Sm/Hf, La/Nb, La/Th, Eu/Ti, and Gd/Ti ratios) translate into high 176Hf/177Hf ratios for given 143Nd/144Nd ratios with time. OIB sources containing this special variety of REE-enriched pelagic sediment should therefore plot above the oceanic basalt array and mixing arrays with these sources are expected to have a shallow slope in a Hf-Nd isotope diagram. Here we present new Hf-Nd isotope and trace element data for EM-1-type OIB from Tristan da Cunha and Gough in the South Atlantic Ocean. The samples from Tristan have a small range in Hf-Nd isotopic composition and plot within the oceanic basalt array in a Hf-Nd isotope diagram. Samples from Gough form a trend with a slope slightly steeper than that of the ocean basalt array in a Hf-Nd isotope diagram. OIB in general have a very restricted range in Gd/Ti and Sm/Hf ratios, and high La/Nb are associated with low Lu/Hf ratios. In detail, samples from Tristan and Gough have the lowest Lu/Hf and highest La/Nb ratios. Thus from the combined Hf-Nd isotope and trace element composition of basalts from Tristan and Gough involvement of this special variety of (REE-enriched) pelagic sediments can be excluded. Similar observations are made, and thus similar arguments hold, for other EM-1-type localities (Walvis ridge [2] and Pitcairn island [3]). Due to the considerable spread in geochemical composition of pelagic or any other group of sediments (e.g. marine sediments with a higher proportion of terrigenous components), it is difficult to attribute characteristic elemental or isotopic signatures to certain groups of sediment. Moreover, subducting sediments are complex mixtures of different types of sediment [1]. Thus it is difficult to find unique evidence either in favor of or against the involvement of sediments in general at Tristan and Gough, or any other individual OIB locality. Also, it appears highly unlikely that sub-arc processing has an equalizing effect on the composition of different subducting sediments [4]. Associating the similar isotopic characteristics of certain OIB groups and/or mantle-end-members (e.g. EM-1) to recycled sediments is therefore also problematic. [1] Plank, T. and C. H. Langmuir, Chem. Geol., 145, 325-394, 1998. [2] Salters, V. J. M. and X. Li, Geochim. Cosmochim. Acta, 68, A554, 2004. [3] Eisele, J., M. Sharma, J. G. Galer, J. Blichert-Toft, C. W. Devey and A. W. Hofmann, Earth Plan. Sci. Lett., 196, 197-212, 2002. [4] Johnson, M. C. and T. Plank, Geochem., Geophys., Geosys., 1, pp. 29, 1999.

Do Hf isotopes in magmatic zircons represent those of their host rocks?

NASA Astrophysics Data System (ADS)

Wang, Di; Wang, Xiao-Lei; Cai, Yue; Goldstein, Steven L.; Yang, Tao

2018-04-01

Lu-Hf isotopic system in zircon is a powerful and widely used geochemical tracer in studying petrogenesis of magmatic rocks and crustal evolution, assuming that zircon Hf isotopes can represent initial Hf isotopes of their parental whole rock. However, this assumption may not always be valid. Disequilibrium partial melting of continental crust would preferentially melt out non-zircon minerals with high time-integrated Lu/Hf ratios and generate partial melts with Hf isotope compositions that are more radiogenic than those of its magma source. Dissolution experiments (with hotplate, bomb and sintering procedures) of zircon-bearing samples demonstrate this disequilibrium effect where partial dissolution yielded variable and more radiogenic Hf isotope compositions than fully dissolved samples. A case study from the Neoproterozoic Jiuling batholith in southern China shows that about half of the investigated samples show decoupled Hf isotopes between zircons and the bulk rocks. This decoupling could reflect complex and prolonged magmatic processes, such as crustal assimilation, magma mixing, and disequilibrium melting, which are consistent with the wide temperature spectrum from ∼630 °C to ∼900 °C by Ti-in-zircon thermometer. We suggest that magmatic zircons may only record the Hf isotopic composition of their surrounding melt during crystallization and it is uncertain whether their Hf isotopic compositions can represent the primary Hf isotopic compositions of the bulk magmas. In this regard, using zircon Hf isotopic compositions to trace crustal evolution may be biased since most of these could be originally from disequilibrium partial melts.

Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim

NASA Technical Reports Server (NTRS)

Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.

2013-01-01

Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

Can the evolution of nitrogen cycle be traced by the N isotopic composition in mica?

NASA Astrophysics Data System (ADS)

Pinti, D. L.; Hashizume, K.

2011-12-01

A significant portion of nitrogen present in sedimentary rocks has a biological origin, trapped either in organic form, or as ammonium ion substituting potassium in mica. Mica might preserve biological N isotopic signatures (δ15N) in the geological record, allowing the evolution of the N cycle to be traced. However, diagenetic or metamorphic events can modify the pristine N isotopic signature leading to inaccurate interpretations. For example, devolatilization of the rock leads to a reduction in the N abundance and a contemporary increase of the δ15N because 14N escapes faster than 15N. We measured N isotopic compositions in whole rock, mica and feldspars separates from two Archean suites of cherts: 3.5 Ga Kitty's Gap and North Pole sequences in Pilbara, Western Australia and from the 3.45 Ga Hooggenoeg Fm, Barberton Greenstone Belt, South Africa. N was compared with the argon elemental and isotopic composition, because a relation between NH4+, which replaces K+ and radiogenic 40Ar*, which is produced by electron capture of K+ is expected. Both Pilbara and Barberton cherts show a clear correlation between N and 40Ar*, confirming the occurrence of a common speciation. K-Ar dating of the Hooggenoeg Formation mica and feldspars give ages of 2.1 and 1.1 Ga, respectively, indicating that loosely-bounded noble gas 40Ar* is lost from the host mineral during known metamorphic events. Observed correlations between 40Ar* and N suggests that nitrogen, although more strongly bounded as ammonium is also lost, possibly leading to isotopic fractionation. Measured δ15N values, however, are relatively constant (+8.1±0.6% for whole rock and +10.9±1.2% for mica) and do not display an inverse correlation with N abundances. This suggests either 1) that isotopic fractionation is not produced during N loss or; 2) that a process other than devolatilization fractionate N isotopes. Measured δ15N values are at levels far greater than those expected for Early Archean kerogens (0±2%) thus suggesting that fractionation took place but probably is induced by a process other than devolatilization. Step-combustion analyses of N and Ar from Kitty's Gap cherts reveals the presence of an inverse correlation between δ15N values and the 40Ar*/N ratios indicating mixing between two isotopically distinct components. The first, released at temperatures between 400° and 700° C from hydrous minerals, has a δ15N value close or below 0% and is accompanied by radiogenic Ar. The second, void of radiogenic Ar, is released at temperatures >800° C from anhydrous phases and has a δ15N value of +6 to +8%. The first component is likely ammonium replacing K in mica while the second is possibly ammonium adsorbed in-between negatively charged layers of clay minerals. Upon dehydration, the inter-layer site will be "closed", and loosely adsorbed cations are finally trapped in the mineral while noble gas Ar is lost. The higher δ15N in mica is possibly due either to (1) trapping of N representing a later (post-Archean) event, or; (2) fractionation of N with negative δ15N value due to partial release of N from the adsorption site. Mixing between different aliquots of these two components might possibly explain the observed N isotopic variability among micas in the Archean.

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.

Groundwater, springs, and stream flow generation in an alpine meadow of a tropical glacierized catchment

NASA Astrophysics Data System (ADS)

Gordon, R.; Lautz, L. K.; McKenzie, J. M.; Mark, B. G.; Chavez, D.

2013-12-01

Melting tropical glaciers supply approximately half of dry season stream discharge in glacierized valleys of the Cordillera Blanca, Peru. The remainder of streamflow originates as groundwater stored in alpine meadows, moraines and talus slopes. A better understanding of the dynamics of alpine groundwater, including sources and contributions to streamflow, is important for making accurate estimates of glacial inputs to the hydrologic budget, and for our ability to make predictions about future water resources as glaciers retreat. Our field study, conducted during the dry season in the Llanganuco valley, focused on a 0.5-km2 alpine meadow complex at 4400 m elevation, which includes talus slopes, terminal moraines, and a debris fan. Two glacial lakes and springs throughout the complex feed a network of stream channels that flow across the meadow (~2 km total length). We combined tracer measurements of stream and spring discharge and groundwater-surface water exchange with synoptic sampling of water isotopic and geochemical composition, in order to characterize and quantify contributions to streamflow from different geomorphic features. Surface water inputs to the stream channels totaled 58 l/s, while the stream gained an additional 57 l/s from groundwater inputs. Water chemistry is primarily controlled by flowpath type (surface/subsurface) and length, as well as bedrock lithology, while stable water isotopic composition appears to be controlled by water source (glacial lake, meadow or deep groundwater). Stream water chemistry is most similar to meadow groundwater springs, but isotopic composition suggests that the majority of stream water, which issues from springs at the meadow/fan interface, is from the same glacial source as the up-gradient lake. Groundwater sampled from piezometers in confined meadow aquifers is unique in both chemistry and isotopic composition, but does not contribute a large percentage of stream water exiting this small meadow, as quantified by discharge measurements and isotopic mixing. However, we expect that as streams flow down through extensive meadows and wetlands in many Cordillera Blanca valleys, meadow groundwater is a more significant contributor to streamflow. Results from this small, high meadow in Llanganuco will be compared to a larger and lower-elevation meadow system in the Quilcayhuanca valley.

A Lithospheric Origin for the Elk Creek Carbonatite Complex, SE Nebraska?

NASA Astrophysics Data System (ADS)

Farmer, G. L.

2015-12-01

The Elk Creek carbonatite complex in southeastern Nebraska is part of a widespread Cambrian-Ordovician alkali igneous event that affected much of North America during and after the break-up of the Rodinian supercontinent. We conducted whole rock and mineral Nd, Sr, Pb and Hf isotopic analyses of drill cores obtained from this complex in order to assess the source regions of the parental carbonatite magma. Low precision laser ablation U-Pb age determinations from individual zircon grains separated from carbonate-rich "syenites" range from 480 +/- 20 Ma to 540+/- 14 Ma. Whole rock Nd, Sr and Pb isotopic compositions all plot on Cambrian (~550 Ma) isochrons, implying that the carbonatites crystallized from melts with homogeneous radiogenic isotopic compositions. Initial ɛNd and ɛHf are well defined at ~+2 and ~0, respectively, while initial 87Sr/86Sr values are more variable and range from 0.7028 to 0.7058. The contemporaneously emplaced State Line kimberlites in the Front Range of north central Colorado share the same Nd and Sr isotopic compositions imply that sources of these rocks were similar and geographically widespread. Overall, the isotopic compositions are those expected from "Group 1" alkaline igneous rocks, usually interpreted as derivates from the sublithospheric mantle. Cretaceous-Tertiary alkaline rocks in North America generally belong to "Group 1" and may have originated in this fashion (Genet et al., 2014, Earth Planet. Sci. Lett.). An alternative possibility is that the Cambrian-Ordovician carbonatites and kimberlites were derived from underlying, carbonated portions of the lithospheric mantle that formed after the original stabilization of the latter in the Paleoproterozoic. Nd and Hf depleted mantle model ages for the Elk Creek and State Line alkaline rocks range from ~0.8 Ga to ~1.1 Ga and allow the possibility that both sets of intrusive rocks represent melting of mantle metasomatized either during or after the assembly of Rodinia. Widespread thinning and heating of the metasomatized mantle during the subsequent breakup of Rodinia could have led to the widespread kimberlite and carbonatite magmatism observed in North America during the Cambrian.

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.

Water content, speciation and isotopic composition in volcanic glass: an open window on magma degassing processes or paleoclimate?

NASA Astrophysics Data System (ADS)

Martin, Erwan; Bindeman, Ilya; Balan, Etienne; Palandri, Jim; Seligman, Angela; Villemant, Benoit

2016-04-01

The content, speciation and isotopic composition of water in volcanic glass have been used for decades as recorder of magma degassing or late glass rehydration processes. Magmatic or paleoclimate information are derived depending on the primary (magmatic) or meteoric (secondary) origin of water. In this study, we attempt to discriminate residual magmatic from secondary meteoric water in volcanic glass. Using samples from different geological settings and different climatic conditions, we show that the H-isotope composition and water content measured via a TC/EA-MAT253 system in volcanic glass alone are not always sufficient to provide clear distinction between magmatic and meteoric origin. However, it is quite easy to resolve δD evolution during post-deposit rehydration by meteoric water from magma degassing when volcanic glass have a δD <-100‰ or >-50‰ and [H2O]tot >1.5-2wt.%. Water speciation inferred from near-infrared spectroscopy also provides valuable information complementary to isotopic and total water measurements. During magma degassing (typically with [H2O]tot decreasing from 6wt.% to ~0wt.% water) H2O/OH is expected to decrease from 2 to close to 0. However, our dataset shows the opposite trend with an increase of H2O/OH from 2 to ~5. We interpret it as post deposit rehydration of the volcanic glass. Overall our results show that the discrimination of the water origin is essential to discuss magma degassing processes or paleoclimatic reconstitutions. The present study of hydrous glass supports the use of H-isotopes of volcanic glass to discuss paleoclimate reconstitution in a specific region. To this purpose, the volcanic glass has to be almost fully rehydrated in order to fingerprint the isotopic composition of the rehydration water. A sharp time constrain can be obtained if the full rehydration occurs quickly after the eruption. This is most likely to occur in meters thick volcanic pyroclast deposits that undergo slow cooling rates and thus can stay at few hundreds °C for a time long enough to ensure complete chemical reaction (few to hundreds of years) after the eruption but still short on a geological scale.

Cryogenic distillation facility for isotopic purification of protium and deuterium

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

Alekseev, I.; Arkhipov, Ev.; Bondarenko, S.

Isotopic purification of the protium and deuterium is an important requirement of many physics experiments. A cryogenic facility for high-efficiency separation of hydrogen isotopes with a cryogenic distillation column as the main element is described. The instrument is portable, so that it can be used at the experimental site. It was designed and built at the Petersburg Nuclear Physics Institute, Gatchina, Russia. Fundamental operating parameters have been measured including a liquid holdup in the column packing, the pressure drops across the column and the purity of the product at different operating modes. A mathematical model describes expected profiles of hydrogenmore » isotope concentration along the distillation column. An analysis of ortho-parahydrogen isomeric composition by gas chromatography was used for evaluation of the column performance during the tuning operations. The protium content during deuterium purification (≤100 ppb) was measured using gas chromatography with accumulation of the protium in the distillation column. A high precision isotopic measurement at the Institute of Particle Physics, ETH-Zurich, Switzerland, provided an upper bound of the deuterium content in protium (≤6 ppb), which exceeds all commercially available products.« less

Tracing subducted crustal materials in the mantle by using magnesium isotopes

NASA Astrophysics Data System (ADS)

Teng, F. Z.

2016-12-01

Recent studies show that some continental basalt, mantle-metasomatised peridotite and cratonic eclogite have heterogeneous Mg isotopic compositions. These isotopically distinct Mg isotopic compositions have been explained by the incorporation of subducted materials in their mantle sources though the detailed mechanisms are still not well understood. In particular, how Mg-poor crustal materials can modify Mg isotopic systematics of Mg-rich mantle is unknown. Subduction zones are the most efficient sites for crust and mantle interactions, hence should be where the most prominent Mg isotopic variation occurs. However, to date, little is known on Mg isotope systematics in the subduction factory. Here I first review and report new Mg isotopic data for arc lava, subarc peridotite and the subducted slab (marine sediment, altered basalt and abyssal peridotite), then use them to constrain the origins of mantle Mg isotopic heterogeneity and lay the foundation for using Mg isotopes as new tools for tracing crust-mantle interactions. The main conclusions are 1) fluid-rock interactions can modify Mg isotopic systematics of abyssal peridotites; 2) island arc lavas have non-MORB Mg isotopic compositions, reflecting distinct surbarc mantle Mg isotopic signature; 3) continental arcs have non-MORB Mg isotopic compositions, likely resulting from crustal contamination and 4) the isotopically heterogeneous continental basalts are mainly produced by mixing of isotopically distinct magmas instead of being partial melting products of metasomatised mantle peridotites.

The role of mantle-hybridization and crustal contamination in the petrogenesis of lithospheric mantle-derived alkaline rocks: constraints from Os and Hf isotopes

NASA Astrophysics Data System (ADS)

Mayer, B.; Jung, S.; Brauns, M.; Münker, C.

2018-06-01

The Rhön area as part of the Central European Volcanic Province (CEVP) hosts an unusual suite of Tertiary 24-Ma old hornblende-bearing alkaline basalts that provide insights into melting and fractionation processes within the lithospheric mantle. These chemically primitive to slightly evolved and isotopically (Sr, Nd, Pb) depleted basalts have slightly lower Hf isotopic compositions than respective other CEVP basalts and Os isotope compositions more radiogenic than commonly observed for continental intraplate alkaline basalts. These highly radiogenic initial 187Os/188Os ratios (0.268-0.892) together with their respective Sr-Nd-Pb isotopic compositions are unlikely to result from crustal contamination alone, although a lack of Os data for lower crustal rocks from the area and limited data for CEVP basalts or mantle xenoliths preclude a detailed evaluation. Similarly, melting of the same metasomatized subcontinental lithospheric mantle as inferred for other CEVP basalts alone is also unlikely, based on only moderately radiogenic Os isotope compositions obtained for upper mantle xenoliths from elsewhere in the province. Another explanation for the combined Nd, Sr and Os isotope data is that the lavas gained their highly radiogenic Os isotope composition through a mantle "hybridization", metasomatism process. This model involves a mafic lithospheric component, such as an intrusion of a sublithospheric primary alkaline melt or a melt derived from subducted oceanic material, sometime in the past into the lithospheric mantle where it metasomatized the ambient mantle. Later at 24 Ma, thermal perturbations during rifting forced the isotopically evolved parts of the mantle together with the peridotitic ambient mantle to melt. This yielded a package of melts with highly correlated Re/Os ratios and radiogenic Os isotope compositions. Subsequent movement through the crust may have further altered the Os isotope composition although this effect is probably minor for the majority of the samples based on radiogenic Nd and unradiogenic Sr isotope composition of the lavas. If the radiogenic Os isotope composition can be explained by a mantle-hybridization and metasomatism model, the isotopic compositions of the hornblende basalts can be satisfied by ca. 5-25% addition of the mafic lithospheric component to an asthenospheric alkaline magma. Although a lack of isotope data for all required endmembers make this model somewhat speculative, the results show that the Re-Os isotope system in continental basalts is able to distinguish between crustal contamination and derivation of continental alkaline lavas from isotopically evolved peridotitic lithosphere that was contaminated by mafic material in the past and later remelted during rifting. The Hf isotopic compositions are slightly less radiogenic than in other alkaline basalts from the province and indicate the derivation of the lavas from low Lu-Hf parts of the lithospheric mantle. The new Os and Hf isotope data constrain a new light of the nature of such metasomatizing agents, at least for these particular rocks, which represent within the particular volcanic complex the first product of the volcanism.

The silicon isotope composition of the upper continental crust

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

Controls on the barium isotope compositions of marine sediments

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

ImagingReso: A Tool for Neutron Resonance Imaging

DOE PAGES

Zhang, Yuxuan; Bilheux, Jean -Christophe

2017-11-01

ImagingReso is an open-source Python library that simulates the neutron resonance signal for neutron imaging measurements. By defining the sample information such as density, thickness in the neutron path, and isotopic ratios of the elemental composition of the material, this package plots the expected resonance peaks for a selected neutron energy range. Various sample types such as layers of single elements (Ag, Co, etc. in solid form), chemical compounds (UO 3, Gd 2O 3, etc.), or even multiple layers of both types can be plotted with this package. As a result, major plotting features include display of the transmission/attenuation inmore » wavelength, energy, and time scale, and show/hide elemental and isotopic contributions in the total resonance signal.« less

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

Valysaev, B.M.; Erokhin, V.E.; Grinchenko, Y.I.

A study has been made of the isotopic composition of the carbon in methane and carbon dioxide, as well as hydrogen in the methane, in the gases of mud volcanoes, for all main mud volcano areas in the USSR. The isotopic composition of carbon and hydrogen in methane shows that the gases resemble those of oil and gas deposits, while carbon dioxide of these volcanoes has a heavier isotopic composition with a greater presence of ''ultraheavy'' carbon dioxide. By the chemical and isotopic composition of gases, Azerbaidzhan and South Sakhalin types of mud volcano gases have been identified, as wellmore » as Bulganak subtypes and Akhtala and Kobystan varieties. Correlations are seen between the isotopic composition of gases and the geological build of mud volcano areas.« less

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

PubMed

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

2017-10-01

Natural perchlorate (ClO 4 - ) in soil and groundwater exhibits a wide range in stable isotopic compositions (δ 37 Cl, δ 18 O, and Δ 17 O), indicating that ClO 4 - may be formed through more than one pathway and/or undergoes post-depositional isotopic alteration. Plants are known to accumulate ClO 4 - , but little is known about their ability to alter its isotopic composition. We examined the potential for plants to alter the isotopic composition of ClO 4 - in hydroponic and field experiments conducted with snap beans (Phaseolus vulgaris L.). In hydroponic studies, anion ratios indicated that ClO 4 - was transported from solutions into plants similarly to NO 3 - but preferentially to Cl - (4-fold). The ClO 4 - isotopic compositions of initial ClO 4 - reagents, final growth solutions, and aqueous extracts from plant tissues were essentially indistinguishable, indicating no significant isotope effects during ClO 4 - uptake or accumulation. The ClO 4 - isotopic composition of field-grown snap beans was also consistent with that of ClO 4 - in varying proportions from irrigation water and precipitation. NO 3 - uptake had little or no effect on NO 3 - isotopic compositions in hydroponic solutions. However, a large fractionation effect with an apparent ε ( 15 N/ 18 O) ratio of 1.05 was observed between NO 3 - in hydroponic solutions and leaf extracts, consistent with partial NO 3 - reduction during assimilation within plant tissue. We also explored the feasibility of evaluating sources of ClO 4 - in commercial produce, as illustrated by spinach, for which the ClO 4 - isotopic composition was similar to that of indigenous natural ClO 4 - . Our results indicate that some types of plants can accumulate and (presumably) release ClO 4 - to soil and groundwater without altering its isotopic characteristics. Concentrations and isotopic compositions of ClO 4 - and NO 3 - in plants may be useful for determining sources of fertilizers and sources of ClO 4 - in their growth environments and consequently in food supplies. Copyright © 2017 Elsevier B.V. All rights reserved.

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

USGS Publications Warehouse

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

2017-01-01

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

Stable carbon isotope analysis reveals widespread drought stress in boreal black spruce forests.

PubMed

Walker, Xanthe J; Mack, Michelle C; Johnstone, Jill F

2015-08-01

Unprecedented rates of climate warming over the past century have resulted in increased forest stress and mortality worldwide. Decreased tree growth in association with increasing temperatures is generally accepted as a signal of temperature-induced drought stress. However, variations in tree growth alone do not reveal the physiological mechanisms behind recent changes in tree growth. Examining stable carbon isotope composition of tree rings in addition to tree growth can provide a secondary line of evidence for physiological drought stress. In this study, we examined patterns of black spruce growth and carbon isotopic composition in tree rings in response to climate warming and drying in the boreal forest of interior Alaska. We examined trees at three nested scales: landscape, toposequence, and a subsample of trees within the toposequence. At each scale, we studied the potential effects of differences in microclimate and moisture availability by sampling on northern and southern aspects. We found that black spruce radial growth responded negatively to monthly metrics of temperature at all examined scales, and we examined ∆(13)C responses on a subsample of trees as representative of the wider region. The negative ∆(13)C responses to temperature reveal that black spruce trees are experiencing moisture stress on both northern and southern aspects. Contrary to our expectations, ∆(13)C from trees on the northern aspect exhibited the strongest drought signal. Our results highlight the prominence of drought stress in the boreal forest of interior Alaska. We conclude that if temperatures continue to warm, we can expect drought-induced productivity declines across large regions of the boreal forest, even for trees located in cool and moist landscape positions. © 2015 John Wiley & Sons Ltd.

The Origin of Silicic Arc Crust - Insights from the Northern Pacific Volcanic Arcs through Space and Time

NASA Astrophysics Data System (ADS)

Straub, S. M.; Kelemen, P. B.

2016-12-01

The remarkable compositional similarities of andesitic crust at modern convergent margins and the continental crust has long evoked the hypothesis of similar origins. Key to understanding either genesis is understanding the mode of silica enrichment. Silicic crust cannot be directly extracted from the upper mantle. Hence, in modern arcs, numerous studies - observant of the pervasive and irrefutable evidence of melt mixing - proposed that arc andesites formed by mixing of mantle-derived basaltic melts and fusible silicic material from the overlying crust. Mass balance requires the amount of silicic crust in such hybrid andesites to be on the order to tens of percent, implying that their composition to be perceptibly influenced by the various crustal basements. In order to test this hypothesis, major and trace element compositions of mafic and silicic arc magmas with arc-typical low Ce/Pb< 10 of Northern Pacific arcs (Marianas through Mexico) were combined with Pb isotope ratios. Pb isotope ratios are considered highly sensitive to crustal contamination, and hence should reflect the variable composition of the oceanic and continental basement on which these arcs are constructed. In particular, in thick-crust continental arcs where the basement is isotopically different from the mantle and crustal assimilation thought to be most prevalent, silicic magmas must be expected to be distinct from those of the associated mafic melts. However, in a given arc, the Pb isotope ratios are constant with increasing melt silica regardless of the nature of the basement. This observation argues against a melt origin of silicic melts from the crustal basement and suggest them to be controlled by the same slab flux as their co-eval mafic counterparts. This inference is validated by the spatial and temporal pattern of arc Pb isotope ratios along the Northern Pacific margins and throughout the 50 million years of Cenozoic evolution of the Izu Bonin Mariana arc/trench system that are can be related to with systematic, `real-time' changes in the composition of the slab flux with no role of the crustal basement. In summary, these data suggest that that silicic melts are ultimately genetically linked to the mafic co-eval series from the mantle, by such mechanisms as fractional crystallization, or melt-rock reactions, or a combination of both.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Carbon isotopic composition of individual Precambrian microfossils

NASA Technical Reports Server (NTRS)

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

2000-01-01

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

Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

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

Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.

Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotopemore » observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18O v ranged from –40.2 to –15.9 ‰ and δ 2H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1) indicate that regional evaporation can account for 40 to 60 % of the PBL water vapor. These estimates are in relatively good agreement with that derived from numerical weather model simulations. This relatively large fraction of evaporation-derived water vapor implies that evaporation has an important impact on the precipitation recycling ratio within the region. In conclusion, based on multiple constraints, we estimate that the summer season recycling fraction is about 30 %, indicating a potentially important link with convective precipitation.« less

Investigating the source, transport, and isotope composition of water vapor in the planetary boundary layer

DOE PAGES

Griffis, Timothy J.; Wood, Jeffrey D.; Baker, John M.; ...

2016-04-25

Increasing atmospheric humidity and convective precipitation over land provide evidence of intensification of the hydrologic cycle – an expected response to surface warming. The extent to which terrestrial ecosystems modulate these hydrologic factors is important to understand feedbacks in the climate system. We measured the oxygen and hydrogen isotope composition of water vapor at a very tall tower (185 m) in the upper Midwest, United States, to diagnose the sources, transport, and fractionation of water vapor in the planetary boundary layer (PBL) over a 3-year period (2010 to 2012). These measurements represent the first set of annual water vapor isotopemore » observations for this region. Several simple isotope models and cross-wavelet analyses were used to assess the importance of the Rayleigh distillation process, evaporation, and PBL entrainment processes on the isotope composition of water vapor. The vapor isotope composition at this tall tower site showed a large seasonal amplitude (mean monthly δ 18O v ranged from –40.2 to –15.9 ‰ and δ 2H v ranged from –278.7 to –113.0 ‰) and followed the familiar Rayleigh distillation relation with water vapor mixing ratio when considering the entire hourly data set. However, this relation was strongly modulated by evaporation and PBL entrainment processes at timescales ranging from hours to several days. The wavelet coherence spectra indicate that the oxygen isotope ratio and the deuterium excess ( d v) of water vapor are sensitive to synoptic and PBL processes. According to the phase of the coherence analyses, we show that evaporation often leads changes in d v, confirming that it is a potential tracer of regional evaporation. Isotope mixing models indicate that on average about 31 % of the growing season PBL water vapor is derived from regional evaporation. However, isoforcing calculations and mixing model analyses for high PBL water vapor mixing ratio events ( > 25 mmol mol –1) indicate that regional evaporation can account for 40 to 60 % of the PBL water vapor. These estimates are in relatively good agreement with that derived from numerical weather model simulations. This relatively large fraction of evaporation-derived water vapor implies that evaporation has an important impact on the precipitation recycling ratio within the region. In conclusion, based on multiple constraints, we estimate that the summer season recycling fraction is about 30 %, indicating a potentially important link with convective precipitation.« less

Strontium and barium isotopes in presolar silicon carbide grains measured with CHILI—two types of X grains

DOE PAGES

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; ...

2017-05-10

Here, we used CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis of small samples, to analyze strontium, zirconium, and barium isotopes in 22 presolar silicon carbide grains. Twenty of the grains showed detectable strontium and barium, but none of the grains had enough zirconium to be detected with CHILI. Nine grains were excluded from further consideration since they showed very little signals (<1000 counts) for strontium as well as for barium. Among the 11 remaining grains, we found three X grains. The discovery of three supernova grains among only 22 grainsmore » was fortuitous, because only ~1% of presolar silicon carbide grains are type X, but was confirmed by silicon isotopic measurements of grain residues with NanoSIMS. And while one of the X grains showed strontium and barium isotope patterns expected for supernova grains, the two other supernova grains have 87Sr/86Sr < 0.5, values never observed in any natural sample before. From their silicon isotope ratios, the latter two grains can be classified as X2 grains, while the former grain belongs to the more common X1 group. The differences of these grains in strontium and barium isotopic composition constrain their individual formation conditions in Type II supernovae.« less

Strontium and barium isotopes in presolar silicon carbide grains measured with CHILI—two types of X grains

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

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.

Here, we used CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis of small samples, to analyze strontium, zirconium, and barium isotopes in 22 presolar silicon carbide grains. Twenty of the grains showed detectable strontium and barium, but none of the grains had enough zirconium to be detected with CHILI. Nine grains were excluded from further consideration since they showed very little signals (<1000 counts) for strontium as well as for barium. Among the 11 remaining grains, we found three X grains. The discovery of three supernova grains among only 22 grainsmore » was fortuitous, because only ~1% of presolar silicon carbide grains are type X, but was confirmed by silicon isotopic measurements of grain residues with NanoSIMS. And while one of the X grains showed strontium and barium isotope patterns expected for supernova grains, the two other supernova grains have 87Sr/86Sr < 0.5, values never observed in any natural sample before. From their silicon isotope ratios, the latter two grains can be classified as X2 grains, while the former grain belongs to the more common X1 group. The differences of these grains in strontium and barium isotopic composition constrain their individual formation conditions in Type II supernovae.« less

Thallium isotope variations in an ore-bearing continental igneous setting: Collahuasi Formation, northern Chile

NASA Astrophysics Data System (ADS)

Baker, R. G. A.; Rehkämper, M.; Ihlenfeld, C.; Oates, C. J.; Coggon, R.

2010-08-01

Thallium is a highly incompatible element and a large fraction of the bulk silicate Earth Tl budget is, therefore, expected to reside in the continental crust. Nonetheless, the Tl isotope systematics of continental rocks are essentially unexplored at present. Here, we present new Tl isotope composition and concentration data for a suite of 36 intrusive and extrusive igneous rocks from the vicinity of porphyry Cu deposits in the Collahuasi Formation of the Central Andes in northern Chile. The igneous lithologies of the rocks are variably affected by the hydrothermal alteration that accompanied the formation of the Cu deposits. The samples display Tl concentrations that vary by more than an order of magnitude, from 0.1 to 3.2 μg/g, whilst ɛ 205Tl ranges between -5.1 and +0.1 (ɛ 205Tl is the deviation of the 205Tl/ 203Tl isotope ratio of a sample from a standard in parts per 10 4). These variations are primarily thought to be a consequence of hydrothermal alteration processes, including metasomatic transport of Tl, and formation/breakdown of Tl-bearing minerals, which are associated with small but significant Tl isotope effects. The Tl abundances show excellent correlations with both K and Rb concentrations but no co-variation with Cu. This demonstrates that Tl displays only limited chalcophile affinity in the continental crust of the Collahuasi Formation, but behaves as a lithophile element with a distribution that is primarily governed by partitioning of Tl + into K +-bearing phases. Collahuasi samples with propylitic alteration features, which are derived from the marginal parts of the hydrothermal systems, have, on average, slightly lighter Tl isotope compositions than rocks from the more central sericitic and argillic alteration zones. This small but statistically significant difference most likely reflects preferential retention of isotopically heavy Tl in alteration phases, such as white micas and clays, which formed during sericitic and argillic alteration.

Tungsten isotopes and the origin of the Moon

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

Kruijer, Thomas S.; Kleine, Thorsten

Here, the giant impact model of lunar origin predicts that the Moon mainly consists of impactor material. As a result, the Moon is expected to be isotopically distinct from the Earth, but it is not. To account for this unexpected isotopic similarity of the Earth and Moon, several solutions have been proposed, including (i) post-giant impact Earth–Moon equilibration, (ii) alternative models that make the Moon predominantly out of proto-Earth mantle, and (iii) formation of the Earth and Moon from an isotopically homogeneous disk reservoir. Here we use W isotope systematics of lunar samples to distinguish between these scenarios. We reportmore » high-precision 182W data for several low-Ti and high-Ti mare basalts, as well as for Mg-suite sample 77215, and lunar meteorite Kalahari 009, which complement data previously obtained for KREEP-rich samples. In addition, we utilize high-precision Hf isotope and Ta/W ratio measurements to empirically quantify the superimposed effects of secondary neutron capture on measured 182W compositions. Our results demonstrate that there are no resolvable radiogenic 182W variations within the Moon, implying that the Moon differentiated later than 70 Ma after Solar System formation. In addition, we find that samples derived from different lunar sources have indistinguishable 182W excesses, confirming that the Moon is characterized by a small, uniform ~+26 parts-per-million excess in 182W over the present-day bulk silicate Earth. This 182W excess is most likely caused by disproportional late accretion to the Earth and Moon, and after considering this effect, the pre-late veneer bulk silicate Earth and the Moon have indistinguishable 182W compositions. Mixing calculations demonstrate that this Earth–Moon 182W similarity is an unlikely outcome of the giant impact, which regardless of the amount of impactor material incorporated into the Moon should have generated a significant 182W excess in the Moon. Consequently, our results imply that post-giant impact processes might have modified 182W, leading to the similar 182W compositions of the pre-late veneer Earth's mantle and the Moon.« less

The influence of authigenic clay formation on the mineralogy and stable isotopic record of lacustrine carbonates

NASA Astrophysics Data System (ADS)

Bristow, Thomas F.; Kennedy, Martin J.; Morrison, Keith D.; Mrofka, David D.

2012-08-01

The mineralogical, compositional and stable isotopic variability of lacustrine carbonates are frequently used as proxies for ancient paleoenvironmental change in continental settings, under the assumption that precipitated carbonates reflect conditions and chemistry of ancient lake waters. In some saline and alkaline lake systems, however, authigenic clay minerals, forming at or near the sediment water interface, are a major sedimentary component. Often these clays are rich in Mg, influencing the geochemical budget of lake waters, and are therefore expected to influence the properties of contemporaneous authigenic carbonate precipitates (which may also contain Mg). This paper documents evidence for a systematic feedback between clay mineral and carbonate authigenesis through multiple precessionally driven, m-scale sedimentary cycles in lacustrine oil-shale deposits of the Eocene Green River Formation from the Uinta Basin (NE Utah). In the studied section, authigenic, Mg-rich, trioctahedral smectite content varies cyclically between 9 and 39 wt.%. The highest concentrations occur in oil-shales and calcareous mudstones deposited during high lake level intervals that favored sedimentary condensation, lengthening the time available for clay diagenesis and reducing dilution by other siliciclastic phases. An inverse relation between dolomite percentage of carbonate and trioctahedral smectite abundance suggests the Mg uptake during clay authigenesis provides a first order control on carbonate mineralogy that better explains carbonate mineralogical trends than the possible alternative controls of (1) variable Mg/Ca ratios in lake water and (2) degree of microbial activity in sediments. We also observe that cyclical change in carbonate mineralogy, believed to be induced by clay authigenesis, also causes isotopic covariation between δ13CPDB and δ18OPDB of bulk sediments because of differences in the equilibrium fractionation factors of dolomite and calcite (˜2‰ and ˜2.6%, respectively). This provides an alternative mechanism for the common pattern of isotopic covariation, which is typically attributed to the effect of simultaneous changes in water balance and biological activity on the carbon and oxygen isotopic composition of lake waters. These findings may help improve paleoenvironmental reconstructions based on lacustrine carbonate records by adding to the factors known to influence the mineralogical, compositional and stable isotopic signals recorded by lacustrine carbonates.

Tungsten isotopes and the origin of the Moon

DOE PAGES

Kruijer, Thomas S.; Kleine, Thorsten

2017-08-04

Here, the giant impact model of lunar origin predicts that the Moon mainly consists of impactor material. As a result, the Moon is expected to be isotopically distinct from the Earth, but it is not. To account for this unexpected isotopic similarity of the Earth and Moon, several solutions have been proposed, including (i) post-giant impact Earth–Moon equilibration, (ii) alternative models that make the Moon predominantly out of proto-Earth mantle, and (iii) formation of the Earth and Moon from an isotopically homogeneous disk reservoir. Here we use W isotope systematics of lunar samples to distinguish between these scenarios. We reportmore » high-precision 182W data for several low-Ti and high-Ti mare basalts, as well as for Mg-suite sample 77215, and lunar meteorite Kalahari 009, which complement data previously obtained for KREEP-rich samples. In addition, we utilize high-precision Hf isotope and Ta/W ratio measurements to empirically quantify the superimposed effects of secondary neutron capture on measured 182W compositions. Our results demonstrate that there are no resolvable radiogenic 182W variations within the Moon, implying that the Moon differentiated later than 70 Ma after Solar System formation. In addition, we find that samples derived from different lunar sources have indistinguishable 182W excesses, confirming that the Moon is characterized by a small, uniform ~+26 parts-per-million excess in 182W over the present-day bulk silicate Earth. This 182W excess is most likely caused by disproportional late accretion to the Earth and Moon, and after considering this effect, the pre-late veneer bulk silicate Earth and the Moon have indistinguishable 182W compositions. Mixing calculations demonstrate that this Earth–Moon 182W similarity is an unlikely outcome of the giant impact, which regardless of the amount of impactor material incorporated into the Moon should have generated a significant 182W excess in the Moon. Consequently, our results imply that post-giant impact processes might have modified 182W, leading to the similar 182W compositions of the pre-late veneer Earth's mantle and the Moon.« less

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.

Modeling the influence of a reduced equator-to-pole sea surface temperature gradient on the distribution of water isotopes in the Eocene

NASA Astrophysics Data System (ADS)

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

2009-12-01

Proxy-based climate reconstructions suggest the existence of a strongly reduced equator-to-pole temperature gradient during most of the Early Eocene. With the realization that the Eocene Arctic Ocean was covered with enormous quantities of the free floating freshwater fern Azolla, new questions related to Eocene (global) hydrological cycling facilitating these blooms arose. Changes in hydrological cycling, as a consequence of a reduced temperature gradient, are expected to be most clearly reflected in the isotopic composition (D, 18O) of precipitation. The interpretation of water isotopic records to quantitatively estimate past precipitation patterns is, however, hampered by the lack of detailed information on changes in their spatial and temporal distribution. Using the isotope-enabled global circulation model, Community Atmosphere Model v.3 (isoCAM3), relationships between water isotopes and past climates can be simulated. Here we examine the influence of a reduced meridional sea surface temperature gradient on the spatial distribution of precipitation and its isotopic composition in an Eocene setting. Overall, our combination of Eocene climate forcings, with superimposed TEX86-derived SST estimates and elevated pCO2 concentrations, produces a climate that agrees well with proxy data in locations around the globe. It shows the presence of an intensified hydrological cycle with precipitation exceeding evaporation in the Arctic region. The Eocene model runs with a significantly reduced equator-to-pole temperature gradient in a warmer more humid world predict occurrence of less depleted precipitation, with δD values ranging only between 0 and -140‰ (as opposed to the present-day range of 0 to -300‰). Combining new results obtained from compound specific isotope analyses on terrestrially derived n-alkanes extracted from Eocene sediments, and model calculations, shows that the model not only captures the main features, but reproduces isotopic values quantitatively as well. This combination of modeling outcomes and independent stable isotope records thus confirms independently the validity of the earlier, proxy-based, inferred reduced meridional temperature gradient.

Oxygen isotope constraints on the alteration temperatures of CM chondrites

NASA Astrophysics Data System (ADS)

Verdier-Paoletti, Maximilien J.; Marrocchi, Yves; Avice, Guillaume; Roskosz, Mathieu; Gurenko, Andrey; Gounelle, Matthieu

2017-01-01

We report a systematic oxygen isotopic survey of Ca-carbonates in nine different CM chondrites characterized by different degrees of alteration, from the least altered known to date (Paris, 2.7-2.8) to the most altered (ALH 88045, CM1). Our data define a continuous trend that crosses the Terrestrial Fractionation Line (TFL), with a general relationship that is indistinguishable within errors from the trend defined by both matrix phyllosilicates and bulk O-isotopic compositions of CM chondrites. This bulk-matrix-carbonate (BMC) trend does not correspond to a mass-dependent fractionation (i.e., slope 0.52) as it would be expected during fluid circulation along a temperature gradient. It is instead a direct proxy of the degree of O-isotopic equilibration between 17,18O-rich fluids and 16O-rich anhydrous minerals. Our O-isotopic survey revealed that, for a given CM, no carbonate is in O-isotopic equilibrium with its respective surrounding matrix. This precludes direct calculation of the temperature of carbonate precipitation. However, the O-isotopic compositions of alteration water in different CMs (inferred from isotopic mass-balance calculation and direct measurements) define another trend (CMW for CM Water), parallel to BMC but with a different intercept. The distance between the BMC and CMW trends is directly related to the temperature of CM alteration and corresponds to average carbonates and serpentine formation temperatures of 110 °C and 75 °C, respectively. However, carbonate O-isotopic variations around the BMC trend indicate that they formed at various temperatures ranging between 50 and 300 °C, with 50% of the carbonates studied here showing precipitation temperature higher than 100 °C. The average Δ17O and the average carbonate precipitation temperature per chondrite are correlated, revealing that all CMs underwent similar maximum temperature peaks, but that altered CMs experienced protracted carbonate precipitation event(s) at lower temperatures than the least altered CMs. Our data suggest that the Δ17O value of Ca-carbonates could be a reliable proxy of the degree of alteration experienced by CM chondrites.

Reconstruction of the Nd isotope composition of seawater on epicontinental seas: Testing the potential of Fe-Mn oxyhydroxide coatings on foraminifera tests for deep-time investigations

NASA Astrophysics Data System (ADS)

Charbonnier, Guillaume; Pucéat, Emmanuelle; Bayon, Germain; Desmares, Delphine; Dera, Guillaume; Durlet, Christophe; Deconinck, Jean-François; Amédro, Francis; Gourlan, Alexandra T.; Pellenard, Pierre; Bomou, Brahimsamba

2012-12-01

The Fe-Mn oxide fraction leached from deep-sea sediments has been increasingly used to reconstruct the Nd isotope composition of deep water masses, that can be used to track changes in oceanic circulation with a high temporal resolution. Application of this archive to reconstruct the Nd isotope composition of bottom seawater in shallow shelf environments remained however to be tested. Yet as the Nd isotope composition of seawater on continental margins is particularly sensitive to changes in erosional inputs, establishment of neritic seawater Nd isotope evolution around areas of deep water formation would be useful to discriminate the influence of changes in oceanic circulation and in isotopic composition of erosional inputs on the Nd isotope record of deep waters. The purpose of this study is to test the potential of Fe-Mn coatings leached from foraminifera tests to reconstruct the Nd isotope composition of seawater in shelf environments for deep-time intervals. Albian to Turonian samples from two different outcrops have been recovered, from the Paris Basin (Wissant section, northern France) and from the Western Interior Seaway (Hot Spring, South Dakota, USA), that were deposited in epicontinental seas. Rare Earth Element (REE) spectra enriched in middle REEs in the foraminifera leach at Wissant highlight the presence of Fe-Mn oxides. The similarity of the Nd isotopic signal of the Fe-Mn oxide fraction leached from foraminifera tests with that of fish teeth suggests that Fe-Mn oxides coating foraminifera can be good archives of shelf bottom seawater Nd isotopic composition. Inferred bottom shelf water Nd isotope compositions at Wissant range from -8.5 to -9.7 ɛ-units, about 1.5-2 ɛ-units higher than that of the contemporaneous local detrital fraction. At Hot Spring, linear REE spectra characterizing foraminifera leach may point to an absence of authigenic marine Fe-Mn oxide formation in this area during the Late Cenomanian-Early Turonian, consistent with dysoxic to anoxic conditions at Hot Spring, contemporaneous to an Oceanic Anoxic Event. The similarity of the Nd isotopic signal of the carbonate matrix of foraminifera with that of fish teeth suggests that it records the Nd isotope composition of bottom shelf seawater as well. Inferred bottom shelf water Nd isotope compositions at Hot Spring are quite radiogenic, between -7 and -6 ɛ-units, about 2.5-4 ɛ-units higher than that of the contemporaneous local detrital fraction. In contrast, in both sections Fe-Mn oxides leached directly from the decarbonated sediment tend to yield a less radiogenic Nd isotopic composition, typically between 0.2 and 0.8 ɛ-units lower, that is intermediate between that of fish teeth and of the detrital fraction. This suggests the contribution of pre-formed continental Fe-Mn oxides to the Nd isotopic signal, along with authigenic marine oxides, or a detrital contamination during leaching.

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

NASA Astrophysics Data System (ADS)

Nielson, Kristine E.; Bowen, Gabriel J.

2010-03-01

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

Isotopologue Distributions of Peptide Product Ions by Tandem Mass Spectrometry: Quantitation of Low Levels of Deuterium Incorporation1

PubMed Central

Wang, Benlian; Sun, Gang; Anderson, David R.; Jia, Minghong; Previs, Stephen; Anderson, Vernon E.

2007-01-01

Protonated molecular peptide ions and their product ions generated by tandem mass spectrometry appear as isotopologue clusters due to the natural isotopic variations of carbon, hydrogen, nitrogen, oxygen and sulfur. Quantitation of the isotopic composition of peptides can be employed in experiments involving isotope effects, isotope exchange, isotopic labeling by chemical reactions, and studies of metabolism by stable isotope incorporation. Both ion trap and quadrupole-time of flight mass spectrometry are shown to be capable of determining the isotopic composition of peptide product ions obtained by tandem mass spectrometry with both precision and accuracy. Tandem mass spectra obtained in profile-mode of clusters of isotopologue ions are fit by non-linear least squares to a series of Gaussian peaks (described in the accompanying manuscript) which quantify the Mn/M0 values which define the isotopologue distribution (ID). To determine the isotopic composition of product ions from their ID, a new algorithm that predicts the Mn/M0 ratios is developed which obviates the need to determine the intensity of all of the ions of an ID. Consequently a precise and accurate determination of the isotopic composition a product ion may be obtained from only the initial values of the ID, however the entire isotopologue cluster must be isolated prior to fragmentation. Following optimization of the molecular ion isolation width, fragmentation energy and detector sensitivity, the presence of isotopic excess (2H, 13C, 15N, 18O) is readily determined within 1%. The ability to determine the isotopic composition of sequential product ions permits the isotopic composition of individual amino acid residues in the precursor ion to be determined. PMID:17559791

Nucleosynthetic Heterogeneity Controls Vanadium Isotope Variations in Bulk Chondrites

NASA Technical Reports Server (NTRS)

Nielsen, S. G.; Righter, K.; Wu, F.; Owens, J. D.; Prytulak, J.; Burton, K.; Parkinson, I.; Davis, D.

2018-01-01

The vanadium (V) isotope composition of early solar system materials have been hypothesized to be sensitive to high energy irradiation that originated from the young Sun. Vanadium has two isotopes with masses 50 and 51 that have (51)V/(50)V ratio of approximately 410. High energy irradiation produces (50)V from various target isotopes of Ti, Cr and Fe, which would result in light V isotope compositions (expressed as delta (51)V in per mille = 1000 x (((51)V/(50)V(sub sample)/(51)V/(50)V(sub AlfaAesar)) - 1)) relative to a presumably chondritic starting composition. Recently published V isotope data for calcium aluminium inclusions (CAIs) has revealed some very negative values relative to chondrites (by almost -4 per mille) that were indeed interpreted to reflect irradiation processes despite the fact that the studied CAIs all exhibited significant initial abundances of (10)Be, while only a few CAIs displayed light V isotope compositions. It is difficult to relate V isotope variations directly to a singular process because V only possesses two isotopes. Therefore, V isotope variations can principally be produced both mass dependent and independent processes. Mass dependent kinetic stable isotope fractionation is common in CAIs for refractory elements due to partial condensation/evaporation processes. The element strontium (Sr) has an almost identical condensation temperature to V and studies of stable Sr isotope compositions in CAIs reveal both heavy and light values relative to chondrites of several permil. These variations are similar in magnitude to those reported for V isotopes in CAIs, which suggests it is possible that some of the V isotope variation in CAIs could be due to kinetic stable isotope fractionation during condensation/evaporation processes.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile - Marine sources and diagenetic effects.

PubMed

Lucassen, Friedrich; Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very heavy values generate a compositionally unique material. These compositions trace the presence of guano in natural ecosystems and its use as fertilizer in present and past agriculture.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile – Marine sources and diagenetic effects

PubMed Central

Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A.

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very heavy values generate a compositionally unique material. These compositions trace the presence of guano in natural ecosystems and its use as fertilizer in present and past agriculture. PMID:28594902

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.

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

Isotopic composition of atmospheric moisture from pan water evaporation measurements.

PubMed

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

2015-01-01

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

Stable Isotope Systematics in Grasshopper Assemblages Along an Elevation Gradient, Colorado

NASA Astrophysics Data System (ADS)

Kohn, M. J.; Evans, S.; Dean, J.; Nufio, C.

2012-12-01

Insects comprise over three quarters of all animal species, yet studies of body water isotopic composition are limited to only the cockroach, the hoverfly, and chironomid flies. These studies suggest that oxygen and hydrogen isotopic compositions in body water are primarily controlled by dietary water sources, with modification from respiratory and metabolic processes. In particular, outward diffusion of isotopically depleted water vapor through insect spiracles at low humidity enriches residual body water in 18O and 2H (D). Stable isotope compositions (δ18O and δD) also respond to gradients in elevation and humidity, but these influences remain poorly understood. In this study, we measured grasshopper body water and local vegetation isotopic compositions along an elevation gradient in Colorado to evaluate three hypotheses: 1) Insect body water isotopic composition is directly related to food source water composition 2) Water vapor transport alters body water isotopic compositions relative to original diet sources, and 3) Elevation gradients influence isotopic compositions in insect body water. Thirty-five species of grasshopper were collected from 14 locations in Colorado grasslands, ranging in elevation from 450 to 800 meters (n=131). Body water was distilled from previously frozen grasshopper specimens using a vacuum extraction line, furnaces (90 °C), and liquid nitrogen traps. Water samples were then analyzed for δ18O and δD on an LGR Liquid Water Isotope Analyzer, housed in the Department of Geosciences, Boise State University. Grasshopper body water isotopic compositions show wide variation, with values ranging between -76.64‰ to +42.82‰ in δD and -3.06‰ to +26.78‰ in δ18O. Precipitation δ18O values over the entire Earth excluding the poles vary by approximately 30‰, comparable to the total range measured in our single study area. Most grasshopper values deviate from the global meteoric water line relating δ18O and δD in precipitation, consistent with evaporative enrichment in food (plants) due to plant transpiration. However, grasshopper body water from any given location is further enriched in 18O and D relative to food. Isotopic values decrease slightly with increasing elevation, but some specific grasshopper species appear more sensitive to elevation. Overall, evaporative enrichment of 18O and D in this relatively dry environment appears the strongest factors influencing grasshopper compositions.

The isotopic imprint of fixed nitrogen elimination in the redox transition zone of Lake Lugano, Switzerland

NASA Astrophysics Data System (ADS)

Wenk, Christine; Blees, Jan; Niemann, Helge; Zopfi, Jakob; Schubert, Carsten J.; Veronesi, Mauro; Simona, Marco; Koba, Keisuke; Lehmann, Moritz F.

2010-05-01

Nitrogen (N) loading in lakes from natural and anthropogenic sources is partially mitigated by microbially mediated processes that take place in redox transition zones (RTZ) in the water column and in sediments. However, the role of lakes as a terrestrial sink of fixed N is still poorly constrained. Furthermore, modes of suboxic N2 (and N2O) production other than canonical denitrification (e.g. anaerobic ammonium oxidation, or anammox) have barely been investigated in lakes, and the microbial communities involved in N transformations in lacustrine RTZ are mostly unknown. The isotopic composition of dissolved nitrogen species can serve as a reliable indicator of N-transformations in aquatic environments. However, the successful application of N (and O) isotope measurements in natural systems requires a solid understanding of the various N-transformation-specific isotope effects. The deep, south-alpine Lake Lugano, with a permanent chemocline in its North Basin, is an excellent model system for a biogeochemically dynamic lake, in which to study N isotope ratio variations associated with fixed N elimination and regeneration processes. We present the first comprehensive dataset of hydrochemical parameters (including N2/Ar and dissolved N2O concentrations), natural abundance stable isotope ratios of dissolved inorganic nitrogen (DIN) compounds (nitrate, nitrite, ammonium, dinitrogen, nitrous oxide), and the isotopomeric composition of water column N2O for the North Basin of Lake Lugano. Isotopic data will be integrated with molecular microbiological phylogenetic analyses and results from incubation experiments with 15N-labeled N-substrates. Strong gradients in DIN concentrations, as well as in the N and O isotope (and isotopomeric) compositions of nitrate and N2O towards the redox-transition zone indicate nitrate reduction, occurring with a high community N-fractionation. The site preference of N2O isotopomers above the chemocline indicates that the N2O is not only produced by denitrification. Furthermore, the ratio of nitrate N versus O isotope enrichment is 0.6, significantly lower than the ratio expected for sole water column denitrification. Ammonium concentrations in the hypolimnion constantly decrease to 0µM at about 20m below the oxycline, suggesting that anammox, the anaerobic oxidation of ammonium, takes place below the RTZ. First results from 16S rDNA analysis confirmed the presence of anammox bacteria (Candidatus ‘Kuenenia') in the water column. Further phylogenetic and isotope-labeling experiments will provide more information on the spatial and seasonal distribution of anammox bacteria in the water column, on the quantitative partitioning between the candidate N elimination processes, and thus likely on the N isotope fractionation of single N transformation pathways.

Palaeotemperature estimation in the Holsteinian Interglacial (MIS 11) based on oxygen isotopes of aquatic gastropods from eastern Poland

NASA Astrophysics Data System (ADS)

Szymanek, Marcin

2017-12-01

For quantitative estimation of past water temperature of four Holsteinian (MIS 11) palaeolakes from eastern Poland, the oxygen isotope palaeothermometer was applied to shells of the aquatic gastropods Viviparus diluvianus and Valvata piscinalis. The δ18O composition of their shells demonstrated the average growth-season water temperatures during the mesocratic stage of the interglacial (Ortel Królewski Lake), during its climatic optimum - the Carpinus-Abies Zone (Ossówka-Hrud, Roskosz and Szymanowo Lakes), and in the post-optimum (Szymanowo Lake). The calculation was based on δ18OShell values and the δ18OWater assumed for the Holsteinian from the modern oxygen isotope composition of precipitation and the expected amount of evaporative enrichment. The mean oxygen isotope palaeotemperatures of Ortel Królewski lake waters were in the range of 18.1-21.9°C and were uniform for the Taxus and Pinus-Larix zones. Ossówka-Hrud and Roskosz Lakes had mean temperatures of 17.4-21.0°C during the climatic optimum, whereas the temperature of Szymanowo lake waters was estimated at 20.6-21.7°C at that time. These values are concordant with the pollen-inferred July air temperatures noted during the Holsteinian in eastern Poland. Relatively high values of 25°C in the post-optimum noted at Szymanowo were connected with the presence of a shallow and warm isolated bay indicated by pollen and mollusc records.

Effects of climate change on nutrition and genetics of White-tailed Ptarmigan

USGS Publications Warehouse

Oyler-McCance, Sara J.; Stricker, Craig A.; St. John, Judy; Braun, Clait E.; Wann, Gregory T.; Aldridge, Cameron L.; Sandercock, Brett K.; Martin, Kathy; Segelbacher, Gernot

2011-01-01

White-tailed Ptarmigan (Lagopus leucura) are well suited as a focal species for the study of climate change because they are adapted to cool, alpine environments that are expected to undergo unusually rapid climate change. We compared samples collected in the late 1930s, the late 1960s, and the late 2000s using molecular genetic and stable isotope methods in an effort to determine whether White-tailed Ptarmigan on Mt. Evans, Colorado, have experiences recent environmental changes resulting in shifts in genetic diversity, gene frequency, and nutritional ecology. We genotyped 115 individuals spanning the three time periods, using nine polymorphic microsatellite loci in our genetic analysis. These samples were also analyzed for stable carbon and nitrogen isotopic composition. We found a slight trend of lower heterozygosity through time, and allelic richness values were significantly lower in more recent times, but not significantly using an alpha of 0.05 (P 13C and δ15N values decreased significantly across time periods, whereas the range in isotope values increased consistently from the late 1930s to the late time periods. Inferred changes in the nutritional ecology of White-tailed Ptarmigan on Mt. Evans relate primarily to increased atmospheric deposition of nutrients that likely influenced foraging habits and tundra plant composition and nutritional quality. Future work seeks to integrate genetic and isotopic data with long-term demographics to develop a detailed understanding of the interaction among environmental stressors on the long-term viability of ptarmigan populations.

Nitrogen Isotope Evidence for a Shift in Eastern Beringian Nitrogen Cycle after the Terminal Pleistocene

NASA Astrophysics Data System (ADS)

Tahmasebi, F.; Longstaffe, F. J.; Zazula, G.

2016-12-01

The loess deposits of eastern Beringia, a region in North America between 60° and 70°N latitude and bounded by Chukchi Sea to the west and the Mackenzie River to the east, are a magnificent repository of Late Pleistocene megafauna fossils. The stable carbon and nitrogen isotope compositions of these fossils are measured to determine the paleodiet of these animals, and hence the paleoenvironment of this ecosystem during the Quaternary. For this approach to be most successful, however, requires consideration of possible changes in nutrient cycling and hence the carbon and nitrogen isotopic compositions of vegetation in this ecosystem. To test for such a shift following the terminal Pleistocene, we analyzed the stable carbon and nitrogen isotope compositions of modern plants and bone collagen of Arctic ground squirrels from Yukon Territory, and fossil plants and bones recovered from Late Pleistocene fossil Arctic ground squirrel nests. The data for modern samples provided a measure of the isotopic fractionation between ground squirrel bone collagen and their diet. The over-wintering isotopic effect of decay on typical forage grasses was also measured to evaluate its role in determining fossil plant isotopic compositions. The grasses showed only a minor change ( 0-1 ‰) in carbon isotope composition, but a major change ( 2-10 ‰) in nitrogen isotope composition over the 317-day experiment. Based on the modern carbon isotope fractionation between ground squirrel bone collagen and their diet, the modern vegetation carbon isotopic baseline provides a suitable proxy for the Late Pleistocene of eastern Beringia, after accounting for the Suess effect. However, the predicted nitrogen isotope composition of vegetation comprising the diet of fossil ground squirrels remains 2.5 ‰ higher than modern grasslands in this area, even after accounting for possible N-15 enrichment during decay. This result suggests a change in N cycling in this region since the Late Pleistocene.

Thallium isotope composition of the upper continental crust and rivers - An investigation of the continental sources of dissolved marine thallium

USGS Publications Warehouse

Nielsen, S.G.; Rehkamper, M.; Porcelli, D.; Andersson, P.; Halliday, A.N.; Swarzenski, P.W.; Latkoczy, C.; Gunther, D.

2005-01-01

The thallium (Tl) concentrations and isotope compositions of various river and estuarine waters, suspended riverine particulates and loess have been determined. These data are used to evaluate whether weathering reactions are associated with significant Tl isotope fractionation and to estimate the average Tl isotope composition of the upper continental crust as well as the mean Tl concentration and isotope composition of river water. Such parameters provide key constraints on the dissolved Tl fluxes to the oceans from rivers and mineral aerosols. The Tl isotope data for loess and suspended riverine detritus are relatively uniform with a mean of ??205Tl = -2.0 ?? 0.3 (??205Tl represents the deviation of the 205Tl/203Tl isotope ratio of a sample from NIST SRM 997 Tl in parts per 104). For waters from four major and eight smaller rivers, the majority were found to have Tl concentrations between 1 and 7 ng/kg. Most have Tl isotope compositions very similar (within ??1.5 ??205Tl) to that deduced for the upper continental crust, which indicates that no significant Tl isotope fractionation occurs during weathering. Based on these results, it is estimated that rivers have a mean natural Tl concentration and isotope composition of 6 ?? 4 ng/kg and ??205Tl = -2.5 ?? 1.0, respectively. In the Amazon estuary, both additions and losses of Tl were observed, and these correlate with variations in Fe and Mn contents. The changes in Tl concentrations have much lower amplitudes, however, and are not associated with significant Tl isotope effects. In the Kalix estuary, the Tl concentrations and isotope compositions can be explained by two-component mixing between river water and a high-salinity end member that is enriched in Tl relative to seawater. These results indicate that Tl can display variable behavior in estuarine systems but large additions and losses of Tl were not observed in the present study. Copyright ?? 2005 Elsevier Ltd.

Deciphering the iron isotope message of the human body

NASA Astrophysics Data System (ADS)

Walczyk, Thomas; von Blanckenburg, Friedhelm

2005-04-01

Mass-dependent variations in isotopic composition are known since decades for the light elements such as hydrogen, carbon or oxygen. Multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) and double-spike thermal ionization mass spectrometry (TIMS) permit us now to resolve small variations in isotopic composition even for the heavier elements such as iron. Recent studies on the iron isotopic composition of human blood and dietary iron sources have shown that lighter iron isotopes are enriched along the food chain and that each individual bears a certain iron isotopic signature in blood. To make use of this finding in biomedical research, underlying mechanisms of isotope fractionation by the human body need to be understood. In this paper available iron isotope data for biological samples are discussed within the context of isotope fractionation concepts and fundamental aspects of human iron metabolism. This includes evaluation of new data for body tissues which show that blood and muscle tissue have a similar iron isotopic composition while heavier iron isotopes are concentrated in the liver. This new observation is in agreement with our earlier hypothesis of a preferential absorption of lighter iron isotopes by the human body. Possible mechanisms for inducing an iron isotope effect at the cellular and molecular level during iron uptake are presented and the potential of iron isotope effects in human blood as a long-term measure of dietary iron absorption is discussed.

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

NASA Astrophysics Data System (ADS)

Trayler, Robin B.; Kohn, Matthew J.

2017-02-01

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

Lead isotope compositions of Late Cretaceous and early Tertiary igneous rocks and sulfide minerals in Arizona: Implications for the sources of plutons and metals in porphyry copper deposits

USGS Publications Warehouse

Bouse, R.M.; Ruiz, J.; Titley, S.R.; Tosdal, R.M.; Wooden, J.L.

1999-01-01

Porphyry copper deposits in Arizona are genetically associated with Late Cretaceous and early Tertiary igneous complexes that consist of older intermediate volcanic rocks and younger intermediate to felsic intrusions. The igneous complexes and their associated porphyry copper deposits were emplaced into an Early Proterozoic basement characterized by different rocks, geologic histories, and isotopic compositions. Lead isotope compositions of the Proterozoic basement rocks define, from northwest to southeast, the Mojave, central Arizona, and southeastern Arizona provinces. Porphyry copper deposits are present in each Pb isotope province. Lead isotope compositions of Late Cretaceous and early Tertiary plutons, together with those of sulfide minerals in porphyry copper deposits and of Proterozoic country rocks, place important constraints on genesis of the magmatic suites and the porphyry copper deposits themselves. The range of age-corrected Pb isotope compositions of plutons in 12 Late Cretaceous and early Tertiary igneous complexes is 206Pb/204Pb = 17.34 to 22.66, 207Pb/204Pb = 15.43 to 15.96, and 208Pb/204Pb = 37.19 to 40.33. These Pb isotope compositions and calculated model Th/U are similar to those of the Proterozoic rocks in which the plutons were emplaced, thereby indicating that Pb in the younger rocks and ore deposits was inherited from the basement rocks and their sources. No Pb isotope differences distinguish Late Cretaceous and early Tertiary igneous complexes that contain large economic porphyry copper deposits from less rich or smaller deposits that have not been considered economic for mining. Lead isotope compositions of Late Cretaceous and early Tertiary plutons and sulfide minerals from 30 metallic mineral districts, furthermore, require that the southeastern Arizona Pb province be divided into two subprovinces. The northern subprovince has generally lower 206Pb/204Pb and higher model Th/U, and the southern subprovince has higher 206Pb/204Pb and lower model Th/U. These Pb isotope differences are inferred to result from differences in their respective post-1.7 Ga magmatic histories. Throughout Arizona, Pb isotope compositions of Late Cretaceous and early Tertiary plutons and associated sulfide minerals are distinct from those of Jurassic plutons and also middle Tertiary igneous rocks and sulfide minerals. These differences most likely reflect changes in tectonic setting and magmatic sources. Within Late Cretaceous and early Tertiary igneous complexes that host economic porphyry copper deposits, there is commonly a decrease in Pb isotope composition from older to younger plutons. This decrease in Pb isotope values with time suggests an increasing involvement of crust with lower U/Pb than average crust in the source(s) of Late Cretaceous and early Tertiary magmas. Lead isotope compositions of the youngest porphyries in the igneous complexes are similar to those in most sulfide minerals within the associated porphyry copper deposit. This Pb isotope similarity argues for a genetic link between them. However, not all Pb in the sulfide minerals in porphyry copper deposits is magmatically derived. Some sulfide minerals, particularly those that are late stage, or distal to the main orebody, or in Proterozoic or Paleozoic rocks, have elevated Pb isotope compositions displaced toward the gross average Pb isotope composition of the local country rocks. The more radiogenic isotopic compositions argue for a contribution of Pb from those rocks at the site of ore deposition. Combining the Pb isotope data with available geochemical, isotopic, and petrologic data suggests derivation of the young porphyry copper-related plutons, most of their Pb, and other metals from a hybridized lower continental crustal source. Because of the likely involvement of subduction-related mantle-derived basaltic magma in the hybridized lower crustal source, an indiscernible mantle contribution is probable in the porphyry magmas. Clearly, in addition

Isotopic Compositions of the Elements, 2001

NASA Astrophysics Data System (ADS)

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

2005-03-01

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

Phantom Archean crust in Mangaia hotspot lavas and the meaning of heterogeneous mantle

NASA Astrophysics Data System (ADS)

Herzberg, C.; Cabral, R. A.; Jackson, M. G.; Vidito, C.; Day, J. M. D.; Hauri, E. H.

2014-06-01

Lavas from Mangaia in the Cook-Austral island chain, Polynesia, define an HIMU (or high μ, where μ=U238/Pb204) global isotopic end-member among ocean island basalts (OIB) with the highest 206,207,208Pb/204Pb. This geochemical signature is interpreted to reflect a recycled oceanic crust component in the mantle source. Mass independently fractionated (MIF) sulfur isotopes indicate that Mangaia lavas sampled recycled Archean material that was once at the Earth's surface, likely hydrothermally-modified oceanic crust. Recent models have proposed that crust that is subducted and then returned to the surface in a mantle plume is expected to transform to pyroxenite/eclogite during transit through the mantle. Here we examine this hypothesis for Mangaia using high-precision electron microprobe analysis on olivine phenocrysts. Contrary to expectations of a crustal component and, hence pyroxenite, results show a mixed peridotite and pyroxenite source, with peridotite dominating. If the isotopic compositions were inherited from subduction of recycled oceanic crust, our work shows that this source has phantom-like properties in that it can have its lithological identity destroyed while its isotope ratios are preserved. This may occur by partial melting of the pyroxenite and injection of its silicic melts into the surrounding mantle peridotite, yielding a refertilized peridotite. Evidence from one sample reveals that not all pyroxenite in the melting region was destroyed. Identification of source lithology using olivine phenocryst chemistry can be further compromised by magma chamber fractional crystallization, recharge, and mixing. We conclude that the commonly used terms mantle “heterogeneities” and “streaks” are ambiguous, and distinction should be made of its lithological and isotopic properties.

Utility of stable isotope analysis in studying foraging ecology of herbivores: Examples from moose and caribou

USGS Publications Warehouse

Ben-David, Merav; Shochat, Einav; Adams, Layne G.

2001-01-01

Recently, researchers emphasized that patterns of stable isotope ratios observed at the individual level are a result of an interaction between ecological, physiological, and biochemical processes. Isotopic models for herbivores provide additional complications because those mammals consume foods that have high variability in nitrogen concentrations. In addition, distribution of amino acids in plants may differ greatly from that required by a herbivore. At northern latitudes, where the growing season of vegetation is short, isotope ratios in herbivore tissues are expected to differ between seasons. Summer ratios likely reflect diet composition, whereas winter ratios would reflect diet and nutrient recycling by the animals. We tested this hypothesis using data collected from blood samples of caribou (Rangifer tarandus) and moose (Alces alces) in Denali National Park and Preserve, Alaska, USA. Stable isotope ratios of moose and caribou were significantly different from each other in late summer-autumn and winter. Also, late summer-autumn and winter ratios differed significantly between seasons in both species. Nonetheless, we were unable to evaluate whether differences in seasonal isotopic ratios were a result of diet selection or a response to nutrient recycling. We believe that additional studies on plant isotopic ratios as related to ecological factors in conjunction with investigations of diet selection by the herbivores will enhance our understanding of those interactions. Also, controlled studies investigating the relation between diet and physiological responses in herbivores will increase the utility of isotopic analysis in studying foraging ecology of herbivores.

New Hafnium Isotope and Trace Element Constraints on the Role of a Plume in Genesis of the Eastern Snake River Plain Basalts, Idaho

NASA Astrophysics Data System (ADS)

Taylor, R. D.; Reid, M. R.; Blichert-Toft, J.

2009-12-01

Bimodal volcanism associated with the eastern Snake River Plain (ESRP)-Yellowstone Plateau province has persisted since approximately 16 Ma. A time-transgressive track of rhyolitic eruptions which young progressively to the east and parallel the motion of the North American plate are overlain by younger basalts with no age progression. Interpretations for the origin of these basalts range from a thermo-chemical mantle plume to incipient melting of the shallow upper mantle, and remain controversial. The enigmatic ESRP basalts are characterized by high 3He/4He, diagnostic of a plume source, but also by lithophile radiogenic isotope signatures that are more enriched than expected for plume-derived OIBs. These features could possibly be caused by isotopic decoupling associated with shallow melting of a hybridized upper mantle, or derivation from an atypical mantle plume, or both by way of mixing. New Hf isotope and trace element data further constrain potential sources for the ESRP basalts. Their Hf isotopic signatures (ɛHf = +0.1 to -5.8) are moderately enriched and consistently fall above or in the upper part of the field of OIBs, with similar Nd isotope signatures (ɛNd = -2.0 to -5.8), indicating a source with high time-integrated Lu/Hf compared with Sm/Nd. The isotopic compositions of the basalts lie between those of Archean SCML and a more depleted end-member source, suggestive of contributions from at least two sources. The grouping of isotopic characteristics is compact compared to other regional volcanism, implying that the hybridization process is highly reproducible within the ESRP. Minor localized differences in isotopic composition may signify local variations in the relative proportions of the end-members. Trace element patterns also support genesis of the ESRP basalts from an enriched source. Our data detect evidence of deeper contributions derived from the garnet-stability field, and a greater affinity of the trace element signatures to plume sources than to sources in the mantle lithosphere. The Hf isotope and trace element characteristics of the ESRP basalts thus support a model of derivation from a deep mantle plume with additional melt contributions and isotopic overprinting from SCML.

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

NASA Astrophysics Data System (ADS)

Watkins, James M.; DePaolo, Donald J.; Ryerson, Frederick J.; Peterson, Brook T.

2011-06-01

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl 2Si 2O 8; denoted AN), albite (NaAlSi 3O 8; denoted AB), and diopside (CaMgSi 2O 6; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D Ca/ D Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D Ca/ D Si ≈ 1. In the AB-DI experiment, D Ca/ D Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D Mg/ D Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids. The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation ( D Ca) to the diffusivity of silicon ( D Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D cation/ D Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and Dcation/D, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.

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

Treesearch

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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.

Influences on the stable oxygen and carbon isotopes in gerbillid rodent teeth in semi-arid and arid environments: Implications for past climate and environmental reconstruction

NASA Astrophysics Data System (ADS)

Jeffrey, Amy; Denys, Christiane; Stoetzel, Emmanuelle; Lee-Thorp, Julia A.

2015-10-01

The stable isotope composition of small mammal tissues has the potential to provide detailed information about terrestrial palaeoclimate and environments, because their remains are abundant in palaeontological and archaeological sites, and they have restricted home ranges. Applications to the Quaternary record, however, have been sparse and limited by an acute lack of understanding of small mammal isotope ecology, particularly in arid and semi-arid environments. Here we document the oxygen and carbon isotope composition of Gerbillinae (gerbil) tooth apatite across a rainfall gradient in northwestern Africa, in order to test the relative influences of the 18O/16O in precipitation or moisture availability on gerbil teeth values, the sensitivity of tooth apatite 13C/12C to plant responses to moisture availability, and the influence of developmental period on the isotopic composition of gerbil molars and incisors. The results show that the isotopic composition of molars and incisors from the same individuals differs consistent with the different temporal periods reflected by the teeth; molar teeth are permanently rooted and form around the time of birth, whereas incisors grow continuously. The results indicate that tooth choice is an important consideration for applications as proxy Quaternary records, but also highlights a new potential means to distinguish seasonal contexts. The oxygen isotope composition of gerbil tooth apatite is strongly correlated with mean annual precipitation (MAP) below 600 mm, but above 600 mm the teeth reflect the oxygen isotope composition of local meteoric water instead. Predictably, the carbon isotope composition of the gerbil teeth reflected C3 and C4 dietary inputs, however arid and mesic sites could not be distinguished because of the high variability displayed in the carbon isotope composition of the teeth due to the microhabitat and short temporal period reflected by the gerbil. We show that the oxygen isotope composition of small mammal teeth strongly reflects moisture availability in semi-arid and arid environments and would provide an excellent record of palaeo-aridity in a terrestrial setting. The results illustrate that an understanding of an animal's physiology is essential for interpreting the animal's isotopic responses to external contexts, especially in arid zones.

Stable lead isotopic analyses of historic and contemporary lead contamination of San Francisco Bay estuary

USGS Publications Warehouse

Ritson, P.I.; Bouse, R.M.; Flegal, A.R.; Luoma, S.N.

1999-01-01

Variations in stable lead isotopic composition (240Pb, 206Pb, 207Pb, 208Pb) in three sediment cores from the San Francisco Bay estuary document temporal changes in sources of lead during the past two centuries. Sediment, with lead from natural geologic sources, and relatively homogeneous lead isotopic compositions are overlain by sediments whose isotopic compositions indicate change in the sources of lead associated with anthropogenic modification of the estuary. The first perturbations of lead isotopic composition in the cores occur in the late 1800s concordant with the beginning of industrialization around the estuary. Large isotopic shifts, toward lower 206Pb/207Pb, occur after the turn of the century in both Richardson and San Pablo Bays. A similar relationship among lead isotopic compositions and lead concentrations in both Bays suggest contamination from the same source (a lead smelter). The uppermost sediments (post 1980) of all cores also have a relatively homogenous lead isotopic composition distinct from pre-anthropogenic and recent aerosol signatures. Lead isotopic compositions of leachates from fourteen surface sediments and five marsh samples from the estuary were also analyzed. These analyses suggest that the lead isotopic signature identified in the upper horizons of the cores is spatially homogeneous among recently deposited sediments throughout the estuary. Current aerosol lead isotopic compositions [Smith, D.R., Niemeyer, S., Flegal, A.R., 1992. Lead sources to California sea otters: industrial inputs circumvent natural lead biodepletion mechanisms. Environmental Research 57, 163-175] are distinct from the isotopic compositions of the surface sediments, suggesting that the major source of lead is cycling of historically contaminated sediments back through the water column. Both the upper core sediments and surface sediments apparently derive their lead predominantly from sources internal to the estuary. These results support the idea that geochemical cycling of lead between sediments and water accounts for persistently elevated lead concentrations in the water column despite 10-fold reduction of external source inputs to San Francisco Bay [Flegal, A.R., Rivera-Duarte, I., Ritson, P.I., Scelfo, G., Smith, G.J., Gordon, M., Sanudo-Wilhelmy, S.A., 1996. Metal contamination in San Francisco Waters: historic perturbations, contemporary concentrations, and future considerations in San Francisco Bay. In: Hollobaugh, J.T. (Ed.), The Ecosystem. AAAS, pp. 173-188].

Isotopic compositions of the elements, 2001

USGS Publications Warehouse

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

2005-01-01

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

Calcium Isotopic Compositions of Forearc Sediments from DSDP Site 144

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2004-05-01

Recent developments in MC-ICP-MS technology allow high precision measurements of heavy stable isotopes, such as Cu and Zn isotopes, which have been shown to undergo biotic or abiotic fractionation (1). Application of Zn isotopes to the study of aquatic ecosystems has already shown some interesting perspectives in their potential use as biogeochemical tracers in deep ocean carbonates (2) or Fe-Mn nodules (3). However, until now no investigation of possible Cu and Zn isotopic fractionation has been carried out within estuaries that are important pathways for hydrological and geochemical cycling of metals. Cu and Zn isotope geochemistry has been studied in sandy to loamy surface sediments (top 20 cm) and in suspended particulate matter (SPM) along a transect in a strong tidal estuary, the Scheldt estuary situated in Belgium and the Netherlands (November 2002). Further to separation of Cu, Fe and Zn by one step ion-exchange chromatography, Cu and Zn isotopic ratios are measured with a "Nu-Plasma" MC-ICP-MS. Instrumental mass bias is corrected using reference materials (Zn JMC, Cu NIST SRM 976 and Ga JMC standard) by simultaneous standard-sample bracketing and external normalization (500 ppb Zn doping for Cu isotopic analyses in static mode and 250 ppb Ga doping for Zn isotopic analyses in dynamic mode), together with a Ni correction. These methods lead to long-term reproducibility (2σ at 95 % confidence level) of ± 0.07 per mil for δ 66Zn (n=100 over 7 analysis sessions) and ± 0.06 per mil for δ 65Cu (n=120 over 8 analysis sessions) for 500 ppb of reference material. Average beam intensities are 6 V/ppm. Precise and reproducible results are obtained for concentration as low as 100 ppb for Cu and Zn. Expected Cu and Zn enrichment in SPM (120 ppm and 1200 ppm respectively) and sediments (being 6 to 10 times lower than SPM) in the upper estuary and progressive decrease in metal content by mixing downstream of the maximum turbidity zone (MTZ, around 5 psu) are observed. Results show that variations in Cu and Zn isotopic composition are smaller in SPM (δ 66Zn varying from 0.35 to 0.17 and δ 65Cu from -0.13 to 0.18) than in sediments. Cu and Zn isotopic signatures of sediments show a clear trend of lighter isotopes removal from the MTZ seaward with δ 66Zn varying from 0.21 at 2 psu to 1.11 per mil at 33 psu (and δ 65Cu = -0.37 to 0.24). In contrast, Zn isotopic compositions in SPM are more homogeneous with average δ 66Zn of 0.24 ± 0.18 over all the transect. Cu isotopic composition in SPM are very constant downstream of the MTZ with average δ 65Cu =-0.06 ± 0.08 but become more scattered within MTZ (varying from -0.04 to 0.18). These preliminary results pinpoint important variations in Cu and Zn isotopic compositions within estuarine systems and contrasted isotopic signatures in Cu and Zn between SPM and sediments. Results suggest the important role of early diagenesis in the isotope geochemistry of heavy metals in estuarine environment. This study provides a stepping stone for further investigation of interacting processes involved in controlling the cycling of metals in the Scheldt estuary. (1) Zhu et al., Earth Planet. Sci. Lett. 200 (2002), 47-62 (2) Pichat et al., Earth Planet. Sci. Lett. 6598 (2003), 1-12 (3) Maréchal et al., Geochem. Geophys. Geosyt., 1 (2000), GC000029

Oxygen Isotopic Analyses of Water Extracted from the Martian Meteorite NWA 7034

NASA Astrophysics Data System (ADS)

Nunn, M.; Agee, C. B.; Thiemens, M. H.

2012-12-01

Introduction: The NWA 7034 meteorite has been identified as Martian, but it is distinct from the Shergottite-Nakhlite-Chassignite (SNC) grouping of meteorites in its petrology (it is the only known Martian basaltic breccia) and bulk silicate oxygen isotopic composition (Δ17O = 0.56 ± 0.06 ‰, where Δ17O = δ17O - 0.528 x δ18O, compared to the average SNC Δ17O ≈ 0.3 ‰) [e.g., 1-2]. We report here measurements of the oxygen isotopic composition of water extracted from NWA 7034 by stepwise heating. Methods: A piece (~1.2g) of NWA 7034 was pumped to vacuum until outgassing had stopped before heating to 50, 150, 320, 500, and 1000°C. The sample was maintained at each temperature step for at least one hour while collecting evolved volatiles in a liquid nitrogen cold trap. Water was selectively converted to molecular oxygen, the oxygen isotopic composition of which was then measured on a double collecting isotope ratio mass spectrometer. Results: Our stepwise heating experiments indicate NWA 7034 contains 3330ppm water, and this water has an average oxygen isotopic composition of Δ17O = 0.330 ± 0.011‰. The oxygen isotopic composition of water in NWA 7034 is unlike that of the silicates from which it is extracted (Δ17O = 0.56 ± 0.06 ‰) but is comparable to the average SNC silicate composition (Δ17O ≈ 0.3 ‰). However, there is no consensus on the oxygen isotopic composition of water in SNCs because aliquots of water extracted from different samples (separate pieces of a single meteorite or from different meteorites) have different oxygen isotopic compositions [3]. Furthermore, carbonates and sulfates extracted from SNCs also possess distinct oxygen isotopic compositions [4]. The variation in oxygen isotopic composition among these phases most likely results from the existence of isotopically distinct oxygen reservoirs on Mars that were not equilibrated. On Earth, interaction of ozone (O3) and carbon dioxide (CO2) leads to a mass independent oxygen isotopic composition of atmospheric CO2 [5]. This anomaly is transferred by exchange from CO2 to water and subsequently to secondary minerals. The much larger CO2 to water ratio on Mars could allow this process to introduce a measurable oxygen isotopic anomaly to sulfates, carbonates, and water. The magnitude and variability of this anomaly would depend on the formation mechanism of the species (particularly the source of oxygen), as is consistent with measurements to date of phases in SNCs. References: [1] Franchi, I.A., et al. (1999) MAPS 34, 657-661. [2] Rumble, D. and Irving, A.J. (2009) LPSC XXXX, #2293 [3] Karlsson, H.R., et al. (1992) Science 255, 1409-1411. [4] Farquhar, J. and Thiemens, M.H. (2000) J. Geophys. Res. 105, 11991-11997. [5] Yung, Y.L., et al. (1991) Geophys. Res. Lett. 18, 13-16.

Revealing magma degassing below closed-conduit active volcanoes: Geochemical features of volcanic rocks versus fumarolic fluids at Vulcano (Aeolian Islands, Italy)

NASA Astrophysics Data System (ADS)

Mandarano, Michela; Paonita, Antonio; Martelli, Mauro; Viccaro, Marco; Nicotra, Eugenio; Millar, Ian L.

2016-04-01

The elemental and isotopic compositions of noble gases (He, Ne, and Ar) in olivine- and clinopyroxene-hosted fluid inclusions have been measured for rocks at various degrees of evolution and belonging to high-K calcalkaline-shoshonitic and shoshonitic-potassic series in order to cover the entire volcanological history of Vulcano Island (Italy). The major- and trace-element concentrations and the Sr- and Pb-isotope compositions for whole rocks were integrated with data obtained from the fluid inclusions. 3He/4He in fluid inclusions is within the range of 3.30 and 5.94 R/Ra, being lower than the theoretical value for the deep magmatic source expected for Vulcano Island (6.0-6.2 R/Ra). 3He/4He of the magmatic source is almost constant throughout the volcanic history of Vulcano. Integration of the He- and Sr-isotope systematics leads to the conclusion that a decrease in the He-isotope ratio of the rocks is mainly due to the assimilation of 10-25% of a crustal component similar to the Calabrian basement. 3He/4He shows a negative correlation with Sr isotopes except for the last-erupted Vulcanello latites (Punta del Roveto), which have anomalously high He isotope ratios. This anomaly has been attributed to a flushing process by fluids coming from the deepest reservoirs, since an input of deep magmatic volatiles with high 3He/4He values increases the He-isotope ratio without changing 87Sr/86Sr. A comparison of the He-isotope ratios between fluid inclusions and fumarolic gases shows that only the basalts of La Sommata and the latites of Vulcanello have comparable values. Taking into account that the latites of Vulcanello relate to one of the most-recent eruptions at Vulcano (in the 17th century), we infer that the most probable magma which actually feeds the fumarolic emissions is a latitic body that ponded at about 3-3.5 km of depth and is flushed by fluids coming from a deeper and basic magma.

Revealing the magmas degassing below closed-conduit active volcanoes: noble gases in volcanic rocks versus fumarolic fluids at Vulcano (Aeolian Islands, Italy)

NASA Astrophysics Data System (ADS)

Mandarano, Michela; Paonita, Antonio; Martelli, Mauro; Viccaro, Marco; Nicotra, Eugenio; Millar, Ian L.

2016-04-01

With the aim to constrain the nature of magma currently feeding the fumarolic field of Vulcano, we measured the elemental and isotopic compositions of noble gases (He, Ne, and Ar) in olivine- and clinopyroxene-hosted fluid inclusions in high-K calcalcaline-shoshonitic and shoshonitic-potassic series so as to cover the entire volcanological history of Vulcano Island (Italy). The major and trace-element concentrations and the Sr- and Pb-isotope compositions for whole rocks were integrated with data obtained from the fluid inclusions. 3He/4He in fluid inclusions is within the range of 3.30 and 5.94 R/Ra, being lower than the value for the deep magmatic source expected for Vulcano Island (6.0-6.2 R/Ra). 3He/4He of the magmatic source is almost constant throughout the volcanic record of Vulcano. Integration of the He- and Sr-isotope systematics leads to the conclusion that a decrease in the He-isotope ratio of the rocks is mainly due to the assimilation of 10-25% of a crustal component similar to the Calabrian basement. 3He/4He shows a negative correlation with Sr isotopes except for the last-emitted Vulcanello latites (Punta del Roveto), which have high He- and Sr-isotope ratios. This anomaly has been attributed to a flushing process by fluids coming from the deepest reservoirs. Indeed, an input of deep magmatic volatiles with high 3He/4He values increases the He-isotope ratio without changing 87Sr/86Sr. A comparison of the He isotope ratios between fluid inclusions and fumarolic gases showed that only the basalts of La Sommata and the latites of Vulcanello have comparable values. Taking into account that the latites of Vulcanello relate to one of the most-recent eruptions at Vulcano (in the 17th century), we infer that that the most probable magma which actually feeds the fumarolic emissions is a latitic body ponding at about 3-3.5 km of depth and flushed by fluids coming from a deeper and basic magma.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

[Sources of Methane in the Boreal Region

NASA Technical Reports Server (NTRS)

1998-01-01

In determining the global methane budget the sources of methane must be balanced with the sinks and atmospheric inventory. The approximate contribution of the different methane sources to the budget has been establish showing the major terrestrial inputs as rice, wetlands, bogs, fens, and tundra. Measurements and modeling of production in these sources suggest that temperature, water table height and saturation along with substratum composition are important in controlling methane production and emission. The isotopic budget of 13 C and D/H in methane can be used as a tool to clarify the global budget. This approach has achieved success at constraining the inputs. Studies using the isotopic approach place constraints on global methane production from different sources. Also, the relation between the two biogenic production pathways, acetate fermentation and CO2 reduction, and the effect of substratum composition can be made using isotope measurements shows the relation between the different biogenic, thermogenic and anthropogenic sources of methane as a function of the carbon and hydrogen isotope values for each source and the atmosphere, tropospheric composition. Methane emissions from ponds and fens are a significant source in the methane budget of the boreal region. An initial study in 1993 and 1994 on the isotopic composition of this methane source and the isotopic composition in relation to oxidation of methane at the sediment surface of the ponds or fen was conducted as part of our BOREAS project. The isotopic composition of methane emitted by saturated anoxic sediment is dependent on the sediment composition and geochemistry, but will be influenced by in situ oxidation, in part, a function of rooted plant activity. The influence of oxidation mediated by rooted plant activities on the isotopic composition of methane is not well known and will depend on the plant type, sediment temperature, and numerous other variables. Information on this isotopic composition is important in both understanding the bio-geochemistry of the system and also in determining the regional and global inputs for the methane isotope budget. In determining the destruction of methane for balancing the atmospheric methane budget soil oxidation must be considered.

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

PubMed

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

2017-05-24

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

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

NASA Astrophysics Data System (ADS)

Peto, M. K.; Mukhopadhyay, S.

2012-12-01

Although convection models do not preclude preservation of smaller mantle regions with more pristine composition throughout Earth's history, it has been widely assumed that the moon forming giant impact likely homogenizes the whole mantle following a magma ocean that extended all the way to the bottom of the mantle. Recent findings of tungsten and xenon heterogeneities in the mantle [1,2,3,4], however, imply that i) the moon forming giant impact may not have homogenized the whole mantle and ii) plate tectonics was inefficient in erasing early formed compositional differences, particularly for the xenon isotopes. Therefore, the xenon isotope composition in the present day mantle still preserves a memory of early Earth processes. However, determination of the xenon isotopic composition of the mantle source is still scarce, since the mantle composition is overprinted by post-eruptive atmospheric contamination in basalts erupted at ocean islands and mid ocean ridges. The xenon composition of the depleted upper mantle has been defined by the gas rich sample, 2πD43 (also known as "popping rock"), from the North Atlantic (13° 469`N). However, the composition of a single sample is not likely to define the composition of the upper mantle, especially since popping rock has an "enriched" trace element composition. We will present Ne, Ar and Xe isotope data on MORB glass samples with "normal" helium isotope composition (8±1 Ra) from the Southeast Indian Ridge, the South Atlantic Ridge, the Sojourn Ridge, the Juan de Fuca, the East Pacific Rise, and the Gakkel Ridge. Following the approach of [1], we correct for syn- and post-eruptive atmosphere contamination, and determine the variation of Ar and Xe isotope composition of the "normal" MORB source. We investigate the effect of atmospheric recycling in the variation of MORB mantle 40Ar/36Ar and 129Xe/130Xe ratios, and attempt to constrain the average upper mantle argon and xenon isotopic compositions. [1] Mukhopadhyay, Nature 2012; [2] Tucker et al., EPSL (in review); [3] Moreira et al., Nature 1998 [4] Touboul et al., Science 2012.

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

NASA Astrophysics Data System (ADS)

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

2012-08-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-08-01

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

Isotope effects on the optical spectra of semiconductors

NASA Astrophysics Data System (ADS)

Cardona, Manuel; Thewalt, M. L. W.

2005-10-01

Since the end of the cold war, macroscopic amounts of separated stable isotopes of most elements have been available “off the shelf” at affordable prices. Using these materials, single crystals of many semiconductors have been grown and the dependence of their physical properties on isotopic composition has been investigated. The most conspicuous effects observed have to do with the dependence of phonon frequencies and linewidths on isotopic composition. These affect the electronic properties of solids through the mechanism of electron-phonon interaction, in particular, in the corresponding optical excitation spectra and energy gaps. This review contains a brief introduction to the history, availability, and characterization of stable isotopes, including their many applications in science and technology. It is followed by a concise discussion of the effects of isotopic composition on the vibrational spectra, including the influence of average isotopic masses and isotopic disorder on the phonons. The final sections deal with the effects of electron-phonon interaction on energy gaps, the concomitant effects on the luminescence spectra of free and bound excitons, with particular emphasis on silicon, and the effects of isotopic composition of the host material on the optical transitions between the bound states of hydrogenic impurities.

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

USGS Publications Warehouse

Meier, A.L.

1982-01-01

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

Stable Isotope Anatomy of Tropical Cyclone Ita, North-Eastern Australia, April 2014

PubMed Central

Munksgaard, Niels C.; Zwart, Costijn; Kurita, Naoyuki; Bass, Adrian; Nott, Jon; Bird, Michael I.

2015-01-01

The isotope signatures registered in speleothems during tropical cyclones (TC) provides information about the frequency and intensity of past TCs but the precise relationship between isotopic composition and the meteorology of TCs remain uncertain. Here we present continuous δ18O and δ2H data in rainfall and water vapour, as well as in discrete rainfall samples, during the passage of TC Ita and relate the evolution in isotopic compositions to local and synoptic scale meteorological observations. High-resolution data revealed a close relationship between isotopic compositions and cyclonic features such as spiral rainbands, periods of stratiform rainfall and the arrival of subtropical and tropical air masses with changing oceanic and continental moisture sources. The isotopic compositions in discrete rainfall samples were remarkably constant along the ~450 km overland path of the cyclone when taking into account the direction and distance to the eye of the cyclone at each sampling time. Near simultaneous variations in δ18O and δ2H values in rainfall and vapour and a near-equilibrium rainfall-vapour isotope fractionation indicates strong isotopic exchange between rainfall and surface inflow of vapour during the approach of the cyclone. In contrast, after the passage of spiral rainbands close to the eye of the cyclone, different moisture sources for rainfall and vapour are reflected in diverging d-excess values. High-resolution isotope studies of modern TCs refine the interpretation of stable isotope signatures found in speleothems and other paleo archives and should aim to further investigate the influence of cyclone intensity and longevity on the isotopic composition of associated rainfall. PMID:25742628

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

PubMed

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

2009-09-01

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

Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

NASA Astrophysics Data System (ADS)

Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

2017-08-01

Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

Intramolecular Isotopic Studies: Chemical Enhancements and Alternatives

NASA Astrophysics Data System (ADS)

Hayes, J. M.

2016-12-01

As mass spectroscopic and NMR-based methods now appropriately flourish, chemical techniques should not be forgotten. First, the methods developed by pioneering intramolecular analysts can be reapplied to new samples. Second, they can be extended. The synthesis of intramolecular isotopic standards is particularly important and straightforward. It requires only that a chemical reaction has no secondary products. An example is provided by the addition of carbon dioxide to a Grignard reagent. The reaction proceeds with an isotope effect. The isotopic composition of the carboxyl group in the acid which is produced is thus not equal to that of the starting carbon dioxide but the unconsumed CO2 can be recovered and analyzed. A simple titration can show that all the rest of the CO2 is in the product acid. The isotopic composition of the carboxyl group can then be calculated by difference. The product is an intramolecular isotopic standard, an organic molecule in which the isotopic composition of a specific carbon position is known accurately. Both analysts and reviewers can thus gain invaluable confidence in the accuracy of instrumental results. A second example: the haloform reaction quantitatively degrades methyl ketones, producing a carboxylic acid which can be decarboxylated to determine the isotopic composition of the parent carbonyl and a haloform (CHI3, for example) that can be combusted to determine the isotopic composition of the methyl group. Ketones thus analyzed can be combined with Grignard reagents to yield carbon skeletons in which the isotopic compositions of internal and terminal -CH2- and -CH3 groups are known accurately. In general, analysts accustomed to demanding quantitative reactions should remember the power of mass balances and recognize that many organic-chemical reactions, while not quantitative, lack side products and can be driven to the total consumption of at least one reactant.

Testing the chondrule-rich accretion model for planetary embryos using calcium isotopes

NASA Astrophysics Data System (ADS)

Amsellem, Elsa; Moynier, Frédéric; Pringle, Emily A.; Bouvier, Audrey; Chen, Heng; Day, James M. D.

2017-07-01

Understanding the composition of raw materials that formed the Earth is a crucial step towards understanding the formation of terrestrial planets and their bulk composition. Calcium is the fifth most abundant element in terrestrial planets and, therefore, is a key element with which to trace planetary composition. However, in order to use Ca isotopes as a tracer of Earth's accretion history, it is first necessary to understand the isotopic behavior of Ca during the earliest stages of planetary formation. Chondrites are some of the oldest materials of the Solar System, and the study of their isotopic composition enables understanding of how and in what conditions the Solar System formed. Here we present Ca isotope data for a suite of bulk chondrites as well as Allende (CV) chondrules. We show that most groups of carbonaceous chondrites (CV, CI, CR and CM) are significantly enriched in the lighter Ca isotopes (δ 44 / 40 Ca = + 0.1 to + 0.93 ‰) compared with bulk silicate Earth (δ 44 / 40 Ca = + 1.05 ± 0.04 ‰, Huang et al., 2010) or Mars, while enstatite chondrites are indistinguishable from Earth in Ca isotope composition (δ 44 / 40 Ca = + 0.91 to + 1.06 ‰). Chondrules from Allende are enriched in the heavier isotopes of Ca compared to the bulk and the matrix of the meteorite (δ 44 / 40 Ca = + 1.00 to + 1.21 ‰). This implies that Earth and Mars have Ca isotope compositions that are distinct from most carbonaceous chondrites but that may be like chondrules. This Ca isotopic similarity between Earth, Mars, and chondrules is permissive of recent dynamical models of planetary formation that propose a chondrule-rich accretion model for planetary embryos.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the oxygen isotope composition of ambient CO2. This non-destructive approach was tested through laboratory incubations of air-dried soils that were re-wetted with water of known isotopic composition. Performance was assessed by comparing estimates of the soil water oxygen isotope composition derived from open chamber flux measurements with those measured in the irrigation water and soil water extracted following incubations. The influence of soil pH and bovine carbonic anhydrase additions on these estimates was also investigated. Coherent values were found between the soil water composition estimates obtained from the dual steady state approach and those measured for irrigation waters. Estimates of carbonic anhydrase activity made using this approach also reflected well artificial increases to the concentration of carbonic anhydrase and indicated that this activity was sensitive to soil pH.

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may develop in kinetically limited systems, which propagates with the advection speed of the incoming fluid and is, therefore, traveling fastest. The results show that oxygen isotope signatures at thermal fronts recorded in rocks and veins that experienced isotope exchange with fluids can easily be misinterpreted, namely if bulk analytical techniques are applied. However, stable isotope microanalysis on precipitated minerals may - if later isotope exchange is kinetically limited - provide a valuable archive of the transient thermal and hydrological evolution of a system.

Global Trophic Position Comparison of Two Dominant Mesopelagic Fish Families (Myctophidae, Stomiidae) Using Amino Acid Nitrogen Isotopic Analyses

PubMed Central

Choy, C. Anela; Davison, Peter C.; Drazen, Jeffrey C.; Flynn, Adrian; Gier, Elizabeth J.; Hoffman, Joel C.; McClain-Counts, Jennifer P.; Miller, Todd W.; Popp, Brian N.; Ross, Steve W.; Sutton, Tracey T.

2012-01-01

The δ15N values of organisms are commonly used across diverse ecosystems to estimate trophic position and infer trophic connectivity. We undertook a novel cross-basin comparison of trophic position in two ecologically well-characterized and different groups of dominant mid-water fish consumers using amino acid nitrogen isotope compositions. We found that trophic positions estimated from the δ15N values of individual amino acids are nearly uniform within both families of these fishes across five global regions despite great variability in bulk tissue δ15N values. Regional differences in the δ15N values of phenylalanine confirmed that bulk tissue δ15N values reflect region-specific water mass biogeochemistry controlling δ15N values at the base of the food web. Trophic positions calculated from amino acid isotopic analyses (AA-TP) for lanternfishes (family Myctophidae) (AA-TP ∼2.9) largely align with expectations from stomach content studies (TP ∼3.2), while AA-TPs for dragonfishes (family Stomiidae) (AA-TP ∼3.2) were lower than TPs derived from stomach content studies (TP∼4.1). We demonstrate that amino acid nitrogen isotope analysis can overcome shortcomings of bulk tissue isotope analysis across biogeochemically distinct systems to provide globally comparative information regarding marine food web structure. PMID:23209656

Global trophic position comparison of two dominant mesopelagic fish families (Myctophidae, Stomiidae) using amino acid nitrogen isotopic analyses

USGS Publications Warehouse

Choy, C. Anela; Davison, Peter C.; Drazen, Jeffrey C.; Flynn, Adrian; Gier, Elizabeth J.; Hoffman, Joel C.; McClain-Counts, Jennifer P.; Miller, Todd W.; Popp, Brian N.; Ross, Steve W.; Sutton, Tracey T.

2012-01-01

The δ15N values of organisms are commonly used across diverse ecosystems to estimate trophic position and infer trophic connectivity. We undertook a novel cross-basin comparison of trophic position in two ecologically well-characterized and different groups of dominant mid-water fish consumers using amino acid nitrogen isotope compositions. We found that trophic positions estimated from the δ15N values of individual amino acids are nearly uniform within both families of these fishes across five global regions despite great variability in bulk tissue δ15N values. Regional differences in the δ15N values of phenylalanine confirmed that bulk tissue δ15N values reflect region-specific water mass biogeochemistry controlling δ15N values at the base of the food web. Trophic positions calculated from amino acid isotopic analyses (AA-TP) for lanternfishes (family Myctophidae) (AA-TP ~2.9) largely align with expectations from stomach content studies (TP ~3.2), while AA-TPs for dragonfishes (family Stomiidae) (AA-TP ~3.2) were lower than TPs derived from stomach content studies (TP~4.1). We demonstrate that amino acid nitrogen isotope analysis can overcome shortcomings of bulk tissue isotope analysis across biogeochemically distinct systems to provide globally comparative information regarding marine food web structure.

Using multiple isotopes to understand the source of ingredients used in golden beverages

NASA Astrophysics Data System (ADS)

Wynn, J. G.

2011-12-01

Traditionally, beer contains 4 simple ingredients: water, barley, hops and yeast. Each of these ingredients used in the brewing process contributes some combination of a number of "traditional" stable isotopes (i.e., isotopes of H, C, O, N and S) to the final product. As an educational exercise in an "Analytical Techniques in Geology" course, a group of students analyzed the isotopic composition of the gas, liquid and solid phases of a variety of beer samples collected from throughout the world (including other beverages). The hydrogen and oxygen isotopic composition of the water followed closely the isotopic composition of local meteoric water at the source of the brewery, although there is a systematic offset from the global meteoric water line that may be due to the effects of CO2-H2O equilibration. The carbon isotopic composition of the CO2 reflected that of the solid residue (the source of carbon used as a fermentation substrate), but may potentially be modified by addition of gas-phase CO2 from an inorganic source. The carbon isotopic composition of the solid residue similarly tracks that of the fermentation substrate, and may indicate some alcohol fermented from added sugars in some cases. The nitrogen isotopic composition of the solid residue was relatively constant, and may track the source of nitrogen in the barley, hops and yeast. Each of the analytical methods used is a relatively standard technique used in geological applications, making this a "fun" exercise for those involved, and gives the students hands-on experience with a variety of analytes from a non-traditional sample material.

The ruthenium isotopic composition of the oceanic mantle

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Anomaly Detection in Gamma-Ray Vehicle Spectra with Principal Components Analysis and Mahalanobis Distances

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

Tardiff, Mark F.; Runkle, Robert C.; Anderson, K. K.

2006-01-23

The goal of primary radiation monitoring in support of routine screening and emergency response is to detect characteristics in vehicle radiation signatures that indicate the presence of potential threats. Two conceptual approaches to analyzing gamma-ray spectra for threat detection are isotope identification and anomaly detection. While isotope identification is the time-honored method, an emerging technique is anomaly detection that uses benign vehicle gamma ray signatures to define an expectation of the radiation signature for vehicles that do not pose a threat. Newly acquired spectra are then compared to this expectation using statistical criteria that reflect acceptable false alarm rates andmore » probabilities of detection. The gamma-ray spectra analyzed here were collected at a U.S. land Port of Entry (POE) using a NaI-based radiation portal monitor (RPM). The raw data were analyzed to develop a benign vehicle expectation by decimating the original pulse-height channels to 35 energy bins, extracting composite variables via principal components analysis (PCA), and estimating statistically weighted distances from the mean vehicle spectrum with the mahalanobis distance (MD) metric. This paper reviews the methods used to establish the anomaly identification criteria and presents a systematic analysis of the response of the combined PCA and MD algorithm to modeled mono-energetic gamma-ray sources.« less

The influence of diet on the δ 13C of shell carbon in the pulmonate snail Helix aspersa

NASA Astrophysics Data System (ADS)

Stott, Lowell D.

2002-02-01

The influence of diet and atmospheric CO 2 on the carbon isotope composition of shell aragonite and shell-bound organic carbon in the pulmonate snail Helix aspersa raised in the laboratory was investigated. Three separate groups of snails were raised on romaine lettuce (C3 plant, δ 13C=-25.8‰), corn (C4 plant, δ 13C=-10.5‰), and sour orange ( 12C-enriched C3 plant, δ 13C=-39.1‰). The isotopic composition of body tissues closely tracked the isotopic composition of the snail diet as demonstrated previously. However, the isotopic composition of the acid insoluble organic matrix extracted from the aragonite shells does not track diet in all groups. In snails that were fed corn the isotopic composition of the organic matrix was more negative than the body by as much as 5‰ whereas the matrix was approximately 1‰ heavier than the body tissues in snails fed a diet of C3 plant material. These results indicate that isotopic composition of the organic matrix carbon cannot be used as an isotopic substrate for paleodietary reconstructions without first determining the source of the carbon and any associated fractionations. The isotopic composition of the shell aragonite is offset from the body tissues by 12.3‰ in each of the culture groups. This offset was not influenced by the consumption of carbonate and is not attributable to the diffusion of atmospheric CO 2 into the hemolymph. The carbon isotopic composition of shell aragonite is best explained in terms of equilibrium fractionations associated with exchange between metabolic CO 2 and HCO 3 in the hemolymph and the fractionation associated with carbonate precipitation. These results differ from previous studies, based primarily on samples collected in the field, that have suggested atmospheric carbon dioxide contributes significantly to the shell δ 13C. The culture results indicate that the δ 13C of aragonite is a good recorder of the isotopic composition of the snail body tissue, and therefore a better recorder of diet than is the insoluble shell organic carbon. Because the systematic fractionation of carbon isotopes within the snail is temperature dependent, the δ 13C of the shell could provide an independent technique for estimating paleotemperature changes.

Strontium and neodymium isotopes in hot springs on the East Pacific Rise and Guaymas Basin

NASA Technical Reports Server (NTRS)

Piepgras, D. J.; Wasserburg, G. J.

1985-01-01

Solutions collected from 21 deg N, East Pacific Rise (Epr) and Guaymas Basin, Gulf of California, are analyzed for Nd isotopic composition and Sm and Nd concentrations. The results indicate extensive but not complete isotopic exchange with Sr in the depleted oceanic crust and that Sr concentrations in these solutions are buffered. In contrast, the Nd data exhibit a wide range in isotopic composition and concentration between vents. Many samples show substantial contributions from MORB, but all have isotopic compositions below MORB, in spite of enrichments in Nd up to 100 times seawater. It is shown that the fluids must exchange Nd with a sedimentary reservoir having an isotopic composition less than Pacific seawater. Low-temperature reactions with metalliferous sediments on the flanks of the EPR may provide such a source. Using a simple box method, estimates of the hydrothermal fluxes of Nd are compared to fluxes which are necessary to maintain a radiogenic isotopic composition of about -3 in the Pacific against the influx of Antarctic waters. It is concluded that erosion from island arcs is the main source of radiogenic Nd in the Pacific.

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

PubMed

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

2016-02-01

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

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.

Triple oxygen isotope composition of leaf waters in Mpala, central Kenya

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Variation of δ2H, δ18O & δ13C in crude palm oil from different regions in Malaysia: Potential of stable isotope signatures as a key traceability parameter.

PubMed

Muhammad, Syahidah Akmal; Seow, Eng-Keng; Mohd Omar, A K; Rodhi, Ainolsyakira Mohd; Mat Hassan, Hasnuri; Lalung, Japareng; Lee, Sze-Chi; Ibrahim, Baharudin

2018-01-01

A total of 33 crude palm oil samples were randomly collected from different regions in Malaysia. Stable carbon isotopic composition (δ 13 C) was determined using Flash 2000 elemental analyzer while hydrogen and oxygen isotopic compositions (δ 2 H and δ 18 O) were analyzed by Thermo Finnigan TC/EA, wherein both instruments were coupled to an isotope ratio mass spectrometer. The bulk δ 2 H, δ 18 O and δ 13 C of the samples were analyzed by Hierarchical Cluster Analysis (HCA), Principal Component Analysis (PCA) and Orthogonal Partial Least Square-Discriminant Analysis (OPLS-DA). Unsupervised HCA and PCA methods have demonstrated that crude palm oil samples were grouped into clusters according to respective state. A predictive model was constructed by supervised OPLS-DA with good predictive power of 52.60%. Robustness of the predictive model was validated with overall accuracy of 71.43%. Blind test samples were correctly assigned to their respective cluster except for samples from southern region. δ 18 O was proposed as the promising discriminatory marker for discerning crude palm oil samples obtained from different regions. Stable isotopes profile was proven to be useful for origin traceability of crude palm oil samples at a narrower geographical area, i.e. based on regions in Malaysia. Predictive power and accuracy of the predictive model was expected to improve with the increase in sample size. Conclusively, the results in this study has fulfilled the main objective of this work where the simple approach of combining stable isotope analysis with chemometrics can be used to discriminate crude palm oil samples obtained from different regions in Malaysia. Overall, this study shows the feasibility of this approach to be used as a traceability assessment of crude palm oils. Copyright © 2017 The Chartered Society of Forensic Sciences. Published by Elsevier B.V. All rights reserved.

Pb, Sr, and Nd isotopic compositions of a suite of Late Archean, igneous rocks, eastern Beartooth Mountains: implications for crust-mantle evolution

USGS Publications Warehouse

Wooden, J.L.; Mueller, P.A.

1988-01-01

A series of compositionally diverse, Late Archean rocks (2.74-2.79 Ga old) from the eastern Beartooth Mountains, Montana and Wyoming, U.S.A., have the same initial Pb, Sr, and Nd isotopic ratios. Lead and Sr initial ratios are higher and Nd initial ratios lower than would be expected for rocks derived from model mantle sources and strongly indicate the involvement of an older crustal reservoir in the genesis of these rocks. Crustal contamination during emplacement can be ruled out for a variety of reasons. Instead a model involving subduction of continental detritus and contamination of the overlying mantle as is often proposed for modern subduction environments is preferred. This contaminated mantle would have all the isotopic characteristics of mantle enriched by internal mantle metasomatism but would require no long-term growth or changes in parent to daughter element ratios. This contaminated mantle would make a good source for some of the Cenozoic mafic volcanics of the Columbia River, Snake River Plain, and Yellowstone volcanic fields that are proposed to come from ancient, enriched lithospheric mantle. The isotopic characteristics of the 2.70 Ga old Stillwater Complex are a perfect match for the proposed contaminated mantle which provides an alternative to crustal contamination during emplacement. The Pb isotopic characteristics of the Late Archean rocks of the eastern Beartooth Mountains are similar to those of other Late Archean rocks of the Wyoming Province and suggest that Early Archean, upper crustal rocks were common in this terrane. The isotopic signatures of Late Archean rocks in the Wyoming Province are distinctive from those of other Archean cratons in North America which are dominated by a MORB-like, Archean mantle source (Superior Province) and/or a long-term depleted crustal source (Greenland). ?? 1988.

Paloma: In-situ Measurement of The Elemental and Isotopic Composition of The Mars Atmosphere

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Correia, J.-J.; Covinhes, J.; Goulpeau, G.; Leblanc, F.; Malique, Ch.; Sarda, P.; Schaetzel, P.; Sabroux, J.-C.; Ferry, C.; Richon, P.; Pineau, J.-F.; Desjean, M.-C.

The PALOMA instrument, presently under study in the frame of the NASA/CNES Mars exploration program, is devoted to the accurate measurement of isotopic and el- emental ratios in Mars atmosphere. It consists of a mass spectrometer coupled with a gas preparation line for separation of reactive and noble gas species, and noble gas species (and reactive gases) from each other, by chemical and cryogenic trapping, and possibly permeation techniques. This instrument, ranked among the most important four types of measurement recommended by the US Committee on Planetary and Lu- nar Exploration (COMPLEX), will be proposed as a part of the payload of the 07 NASA smart landers. The general objectives of PALOMA are to provide instanta- neous and time-varying patterns of noble gas isotopic spectra, and stable isotopes. Such measurements will allow to improve our general understanding of volatile cy- cles on Mars, and to better decipher the history of the atmosphere and climate. Past escape processes, exchanges between solid planet and atmosphere, post-accretional addition of volatil-rich matter from comets, are expected to have imprinted specific isotopic signatures. Although these signatures are strongly interlocked, a compara- tive Earth-Mars approach may allow to discriminate between them, and therefore to reconstruct the history of Martian volatiles. The evolution of atmospheric mass and composition may have had a major impact on climate evolution, e.g. through massive escape of carbon dioxide and water. In addition, precise measurements of isotopes in the present Mars atmosphere are the most promising way on the short term to confirm that SNC meteorites are from Martian origin. PALOMA also includes a small separate device for measuring ambient natural radioactivity, which might provide information about the presence of a near subsurface permafrost, possible residual volcanic activity, vertical mixing rate in the boundary layer.

Sr isotopic tracer study of the Samail ophiolite, Oman.

USGS Publications Warehouse

Lanphere, M.A.; Coleman, R.G.; Hopson, C.A.

1981-01-01

Rb and Sr concentrations and Sr-isotopic compositions were measured in 41 whole-rock samples and 12 mineral separates from units of the Samail ophiolite, including peridotite, gabbro, plagiogranite, diabase dykes, and gabbro and websterite dykes within the metamorphic peridotite. Ten samples of cumulate gabbro from the Wadir Kadir section and nine samples from the Wadi Khafifah section have 87Sr/86Sr ratios of 0.70314 + or - 0.00030 and 0.70306 + or - 0.00034, respectively. The dispersion in Sr- isotopic composition may reflect real heterogeneities in the magma source region. The average Sr-isotopic composition of cumulate gabbro falls in the range of isotopic compositions of modern MORB. The 87Sr/86Sr ratios of noncumulate gabbro, plagiogranite, and diabase dykes range 0.7034-0.7047, 0.7038-0.7046 and 0.7037- 0.7061, respectively. These higher 87Sr/86Sr ratios are due to alteration of initial magmatic compositions by hydrothermal exchange with sea-water. Mineral separates from dykes that cut harzburgite tectonite have Sr-isotopic compositions which agree with that of cumulate gabbro. These data indicate that the cumulate gabbro and the different dykes were derived from partial melting of source regions that had similar long-term histories and chemical compositions.-T.R.

Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations

NASA Technical Reports Server (NTRS)

Piepgras, D. J.; Wasserburg, G. J.

1987-01-01

The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.

Sm-Nd in marine carbonates and phosphates - Implications for Nd isotopes in seawater and crustal ages

NASA Technical Reports Server (NTRS)

Shaw, H. F.; Wasserburg, G. J.

1985-01-01

The possibility of establishing a record of variations in the isotopic composition of Nd in seawater over geologic time is explored. To construct such a record, a phase must be identified which incorporated Nd with the same isotopic composition as seawater at the time of its formation, preserves that composition, and which is relatively common in sediments. To evaluate the suitability of carbonates and phosphates, the Rb, Sr, Sm, and Nd concentrations and the Nd and Sr isotopic composition of a variety of modern and ancient marine calcite, aragonite, and apatite samples have been measured and the results are presented and discussed.

C-12/C-13 Ratio in Ethane on Titan and Implications for Methane's Replenishment

NASA Technical Reports Server (NTRS)

Jennings, Donald E.; Romani, Paul N.; Bjoraker, Gordon L.; Sada, Pedro V.; Nixon, Conor A.; Lunsford, Allen W.; Boyle, Robert J.; Hesman, Brigette E.; McCabe, George H.

2009-01-01

The C-12/C-13 abundance ratio in ethane in the atmosphere of Titan has been measured at 822 cm(sup -1) from high spectral resolution ground-based observations. The value 89(8), coincides with the telluric standard and also agrees with the ratio seen in the outer planets. It is almost identical to the result for ethane on Titan found by the composite infrared spectrometer (CIRS) on Cassini. The C-12/C-13 ratio for ethane is higher than the ratio measured in atmospheric methane by Cassini/Huygens GCMS, 82.3(l), representing an enrichment of C-12 in the ethane that might be explained by a kinetic isotope effect of approximately 1.1 in the formation of methyl radicals. If methane is being continuously resupplied to balance photochemical destruction, then we expect the isotopic composition in the ethane product to equilibrate at close to the same C-12/C-13 ratio as that in the supply. The telluric value of the ratio in ethane then implies that the methane reservoir is primordial.

Fingerprints of carbon, nitrogen, and silicon isotopes in small interstellar SiC grains from the Murchison meteorite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Geiss, Johannes; Buehler, Fritz; Neuenschwander, Juerg; Amari, Sachiko; Lewis, Roy S.

1993-01-01

We report ion microprobe determinations of the carbon, nitrogen, and silicon isotopic compositions of small SiC grains from the Murchison CM2 chondrite. Analyses were made on samples containing variable numbers of grains and on 14 individual grains. In some cases the multiple-grain sample compositions were probably dominated by only one or two grains. Total ranges observed are given. Only a few grains show values near the range limits. Both the total ranges of carbon and nitrogen isotopic compositions, and even the narrower ranges typical for the majority of the grains, are similar to those observed for larger SiC grains. Two rare components appear to be present in the smaller-size fraction, one characterized by C-12/C-13 about 12-16 and the other by very heavy nitrogen. The carbon and nitrogen isotopic compositions qualitatively may reflect hydrostatic H-burning via the CNO cycle and He-burning in red giants, as well as explosive H-burning in novae. The silicon isotopic compositions of most grains qualitatively show what is the signature of He-burning. The silicon isotopic composition of one grain, however, suggests a different process.

CARBON AND OXYGEN ISOTOPIC RATIOS FOR NEARBY MIRAS

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

Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar, E-mail: khinkle@noao.edu, E-mail: thomas.lebzelter@univie.ac.at, E-mail: straniero@oa-teramo.inaf.it

2016-07-01

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

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

NASA Astrophysics Data System (ADS)

Liu, Nan; Stephan, Thomas; Boehnke, Patrick; Nittler, Larry R.; Meyer, Bradley S.; O’D. Alexander, Conel M.; Davis, Andrew M.; Trappitsch, Reto; Pellin, Michael J.

2018-03-01

We report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB (14N/15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains (14N/15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likely originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars’ pre-SN evolution rather than from an explosive neutron-capture process. In addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

DOE PAGES

Liu, Nan; Stephan, Thomas; Boehnke, Patrick; ...

2018-03-16

In this paper, we report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB ( 14N/ 15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains ( 14N/ 15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likelymore » originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars' pre-SN evolution rather than from an explosive neutron-capture process. Finally, in addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.« less

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

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

Liu, Nan; Stephan, Thomas; Boehnke, Patrick

In this paper, we report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB ( 14N/ 15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains ( 14N/ 15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likelymore » originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars' pre-SN evolution rather than from an explosive neutron-capture process. Finally, in addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.« less

Carbon, nitrogen, magnesium, silicon, and titanium isotopic compositions of single interstellar silicon carbide grains from the Murchison carbonaceous chondrite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Amari, Sachiko; Zinner, Ernst; Ireland, Trevor; Lewis, Roy S.

1994-01-01

Seven hundred and twenty SiC grains from the Murchison CM2 chondrite, ranging in size from 1 to 10 micrometers, were analyzed by ion microprobe mass spectrometry for their C-isotopic compositions. Subsets of the grains were also analyzed for N (450 grains), Si (183 grains), Mg (179 grains), and Ti (28 grains) isotopes. These results are compared with previous measurements on 41 larger SiC grains (up to 15 x 26 micrometers) from a different sample of Murchison analyzed by Virag et al. (1992) and Ireland, Zinner, & Amari (1991a). All grains of the present study are isotopically anomalous with C-12/C-13 ratios ranging from 0.022 to 28.4 x solar, N-14/N-15 ratios from 0.046 to 30 x solar, Si-29/Si-28 from 0.54 to 1.20 x solar, Si-30/Si-28 from 0.42 to 1.14 x solar, Ti-49/Ti-48 from 0.96 to 1.95 x solar, and Ti-50/Ti-48 from 0.94 to 1.39 x solar. Many grains have large Mg-26 excesses from the decay of Al-26 with inferred Al-26/Al-27 ratios ranging up to 0.61, or 12,200 x the ratio of 5 x 10(exp -5) inferred for the early solar system. Several groups can be distinguished among the SiC grains. Most of the grains have C-13 and N-14 excesses, and their Si isotopic compositions (mostly excesses in Si-29 and Si-30) plot close to a slope 1.34 line on a Delta Si-29/Si-28 versus Delta Si-30/Si-28 three-isotope plot. Grains with small C-12/C-13 ratios (less than 10) tend to have smaller or no N-14 excesses and high Al-26/Al-27 ratios (up to 0.01). Grains with C-12/C-13 greater than 150 fall into two groups: grains X have N-15 excesses and Si-29 and Si-30 deficits and the highest (0.1 to 0.6) Al-26/Al-27 ratios; grains Y have N-14 excesses and plot on a slope 0.35 line on a Si three-isotope plot. In addition, large SiC grains of the Virag et al. (1992) study fall into three-distinct clusters according to their C-, Si-, and Ti-isotopic compositions. The isotopic diversity of the grains and the clustering of their isotopic compositions imply distinct and multiple stellar sources. The C- and N-isotopic compositions of most grains are consistent with H-burning in the CNO cycle. These and s-process Kr, Xe, Ba, and Nd suggest asymptotic giant branch (AGB) or Wolf-Rayet stars as likely sources for the grains, but existing models of nucleosynthesis in these stellar sites fail to account in detail for all the observed isotopic compositions. Special problems are posed by grains with C-12/C-13 less than 10 and almost normal and heavy N-isotopic compositions. Also the Si- and Ti-isotopic compositions, with excesses in Si-29 and Si-30 relative to Si-28 and excesses in all Ti isotopes relative to Ti-48, do not precisely conform with the compositions predicted for slow neutron capture. Additional theoretical efforts are needed to achieve an understanding of the isotopic composition of the SiC grains and their stellar sources.

Rb-Sr and Sm-Nd Ages of Zagami DML and SR Isotopic Heterogeneity in Zagami

NASA Technical Reports Server (NTRS)

Nyquist, L.aurenceE.; Shih, C.-Y.; Reese, Y. D.

2010-01-01

Zagami contains lithologic heterogeneity suggesting that it did not form in a homogeneous, thick lava flow [1]. We have previously investigated the Sr and Nd isotopic systematics of Coarse-Grained (CG) and Fine-Grained (FG) lithologies described by [2]. Both appear to belong to Normal Zagami (NZ) [1,3], but their initial Sr-isotopic compositions differ [4,5]. Here we report new analyses of the Dark Mottled Lithology (DML, [3]) that show its age and initial Sr and Nd isotopic compositions to be identical within error limits with those of CG, but Sr initial isotopic compositions differ from those of FG.

Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites.

PubMed

Van Kooten, Elishevah M M E; Wielandt, Daniel; Schiller, Martin; Nagashima, Kazuhide; Thomen, Aurélien; Larsen, Kirsten K; Olsen, Mia B; Nordlund, Åke; Krot, Alexander N; Bizzarro, Martin

2016-02-23

The short-lived (26)Al radionuclide is thought to have been admixed into the initially (26)Al-poor protosolar molecular cloud before or contemporaneously with its collapse. Bulk inner Solar System reservoirs record positively correlated variability in mass-independent (54)Cr and (26)Mg*, the decay product of (26)Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling (26)Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last addition of stellar-derived (26)Al has not been identified yet but may be preserved in planetesimals that accreted in the outer Solar System. We show that metal-rich carbonaceous chondrites and their components have a unique isotopic signature extending from an inner Solar System composition toward a (26)Mg*-depleted and (54)Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived (26)Al. The (26)Mg* and (54)Cr compositions of bulk metal-rich chondrites require significant amounts (25-50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals that accreted beyond the orbits of the gas giants. The lack of evidence for this material in other chondrite groups requires isolation from the outer Solar System, possibly by the opening of disk gaps from the early formation of gas giants.

Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites

PubMed Central

Van Kooten, Elishevah M. M. E.; Wielandt, Daniel; Schiller, Martin; Nagashima, Kazuhide; Thomen, Aurélien; Olsen, Mia B.; Nordlund, Åke; Krot, Alexander N.; Bizzarro, Martin

2016-01-01

The short-lived 26Al radionuclide is thought to have been admixed into the initially 26Al-poor protosolar molecular cloud before or contemporaneously with its collapse. Bulk inner Solar System reservoirs record positively correlated variability in mass-independent 54Cr and 26Mg*, the decay product of 26Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling 26Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last addition of stellar-derived 26Al has not been identified yet but may be preserved in planetesimals that accreted in the outer Solar System. We show that metal-rich carbonaceous chondrites and their components have a unique isotopic signature extending from an inner Solar System composition toward a 26Mg*-depleted and 54Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived 26Al. The 26Mg* and 54Cr compositions of bulk metal-rich chondrites require significant amounts (25–50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals that accreted beyond the orbits of the gas giants. The lack of evidence for this material in other chondrite groups requires isolation from the outer Solar System, possibly by the opening of disk gaps from the early formation of gas giants. PMID:26858438

Spatially-resolved isotopic study of carbon trapped in ∼3.43 Ga Strelley Pool Formation stromatolites

NASA Astrophysics Data System (ADS)

Flannery, David T.; Allwood, Abigail C.; Summons, Roger E.; Williford, Kenneth H.; Abbey, William; Matys, Emily D.; Ferralis, Nicola

2018-02-01

The large isotopic fractionation of carbon associated with enzymatic carbon assimilation allows evidence for life's antiquity, and potentially the early operation of several extant metabolic pathways, to be derived from the stable carbon isotope record of sedimentary rocks. Earth's organic carbon isotope record extends to the Late Eoarchean-Early Paleoarchean: the age of the oldest known sedimentary rocks. However, complementary inorganic carbon reservoirs are poorly represented in the oldest units, and commonly reported bulk organic carbon isotope measurements do not capture the micro-scale isotopic heterogeneities that are increasingly reported from younger rocks. Here, we investigated the isotopic composition of the oldest paired occurrences of sedimentary carbonate and organic matter, which are preserved as dolomite and kerogen within textural biosignatures of the ∼3.43 Ga Strelley Pool Formation. We targeted least-altered carbonate phases in situ using microsampling techniques guided by non-destructive elemental mapping. Organic carbon isotope values were measured by spatially-resolved bulk analyses, and in situ using secondary ion mass spectrometry to target microscale domains of organic material trapped within inorganic carbon matrixes. Total observed fractionation of 13C ranges from -29 to -45‰. Our data are consistent with studies of younger Archean rocks that host biogenic stromatolites and organic-inorganic carbon pairs showing greater fractionation than expected for Rubisco fixation alone. We conclude that organic matter was fixed and/or remobilized by at least one metabolism in addition to the CBB cycle, possibly by the Wood-Ljungdahl pathway or methanogenesis-methanotrophy, in a shallow-water marine environment during the Paleoarchean.

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

NASA Astrophysics Data System (ADS)

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

2003-12-01

Bioapatite, the principal inorganic phase comprising bone, commonly contains a small fraction of carbonate, which has been substituted into the phosphate structure during bone formation. The isotopic compositions of both the phosphate oxygen and the structural carbonate oxygen are now commonly used in palaeoclimatological and bioarchaeological investigations. The potential for post-mortem alteration of these isotopic compositions, therefore, is of interest, with the behaviour of structural carbonate being of most concern. In bioarchaeological studies, alteration of bone isotopic compositions has the potential to occur not only during low-temperature processes associated with burial but also during food preparation involving heating (burning, boiling). Here, we examine the stable isotopic behaviour of structural carbonate oxygen and carbon, and coexisting phosphate oxygen during the burning of bone. Freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned and incrementally heated from 25 to 900° C, in 25° intervals. The samples were then ground to a standardized grain-size (45<63μ m), and changes in bioapatite crystallinity (CI) were determined using powder X-ray diffraction (pXRD), and Fourier transform infra-red spectroscopy (FTIR). Combined differential thermal and thermogravimetric analyses (DTA/TG) were used to evaluate weight loss and associated reactions during heating. Stable carbon isotope compositions of the bioapatite remain relatively constant (+/-1‰ ) during heating to 650° C. A 4‰ increase in stable carbon isotopic composition then occurs between 650-750° C, accompanied by an increase in CI, followed by a 10‰ decline at temperatures above 800° C, as carbonate carbon is lost. Carbonate and phosphate oxygen isotopic compositions are correlated over the entire heating range, with carbonate being enriched relative to phosphate by about 8-10‰ below 500° C, 5-6‰ between 500-700° C, and 8-10‰ above 700° C. CI and oxygen isotopic compositions of carbonate and phosphate are not well correlated. Only modest CI changes are recorded from 25-675° C, compared with much larger changes in oxygen isotopic composition, especially above 300° C. On average, original isotopic compositions are largely preserved for both phosphate (+/-1‰ ) and carbonate (+/-2‰ ) oxygen at <300° C. At higher temperatures, however, both phosphate and carbonate oxygen in the bioapatite are systematically depleted of oxygen-18 relative to original values.

Variation in the carbon and oxygen isotope composition of plant biomass and its relationship to water-use efficiency at the leaf- and ecosystem-scales in a northern Great Plains grassland.

PubMed

Flanagan, Lawrence B; Farquhar, Graham D

2014-02-01

Measurements of the carbon (δ(13) Cm ) and oxygen (δ(18) Om ) isotope composition of C3 plant tissue provide important insights into controls on water-use efficiency. We investigated the causes of seasonal and inter-annual variability in water-use efficiency in a grassland near Lethbridge, Canada using stable isotope (leaf-scale) and eddy covariance measurements (ecosystem-scale). The positive relationship between δ(13) Cm and δ(18) Om values for samples collected during 1998-2001 indicated that variation in stomatal conductance and water stress-induced changes in the degree of stomatal limitation of net photosynthesis were the major controls on variation in δ(13) Cm and biomass production during this time. By comparison, the lack of a significant relationship between δ(13) Cm and δ(18) Om values during 2002, 2003 and 2006 demonstrated that water stress was not a significant limitation on photosynthesis and biomass production in these years. Water-use efficiency was higher in 2000 than 1999, consistent with expectations because of greater stomatal limitation of photosynthesis and lower leaf ci /ca during the drier conditions of 2000. Calculated values of leaf-scale water-use efficiency were 2-3 times higher than ecosystem-scale water-use efficiency, a difference that was likely due to carbon lost in root respiration and water lost during soil evaporation that was not accounted for by the stable isotope measurements. © 2013 John Wiley & Sons Ltd.

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.

[Tracing Sources of Sulfate Aerosol in Nanjing Northern Suburb Using Sulfur and Oxygen Isotopes].

PubMed

Wei, Ying; Guo, Zhao-bing; Ge, Xin; Zhu, Sheng-nan; Jiang, Wen-juan; Shi, Lei; Chen, Shu

2015-04-01

Abstract: To trace the sources of sulfate contributing to atmospheric aerosol, PM2.5 samples for isotopic analysis were collected in Nanjing northern suburb during January 2014. The sulfur and oxygen isotopic compositions of sulfate from these samples were determined by EA-IRMS. Source identification and apportionment were carried out using stable isotopic and chemical evidences, combined with absolute principal component analysis (APCA) method. The Δ34S values of aerosol sulfate ranged from 2.7 per thousand to 6.4 per thousand, with an average of 5.0 per thousand ± 0.9 per thousand, while the Δ18O values ranged from 10.6 per thousand to 16.1 per thousand, with an average of 12.5 per thousand ± 1.37 per thousand. In conjunction with air mass trajectories, the results suggested that aerosol sulfates were controlled by a dominance of local anthropogenic sulfate, followed by the contributions of long-distance transported sulfate. There was a minor effect of some other low-Δ34S valued sulfates, which might be expected from biogenic sources. Absolute principal component analysis results showed that the contributions of anthropogenic sulfate and long-distance transported sulfate were 46.74% and 31.54%, respectively.

Rainfall Type as a Dominant Control of the Isotopic Composition of Precipitation in the South Central United States

NASA Astrophysics Data System (ADS)

Sun, C.; Shanahan, T. M.; Partin, J. W.

2017-12-01

The processes that control the isotopic composition of precipitation in the mid-latitudes are understudied compared to the high and low latitudes, but are critical for interpreting paleo records using isotope proxies. To better understand these processes, we investigated changes of isotopic composition of rainwater in Central Texas using 20 months of event-based rainwater collection. We find that in both the event-based data and the monthly data from the Waco GNIP station, the dominant control on the isotopic composition of precipitation is the proportion that is derived from convective systems. This finding is consistent with previously reported data largely from tropical localities (Aggarwal et al., 2016), where large organized convective systems lead to high rainfall amounts and isotopically depleted precipitation. Although there are seasonal differences in the dominant rainfall types over the South Central US, with winter precipitation almost entirely stratiform, seasonality plays very little role in the net isotopic composition of precipitation because the total contribution during winter is small compared with spring, summer and fall. We also find that changes of source have little effect on the isotopic composition of rainfall, as the majority of the moisture is derived from the Gulf of Mexico with little influence of reevaporation or mixing. The majority of the warm season precipitation in the South Central US occurs in association with mesoscale convective systems (MCSs) and the development of these systems plays a critical role in the overall isotopic signature of precipitation. MCSs are characterized by a combination of intense, organized convection at their leading edges and trailing stratiform precipitation. Larger MCSs tend to contain higher proportions of stratiform rainfall and as a result, have isotopically depleted values. Proxy records from this region displaying more negative isotope values in the past should therefore be interpreted with caution as they could reflect either increases in cool versus warm season precipitation or changes in the intensity of warm season MCSs.

Silicon Isotopic Fractionation of CAI-like Vacuum Evaporation Residues

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

Knight, K; Kita, N; Mendybaev, R

2009-06-18

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquidsmore » (Richter et al., 2002, 2007a). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, {alpha}{sub Si}, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that {alpha}{sub Si} = 0.98985 {+-} 0.00044 (2{sigma}) for {sup 29}Si/{sup 28}Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 C. This value is different from what has been reported for evaporation of liquid Mg{sub 2}SiO{sub 4} (Davis et al., 1990) and of a melt with CI chondritic proportions of the major elements (Wang et al., 2001). There appears to be some compositional control on {alpha}{sub Si}, whereas no compositional effects have been reported for {alpha}{sub Mg}. We use the values of {alpha}Si and {alpha}Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.« less

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.

Molybdenum isotope fractionation in the mantle

NASA Astrophysics Data System (ADS)

Liang, Yu-Hsuan; Halliday, Alex N.; Siebert, Chris; Fitton, J. Godfrey; Burton, Kevin W.; Wang, Kuo-Lung; Harvey, Jason

2017-02-01

We report double-spike molybdenum (Mo) isotope data for forty-two mafic and fifteen ultramafic rocks from diverse locations and compare these with results for five chondrites. The δ98/95Mo values (normalized to NIST SRM 3134) range from -0.59 ± 0.04 to +0.10 ± 0.08‰. The compositions of one carbonaceous (CI) and four ordinary chondrites are relatively uniform (-0.14 ± 0.01‰, 95% ci (confidence interval)) in excellent agreement with previous data. These values are just resolvable from the mean of 10 mid-ocean ridge basalts (MORBs) (0.00 ± 0.02‰, 95% ci). The compositions of 13 mantle-derived ultramafic xenoliths from Kilbourne Hole, Tariat and Vitim are more diverse (-0.39 to -0.07‰) with a mean of -0.22 ± 0.06‰ (95% ci). On this basis, the isotopic composition of the bulk silicate Earth (BSE or Primitive Mantle) is within error identical to chondrites. The mean Mo concentration of the ultramafic xenoliths (0.19 ± 0.07 ppm, 95% ci) is similar in magnitude to that of MORB (0.48 ± 0.13 ppm, 95% ci), providing evidence, either for a more compatible behaviour than previously thought or for selective Mo enrichment of the subcontinental lithospheric mantle. Intraplate and ocean island basalts (OIBs) display significant isotopic variability within a single locality from MORB-like to strongly negative (-0.59 ± 0.04‰). The most extreme values measured are for nephelinites from the Cameroon Line and Trinidade, which also have anomalously high Ce/Pb and low Mo/Ce relative to normal oceanic basalts. δ98/95Mo correlates negatively with Ce/Pb and U/Pb, and positively with Mo/Ce, explicable if a phase such as an oxide or a sulphide liquid selectively retains isotopically heavy Mo in the mantle and fractionates its isotopic composition in low degree partial melts. If residual phases retain Mo during partial melting, it is possible that the [Mo] for the BSE may be misrepresented by values estimated from basalts. This would be consistent with the high Mo concentrations of all the ultramafic xenoliths of 40-400 ppb, similar to or, significantly higher than, current estimates for the BSE (39 ppb). On this basis a revised best estimate of the Mo content in the BSE based on these concentrations would be in the range 113-180 ppb, significantly higher than previously assumed. These values are similar to the levels of depletion in the other refractory moderately siderophile elements W, Ni and Co. A simpler explanation may be that the subcontinental lithospheric mantle has been selectively enriched in Mo leading to the higher concentrations observed. Cryptic melt metasomatism would be difficult to reconcile with the high Mo/Ce of the most LREE depleted xenoliths. Ancient Mo-enriched subducted components would be expected to have heavy δ98/95Mo, which is not observed. The Mo isotope composition of the BSE, cannot be reliably resolved from that of chondrites at this time despite experimental evidence for metal-silicate fractionation. An identical isotopic composition might result from core-mantle differentiation under very high temperatures such as were associated with the Moon-forming Giant Impact, or from the BSE inventory reflecting addition of moderately siderophile elements from an oxidised Moon-forming impactor (O'Neill, 1991). However, the latter would be inconsistent with the non-chondritic radiogenic W isotopic composition of the BSE. Based on mantle fertility arguments, Mo in the BSE could even be lighter (lower 98/95Mo) than that in chondrites, which might be explained by loss of S rich liquids from the BSE during core formation (Wade et al., 2012). Such a late removal model is no longer required to explain the Mo concentration of the BSE if its abundance is in fact much higher, and similar to the values for ultramafic xenoliths.

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

2004-01-01

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-08-01

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

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.

The role of stable isotopes in understanding rainfall interception processes: a review

EPA Science Inventory

The isotopic composition of water transmitted by the canopy as throughfall or stemflow reflects important hydrologic processes occurring in the canopy. A synthesis of the literature shows that complex spatiotemporal variations of isotopic composition are created by canopy interce...

Metal stable isotopes in weathering and hydrology: Chapter 10

USGS Publications Warehouse

Bullen, Thomas D.; Holland, Heinrich; Turekian, K.

2014-01-01

This chapter highlights some of the major developments in the understanding of the causes of metal stable isotope compositional variability in and isotope fractionation between natural materials and provides numerous examples of how that understanding is providing new insights into weathering and hydrology. At this stage, our knowledge of causes of stable isotope compositional variability among natural materials is greatest for the metals lithium, magnesium, calcium, and iron, the isotopes of which have already provided important information on weathering and hydrological processes. Stable isotope compositional variability for other metals such as strontium, copper, zinc, chromium, barium, molybdenum, mercury, cadmium, and nickel has been demonstrated but is only beginning to be applied to questions related to weathering and hydrology, and several research groups are currently exploring the potential. And then there are other metals such as titanium, vanadium, rhenium, and tungsten that have yet to be explored for variability of stable isotope composition in natural materials, but which may hold untold surprises in their utility. This impressive list of metals having either demonstrated or potential stable isotope signals that could be used to address important unsolved questions related to weathering and hydrology, constitutes a powerful toolbox that will be increasingly utilized in the coming decades.

Using Redwood Tree Ring Chronologies to Obtain the Long-View on California's Coastal Climate

NASA Astrophysics Data System (ADS)

Dawson, T. E.; Roden, J. S.; Voelker, S. L.; Johnstone, J. A.; Ambrose, A.

2014-12-01

Coast redwood (Sequoia sempervirens) occupies a long and narrow range at the land-sea interface from the southern Big Bur region to the California-Oregon boarder. Since mature trees can live in excess of 2000 years, using the interannual variability in the oxygen and carbon stable isotope composition of tree rings obtained from trees growing in different parts of the redwood range holds the potential for obtaining a long-term record of California's coastal climate, including the history of temperatures, low cloud / fog, rainfall and associated climatic drivers of their variation. We analyzed the oxygen and carbon stable isotope composition of tree ring cellulose from both tree cores and whole cross-sectional slabs and compared these data to several regional climate indicies and to published growth chronologies to obtain the long-view on California's coastal climate. Several highlights will be presented and discussed. These include: (1) redwoods faithfully record water sources they use in the oxygen stable isotope composition of their tree ring cellulose; (2) these is both strong watershed- and regional-scale coherence; (3) redwood tree ring carbon isotope composition shows its strongest correlations to tree water status, stand-scale humidity, and at the regional scale to what we term "summer precipitation" anomalies (lack of rain with presence of fog); also (4) that carbon stable isotope composition is very sensitive to within tree and stand microclimate while oxygen stable isotope composition seems to be sensitive to topographic site factors like slope position and proximity to riparian / gully habitats; (5) multivariate climatic analyses reveal that summertime drought recorded in the isotope excursions are most strongly linked to atmospheric circulation anomalies; and (6) that redwood tree rings and their isotope composition provide great potential for reconstructing high-resolution paleo-climate along the California coast.

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.

Real-time isotope monitoring network at the Biosphere 2 Landscape Evolution Observatory resolves meter-to-catchment scale flow dynamics

NASA Astrophysics Data System (ADS)

Volkmann, T. H. M.; Van Haren, J. L. M.; Kim, M.; Harman, C. J.; Pangle, L.; Meredith, L. K.; Troch, P. A.

2017-12-01

Stable isotope analysis is a powerful tool for tracking flow pathways, residence times, and the partitioning of water resources through catchments. However, the capacity of stable isotopes to characterize catchment hydrological dynamics has not been fully exploited as commonly used methodologies constrain the frequency and extent at which isotopic data is available across hydrologically-relevant compartments (e.g. soil, plants, atmosphere, streams). Here, building upon significant recent developments in laser spectroscopy and sampling techniques, we present a fully automated monitoring network for tracing water isotopes through the three model catchments of the Landscape Evolution Observatory (LEO) at the Biosphere 2, University of Arizona. The network implements state-of-the-art techniques for monitoring in great spatiotemporal detail the stable isotope composition of water in the subsurface soil, the discharge outflow, and the atmosphere above the bare soil surface of each of the 330-m2 catchments. The extensive valving and probing systems facilitate repeated isotope measurements from a total of more than five-hundred locations across the LEO domain, complementing an already dense array of hydrometric and other sensors installed on, within, and above each catchment. The isotope monitoring network is operational and was leveraged during several months of experimentation with deuterium-labelled rain pulse applications. Data obtained during the experiments demonstrate the capacity of the monitoring network to resolve sub-meter to whole-catchment scale flow and transport dynamics in continuous time. Over the years to come, the isotope monitoring network is expected to serve as an essential tool for collaborative interdisciplinary Earth science at LEO, allowing us to disentangle changes in hydrological behavior as the model catchments evolve in time through weathering and colonization by plant communities.

The post-Paleozoic chronology and mechanism of 13C depletion in primary marine organic matter

NASA Technical Reports Server (NTRS)

Popp, B. N.; Takigiku, R.; Hayes, J. M.; Louda, J. W.; Baker, E. W.

1989-01-01

Carbon-isotopic compositions of geoporphyrins have been measured from marine sediments of Mesozoic and Cenozoic age in order to elucidate the timing and extent of depletion of 13C in marine primary producers. These results indicate that the difference in isotopic composition of coeval marine carbonates and marine primary photosynthate was approximately 5 to 7 permil greater during the Mesozoic and early Cenozoic than at present. In contrast to the isotopic record of marine primary producers, isotopic compositions of terrestrial organic materials have remained approximately constant for this same interval of time. This difference in the isotopic records of marine and terrestrial organic matter is considered in terms of the mechanisms controlling the isotopic fractionation associated with photosynthetic fixation of carbon. We show that the decreased isotopic fractionation between marine carbonates and organic matter from the Early to mid-Cenozoic may record variations in the abundance of atmospheric CO2.

Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

PubMed

Konegger-Kappel, Stefanie; Prohaska, Thomas

2016-01-01

Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from the vicinity of the Chernobyl NPP [e.g. (240)Pu/(239)Pu = 0.394(2) and (242)Pu/(239)Pu = 0.027(1); Nunnemann et al. (J Alloys Compd 271-273:45-48, 1998)].

Fractionation of Fe isotopes during Fe(II) oxidation by a marine photoferrotroph is controlled by the formation of organic Fe-complexes and colloidal Fe fractions

NASA Astrophysics Data System (ADS)

Swanner, Elizabeth D.; Wu, Wenfang; Schoenberg, Ronny; Byrne, James; Michel, F. Marc; Pan, Yongxin; Kappler, Andreas

2015-09-01

Much interest exists in finding mineralogical, organic, morphological, or isotopic biosignatures for Fe(II)-oxidizing bacteria (FeOB) that are retained in Fe-rich sediments, which could indicate the activity of these organisms in Fe-rich seawater, more common in the Precambrian Era. To date, the effort to establish a clear Fe isotopic signature in Fe minerals produced by Fe(II)-oxidizing metabolisms has been thwarted by the large kinetic fractionation incurred as freshly oxidized aqueous Fe(III) rapidly precipitates as Fe(III) (oxyhydr)oxide minerals at near neutral pH. The Fe(III) (oxyhydr)oxide minerals resulting from abiotic Fe(II) oxidation are isotopically heavy compared to the Fe(II) precursor and are not clearly distinguishable from minerals formed by FeOB isotopically. However, in marine hydrothermal systems and Fe(II)-rich springs the minerals formed are often isotopically lighter than expected considering the fraction of Fe(II) that has been oxidized and experimentally-determined fractionation factors. We measured the Fe isotopic composition of aqueous Fe (Feaq) and the final Fe mineral (Feppt) produced in batch experiment using the marine Fe(II)-oxidizing phototroph Rhodovulum iodosum. The δ56Feaq data are best described by a kinetic fractionation model, while the evolution of δ56Feppt appears to be controlled by a separate fractionation process. We propose that soluble Fe(III), and Fe(II) and Fe(III) extracted from the Feppt may act as intermediates between Fe(II) oxidation and Fe(III) precipitation. Based on 57Fe Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray total scattering, we suggests these Fe phases, collectively Fe(II/III)interm, may consist of organic-ligand bound, sorbed, and/or colloidal Fe(II) and Fe(III) mineral phases that are isotopically lighter than the final Fe(III) mineral product. Similar intermediate phases, formed in response to organic carbon produced by FeOB and inorganic ligands (e.g., SiO44- or PO43-), may form in many natural Fe(II)-oxidizing environments. We propose that the formation of these intermediates is likely to occur in organic-rich systems, and thus may have controlled the ultimate isotopic composition of Fe minerals in systems where Fe(II) was being oxidized by or in the presence of microbes in Earth's past.

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

NASA Astrophysics Data System (ADS)

Akram, W.; Schönbächler, M.

2016-09-01

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

Isotopic compositions of cometary matter returned by Stardust.

PubMed

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

2006-12-15

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

Isotopic Analysis and Evolved Gases

NASA Technical Reports Server (NTRS)

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

1996-01-01

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

Approaches to Plant Hydrogen and Oxygen Isoscapes Generation

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

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

2009-12-01

Plant hydrogen and oxygen isoscapes have been utilized to address important and somewhat disparate research goals. The isotopic composition of leaf water affects the isotopic composition of atmospheric CO2 and O2 and is a logical starting point for understanding the isotopic composition of plant organic compounds since photosynthesis occurs in the leaf water environment. Leaf water isoscapes have been produced largely as part of efforts to understand atmospheric gas isotopic composition. The isotopic composition of plant organic matter has also been targeted for its potential to serve as a proxy for past environmental conditions. Spatially distributed sampling and modeling ofmore » modern plant H & O isoscapes can improve our understanding of the controls of the isotope ratios of compounds such as cellulose or n-alkanes from plants and therefore their utility for paleoreconstructions. Spatially varying plant hydrogen and oxygen isotopes have promise for yielding geographic origin information for a variety of plant products, including objects of criminal forensic interest or food products. The future has rich opportunities for the continued development of mechanistic models, methodologies for the generation of hydrogen and oxygen isoscapes, and cross-disciplinary interactions as these tools for understanding are developed, shared, and utilized to answer large-scale questions.« less

Modelled isotopic fractionation and transient diffusive release of methane from potential subsurface sources on Mars

NASA Astrophysics Data System (ADS)

Stevens, Adam H.; Patel, Manish R.; Lewis, Stephen R.

2017-01-01

We calculate transport timescales of martian methane and investigate the effect of potential release mechanisms into the atmosphere using a numerical model that includes both Fickian and Knudsen diffusion. The incorporation of Knudsen diffusion, which improves on a Fickian description of transport given the low permeability of the martian regolith, means that transport timescales from sources collocated with a putative martian water table are very long, up to several million martian years. Transport timescales also mean that any temporally varying source process, even in the shallow subsurface, would not result in a significant, observable variation in atmospheric methane concentration since changes resulting from small variations in flux would be rapidly obscured by atmospheric transport. This means that a short-lived 'plume' of methane, as detected by Mumma et al. (2009) and Webster et al. (2014), cannot be reconciled with diffusive transport from any reasonable depth and instead must invoke alternative processes such as fracturing or convective plumes. It is shown that transport through the martian regolith will cause a significant change in the isotopic composition of the gas, meaning that methane release from depth will produce an isotopic signature in the atmosphere that could be significantly different than the source composition. The deeper the source, the greater the change, and the change in methane composition in both δ13C and δD approaches -1000 ‰ for sources at a depth greater than around 1 km. This means that signatures of specific sources, in particular the methane produced by biogenesis that is generally depleted in 13CH4 and CH3D, could be obscured. We find that an abiogenic source of methane could therefore display an isotopic fractionation consistent with that expected for biogenic source processes if the source was at sufficient depth. The only unambiguous inference that can be made from measurements of methane isotopes alone is a measured δ13C or δD close to zero or positive implies a shallow, abiogenic source. The effect of transport processes must therefore be carefully considered when attempting to identify the source of any methane observed by future missions, and the severe depletion in heavier isotopologues will have implications for the sensitivity requirements for future missions that aim to measure the isotopic fractionation of methane in the martian atmosphere.

Highly siderophile element constraints on the genesis of Azorean lavas

NASA Astrophysics Data System (ADS)

Waters, C. L.; Watanabe, S.; Olson, K. M.; Walker, R. J.; Widom, E.; Hanan, B. B.; Day, J. M.

2013-12-01

Ocean island basalts (OIB) from the Azores archipelago show incompatible element and Sr-Nd-Hf-Pb isotopic heterogeneity both among different islands and within individual islands. This heterogeneity has commonly been attributed to the presence of a mantle plume delivering diverse recycled materials--including terrigenous sediments, metasomatized subcontinental lithosphere, and oceanic crust--to the melting region beneath the Azores (Turner et al., 1997; Widom and Shirey, 1996; Beier et al., 2007). Despite an abundance of datasets including major and trace element and Sr, Nd, Hf, and Pb isotopic compositions, the origin of elemental and isotopic heterogeneity in the Azores remains vigorously debated. We report new highly siderophile element (HSE: Os, Ir, Pd, Pt, Ru, Re) abundance data alongside major and trace element abundance and Nd-Hf-Os-Pb isotope data for a suite of high MgO (8-17 wt%) lavas from the islands of Sao Miguel, Pico, Faial, and Terceira. These lavas span most of the range of incompatible trace element and Nd-Hf-Pb isotopic heterogeneity observed for the Azores. Because HSEs are largely controlled by sulfide, they provide an alternative to the classic perspective of OIB petrogenesis derived from lithophile elements. The results show distinct fractionation patterns for HSEs from different islands at a similar range of MgO contents. Lavas from Pico and Faial have lower absolute HSE abundances (total HSE abundances ~0.001 × CI chondrite; Ir=0.014-0.133 ppb) and are generally more homogeneous than lavas from Terceira and Sao Miguel (total HSE = ~0.003 × CI chondrite; Ir=0.038-0.657 ppb)). Faial and Pico lavas (IrN* = 0.8×0.3, where IrN* = IrN/[(OsN+RuN)0.5] x 100) also commonly lack the positive relative enrichment in Ir observed in Terceira and Sao Miguel lavas (IrN* = 2.4 ×1.1). In contrast to previous studies of OIB in which HSEs are observed to positively correlate with MgO (e.g., Day, 2013), only Re correlates with MgO, as expected given its moderate incompatibility in silicate systems. All other HSEs show wide variability at similar MgO, broadly correlate with each other, yet do not correlate with Nd-Hf-Pb isotope compositions. Thus, we interpret HSE variability to reflect variations in mantle sulfide source composition and sulfide melting beneath different islands in the Azores hotspot.

The evolution of 13C and 18O isotope composition of DIC in a calcite depositing film of water with isotope exchange between the DIC and a CO2 containing atmosphere, and simultaneous evaporation of the water. Implication to climate proxies from stalagmites: A theoretical model

NASA Astrophysics Data System (ADS)

Dreybrodt, Wolfgang; Romanov, Douchko

2016-12-01

The most widely applied climate proxies in speleothems are the isotope compositions of carbon and oxygen expressed by δ13C and δ18O values. However, mechanisms, which are not related to climate changes, overlay the climate signal. One is the temporal increase of both, δ13C and δ18O values by kinetic processes during precipitation of calcite. Isotope exchange between DIC in the water and the CO2 in the surrounding cave atmosphere can also change isotope composition. Here we present a theoretical model of the temporal isotope evolution of DIC in a thin water layer during precipitation of calcite and simultaneous isotope exchange with the cave atmosphere, and simultaneous evaporation of water. The exchange of oxygen isotopes in the DIC with those in the water is also considered.

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

NASA Astrophysics Data System (ADS)

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

2004-12-01

Many transition metals are essential micronutrients for marine phytoplankton. As a result the expectation is that biological processes play an important, perhaps a dominant, role in their marine isotope geochemistry. These observations raise the prospect of using isotope records to trace transition metal micronutrient usage in the past oceans, an issue that is of importance to the efficiency of the biological pump and atmospheric carbon dioxide. As such, the characterisation of trace metal isotopic fractionations associated with marine primary productivity are an important scientific goal. Here we report fractionations associated with Fe, Cu and Zn sequestration by diatoms, one of the main primary producers in the oceans. Axenic unialgal cultures of Thalassiosira weissflogii and Thalassiosira pseudonana were established in artificial seawater + F/2 medium at 18° C on a 16:8 light:dark cycle. The cultures were filtered to separate diatom material from residual media and analysed for Zn, Cu and Fe concentrations and isotope composition using techniques described elsewhere1,2. Aliquots of the starting medium were also measured for each batch of cultures. The diatom organic material shows small, but consistent and resolvable, positive fractionations (0.1-0.3 per mil) for Fe, Cu and Zn relative to the starting medium. In the case of all three metals, but particularly for Zn (70-95% depending on experiment size), the diatoms had sequestered a large proportion of the available metal, suggesting that the fractionation factor for metal usage by the diatoms is much greater than 1.0001 to 1.0003. Time-series experiments are under way to determine the exact magnitude of the fractionation factor. The mass-balance is supported by the fact that the residual medium is around -0.4 per mil for Zn. The fact that diatoms incorporate trace metals that are isotopically heavier than the nutrient pool is a surprising result, the expectation having been that, as with carbon, the biological usage of trace metals would result in kinetic fractionations3. The positive fractionations necessitate an equilibrium process and, perhaps, active extra-cellular sequestration of trace metals. The second broader implication is that given the proposed role of diatoms in controlling the extreme depletion of Zn in open ocean surface waters, particularly in the Pacific where surface waters are have up to a factor of 250 less Zn than deep waters4, the depletion of the light isotope in surface waters and its enrichment in deep waters are predicted to be extreme. Zn, and other trace metal, isotopes may have an important role in recording this process in the past oceans. 1 C. Archer and D. Vance, 2004, J. Anal. Atom. Spectr. 19, 656-665. 2 J. Bermin, et al., 2004, this volume. 3 Pichat, S et al., 2003, Earth Planet. Sci. Lett. 210, 167-178. 4 Lohan, M.C. et al., 2002, Deep-Sea Res. II 49, 5793-5808.

Making the Moon from a fast-spinning Earth: a giant impact followed by resonant despinning.

PubMed

Ćuk, Matija; Stewart, Sarah T

2012-11-23

A common origin for the Moon and Earth is required by their identical isotopic composition. However, simulations of the current giant impact hypothesis for Moon formation find that most lunar material originated from the impactor, which should have had a different isotopic signature. Previous Moon-formation studies assumed that the angular momentum after the impact was similar to that of the present day; however, Earth-mass planets are expected to have higher spin rates at the end of accretion. Here, we show that typical last giant impacts onto a fast-spinning proto-Earth can produce a Moon-forming disk derived primarily from Earth's mantle. Furthermore, we find that a faster-spinning early Earth-Moon system can lose angular momentum and reach the present state through an orbital resonance between the Sun and Moon.

Heterogeneity of the Caribbean plateau mantle source: Sr, O and He isotopic compositions of olivine and clinopyroxene from Gorgona Island

NASA Astrophysics Data System (ADS)

Révillon, S.; Chauvel, C.; Arndt, N. T.; Pik, R.; Martineau, F.; Fourcade, S.; Marty, B.

2002-12-01

The composition of the mantle plumes that created large oceanic plateaus such as Ontong Java or the Caribbean is still poorly known. Geochemical and isotopic studies on accreted portions of the Caribbean plateau have shown that the plume source was heterogeneous and contained isotopically depleted and relatively enriched portions. A distinctive feature of samples from the Caribbean plateau is their unusual Sr isotopic compositions, which, at a given Nd isotopic ratio, are far higher than in samples from other oceanic plateaus. Sr, O and He isotopic compositions of whole rocks and magmatic minerals (clinopyroxene or olivine) separated from komatiites, gabbros and peridotites from Gorgona Island in Colombia were determined to investigate the origin of these anomalously radiogenic compositions. Sequentially leached clinopyroxenes have Sr isotopic compositions in the range 87Sr/ 86Sr=0.70271-0.70352, systematically lower than those of leached and unleached whole rocks. Oxygen isotopic ratios of clinopyroxene vary within the range δ 18O=5.18-5.35‰, similar to that recorded in oceanic island basalts. He isotopic ratios are high ( R/ Ra=8-19). The lower 87Sr/ 86Sr ratios of most of the clinopyroxenes shift the field of the Caribbean plateau in Nd-Sr isotope diagrams toward more 'normal' values, i.e. a position closer to the field defined by mid-ocean ridge basalts and oceanic-island basalts. Three clinopyroxenes have slightly higher 87Sr/ 86Sr ratios that cannot be explained by an assimilation model. The high 87Sr/ 86Sr and variations of 143Nd/ 144Nd are interpreted as a source characteristic. Trace-element ratios, however, are controlled mainly by fractionation during partial melting. We combine these isotopic data in a heterogeneous plume source model that accounts for the diversity of isotopic signatures recorded on Gorgona Island and throughout the Caribbean plateau. The heterogeneities are related to old recycled oceanic lithosphere in the plume source; the high 3He/ 4He ratios may indicate that the source material once resided in the lower mantle.

Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

NASA Astrophysics Data System (ADS)

Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

2015-12-01

Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity present in single rock samples. This method highlights the potential of single grain isotope mapping of LREE phases such as monazite, allanite, and titanite for understanding both igneous and metamorphic petrogenesis.

Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

NASA Technical Reports Server (NTRS)

Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

1983-01-01

In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

Isotopic compositions of the elements 2013 (IUPAC Technical Report)

USGS Publications Warehouse

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

2016-01-01

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

Relationship between the trajectory of mid-latitude cyclones in the eastern Pacific Ocean and the isotopic composition of snowfall in the Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Vasquez, K. T.; Sickman, J. O.; Heard, A.; Lucero, D.

2013-12-01

Diatoms, preserved in lake sediments, provide a potential archive of snowfall variability in the Sierra Nevada through their sensitivity to changes in water chemistry (a proxy for runoff volume) and by recording the isotopic composition of snow-melt (potentially a proxy for sources of atmospheric moisture). In the Sierra Nevada, we hypothesize that the oxygen isotopic composition of diatom silica is principally controlled by snow and that the isotopic composition of snow varies as a function of the tracks of mid-latitude cyclonic storms in the eastern Pacific Ocean. Snow samples from discrete storms were collected from December 2012 to March 2013 at 2042 meters a.s.l. in Sequoia National Park. The δ18O and δ2H values of the snow samples were measured using a temperature-conversion elemental analyzer coupled to a Delta V isotope ratio mass spectrometer. The isotopic measurements were then coupled to 3, 5 and 7-day air mass back trajectories using the NOAA HYSPLIT model. The measured δ18O values ranged from -17.6 to -7.8 per mil and the δ2H ranged from -119.8 to -73.3 per mil. Both δ18O and δ2H were inversely related to the latitude of the storm origin (R^2 values of 0.67 and 0.57, respectively). Winter storms from the Gulf of Alaska were the most isotopically depleted while storms originating in the subtropical/tropical Pacific were the most isotopically enriched, reflecting the overall latitudinal pattern of ocean-water isotope composition in the Pacific Ocean. Our results suggest that the isotopic composition of Sierra Nevada snowfall is influenced by storm track trajectory and this relationship could be useful in interpreting the climatic significance of δ18O of diatom silica preserved in lake cores.

Overview and Brief History of the Boron Isotope Proxy for Past Seawater pH

NASA Astrophysics Data System (ADS)

Hoenisch, B.; Hemming, G.

2007-05-01

In 1992 Hemming and Hanson (GCA, vol. 56, p. 537-543) showed that a variety of modern marine carbonates revealed a boron isotopic composition close to the isotopic composition of dissolved borate at modern seawater pH, suggesting this was the boron species preferentially adsorbed and incorporated into marine carbonates. With a constant offset between the trigonal and tetrahedrally coordinated boron species and a pH-dependent variation in their fractions, it appeared that this system would be sensitive to pH changes in the natural range of seawater. Accordingly, it was suggested that the boron isotope composition of marine carbonates is a proxy for past seawater pH. Subsequent culture studies with living planktic foraminifers and corals, as well as synthetic precipitation experiments confirmed that the boron isotopic composition follows the isotopic composition of borate across a wide range of seawater pH. In order to use the proxy with confidence, however, all other controls apart from pH need to be thoroughly understood. Recent laboratory and sediment experiments have demonstrated that vital effects and partial shell dissolution have the potential to modify the primary seawater pH signal recorded in the boron isotopic composition of planktic foraminifers. However it has also been shown that careful sample selection allows for avoiding these potential complications. A record of reconstructed surface seawater pH and estimated aqueous PCO2 shows a remarkable match between boron isotope based atmospheric pCO2 estimates and the Vostok ice core CO2 record. This convincingly demonstrates that boron isotopes in planktic foraminifers allow quantitative estimates of atmospheric pCO2 in the past, and confirms that glacial surface ocean pH was ~0.2 units higher compared to interglacial periods. We are going to review and discuss the achievements generated in Gil Hanson's lab over the past 15 years in the light of recent empirical measurements of the boron isotope fractionation between boric acid and borate in seawater.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

Zinc isotopes have been widely applied in the cosmochemical, geochemical, and environmental studies (Moynier et al. 2017). Obtaining precise Zn isotopic data for inter-laboratory comparison is a prerequisite to these applications. Currently, the JMC3-0749L is the primary reference standard for Zn isotopes (Albarède 2004), but it is not commercially available now. Thus, it is necessary to calibrate a new international primary reference standard for Zn isotopic analysis. Chen et al. (2016) showed that NIST SRM 683 (a pure Zn metal nugget of 140 grams) has a δ66ZnJMC of 0.12‰, which is falling within the range of natural Zn isotopic compositions, and it may a good candidate for the next generation of international reference standard (Chen et al. 2016). In order to further examine whether NIST SRM 683 has a homogeneous Zn isotopic composition, we measured more NIST SRM 683 by double-spike methods using MC-ICPMS (Conway et al. 2013). The metal nuggets of NIST SRM 683 were intensively sampled by micro-drilling. Zinc isotope analyses for two nuggets show that they have δ66Zn of 0.14 ± 0.02‰ (2SD, N = 32) and 0.13 ± 0.02‰ (2SD, N = 33), respectively. These values are similar to those of two Zn metal nuggets (0.11 ± 0.02‰ vs. 0.12 ± 0.02‰) reported previously by Chen et al. (2016). We fully dissolved one nugget, producing pure Zn solution with identical Zn isotopic composition with the drilling samples. All results strongly support that NIST SRM 683 is homogeneous in Zn isotopic compositions which could be an ideal candidate for the next reference for Zn isotopes. Tests on more metal nuggets will be performed in a few months for further confirming the Zn isotope compositions and homogeneity. Reference: Albarède et al., 2004. 'The stable isotope geochemistry of copper and zinc', Reviews in Mineralogy and Geochemistry, 55: 409-27. Chen et al., 2016. 'Zinc Isotopic Compositions of NIST SRM 683 and Whole-Rock Reference Materials', Geostandards and Geoanalytical Research, 40: 417-32. Conway et al., 2013. 'A new method for precise determination of iron, zinc and cadmium stable isotope ratios in seawater by double-spike mass spectrometry', Analytica chimica acta, 793: 44-52. Moynier et al., 2017. 'The isotope geochemistry of zinc and copper', Reviews in Mineralogy and Geochemistry, 82: 543-600.

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

Conroy, Jessica L; Cobb, Kim M; Noone, David

The objective of this field campaign was to investigate climatic controls on the stable isotopic composition of water vapor, precipitation, and seawater in the western tropical Pacific. Simultaneous measurements of the stable isotopic composition of vapor and precipitation from April 28 to May 8, 2013, at the Manus Tropical Western Pacific Atmospheric Radiation Measurement site, provided several key insights into the nature of the climate signal archived in precipitation and vapor isotope ratios. We observed a large shift from lower to higher isotopic values in vapor and precipitation because of the passage of a mesoscale convective system west of themore » site and a transition from a regional stormy period into a more quiescent period. During the quiescent period, the stable isotopic composition of vapor and precipitation indicated the predominance of oceanic evaporation in determining the isotopic composition of boundary-layer vapor and local precipitation. There was not a consistent relationship between intra-event precipitation amount at the site and the stable isotopic composition of precipitation, thus challenging simplified assumptions about the isotopic “amount effect” in the tropics on the time scale of individual storms. However, some storms did show an amount effect, and deuterium excess values in precipitation had a significant relationship with several meteorological variables, including precipitation, temperature, relative humidity, and cloud base height across all measured storms. The direction of these relationships points to condensation controls on precipitation deuterium excess values on intra-event time scales. The relationship between simultaneous measurements of vapor and precipitation isotope ratios during precipitation events indicates the ratio of precipitation-to-vapor isotope ratios can diagnose precipitation originating from a vapor source unique from boundary-layer vapor and rain re-evaporation.« less

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.

High-precision 87Sr/86Sr analyses in wines and their use as a geological fingerprint for tracing geographic provenance.

PubMed

Marchionni, Sara; Braschi, Eleonora; Tommasini, Simone; Bollati, Andrea; Cifelli, Francesca; Mulinacci, Nadia; Mattei, Massimo; Conticelli, Sandro

2013-07-17

The radiogenic isotopic compositions of inorganic heavy elements such as Sr, Nd, and Pb of the food chain may constitute a reliable geographic fingerprint, their isotopic ratios being inherited by the geological substratum of the territory of production. The Sr isotope composition of geomaterials (i.e., rocks and soils) is largely variable, and it depends upon the age of the rocks and their nature (e.g., genesis, composition). In this study we developed a high-precision analytical procedure for determining Sr isotopes in wines at comparable uncertainty levels of geological data. With the aim of verifying the possibility of using Sr isotope in wine as a reliable tracer for geographic provenance, we performed Sr isotope analyses of 45 bottled wines from four different geographical localities of the Italian peninsula. Their Sr isotope composition has been compared with that of rocks from the substrata (i.e., rocks) of their vineyards. In addition wines from the same winemaker but different vintage years have been analyzed to verify the constancy with time of the (87)Sr/(86)Sr. Sr isotope compositions have been determined by solid source thermal ionization mass spectrometry following purification of Sr in a clean laboratory. (87)Sr/(86)Sr of the analyzed wines is correlated with the isotopic values of the geological substratum of the vineyards, showing little or no variation within the same vineyard and among different vintages. Large (87)Sr/(86)Sr variation is observed among wines from the different geographical areas, reinforcing the link with the geological substratum of the production territory. This makes Sr isotopes a robust geochemical tool for tracing the geographic authenticity and provenance of wine.

Tracing Life in the Earliest Terrestrial Rock Record

NASA Astrophysics Data System (ADS)

Lepland, A.; van Zuilen, M.; Arrhenius, G.

2001-12-01

The principal method for studying the earliest traces of life in the metamorphosed, oldest (> 3.5 Ga) terrestrial rocks involves determination of isotopic composition of carbon, mainly prevailing as graphite. It is generally believed that this measure can distinguish biogenic graphite from abiogenic varieties. However, the interpretation of life from carbon isotope ratios has to be assessed within the context of specific geologic circumstances requiring (i) reliable protolith interpretation (ii) control of secondary, metasomatic processes, and (iii) understanding of different graphite producing mechanisms and related carbon isotopic systematics. We have carried out a systematic study of abundance, isotopic composition and petrographic associations of graphite in rocks from the ca. 3.8 Ga Isua Supracrustal Belt (ISB) in southern West Greenland. Our study indicates that most of the graphite in ISB occurs in carbonate-rich metasomatic rocks (metacarbonates) while sedimentary units, including banded iron formations (BIFs) and metacherts, have exceedingly low graphite concentrations. Regardless of isotopic composition of graphite in metacarbonate rocks, their secondary origin disqualifies them from providing evidence for traces of life stemming from 3.8 Ga. Recognition of the secondary origin of Isua metacarbonates thus calls for reevaluation of biologic interpretations by Schidlowski et al. (1979) and Mojzsis et al. (1996) that suggested the occurrence of 3.8 Ga biogenic graphite in these rocks. The origin of minute quantities of reduced carbon, released from sedimentary BIFs and metacherts at combustion steps > 700 C remains to be clarified. Its isotopic composition (d13C from -18 to -25%) may hint at a biogenic origin. However, such isotopically light carbon was also found in Proterozoic mafic dykes cross-cutting the metasedimentary units in the ISB. The occurrence of isotopically light, reduced carbon in biologically irrelevant dykes may indicate secondary graphite crystallization from CO2 or CH4- containing fluids that in turn may derive from bioorganic sources. If this were the case, trace amounts of isotopically light secondary graphite can also be expected in metasediments, complicating the usage of light graphite as primary biomarker. The possibility of recent organic contamination, particularly important in low graphite samples, needs also to be considered; it appears as a ubiquitous component released at combustion in the 400 to 500 deg range. - A potential use of the apatite-graphite association as a biomarker has been proposed in the study by Mojzsis et al. (1996). Close inspection of several hundred apatite crystals from Isua BIFs and metacherts did, however, not show an association between these two minerals, moreover graphite is practically absent in these metasediments. In contrast, apatite crystals in the non-sedimentary metacarbonate rocks were found commonly to have invaginations, coatings and inclusions of abundant graphite. Considering that such graphite inclusions in apatite are restricted to the secondary metasomatic carbonate rocks in the ISB this association can not be considered as a primary biomarker in the Isua Supracrustal Belt References: Mojzsis,S.J, .Arrhenius,G., McKeegan, K.D.,.Harrison, T.M.,.Nutman, A.P & C.R.L.Friend.,1996. Nature 384: 55 Schidlowski, M., Appel, P.W.U., Eichmann, R. & Junge, C.E., 1979. Geochim. Cosmochim. Acta 43: 189-190.

Effect Of Substrates On The Fractionation Of Hydrogen Isotopes During Lipid-Biosynthesis By Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, S. S.; Pagani, M.

2010-12-01

Lipids form an important class of proxies for paleoclimatological research, and hydrogen isotope ratios of lipids are being increasingly used for understanding changes in the hydrological system. Proper understanding of hydrogen isotope fractionation during lipid biosynthesis is therefore important and attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis in various organisms. Hydrogen isotope ratios of lipids depend on the hydrogen isotopic composition of the ambient water, hydrogen isotopic composition of NADPH used during biosynthesis, growth conditions, pathways of lipid biosynthesis, and substrates in the case of heterotrophic organisms. Recently it has been observed that NADPH contributes a significant part of the hydrogen in fatty acids synthesized by bacteria during heterotrophic growth (Zhang et al, 2009). As NADPH is formed by reduction of NADP+ during metabolism of substrates, different metabolic pathways form NADPH with different D/H ratios, which in turn results in variation in D/H ratios of lipids (Zhang et al, 2009). Therefore, substrates play a significant role in hydrogen isotopic compositions of lipids. For this study, we are investigating the effects of substrates on hydrogen isotope fractionation during biosynthesis of isoprenoidal lipids by heterotrophically growing halophilic archaea. Haloarcula marismortui is a halophilic archaea which synthesizes Archaeol (a diether lipid) and other isoprenoidal lipids. We have grown Haloarcula marismortui in pure cultures on three different substrates and are in the process of evaluating isotopic variability of Archaeol and other lipids associated with substrate and the D/H composition of ambient water. Our results will be helpful for a better understanding of hydrogen isotope fractionations during lipid synthesis by archaea. Also, halophilic archaea are the only source of archaeol in hypersaline environments. Therefore, our results will also indicate whether archaeol can be used as a proxy of ambient water hydrogen isotopic compositions in hypersaline environments.

A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis

NASA Technical Reports Server (NTRS)

Boehme, Susan E.

1993-01-01

A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

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

NASA Technical Reports Server (NTRS)

Mewaldt, R. A.

1980-01-01

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

Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

NASA Technical Reports Server (NTRS)

Boreham, C. J.; Fookes, C. J.; Popp, B. N.; Hayes, J. M.

1990-01-01

Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

New technique for study on isotopic fractionation between sea water and foraminiferal growing processes

NASA Astrophysics Data System (ADS)

Cang, Shuxi; Shackleton, N. J.

1990-12-01

The stable isotopic δ18O and δ13C composition of foraminiferal shell calcite varies as a function of many factors including temperature and salinity. In order to understand and interpret the variations in the isotopic composition of foraminiferal shell calcite, research has been recently focused on the role of the “vital effects”. Our examination of the lamella structure of several recent planktonic foraminifera indicates that the secretion of sequential lamellae results in multiple lamillae on earlier chambers and a single lamella on the final chamber. We used a very simple procedure to separate the individual whole test of foraminifera into several chambers and measured the isotopic composition of each growth stage chamber. The results indicate that the stable isotopic composition (carbon and oxygen), particularly that of the last two chambers, of the foraminiferal test varies as a function of the individual growing process.

Hafnium isotope stratigraphy of ferromanganese crusts

PubMed

Lee; Halliday; Hein; Burton; Christensen; Gunther

1999-08-13

A Cenozoic record of hafnium isotopic compositions of central Pacific deep water has been obtained from two ferromanganese crusts. The crusts are separated by more than 3000 kilometers but display similar secular variations. Significant fluctuations in hafnium isotopic composition occurred in the Eocene and Oligocene, possibly related to direct advection from the Indian and Atlantic oceans. Hafnium isotopic compositions have remained approximately uniform for the past 20 million years, probably reflecting increased isolation of the central Pacific. The mechanisms responsible for the increase in (87)Sr/(86)Sr in seawater through the Cenozoic apparently had no effect on central Pacific deep-water hafnium.

A Sr and Mg isotopic study of soil and stream waters along an erosional gradient, Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Rosen, V. B.; Maher, K.; Kouba, C. M.; Weinman, B. A.; Yoo, K.; Mudd, S. M.

2012-12-01

Since chemical weathering rates are proposed to regulate atmospheric CO2 concentrations and by extension global temperature over geologic timescales, understanding the relationship between chemical weathering rates and physical erosion is crucial to accurately interpreting Earth's climate history. The rate of supply of fresh minerals to the weathering zone is known to be an important control on chemical weathering rates. However, the consequences of physical erosion on the isotopic composition of weathering-derived solutes are more difficult to assess. This study capitalizes on a series of granitic hillslope transects with different erosion rates but similar climate, vegetation, and bedrock, in order to assess the consequences of erosion on the Sr and Mg isotopic composition of solutes. Reactive transport model simulations of varying complexity have been used to complement the field measurements and to analyze the sensitivity of fluid isotopic compositions to changes in key parameters such as erosion rate, flow rate, and biological cycling. The three hillslopes in the Feather River Basin, California reflect different degrees of channel erosion at their bases—BRC is a hillslope with active channel incision (60% average slope, below the knickpoint), FTA is a hillslope reflecting the transition between the relict and modern-day incising areas (50% average slope, at the knickpoint), and POMD is a 30% average hillslope in the relict landscape above the knickpoint. We measured the major element compositions, as well as the Sr and Mg isotopic compositions of soil water leaches (deionized water leaches), lysimeters, stream waters, and groundwaters by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The 87Sr/86Sr values of soil and stream waters show minimal variation (0.7042 to 0.7046) as a function of soil depth, erosion rate, or sampling season despite abundant radiogenic biotite in the profiles. These results agree with the reactive transport model predictions at high erosion rates, and suggest that soil residence times and isotopic equilibrium times are too short for biotite weathering to influence the solute isotopic composition. In contrast, model results for δ26Mg of the soil waters and minerals suggest that the Mg isotopic composition of the solute changes as a function of erosion rate because of shorter isotopic equilibrium length scales at higher erosion rates. The isotopic reactive transport modeling, combined with hillslope depth profiles and stream water analyses, provides a useful approach for linking the isotopic composition of solutes to erosion rates. This study may provide insights into past and present riverine isotopic compositions, and contribute to our understanding of how surface processes have influenced past atmospheric conditions.

Importance of depth and intensity of convection on the isotopic composition of water vapor as seen from IASI and TES δD observations

NASA Astrophysics Data System (ADS)

Lacour, Jean-Lionel; Risi, Camille; Worden, John; Clerbaux, Cathy; Coheur, Pierre-François

2018-01-01

We use tropical observations of the water vapor isotopic composition, derived from IASI and TES spaceborne measurements, to show that the isotopic composition of water vapor in the free troposphere is sensitive to both the depth and the intensity of convection. We find that for any given precipitation intensity, vapor associated with deep convection is isotopically depleted relative to vapor associated with shallow convection. The intensity of precipitation also plays a role as for any given depth of convection, the relative enrichment of water vapor decreases as the intensity of precipitation increases. Shallow convection, via the uplifting of enriched boundary layer air into the free troposphere and the convective detrainment, enriches the free troposphere. In contrast, deep convection is associated with processes that deplete the water vapor in the free troposphere, such as rain re-evaporation. The results of this study allow for a better identification of the parameters controlling the isotopic composition of the free troposphere and indicate that the isotopic composition of water vapor can be used to evaluate the relative contributions of shallow and deep convection in global models.

Magnesium isotope evidence that accretional vapour loss shapes planetary compositions

PubMed Central

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

What controls silicon isotope fractionation during dissolution of diatom opal?

NASA Astrophysics Data System (ADS)

Wetzel, F.; de Souza, G. F.; Reynolds, B. C.

2014-04-01

The silicon isotope composition of opal frustules from photosynthesising diatoms is a promising tool for studying past changes in the marine silicon cycle, and indirectly that of carbon. Dissolution of this opal may be accompanied by silicon isotope fractionation that could disturb the pristine silicon isotope composition of diatom opal acquired in the surface ocean. It has previously been shown that dissolution of fresh and sediment trap diatom opal in seawater does fractionate silicon isotopes. However, as the mechanism of silicon isotope fractionation remained elusive, it is uncertain whether opal dissolution in general is associated with silicon isotope fractionation considering that opal chemistry and surface properties are spatially and temporally (i.e. opal of different age) diverse. In this study we dissolved sediment core diatom opal in 5 mM NaOH and found that this process is not associated with significant silicon isotope fractionation. Since no variability of the isotope effect was observed over a wide range of dissolution rates, we can rule out the suggestion that back-reactions had a significant influence on the net isotope effect. Similarly, we did not observe an impact of temperature, specific surface area, or degree of undersaturation on silicon isotope partitioning during dissolution, such that these can most likely also be ruled out as controlling factors. We discuss the potential impacts of the chemical composition of the dissolution medium and age of diatom opal on silicon isotope fractionation during dissolution. It appears most likely that the controlling mechanism of silicon isotope fractionation during dissolution is related to the reactivity, or potentially, aluminium content of the opal. Such a dependency would imply that silicon isotope fractionation during dissolution of diatom opal is spatially and temporally variable. However, since the isotope effects during dissolution are small, the silicon isotope composition of diatom opal appears to be robust against dissolution in the deep sea sedimentary environment.

Characteristics of Martian Crustal Materials and Implications for Magmatic Assimilation: Preliminary Re-Os Isotope and Highly Siderophile Element Abundance Data for Nakhlites and Tissint

NASA Astrophysics Data System (ADS)

Mari, N.; Riches, A. J. V.; Hallis, L. J.; Lee, M. R.

2017-07-01

This project, for the first time, aims to integrate nakhlite Os-isotope compositions and HSE abundance data with S-isotope compositions for sample fractions for which textural information is constrained prior to destructive analyses.

Isotopic Composition of Barium in Single Presolar Silicon Carbide Grains

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Soil drying effects on the carbon isotope composition of soil respiration

EPA Science Inventory

Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...

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.

Isotopic anomalies - Chemical memory of Galactic evolution

NASA Technical Reports Server (NTRS)

Clayton, Donald D.

1988-01-01

New mechanisms for the chemical memory of isotopic anomalies are proposed which are based on the temporal change during the chemical evolution of the Galaxy of the isotopic composition of the mean ejecta from stars. Because of the differing temporal evolution of primary and secondary products of nucleosynthesis, the isotopic composition of the bulk interstellar medium changes approximately linearly with time, and thus any dust component having an age different from that of average dust will be isotopically anomalous. Special attention is given to C, O, Mg, Si, and isotopically heavy average-stellar condensates of SiC.

Continental sedimentary processes decouple Nd and Hf isotopes

NASA Astrophysics Data System (ADS)

Garçon, Marion; Chauvel, Catherine; France-Lanord, Christian; Huyghe, Pascale; Lavé, Jérôme

2013-11-01

The neodymium and hafnium isotopic compositions of most crustal and mantle rocks correlate to form the "Terrestrial Array". However, it is now well established that whereas coarse detrital sediments follow this trend, fine-grained oceanic sediments have high Hf ratios relative to their Nd isotopic ratios. It remains uncertain whether this "decoupling" of the two isotopic systems only occurs in the oceanic environment or if it is induced by sedimentary processes in continental settings. In this study, the hafnium and neodymium isotopic compositions of sediments in large rivers is expressly used to constrain the behavior of the two isotopic systems during erosion and sediment transport from continent to ocean. We report major and trace element concentrations together with Nd and Hf isotopic compositions of bedloads, suspended loads and river banks from the Ganges River and its tributaries draining the Himalayan Range i.e. the Karnali, the Narayani, the Kosi and the Marsyandi Rivers. The sample set includes sediments sampled within the Himalayan Range in Nepal, at the Himalayan mountain front, and also downstream on the floodplain and at the outflow of the Ganges in Bangladesh. Results show that hydrodynamic sorting of minerals explains the entire Hf isotopic range, i.e. more than 10 εHf units, observed in the river sediments but does not affect the Nd isotopic composition. Bedloads and bank sediments have systematically lower εHf values than suspended loads sampled at the same location. Coarse-grained sediments lie below or on the Terrestrial Array in an εHf vs. εNd diagram. In contrast, fine-grained sediments, including most of the suspended loads, deviate from the Terrestrial Array toward higher εHf relative to their εNd, as is the case for oceanic terrigenous clays. The observed Nd-Hf decoupling is explained by mineralogical sorting processes that enrich bottom sediments in coarse and dense minerals, including unradiogenic zircons, while surface sediments are enriched in fine material with radiogenic Hf signatures. The data also show that Nd-Hf isotopic decoupling increases with sediment transport in the floodplain to reach its maximum at the river mouth. This implies that the Nd-Hf isotopic decoupling observed in worldwide oceanic clays and river sediments is likely to have the same origin. Finally, we estimated the Nd-Hf isotopic composition of the present-day mantle if oceanic sediments had never been subducted and conclude that the addition of oceanic sediments with their anomalous Nd-Hf isotopic compositions has slowly shifted the composition of the Earth's mantle towards more radiogenic Hf values through time.

On the Origin of GEMS

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.

2004-01-01

GEMS (glass with embedded metal and sulfides) are a major component of anhydrous interplanetary dust particles (IDPs) their physical and chemical characteristics show marked similarities to contemporary interstellar dust. Recent oxygen isotopic measurements confirm that at least a small fraction (less than 5%) of GEMS are demonstrably presolar, while the remainder have ratios that are indistinguishable from solar values. GEMS with solar oxygen isotopic compositions either (1) had their isotopic compositions homogenized through processing in the interstellar medium (ISM), or (2) formed in the early solar system. Isotopic homogenization necessarily implies chemical homogenization, so (interstellar) GEMS compositions should reflect the average composition of dust in the local ISM. We performed a systematic examination of the bulk chemistry of GEMS in primitive IDPs in order to test this hypothesis.

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.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

Measurements on a set of cold-water corals (mainly Desmophyllum dianthus) have suggested that their clumped isotope composition could serve as a promising proxy for reconstructing paleocean temperatures. Such measurements have also offered support for certain isotope models of coral calcification. However, there are differences in the clumped isotope compositions between warm-water and cold-water corals, suggesting that different kinds of corals could have differences in their biocalcification processes. In order to understand the systematics of clumped isotope variations in cold-water corals more fully, we present clumped isotope data from a range of cold-water coral species from the tropical Atlantic and the Southern Ocean.Our samples were either collected live or recently dead (14C ages < 1,000 yrs) with associated temperature data. They include a total of 11 solitary corals and 1 colonial coral from the Atlantic, and 8 solitary corals from the Southern Ocean. The data indicate that coral clumped isotope systematics may be more complicated than previously thought. For example, for the genus Caryophyllia we observe significant variations in clumped isotope compositions for corals which grew at the same temperature with an apparent negative correlation between Δ47 and δ18O, different to patterns previously observed in Desmophyllum. These results indicate that existing isotope models of biocalcification may not apply equally well to all corals. Clumped isotope vital effects may be present in certain cold-water corals as they are in warm-water corals, complicating the use of this paleoclimate proxy.

An open source Bayesian Monte Carlo isotope mixing model with applications in Earth surface processes

NASA Astrophysics Data System (ADS)

Arendt, Carli A.; Aciego, Sarah M.; Hetland, Eric A.

2015-05-01

The implementation of isotopic tracers as constraints on source contributions has become increasingly relevant to understanding Earth surface processes. Interpretation of these isotopic tracers has become more accessible with the development of Bayesian Monte Carlo (BMC) mixing models, which allow uncertainty in mixing end-members and provide methodology for systems with multicomponent mixing. This study presents an open source multiple isotope BMC mixing model that is applicable to Earth surface environments with sources exhibiting distinct end-member isotopic signatures. Our model is first applied to new δ18O and δD measurements from the Athabasca Glacier, which showed expected seasonal melt evolution trends and vigorously assessed the statistical relevance of the resulting fraction estimations. To highlight the broad applicability of our model to a variety of Earth surface environments and relevant isotopic systems, we expand our model to two additional case studies: deriving melt sources from δ18O, δD, and 222Rn measurements of Greenland Ice Sheet bulk water samples and assessing nutrient sources from ɛNd and 87Sr/86Sr measurements of Hawaiian soil cores. The model produces results for the Greenland Ice Sheet and Hawaiian soil data sets that are consistent with the originally published fractional contribution estimates. The advantage of this method is that it quantifies the error induced by variability in the end-member compositions, unrealized by the models previously applied to the above case studies. Results from all three case studies demonstrate the broad applicability of this statistical BMC isotopic mixing model for estimating source contribution fractions in a variety of Earth surface systems.

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.

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

NASA Astrophysics Data System (ADS)

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

2008-02-01

Kaersutitic amphiboles found within a subset of the Martian meteorites have low water contents and variably heavy hydrogen isotope compositions. In order to assess if impact shock-induced devolatilization and hydrogen isotope fractionation were determining factors in these water and isotopic characteristics of the Martian kaersutites, we conducted impact shock experiments on samples of Gore Mountain amphibolite in the Ames Vertical Gun Range (AVGR). A parallel shock experiment conducted on an anorthosite sample indicated that contamination of shocked samples by the AVGR hydrogen propellant was unlikely. Petrographic study of the experimental amphibolite shock products indicates that only ˜ 10% of the shock products experienced levels of damage equivalent to those found in the most highly shocked kaersutite-bearing Martian meteorites (30-35 GPa). Ion microprobe studies of highly shocked hornblende from the amphibolite exhibited elevated water contents (ΔH 2O ˜ 0.1 wt.%) and enriched hydrogen isotope compositions (Δ D ˜ + 10‰) relative to unshocked hornblende. Water and hydrogen isotope analyses of tens of milligrams of unshocked, moderately shocked, and highly shocked hornblende samples by vacuum extraction/uranium reduction and isotope ratio mass spectrometry (IRMS), respectively, are largely consistent with analyses of single grains from the ion microprobe. The mechanisms thought to have produced the excess water in most of the shocked hornblendes are shock-induced reduction of hornblende Fe and/or irreversible adsorption of hydrogen. Addition of the isotopically enriched Martian atmosphere to the Martian meteorite kaersutites via these mechanisms could explain their enriched and variable isotopic compositions. Alternatively, regrouping the water extraction and IRMS analyses on the basis of isotopic composition reveals a small, but consistent, degree of impact-induced devolatilization (˜ 0.1 wt.% H 2O) and H isotope enrichment (Δ D ˜ + 10‰). Extrapolating the shock signature of the regrouped data to grains that experienced Martian meteorite-like shock pressures suggests that shock-induced water losses and hydrogen isotope enrichments could approach 1 wt.% H 2O and Δ D = + 100‰, respectively. If these values are valid, then impact shock effects could explain a substantial fraction of the low water contents and variable hydrogen isotope compositions of the Martian meteorite kaersutites.

FE and MG Isotopic Analyses of Isotopically Unusual Presolar Silicate Grains

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Messenger, S.; Ito, M.; Rahman, Z.

2011-01-01

Interstellar and circumstellar silicate grains are thought to be Mg-rich and Fe-poor, based on astronomical observations and equilibrium condensation models of silicate dust formation in stellar outflows. On the other hand, presolar silicates isolated from meteorites have surprisingly high Fe contents and few Mg-rich grains are observed. The high Fe contents in meteoritic presolar silicates may indicate they formed by a non-equilibrium condensation process. Alternatively, the Fe in the stardust grains could have been acquired during parent body alteration. The origin of Fe in presolar silicates may be deduced from its isotopic composition. Thus far, Fe isotopic measurements of presolar silicates are limited to the Fe-54/Fe-56 ratios of 14 grains. Only two slight anomalies (albeit solar within error) were observed. However, these measurements suffered from contamination of Fe from the adjacent meteorite matrix, which diluted any isotopic anomalies. We have isolated four presolar silicates having unusual O isotopic compositions by focused ion beam (FIB) milling and obtained their undiluted Mg and Fe isotopic compositions. These compositions help to identify the grains stellar sources and to determine the source of Fe in the grains.

Isotopic composition of transpiration and rates of change in leaf water isotopologue storage in response to environmental variables.

PubMed

Simonin, Kevin A; Roddy, Adam B; Link, Percy; Apodaca, Randy; Tu, Kevin P; Hu, Jia; Dawson, Todd E; Barbour, Margaret M

2013-12-01

During daylight hours, the isotope composition of leaf water generally approximates steady-state leaf water isotope enrichment model predictions. However, until very recently there was little direct confirmation that isotopic steady-state (ISS) transpiration in fact exists. Using isotope ratio infrared spectroscopy (IRIS) and leaf gas exchange systems we evaluated the isotope composition of transpiration and the rate of change in leaf water isotopologue storage (isostorage) when leaves were exposed to variable environments. In doing so, we developed a method for controlling the absolute humidity entering the gas exchange cuvette for a wide range of concentrations without changing the isotope composition of water vapour. The measurement system allowed estimation of (18)O enrichment both at the evaporation site and for bulk leaf water, in the steady state and the non-steady state. We show that non-steady-state effects dominate the transpiration isoflux even when leaves are at physiological steady state. Our results suggest that a variable environment likely prevents ISS transpiration from being achieved and that this effect may be exacerbated by lengthy leaf water turnover times due to high leaf water contents. © 2013 John Wiley & Sons Ltd.

Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Kawasaki, Noriyuki; Simon, Steven B.; Grossman, Lawrence; Sakamoto, Naoya; Yurimoto, Hisayoshi

2018-01-01

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of fassaite, indicating co-crystallization of these two minerals during the earliest to intermediate stage of fassaite growth. The melilite and fassaite yield an 26Al-26Mg mineral isochron with an initial value of (26Al/27Al)0 = (5.003 ± 0.075) × 10-5, corresponding to a relative age of 0.05 ± 0.02 Myr from the canonical Al-Mg age of CAIs. These data demonstrate that both 16O-rich and 16O-poor reservoirs existed in the solar nebula at least ∼0.05 Myr after the birth of the Solar System.

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.

Chromium isotope heterogeneity in the mantle

NASA Astrophysics Data System (ADS)

Xia, Jiuxing; Qin, Liping; Shen, Ji; Carlson, Richard W.; Ionov, Dmitri A.; Mock, Timothy D.

2017-04-01

To better constrain the Cr isotopic composition of the silicate Earth and to investigate potential Cr isotopic fractionation during high temperature geological processes, we analyzed the Cr isotopic composition of different types of mantle xenoliths from diverse geologic settings: fertile to refractory off-craton spinel and garnet peridotites, pyroxenite veins, metasomatised spinel lherzolites and associated basalts from central Mongolia, spinel lherzolites and harzburgites from North China, as well as cratonic spinel and garnet peridotites from Siberia and southern Africa. The δ53CrNIST 979 values of the peridotites range from - 0.51 ± 0.04 ‰ (2SD) to + 0.75 ± 0.05 ‰ (2SD). The results show a slight negative correlation between δ53Cr and Al2O3 and CaO contents for most mantle peridotites, which may imply Cr isotopic fractionation during partial melting of mantle peridotites. However, highly variable Cr isotopic compositions measured in Mongolian peridotites cannot be caused by partial melting alone. Instead, the wide range in Cr isotopic composition of these samples most likely reflects kinetic fractionation during melt percolation. Chemical diffusion during melt percolation resulted in light Cr isotopes preferably entering into the melt. Two spinel websterite veins from Mongolia have extremely light δ53Cr values of - 1.36 ± 0.04 ‰ and - 0.77 ± 0.06 ‰, respectively, which are the most negative Cr isotopic compositions yet reported for mantle-derived rocks. These two websterite veins may represent crystallization products from the isotopically light melt that may also metasomatize some peridotites in the area. The δ53Cr values of highly altered garnet peridotites from southern Africa vary from - 0.35 ± 0.04 ‰ (2SD) to + 0.12 ± 0.04 ‰ (2SD) and increase with increasing LOI (Loss on Ignition), reflecting a shift of δ53Cr to more positive values by secondary alteration. The Cr isotopic composition of the pristine, fertile upper mantle is estimated as δ53Cr = - 0.14 ± 0.12 ‰, after corrections for the effects of partial melting and metasomatism. This value is in line with that estimated for the BSE (- 0.12 ± 0.10 ‰) previously.

Reassessment of the NH4 NO3 thermal decomposition technique for calibration of the N2 O isotopic composition.

PubMed

Mohn, Joachim; Gutjahr, Wilhelm; Toyoda, Sakae; Harris, Eliza; Ibraim, Erkan; Geilmann, Heike; Schleppi, Patrick; Kuhn, Thomas; Lehmann, Moritz F; Decock, Charlotte; Werner, Roland A; Yoshida, Naohiro; Brand, Willi A

2016-09-08

In the last few years, the study of N 2 O site-specific nitrogen isotope composition has been established as a powerful technique to disentangle N 2 O emission pathways. This trend has been accelerated by significant analytical progress in the field of isotope-ratio mass-spectrometry (IRMS) and more recently quantum cascade laser absorption spectroscopy (QCLAS). Methods The ammonium nitrate (NH 4 NO 3 ) decomposition technique provides a strategy to scale the 15 N site-specific (SP ≡ δ 15 N α - δ 15 N β ) and bulk (δ 15 N bulk  = (δ 15 N α  + δ 15 N β )/2) isotopic composition of N 2 O against the international standard for the 15 N/ 14 N isotope ratio (AIR-N 2 ). Within the current project 15 N fractionation effects during thermal decomposition of NH 4 NO 3 on the N 2 O site preference were studied using static and dynamic decomposition techniques. The validity of the NH 4 NO 3 decomposition technique to link NH 4 + and NO 3 - moiety-specific δ 15 N analysis by IRMS to the site-specific nitrogen isotopic composition of N 2 O was confirmed. However, the accuracy of this approach for the calibration of δ 15 N α and δ 15 N β values was found to be limited by non-quantitative NH 4 NO 3 decomposition in combination with substantially different isotope enrichment factors for the conversion of the NO 3 - or NH 4 + nitrogen atom into the α or β position of the N 2 O molecule. The study reveals that the completeness and reproducibility of the NH 4 NO 3 decomposition reaction currently confine the anchoring of N 2 O site-specific isotopic composition to the international isotope ratio scale AIR-N 2 . The authors suggest establishing a set of N 2 O isotope reference materials with appropriate site-specific isotopic composition, as community standards, to improve inter-laboratory compatibility. This article is protected by copyright. All rights reserved.

Mechanisms controlling the silicon isotopic compositions of river waters

NASA Astrophysics Data System (ADS)

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

2006-09-01

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

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

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.

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

USGS Publications Warehouse

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

2000-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Isotopic Composition of Carbonates in Antarctic Ordinary Chondrites and Miller Range Nakhlites: Insights into Martian Amazonian Aqueous Alteration

NASA Technical Reports Server (NTRS)

Evans, M. E.; Niles, P. B.; Chapman, P.

2017-01-01

The martian surface contains features of ancient fluvial systems. Stable isotope analysis of carbonates that form in aqueous systems can reveal their formation conditions. The Nakhlite meteorites originally formed on Mars 1.3 Ga and were later exposed to aqueous fluids that left behind carbonate minerals [1], thus analysis of these carbonates can provide data to understand Amazonian climate conditions on Mars. Carbonates found in the Nakhlite meteorites contain a range of delta(sup 13)C values, which may be either martian carbonates or terrestrial contamination. To better under-stand terrestrial weathering products and martian carbonate formation processes, we conducted a set of carbonate isotope analyses on Antarctic meteorites focusing on Miller Range (MIL) Nakhlites as well as Ordinary Chondrites (OCs) (Figure 1)[1-11] [12]. OCs of petrology type H, L, and LL 3-6 were selected since they are not expected to contain preterrestrial carbonates, yet they have visible evaporite minerals on the fusion crust indicating terrestrial alteration. These cryogenically formed terrestrial carbonates may also provide an analog for cryogenic carbonate formation on Mars.

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.

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.

Chapter 16Tracing Nitrogen Sources and Cycling in Catchments

USGS Publications Warehouse

Kendall, Carol

1998-01-01

This chapter focuses on the uses of isotopes to understand water chemistry.I Isotopic compositions generally cannot be interpreted successfully in the absence of other chemical and hydrologic data. The chapter focusses on uses of isotopes in tracing sources and cycling of nitrogen in the water-component of forested catchment, and on dissolved nitrate in shallow waters, nutrient uptake studies in agricultural areas, large-scale tracer experiments, groundwater contamination studies, food-web investigations, and uses of compound-specific stable isotope techniques. Shallow waters moving along a flowpath through a relatively uniform material and reacting with minerals probably do not achieve equilibrium but gradually approach some steady-state composition. The chapter also discusses the use of isotopic techniques to assess impacts of changes in land-management practices and land use on water quality. The analysis of individual molecular components for isotopic composition has much potential as a method for tracing the source, biogeochemistry, and degradation of organic liquids and gases because different materials have characteristic isotope spectrums or biomarkers.

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.

Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone.

PubMed

Wen, Sheng; Yu, Yingxin; Guo, Songjun; Feng, Yanli; Sheng, Guoying; Wang, Xinming; Bi, Xinhui; Fu, Jiamo; Jia, Wanglu

2006-01-01

Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented. Copyright 2006 John Wiley & Sons, Ltd.

Determination of chemical purity and isotopic composition of natural and carbon-13-labeled arsenobetaine bromide standards by quantitative(1)H-NMR.

PubMed

Le, Phuong-Mai; Ding, Jianfu; Leek, Donald M; Mester, Zoltan; Robertson, Gilles; Windust, Anthony; Meija, Juris

2016-10-01

In this study, we report the characterization of three arsenobetaine-certified reference materials by quantitative NMR. We have synthesized an arsenobetaine bromide high-purity standard of natural isotopic composition (ABET-1) and two carbon-13-labeled isotopic standards (BBET-1 and CBET-1). Assignments of the chemical purity and isotopic composition are not trivial in the case of arsenobetaine, and in this study we utilized quantitative(1)H-NMR techniques for the determination of the mass fractions (chemical purity). The isotopic purity of all three standards was also assessed by NMR from the carbon-13 satellite signals. The standards are non-hygroscopic, high-purity (ca. 0.99 g/g), and the carbon-13 enrichment for both isotopic standards is x((13)C)≈0.99. These standards are designed for use as primary calibrators for mass spectrometric determination of arsenobetaine in environmental samples.

Isotopic Analysis of Fingernails as a USGS Open House Demonstration of the Use of Stable Isotopes in Foodweb Studies

NASA Astrophysics Data System (ADS)

Silva, S. R.; Kendall, C.; Young, M. B.; Choy, D.

2011-12-01

The USGS Isotope Tracers Project uses stable isotopes and tritium to add a unique dimension of chemical information to a wide range of environmental investigations. The use and application of isotopes is usually an unfamiliar and even esoteric topic to the general public. Therefore during three USGS open house events, as a public outreach effort, we demonstrated the use of stable isotopes by analyzing nitrogen and carbon isotopes from very small fragments of fingernail from willing participants. We titled the exhibit "You Are What You Eat". The results from all participants were plotted on a graph indicating the general influence of different food groups on the composition of body tissues as represented by fingernails. All participants were assigned a number and no personal-identification information was collected. A subset of participants provided us with an estimate of the number of days a week various foods were eaten and if they were vegetarians, vegans or non-vegetarians. Volunteers from our research group were on hand to explain and discuss fundamental concepts such as how foods attain their isotopic composition, the difference between C3 and C4 plants, the effects of assimilation, trophic enrichment, and the various uses of stable isotopes in environmental studies. The results of the fingernail analyses showed the variation of the range of isotopic compositions among about 400 people at each event, the distinct influence of C4 plants (mainly corn and cane sugar) on our carbon isotopic composition, and the isotopic differences between vegetarians and non vegetarians among other details (http://wwwrcamnl.wr.usgs.gov/isoig/projects/fingernails/). A poll of visitors attending the open house event in 2006 indicated that "You Are What You Eat" was among the most popular exhibits. Following the first two open house events we were contacted by a group of researchers from Brazil who had completed a very similar study. Our collaboration resulted in a publication in the American Journal of Physical Anthropology (Nardoto et al., 2006). This study found that despite global trends toward dietary homogenization, regional differences in food resources and dietary preferences were recorded in the carbon and nitrogen isotopic compositions of fingernails.

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.

13C 18O clumping in speleothems: Observations from natural caves and precipitation experiments

NASA Astrophysics Data System (ADS)

Daëron, M.; Guo, W.; Eiler, J.; Genty, D.; Blamart, D.; Boch, R.; Drysdale, R.; Maire, R.; Wainer, K.; Zanchetta, G.

2011-06-01

The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ 18O. Interpreting speleothem δ 18O records in terms of absolute paleotemperatures and δ 18O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ47 (a geochemical variable reflecting the statistical overabundance of 13C 18O bonds in CO 2 evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ47 value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation. Here we report Δ47 values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ47 and heavier δ 18O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ47 disequilibrium and that of δ 18O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ 18O and Δ47 values, probably inherited from prior degassing within the cave system. In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ47 in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ47 in inorganic carbonates.

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

NASA Astrophysics Data System (ADS)

Parkes, Stephen; Wang, Lixin; McCabe, Matthew

2015-04-01

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

The Inherent Tracer Fingerprint of Captured CO2

NASA Astrophysics Data System (ADS)

Flude, Stephanie; Gyore, Domokos; Stuart, Finlay; Boyce, Adrian; Haszeldine, Stuart; Chalaturnyk, Rick; Gilfillan, Stuart

2017-04-01

Inherent tracers, the isotopic and trace gas composition of captured CO2 streams, are potentially powerful tracers for use in CCS technology [1,2]. Despite this potential, the inherent tracer fingerprint in captured CO2 streams has yet to be robustly investigated and documented [3]. Here, we will present the first high quality systematic measurements of the carbon and oxygen isotopic and noble gas fingerprints measured in anthropogenic CO2 captured from combustion power stations and fertiliser plants, using amine capture, oxyfuel and gasification processes, and derived from coal, biomass and natural gas feedstocks. We will show that δ13C values are mostly controlled by the feedstock composition, as expected. The majority of the CO2 samples exhibit δ18O values similar to atmospheric O2 although captured CO2 samples from biomass and gas feedstocks at one location in the UK are significantly higher. Our measured noble gas concentrations in captured CO2 are generally as expected [2], typically being two orders of magnitude lower in concentration than in atmospheric air. Relative noble gas elemental abundances are variable and often show an opposite trend to that of a water in contact with the atmosphere. Expected enrichments in radiogenic noble gases (4He and 40Ar) for fossil fuel derived CO2 were not always observed due to dilution with atmospheric noble gases during the CO2 generation and capture process. Many noble gas isotope ratios indicate that isotopic fractionation takes place during the CO2 generation and capture processes, resulting in isotope ratios similar to fractionated air. We conclude that phase changes associated with CO2 transport and sampling may induce noble gas elemental and isotopic fractionation, due to different noble gas solubilities between high (liquid or supercritical) and low (gaseous) density CO2. Data from the Australian CO2CRC Otway test site show that δ13C of CO2 will change once injected into the storage reservoir, but that this change is small and can be quantitatively modelled in order to determine the proportion of CO2 that has dissolved into the formation waters. Furthermore, noble gas data from the Otway storage reservoir post-injection, shows evidence of noble gas stripping of formation water and contamination with Kr and Xe related to an earlier injection experiment. Importantly, He data from SaskPower's Aquistore illustrates that injected CO2 will inherit distinctive crustal radiogenic noble gas fingerprints from the subsurface once injected into an undisturbed geological storage reservoir, meaning this could be used to identify unplanned migration of the CO2 to the surface and shallow subsurface [4]. References [1] Mayer et al., (2015) IJGGC, Vol. 37, 46-60 http://dx.doi.org/10.1016/j.ijggc.2015.02.021 [2] Gilfillan et al., (2014) Energy Procedia, Vol. 63, 4123-4133 http://dx.doi.org/10.1016/j.egypro.2014.11.443 [3] Flude et al., (2016) Environ. Sci. Technol., 50 (15), pp 7939-7955 DOI: 10.1021/acs.est.6b01548 [4] Gilfillan et al., (2011) IJGGC, Vol. 5 (6) 1507-1516 http://dx.doi.org/10.1016/j.ijggc.2011.08.008

Return to the Strangelove Ocean?: Preliminary results of carbon and oxygenisotope compositions of post-impact sediments, IODP Expedition 364 "Chicxulub Impact Crater"

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Ikehara, M.; Hayama, H.; Takiguchi, S.; Masuda, S.; Ogura, C.; Fujita, S.; Kurihara, E.; Matsumoto, T.; Oshio, S.; Ishihata, K.; Fuchizawa, Y.; Noda, H.; Sakurai, U.; Yamane, T.; Morgan, J. V.; Gulick, S. P. S.

2017-12-01

The Chicxulub crater in the northern Yucatan Peninsula, Mexico was formed by the asteroid impact at the Cretaceous-Paleogene boundary (66.0 Ma). In early 2016 the IODP Exp. 364 successfully drilled the materials from the topographic peak ring within the crater that was previously identified by seismological observations. A continuous core was recovered. The 112m-thick uppermost part of the continuous core (505.7-1334.7 mbsf) is post-impact sediments, including the PETM, that are mainly composed of carbonate with intercalation of siliciclastics and variable contents of organic carbon. More than 300 samples from the post-impact section were finely powdered for a variety of geochemical analysis. Here we report their carbon and oxygen isotope compositions of the carbonate fraction (mostly in the lower part of the analyzed section) and carbon and nitrogen isotope compositions of organic matter (mostly in the middle-upper part of the analyzed section). Isotope mass spectrometer Isoprime was used for the former analysis, and EA-irMS (elemental analyzer - isotope ratio mass spectrometer) was used for the latter analysis, both at CMCR, Kochi Univ. Depth profile of oxygen isotope compositions of carbonate fraction is variable and somewhat similar to those of Zachos et al. (2001; Science). Carbon isotope compositions of carbonate and organic carbon in the lower part of the analyzed section exhibit some excursions that could correspond to the hyperthemals in the early Paleogene. Their variable nitrogen isotope compositions reflect temporal changes in the style of biogeochemical cycles involving denitrification and nitrogen fixation. Coupled temporal changes in the carbon isotope compositions of organic and carbonate carbon immediately after the K-Pg boundary might support a Strangelove ocean (Kump, 1991; Geology), however high export production (Ba/Ti, nannoplankton and calcisphere blooms, high planktic foram richness, and diverse and abundant micro- and macrobenthic organisms) at the base of the Danian limestone cored during Exp. 364 contradict a Strangelove Ocean.

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.

In Situ Carbon Isotope Analysis by Laser Ablation MC-ICP-MS.

PubMed

Chen, Wei; Lu, Jue; Jiang, Shao-Yong; Zhao, Kui-Dong; Duan, Deng-Fei

2017-12-19

Carbon isotopes have been widely used in tracing a wide variety of geological and environmental processes. The carbon isotope composition of bulk rocks and minerals was conventionally analyzed by isotope ratio mass spectrometry (IRMS), and, more recently, secondary ionization mass spectrometry (SIMS) has been widely used to determine carbon isotope composition of carbon-bearing solid materials with good spatial resolution. Here, we present a new method that couples a RESOlution S155 193 nm laser ablation system with a Nu Plasma II MC-ICP-MS, with the aim of measuring carbon isotopes in situ in carbonate minerals (i.e., calcite and aragonite). Under routine operating conditions for δ 13 C analysis, instrumental bias generally drifts by 0.8‰-2.0‰ in a typical analytical session of 2-3 h. Using a magmatic calcite as the standard, the carbon isotopic composition was determined for a suite of calcite samples with δ 13 C values in the range of -6.94‰ to 1.48‰. The obtained δ 13 C data are comparable to IRMS values. The combined standard uncertainty for magmatic calcite is <0.3‰ (1s). No significant matrix effects have been identified in calcite with the amplitude of chemical composition variation (i.e., MnO, SrO, MgO, or FeO) up to 2.5 wt %. Two modern corals were investigated using magmatic calcite as the calibration standard, and the average δ 13 C values for both corals are similar to the bulk IRMS values. Moreover, coral exhibits significant heterogeneity in carbon isotope compositions, with differences up to 4.85‰ within an individual coral. This study indicates that LA-MC-ICP-MS can serve as an appropriate method to analyze carbon isotopes of carbonate minerals in situ.

Compound-specific Isotope Analysis of Cyanobacterial Pure cultures and Microbial Mats: Effects of Photorespiration?

NASA Technical Reports Server (NTRS)

Jahnke, L. L.; Summons, R. E.

2006-01-01

Microbial mats are considered modern homologs of Precambrian stromatolites. The carbon isotopic compositions of organic matter and biomarker lipids provide clues to the depositional environments of ancient mat ecosystems. As the source of primary carbon fixation for over two billion years, an understanding of cyanobacterial lipid biosynthesis, associated isotopic discriminations, and the influence of physiological factors on growth and isotope expression is essential to help us compare modern microbial ecosystems to their ancient counterparts. Here, we report on the effects of photorespiration (PR) on the isotopic composition of cyanobacteria and biomarker lipids, and on potential PR effects associated with the composition of various microbial mats. The high light, high O2 and limiting CO2 conditions often present at the surface of microbial mats are known to support PR in cyanobacteria. The oxygenase function of ribulose bisphosphate carboxylase/oxygenase can result in photoexcretion of glycolate and subsequent degration by heterotrophic bacteria. We have found evidence which supports an isotopic depletion (increased apparent E) scaled to O2 level associated with growth of Phormidium luridum at low CO2 concentrations (less than 0.04%). Similar to previous studies, isotopic differences between biomass and lipid biomarkers, and between lipid classes were positively correlated with overall fractionation, and should provide a means of estimating the influence of PR on overall isotopic composition of microbial mats. Several examples of microbial mats growing in the hydrothermal waters of Yellowstone National Park and the hypersaline marine evaporation ponds at Guerrero Negro, Baja Sur Mexico will be compared with a view to PR as a possible explanation of the relatively heavy C-isotope composition of hypersaline mats.

What is the iron isotope composition of the Moon?

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

The preservation of long-range transported nitrate in snow at Summit, Greenland (Invited)

NASA Astrophysics Data System (ADS)

Hastings, M. G.

2013-12-01

Nitrate is one of the major anions found in polar and alpine snow, both today and in the past. Deposition of nitrate to snow surfaces results from reactions of nitrogen oxides (NOx) with oxidants in the atmosphere, resulting in the production of HNO3 that is incorporated into precipitation or reacts on the surface of particles. Several factors motivate studying nitrate concentration in ice cores including reconstructing past levels of NOx, tropospheric oxidant concentrations and natural variability in NOx sources. The link between the atmospheric concentration of NOx and nitrate concentration in ice core records is problematic because post-depositional processing, such as photolysis and evaporation, can impact the concentration of nitrate in snow. Recent work has shown that the isotopic ratios of nitrate (15N/14N, 18O/16O, 17O/16O) can be a powerful tool for tracing post-depositional loss of nitrate from surface snow. The isotopic composition of nitrate has been shown to contain information about the source of the nitrate (i.e, NOx sources) and the oxidation processes that convert NOx to nitrate in the atmosphere prior to deposition. Results from a number of studies at Summit, Greenland reveal limited loss of nitrate from surface snow during highly photoactive periods, and the oxygen isotopic signatures in snow nitrate appear to be representative of atmospheric deposition of nitrate from outside of Summit. Higher than expected oxygen isotope ratios (18O/16O, 17O/16O) found in Summit summertime nitrate were expected to be dependent upon local photochemistry in which nitrate in the snow is photolyzed to NOx that is then oxidized above the snow by BrO to reform nitrate (i.e., BrONO2). However, the oxygen isotopic composition of nitrate collected at high time resolution in surface snow does not show any link to local gas phase concentrations of a number of species, including BrO. Furthermore, the combination of nitrogen and oxygen isotope data reveals interesting insights into the contributions of nitrate sources to Summit. There are several important implications of this work including that nitrate at Summit appears to be largely preserved in surface snow during photoactive periods, and that nitrate in snow at Summit also appears to be representative of long-range transported nitrate/NOx. The surface snow work is further substantiated by relationships found between and among seasonally-resolved ice core measurements of the isotopic composition of nitrate, nitrate concentration and a suite of chemical and elemental tracers. The seasonality observed in 15N/14N ratios in an ice core representing accumulation since 1760 C.E. cannot be explained by diffusion or other processes occurring in the firn over time. A marked negative trend in 15N/14N since industrialization, parallels a nearly three-fold increase in nitrate concentration as well as pronounced increases in tracers such as excess lead and non-sea-salt sulfur. This, along with independent estimates of oil burning and transport studies, indicate that North American oil combustion is the primary driver of the modern negative trend in 15N/14N of nitrate. The high, positive 15N/14N ratios found in pre-industrial ice link to biomass burning based upon concentrations of black carbon and ammonium.

Isotope and trace element insights into heterogeneity of subridge mantle

NASA Astrophysics Data System (ADS)

Mallick, Soumen; Dick, Henry J. B.; Sachi-Kocher, Afi; Salters, Vincent J. M.

2014-06-01

Geochemical data for abyssal peridotites are used to determine the relationship to mid-ocean ridge basalts from several locations at ridge segments on the SW Indian Ridge (SWIR), the Mid-Cayman-Rise (MCR), and the Mid-Atlantic Ridge (MAR). Based on chemical and petrological criteria peridotites are categorized as being either dominantly impregnated with melt or being residual after recent melting. Those that are considered impregnated with melt also have isotopic compositions similar to the basalts indicating impregnation by an aggregate MORB melt. A SWIR and MCR residual peridotite Nd-isotopic compositions partly overlap the Nd-isotopic compositions of the basalts but extend to more radiogenic compositions. The differences between peridotite and basalt Nd-isotopic compositions can be explained by incorporating a low-solidus component with enriched isotopic signature in the subridge mantle: a component that is preferentially sampled by the basalts. At the MAR, peridotites and associated basalts have overlapping Nd-isotopic compositions, suggesting a more homogeneous MORB mantle. The combined chemistry and petrography indicates a complex history with several depletion and enrichment events. The MCR data indicate that a low-solidus component can be a ubiquitous component of the asthenosphere. Residual abyssal peridotites from limited geographic areas also show significant chemical variations that could be associated with initial mantle heterogeneities related to events predating the ridge-melting event. Sm-Nd model ages for possible earlier depletion events suggest these could be as old as 2.4 Ga. This article was corrected on 9 JULY 2014. See the end of the full text for details.

Multiple isotope analyses of the pike tapeworm Triaenophorus nodulosus reveal peculiarities in consumer-diet discrimination patterns.

PubMed

Behrmann-Godel, J; Yohannes, E

2015-03-01

Previous studies of dietary isotope discrimination have led to the general expectation that a consumer will exhibit enriched stable isotope levels relative to its diet. Parasite-host systems are specific consumer-diet pairs in which the consumer (parasite) feeds exclusively on one dietary source: host tissue. However, the small numbers of studies previously carried out on isotopic discrimination in parasite-host (ΔXP-HT) systems have yielded controversial results, showing some parasites to be isotopically depleted relative to their food source, while others are enriched or in equilibrium with their hosts. Although the mechanism for these deviations from expectations remains to be understood, possible influences of specific feeding niche or selection for only a few nutritional components by the parasite are discussed. ΔXP-HT for multiple isotopes (δ13C, δ15N, δ34S) were measured in the pike tapeworm Triaenophorus nodulosus and two of its life-cycle fish hosts, perch Perca fluviatilis and pike Esox lucius, within which T. nodulosus occupies different feeding locations. Variability in the value of ΔXP-HT calculated for the parasite and its different hosts indicates an influence of feeding location on isotopic discrimination. In perch liver ΔXP-HT was relatively more negative for all three stable isotopes. In pike gut ΔXP-HT was more positive for δ13C, as expected in conventional consumer-diet systems. For parasites feeding on pike gut, however, the δ15N and δ34S isotope values were comparable with those of the host. We discuss potential causes of these deviations from expectations, including the effect of specific parasite feeding niches, and conclude that ΔXP-HT should be critically evaluated for trophic interactions between parasite and host before general patterns are assumed.

Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature

NASA Astrophysics Data System (ADS)

Hayles, J.; Shen, B.; Homann, M.; Yeung, L.

2017-12-01

One point of contention among geoscientists is whether the 18O/16O ratio of seawater is roughly constant, or if it varies considerably throughout geologic time. On one hand, the oxygen isotope composition of the ocean is thought to be well buffered by high- and low-temperature interactions between seawater and seafloor rocks. If these interactions do not vary on billion-year timescales, the oxygen-isotope compositions of marine sedimentary rocks mostly relate to changes in seawater temperature and global ice volume. On the other hand, long-term cooling of the planetary interior would alter these water-rock interactions leading to a secular change in the oxygen isotope composition of seawater. Models suggest that this secular change would enrich seawater with heavy oxygen isotopes over time. In this study, we present new, high precision, triple-oxygen-isotope (18O/16O, 17O/16O) analyses of marine chert samples from 3.45 Ga to 460Ma. The results of these analyses are paired with a new theoretical quartz-water equilibrium curve and a simplified seawater model to provide possible pairings of δ'18O and Δ'17O for the water which these samples could have formed in equilibrium with. Analysis of the new sample data, in addition to published chert triple oxygen isotope compositions, shows a general trend of older chert samples being progressively incompatible with waters possessing a modern-like seawater triple oxygen isotope composition. Implications on constraining the secular evolution of seawater δ18O and temperature will be discussed.

Impact of topography, climate and moisture sources on isotopic composition (δ18O &δD) of rivers in the Pyrenees: Implications for topographic reconstructions in small orogens

NASA Astrophysics Data System (ADS)

Huyghe, Damien; Mouthereau, Frédéric; Sébilo, Mathieu; Vacherat, Arnaud; Ségalen, Loïc; Richard, Patricia; Biron, Philippe; Bariac, Thierry

2018-02-01

Understanding how orogenic topography controls the spatial distribution and isotopic composition of precipitation is critical for paleoaltitudinal reconstructions. Here, we determine the isotopic composition (δ18O and δD) of 82 small rivers and springs from small catchments in the Pyrenees. Calculation of the deuterium excess (d-excess) parameter allows the distinction of four distinct isotopic provinces with d-excess values of between 15 and 22‰ in the northwest, between 7 and 14‰ in the central northern Pyrenees and between 3 and 11‰ in the northeast. The southern Pyrenees have a homogenous d-excess signature ranging from 7 to 14‰. Our results show significant local moisture recycling and/or rain amount effect in the northwestern Pyrenees, and control by evaporation processes during rainfall events in the southern Pyrenees and for low elevated samples of the northeast of the range. Based on the distribution of d-excess values, we estimate contrasting isotope lapse rates of -2.9/-21.4‰/km (δ18O/δD) in the northwest, -2.7/-21.4‰/km (δ18O/δD) in the north central and -3.7/-31.7‰/km (δ18O/δD) in the northeastern Pyrenees. The southern Pyrenees show distinctly higher lapse rates of -9.5/-77.5‰/km (δ18O/δD), indicating that in this area the altitudinal effect in not the only parameter driving isotopic composition of rivers. Despite their relatively low topographic gradient, the Pyrenees exert a direct control on the isotopic composition of river waters, especially on their northern side. The variations in isotopic composition-elevation relationships documented along the strike of the range are interpreted to reflect an increasing continentality effect driven by wind trajectories parallel to the range, and mixing with Mediterranean air masses. Despite these effects, the measurable orographic effect on precipitation in the Pyrenees proves that the isotopic composition approach for reconstructing past topography is applicable to low-elevation orogens.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

NASA Technical Reports Server (NTRS)

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

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Isotopic coherence of refractory inclusions from CV and CK meteorites: Evidence from multiple isotope systems

NASA Astrophysics Data System (ADS)

Shollenberger, Quinn R.; Borg, Lars E.; Render, Jan; Ebert, Samuel; Bischoff, Addi; Russell, Sara S.; Brennecka, Gregory A.

2018-05-01

Calcium-aluminum-rich inclusions (CAIs) are the oldest dated materials in the Solar System and numerous previous studies have revealed nucleosynthetic anomalies relative to terrestrial rock standards in many isotopic systems. However, most of the isotopic data from CAIs has been limited to the Allende meteorite and a handful of other CV3 chondrites. To better constrain the isotopic composition of the CAI-forming region, we report the first Sr, Mo, Ba, Nd, and Sm isotopic compositions of two CAIs hosted in the CK3 desert meteorites NWA 4964 and NWA 6254 along with two CAIs from the CV3 desert meteorites NWA 6619 and NWA 6991. After consideration of neutron capture processes and the effects of hot-desert weathering, the Sr, Mo, Ba, Nd, and Sm stable isotopic compositions of the samples show clearly resolvable nucleosynthetic anomalies that are in agreement with previous results from Allende and other CV meteorites. The extent of neutron capture, as manifested by shifts in the observed 149Sm-150Sm isotopic composition of the CAIs is used to estimate the neutron fluence experienced by some of these samples and ranges from 8.40 × 1013 to 2.11 × 1015 n/cm2. Overall, regardless of CAI type or host meteorite, CAIs from CV and CK chondrites have similar nucleosynthetic anomalies within analytical uncertainty. We suggest the region that CV and CK CAIs formed was largely uniform with respect to Sr, Mo, Ba, Nd, and Sm isotopes when CAIs condensed and that CAIs hosted in CV and CK meteorites are derived from the same isotopic reservoir.

Large Carbonate Associated Sulfate isotopic variability between brachiopods, micrite, and other sedimentary components in Late Ordovician strata

NASA Astrophysics Data System (ADS)

Present, Theodore M.; Paris, Guillaume; Burke, Andrea; Fischer, Woodward W.; Adkins, Jess F.

2015-12-01

Carbonate Associated Sulfate (CAS) is trace sulfate incorporated into carbonate minerals during their precipitation. Its sulfur isotopic composition is often assumed to track that of seawater sulfate and inform global carbon and oxygen budgets through Earth's history. However, many CAS sulfur isotope records based on bulk-rock samples are noisy. To determine the source of bulk-rock CAS variability, we extracted CAS from different internal sedimentary components micro-drilled from well-preserved Late Ordovician and early Silurian-age limestones from Anticosti Island, Quebec, Canada. Mixtures of these components, whose sulfur isotopic compositions vary by nearly 25‰, can explain the bulk-rock CAS range. Large isotopic variability of sedimentary micrite CAS (34S-depleted from seawater by up to 15‰) is consistent with pore fluid sulfide oxidation during early diagenesis. Specimens recrystallized during burial diagenesis have CAS 34S-enriched by up to 9‰ from Hirnantian seawater, consistent with microbial sulfate reduction in a confined aquifer. In contrast to the other variable components, brachiopods with well-preserved secondary-layer fibrous calcite-a phase independently known to be the best-preserved sedimentary component in these strata-have a more homogeneous isotopic composition. These specimens indicate that seawater sulfate remained close to about 25‰ (V-CDT) through Hirnantian (end-Ordovician) events, including glaciation, mass extinction, carbon isotope excursion, and pyrite-sulfur isotope excursion. The textural relationships between our samples and their CAS isotope ratios highlight the role of diagenetic biogeochemical processes in setting the isotopic composition of CAS.

Bioconversion of Coal: Hydrologic indicators of the extent of coal biodegradation under different redox conditions and coal maturity, Velenje Basin case study, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Grassa, Fausto; Lazar, Jerneja; Jamnikar, Sergej; Zavšek, Simon; McIntosh, Jennifer

2014-05-01

Underground mining of coal and coal combustion for energy has significant environmental impacts. In order to reduce greenhouse gas emissions, other lower -carbon energy sources must be utilized. Coalbed methane (CBM) is an important source of relatively low-carbon energy. Approximately 20% of world's coalbed methane is microbial in origin (Bates et al., 2011). Interest in microbial CBM has increased recently due to the possibility of stimulating methanogenesis. Despite increasing interest, the hydrogeochemical conditions and mechanisms for biodegradation of coal and microbial methane production are poorly understood. This project aims to examine geochemical characteristics of coalbed groundwater and coalbed gases in order to constrain biogeochemical processes to better understand the entire process of coal biodegradation of coal to coalbed gases. A better understanding of geochemical processes in CBM areas may potentially lead to sustainable stimulation of microbial methanogenesis at economical rates. Natural analogue studies of carbon dioxide occurring in the subsurface have the potential to yield insights into mechanisms of carbon dioxide storage over geological time scales (Li et al., 2013). In order to explore redox processes related to methanogenesis and determine ideal conditions under which microbial degradation of coal is likely to occur, this study utilizes groundwater and coalbed gas samples from Velenje Basin. Determination of the concentrations of methane, carbondioxide, nitrogen, oxygen, argon was performed with homemade NIER mass spectrometer. Isotopic composition of carbon dioxide, isotopic composition of methane, isotopic composition of deuterium in methane was determined with Europa-Scientific IRMS with an ANCA-TG preparation module and Thermo Delta XP GC-TC/CF-IRMS coupled to a TRACE GC analyzer. Total alkalinity of groundwater was measured by Gran titration. Major cations were analyzed by ICP-OES and anions by IC method. Isotopic composition of dissolved inorganic carbon was determined by MultiflowBio preparation module. The stable isotope composition of sulphur was determined with a Europa Scientific 20-20 continuous flow IRMS ANCA-SL preparation module. Concentrations of tritium were determined with the electrolytic enrichment method. PHREEQC for Windows was used to perform thermodynamic modelling. The average coalbed gas composition in the coalbed seam is approximately carbon dioxide: methane > 2:1, where a high proportion of CO2 is adsorbed on the lignite structure, while methane is present free in coal fractures. It can be concluded that isotopic composition of carbon in methane from -70.4‰ to -50.0‰ is generated via acetate fermentation and via reduction of carbon dioxide, while isotopic composition of carbon in methane values range from -50.0‰ to -18.8‰, thermogenic methane can be explained by secondary processes, causing enrichment of residual methane with the heavier carbon isotope. Isotopic composition of deuterium in methane range from -343.9‰ to -223.1‰. Isotopic composition of carbon in carbon dioxide values at excavation fields range from -11.0‰ to +5‰ and are endogenic and microbial in origin. The major ion chemistry, redox conditions, stable isotopes and tritium measured in groundwater from the Velenje Basin, suggest that the Pliocene and Triassic aquifers contain distinct water bodies. Groundwater in the Triassic aquifer is dominated by hydrogen carbonate, calcium, magnesium and isotopic composition of dissolved inorganic carbon indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has isotopic composition of oxygen and isotopic composition of deuterium values which plot near surface waters on the local and global meteoric water lines and detectable tritium reflects recent recharge. In contrast, groundwater in the Pliocene aquifers is enriched in magnesium, sodium, calcium, potassium, and silica and has alkalinity and isotopic composition of dissolved inorganic carbon values with low sulphate and nitrate concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and magnesium-rich clay minerals. Pliocene aquifer waters are also depleted in heavier oxygen isotope and heavier deuterium isotope and have tritium concentrations near the detection limit, suggesting these waters are older. References Bates, B.L., McIntosh J.C., Lohse K.A., Brooks P.D. 2011: Influence of groundwater flowpaths, residence times, and nutrients on the extent of microbial methanogenesis in coal beds: Powder River Basin, USA, Chemical geology, 284, 45-61. Li, W., Cheng Y., Wang L., Zhou H., Wang H., Wang L. 2013: Evaluating the security of geological coalbed sequestration of supercritical CO2 reservoirs: The Haishiwan coalfield, China as a natural analogue, International Journal of Greenhouse Gas Control, 13, 102-111.

Noble gases in the moon

NASA Technical Reports Server (NTRS)

Manuel, O. K.; Srinivasan, B.; Hennecke, E. W.; Sinclair, D. E.

1972-01-01

The abundance and isotopic composition of helium, neon, argon, krypton, and xenon which were released by stepwise heating of lunar fines (15601.64) and (15271.65) were measured spectrometrically. The results of a composition of noble gases released from the lunar fines with noble gases in meteorites and in the earth are presented along with the isotopic composition of noble gases in lunar fines, in meteorites, and in the atmosphere. A study of two isotopically distinct components of trapped xenon in carbonaceous chondrites is also included.

Stable Isotope Characteristics of Jarosite: The Acidic Aqueous History of Mars

NASA Technical Reports Server (NTRS)

Earl, Lyndsey D.

2005-01-01

The Mars Rover Opportunity found jarosite (Na(+) or K(+))Fe3SO4(OH)6 at the Meridiani Planum site. This mineral forms from the evaporation of an aqueous acidic sulfate brine. Oxygen isotope compositions may characterize formation conditions but subsequent isotope exchange may have occurred between the sulfate and hydroxide of jarosite and water. The rate of oxygen isotope exchange depends on the acidity and temperature of the brine, but it has not been investigated in detail. We performed laboratory experiments to determine the rate of oxygen isotope exchange under varying acidities and temperatures to learn more about this process. Barium sulfate samples were precipitated weekly from acidic sodium sulfate brines. The oxygen isotope composition of the precipitated sulfate was obtained using a Finnigan MAT253 Isotope Ratio Mass-Spectrometer. The results show that water was trapped in barium sulfate during precipitation. Trapped water may exchange with sulfate when exposed to high temperatures, thus changing the isotope composition of sulfate and the observed fractionation factor of oxygen isotope exchange between sulfate and water. The results of our research will contribute to the understanding of oxygen isotope exchange rates between water and sulfate under acidic conditions and provide experimental knowledge for the dehydration of barium sulfate samples.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ∼20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ∼million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (±2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude less than each of the modern ocean outputs and imparts no isotopic fractionation. Thallium removal into pyrite appears to be associated with a small negative fractionation between -1 and -3 ε205Tl, which renders Tl-depleted waters below the chemocline enriched in isotopically-heavy Tl. Due to the quantitative removal of Tl from euxinic seawater, Tl isotope analyses of the authigenic fraction of underlying euxinic sediments from both the Black Sea and Cariaco Basin capture the Tl isotope value of the oxic portion of their respective water column with no net isotope fractionation. Since the Tl isotope composition of seawater is largely dictated by the relative fraction of Mn-oxide burial versus oceanic crust alteration, we contend that the Tl isotope composition of authigenic Tl in black shales, deposited under euxinic conditions but well-connected to the open ocean, can be utilized to reconstruct the Tl isotope composition of seawater, and thus to reconstruct the global history of Mn-oxide burial.

Iron isotope composition of particles produced by UV-femtosecond laser ablation of natural oxides, sulfides, and carbonates.

PubMed

d'Abzac, Francois-Xavier; Beard, Brian L; Czaja, Andrew D; Konishi, Hiromi; Schauer, James J; Johnson, Clark M

2013-12-17

The need for femtosecond laser ablation (fs-LA) systems coupled to MC-ICP-MS to accurately perform in situ stable isotope analyses remains an open question, because of the lack of knowledge concerning ablation-related isotopic fractionation in this regime. We report the first iron isotope analysis of size-resolved, laser-induced particles of natural magnetite, siderite, pyrrhotite, and pyrite, collected through cascade impaction, followed by analysis by solution nebulization MC-ICP-MS, as well as imaging using electron microscopy. Iron mass distributions are independent of mineralogy, and particle morphology includes both spheres and agglomerates for all ablated phases. X-ray spectroscopy shows elemental fractionation in siderite (C-rich agglomerates) and pyrrhotite/pyrite (S-rich spheres). We find an increase in (56)Fe/(54)Fe ratios of +2‰, +1.2‰, and +0.8‰ with increasing particle size for magnetite, siderite, and pyrrhotite, respectively. Fe isotope differences in size-sorted aerosols from pyrite ablation are not analytically resolvable. Experimental data are discussed using models of particles generation by Hergenröder and elemental/isotopic fractionation by Richter. We interpret the isotopic fractionation to be related to the iron condensation time scale, dependent on its saturation in the gas phase, as a function of mineral composition. Despite the isotopic variations across aerosol size fractions, total aerosol composition, as calculated from mass balance, confirms that fs-LA produces a stoichiometric sampling in terms of isotopic composition. Specifically, both elemental and isotopic fractionation are produced by particle generation processes and not by femtosecond laser-matter interactions. These results provide critical insights into the analytical requirements for laser-ablation-based stable isotope measurements of high-precision and accuracy in geological samples, including the importance of quantitative aerosol transport to the ICP.

A 50-year record of NOx and SO2 sources in precipitation in the Northern Rocky Mountains, USA

USGS Publications Warehouse

Naftz, D.L.; Schuster, P.F.; Johnson, C.A.

2011-01-01

Ice-core samples from Upper Fremont Glacier (UFG), Wyoming, were used as proxy records for the chemical composition of atmospheric deposition. Results of analysis of the ice-core samples for stable isotopes of nitrogen (??15N, NO3-) and sulfur (??34SO42-), as well as NO3- and SO42- deposition rates from the late-1940s thru the early-1990s, were used to enhance and extend existing National Atmospheric Deposition Program/National Trends Network (NADP/NTN) data in western Wyoming. The most enriched ??34S value in the UFG ice-core samples coincided with snow deposited during the 1980 eruption of Mt. St. Helens, Washington. The remaining ??34S values were similar to the isotopic composition of coal from southern Wyoming. The ??15N values in ice-core samples representing a similar period of snow deposition were negative, ranging from -5.9 to -3.2 % and all fall within the ??15N values expected from vehicle emissions. Ice-core nitrate and sulfate deposition data reflect the sharply increasing U.S. emissions data from 1950 to the mid-1970s. ?? 2011 Naftz et al; licensee Chemistry Central Ltd.

Temperature history of Coregonus artedi in the St. Marys River, Laurentian Great Lakes, inferred from oxygen isotopes in otoliths

USGS Publications Warehouse

Joukhadar, Zeina; Patterson, W.P.; Todd, T.N.; Smith, G.R.

2002-01-01

The population of Coregonus artedi in the St. Marys River, between lakes Superior and Huron, was sampled and otoliths were analyzed for oxygen isotopic composition to determine whether the fish are residents in the St. Marys River and its warm bays or migrants to and from cold Lake Huron. Otoliths were extracted, sectioned, and growth ring-specific samples of calcium carbonate were milled to obtain samples for determination of oxygen isotope ratios (18O values). The 18O values of calcium carbonate (CaCO3) in accretionary structures such as otoliths allow calculation of growth temperatures of the fish, because of differential fractionation of oxygen isotopes at different temperatures. Growth temperatures of 10 St. Marys River lake herring were compared with lake and catch data as well as growth temperatures of lake herring collected from Lake Huron and other ciscoes from the Great Lakes. Results of this analysis indicate that these fish remained in the bays of the St. Marys River for their entire life history. After their second year they grew at average temperatures between 11 C and 13 C, consistent with temperature in the warmer bays of the St. Marys River and 6 C higher than expected for growth of this species in Lake Huron.

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.

Methane transport mechanisms and isotopic fractionation in emergent macrophytes of an Alaskan tundra lake

NASA Technical Reports Server (NTRS)

Chanton, Jeffrey P.; Martens, Christopher S.; Kelley, Cheryl A.; Crill, Patrick M.; Showers, William J.

1992-01-01

The stable carbon isotopic composition of methane associated with and emitted by the two dominant emergent macrophytes abundant in the many Alaskan tundra lakes, Carex rostrata and Arctophila fulva, is determined. The carbon isotopic composition of the methane was -58.6 +/- 0.5 (n=2) for Arctophila and -66.6 +/- 2.5 (n=6) for Carex. The methane emitted by these species is depleted in C-13 by 12 per mil for Arctophila and 18 per mil for Carex relative to methane withdrawn from plant stems 1-2 cm below the waterline. The results suggest more rapid transport of (C-12)H4 relative to (C-13)H4 through plants to the atmosphere. Plant stem methane concentrations ranged from 0.2 to 4.0 percent in Arctophila, with an isotopic composition of -46.1 +/- 4.3 percent (n=8). Carex stem methane concentrations ranged from 150 to 1200 ppm, with an isotopic composition of -48.3 +/- 1.4 per mil (n=3).

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

Hydrogen isotope fractionation during lipid biosynthesis by Haloarcula marismortui

NASA Astrophysics Data System (ADS)

Dirghangi, Sitindra S.; Pagani, Mark

2013-10-01

We studied the controls on the fractionation of hydrogen isotopes during lipid biosynthesis by Haloarcula marismortui, a halophilic archaea, in pure culture experiments by varying organic substrate, the hydrogen isotope composition (D/H) of water, temperature, and salinity. Cultures were grown on three substrates: succinate, pyruvate and glycerol with known hydrogen isotope compositions, and in water with different hydrogen isotopic compositions. All culture series grown on a particular substrate show strong correlations between δDarchaeol and δDwater. However, correlations are distinctly different for cultures grown on different substrates. Our results indicate that the metabolic pathway of substrate exerts a fundamental influence on the δD value of lipids, likely by influencing the D/H composition of NADPH (nicotinamide adenine dinucleotide phosphate), the reducing agent that contributes hydrogen to carbon atoms during lipid biosynthesis. Temperature and salinity have smaller, but similar effects on δDlipid, primarily due to the way temperature and salinity influence growth rate, as well as temperature effects on the activity of enzymes.

Fe isotope composition of bulk chondrules from Murchison (CM2): Constraints for parent body alteration, nebula processes and chondrule-matrix complementarity

NASA Astrophysics Data System (ADS)

Hezel, Dominik C.; Wilden, Johanna S.; Becker, Daniel; Steinbach, Sonja; Wombacher, Frank; Harak, Markus

2018-05-01

Chondrules are a major constituent of primitive meteorites. The formation of chondrules is one of the most elusive problems in cosmochemistry. We use Fe isotope compositions of chondrules and bulk chondrites to constrain the conditions of chondrule formation. Iron isotope compositions of bulk chondrules are so far only known from few studies on CV and some ordinary chondrites. We studied 37 chondrules from the CM chondrite Murchison. This is particularly challenging, as CM chondrites contain the smallest chondrules of all chondrite groups, except for CH chondrites. Bulk chondrules have δ56Fe between -0.62 and +0.24‰ relative to the IRMM-014 standard. Bulk Murchison has as all chondrites a δ56Fe of 0.00‰ within error. The δ56Fe distribution of the Murchison chondrule population is continuous and close to normal. The width of the δ56Fe distribution is narrower than that of the Allende chondrule population. Opaque modal abundances in Murchison chondrules is in about 67% of the chondrules close to 0 vol.%, and in 33% typically up to 6.5 vol.%. Chondrule Al/Mg and Fe/Mg ratios are sub-chondritic, while bulk Murchison has chondritic ratios. We suggest that the variable bulk chondrule Fe isotope compositions were established during evaporation and recondensation prior to accretion in the Murchison parent body. This range in isotope composition was likely reduced during aqueous alteration on the parent body. Murchison has a chondritic Fe isotope composition and a number of chondritic element ratios. Chondrules, however, have variable Fe isotope compositions and chondrules and matrix have complementary Al/Mg and Fe/Mg ratios. In combination, this supports the idea that chondrules and matrix formed from a single reservoir and were then accreted in the parent body. The formation in a single region also explains the compositional distribution of the chondrule population in Murchison.

Tracing subducted sediment inputs to the Ryukyu arc-Okinawa Trough system: Evidence from thallium isotopes

NASA Astrophysics Data System (ADS)

Shu, Yunchao; Nielsen, Sune G.; Zeng, Zhigang; Shinjo, Ryuichi; Blusztajn, Jerzy; Wang, Xiaoyuan; Chen, Shuai

2017-11-01

Sediments are actively subducted in virtually every arc worldwide. However, quantifying their contributions to arc lavas and thereby establishing budgets of how sediments participate in slab-mantle interaction is challenging. In this contribution we use thallium (Tl) abundances and isotopic compositions of lavas from the Ryukyu arc (including south Kyushu) and its back-arc basin, Okinawa Trough, to investigate the influence of sediments from arc to back-arc. We also present extensive geochemical data for sediments and altered oceanic crust (AOC) outboard of the northern (DSDP Sites 296, 442B, 443 and 444) and central (DSDP Sites 294 and 295) part of the Ryukyu arc. The Tl isotopic compositions of sediments change systematically from lighter outboard of northern Ryukyu arc to heavier outboard of central Ryukyu arc. The feature reflects the dominance of terrigenous material and pelagic sedimentation outboard of the northern and central Ryukyu arc, respectively. Central and northern sections of Ryukyu arc and Okinawa Trough display larger range of Tl isotopic variation than southern section, which is consistent with more pelagic provenance for sediments outboard of central and northern Ryukyu arcs than that of expected sediments outboard of southern Ryukyu arc. Identical Tl, Sr, Nd and Pb isotope variations are found when comparing arc and back arc lavas, which indicates that sediments fluxes also account for the Tl isotopic variations in the Okinawa Trough lavas. Two-end-member mixing models of Tl with Pb, Sr and Nd isotopes require sediment inputs of< 1%, 0.1-1% and 0.3-2% by weight to the depleted mantle source to account for all these isotopic compositions of lavas from northern, central and southern portion of the Ryukyu arc and Okinawa Trough. Bulk mixing between mantle and sediment end members predict very similar sediment fluxes when using Tl, Sr, Nd and Pb isotopes, which indicates that fractionation of these elements must have happened after mixing between mantle and sediments. This conclusion is corroborated by model calculations of mixing between sediment melts with fractionated Sr/Nd ratios and mantle wedge, which show that no arc lava plot on such mixing lines. Thus bulk sediment mixing, rather than sediment melt, is required for the generation of the lavas from the Ryukyu arc and Okinawa Trough. The requirement of bulk sediment mixing occurring before trace element fractionation in the sub-arc mantle is consistent with models where mélange layers form at the top of the slab and are the principle source material for arc lavas. In addition, the fact that sediment components observed in the Ryukyu arc and Okinawa Trough lavas are similar, suggests that transport of mélange material to the source regions of the arc and back arc is equally efficient. This feature is most readily explained if mélange material is transported from the slab as diapirs.

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Horan, M.F.; Czamanske, G.K.; Krogstad, E.J.; Fedorenko, V.A.; Kunilov, V.E.

1994-01-01

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have ??Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have ??Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have ??Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ??{lunate}Nd values that range only from -0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. (1) incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. (2) derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. (3) persistence of primordial stratification of rhenium and osmium in the mantle. ?? 1994.

Isotope Geochemistry for Comparative Planetology of Exoplanets

NASA Technical Reports Server (NTRS)

Mandt, K. E.; Atreya, S.; Luspay-Kuti, A.; Mousis, O.; Simon, A.; Hofstadter, M. D.

2017-01-01

Isotope geochemistry has played a critical role in understanding processes at work in and the history of solar system bodies. Application of these techniques to exoplanets would be revolutionary and would allow comparative planetology with the formation and evolution of exoplanet systems. The roadmap for comparative planetology of the origins and workings of exoplanets involves isotopic geochemistry efforts in three areas: (1) technology development to expand observations of the isotopic composition of solar system bodies and expand observations to isotopic composition of exoplanet atmospheres; (2) theoretical modeling of how isotopes fractionate and the role they play in evolution of exoplanetary systems, atmospheres, surfaces and interiors; and (3) laboratory studies to constrain isotopic fractionation due to processes at work throughout the solar system.

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.

Magnesium isotope compositions of Solar System materials determined by double spiking

NASA Astrophysics Data System (ADS)

Hin, R.; Lai, Y. J.; Coath, C.; Elliott, T.

2015-12-01

As a major element, magnesium is of interest for investigating large scale processes governing the formation and evolution of rocky planetary bodies. Determining the Mg isotope composition of the Earth and other planetary bodies has hence been a topic of interest ever since mass-dependent fractionation of 'non-traditional' stable isotopes has been used to study high-temperature processes. Published results, however, suffer from disagreement on the Mg isotope compositions of the Earth and chondrites [1-5], which is attributed to residual matrix effects. Nonetheless, most recent studied have converged towards a homogeneous (chondritic) Mg isotope composition in the Solar System [2-5]. However, in several of the recent studies there is a hint of a systematic difference of about 0.02-0.06‰ in the 26Mg/24Mg isotope compositions of chondrites and Earth. Such difference, however, is only resolvable by taking standard errors, which assumes robust data for homogenous sample sets. The discrepancies between various studies unfortunately undermine the confidence in such robustness and homogeneity. The issues with matrix effects during isotopic analyses can be overcome by using a double spike approach. Such methodology generally requires three isotope ratios to solve for three unknowns, a requirement that cannot be met for Mg. However, using a newly developed approach, we present Mg isotope compositions obtained by critical mixture double spiking. This new approach should allow greater confidence in the robustness of the data and hence enable improvement of. Preliminary data indicate that chondrites have a resolvable ~0.04‰ lighter 26Mg/24Mg than (ultra)mafic rocks from Earth, Mars and the eucrite parent body, which appear indistinguishable from each other. It seems implausible that this difference is caused by magmatic process such as partial melting or crystallisation. More likely, Mg isotopes are fractionated by a non-magmatic process during the formation of planets, e.g. by vapour-condensate fractionation. [1] Wiechert and Halliday, 2007. EPSL 256, 360-371. [2] Bourdon et al., 2010. GCA 74, 5069-5083. [3] Teng et al., 2010. GCA 74, 4150-4166. [4] Chakrabarti and Jacobsen, 2010. EPSl 293, 349-358. [5] Von Strandmann, 2011. GCA 75, 5247-5268.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Oxygen isotope dynamics of atmospheric nitrate over the Antarctic plateau: First combined measurements of ozone and nitrate 17O-excess (Δ17O)

NASA Astrophysics Data System (ADS)

Vicars, William; Savarino, Joël; Erbland, Joseph; Preunkert, Susanne; Jourdain, Bruno; Frey, Markus; Gil, Jaime; Legrand, Michel

2013-04-01

Variations in the isotopic composition of atmospheric nitrate (NO3-) provide novel indicators for important processes in boundary layer chemistry, often acting as source markers for reactive nitrogen (NOx = NO + NO2) and providing both qualitative and quantitative constraints on the pathways that determine its fate. Stable isotope ratios of nitrate (δ15N, δ17O, δ18O) offer direct insight into the nature and magnitude of the fluxes associated with different processes, thus providing unique information regarding phenomena that are often difficult to quantify from concentration measurements alone. The unique and distinctive 17O-excess (Δ17O = δ17O - 0.52 × δ18O ) of ozone (O3), which is transferred to NOx via oxidation reactions in the atmosphere, has been found to be a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O-excess within the NOx cycle is critical in polar areas where there exists the possibility of extending atmospheric interpretations to the glacial/interglacial time scale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C, Antarctica during December 2011 to January 2012. Sampling was conducted within the framework of the OPALE (Oxidant Production over Antarctic Land and its Export) project, thus providing an opportunity to combine our isotopic observations with a wealth of meteorological and chemical data, including in-situ concentration measurements of the gas-phase precursors involved in nitrate production (NOx, O3, OH, HO2, etc.). Furthermore, nitrate isotope analysis has been combined in this study for the first time with parallel observations of the transferrable Δ17O of surface ozone, which was measured concurrently at Dome C using our recently developed analytical approach. This unique dataset has allowed for a direct comparison of observed Δ17O(NO3-) values to those that are calculated solely from local measurements and invoke no assumptions regarding the Δ17O value of ozone and its transfer in the atmosphere. The predicted Δ17O signature for nitrate formed over the Antarctic plateau during OPALE is on the order of (21 ± 2) ‰ when production is assumed to occur only through the OH + NO2 pathway, which is expected to be the dominant formation channel during the continuously sunlit summer. This predicted value is much lower than the values measured for nitrate during OPALE, with observed Δ17O(NO3-) varying in the range of 27 - 31 ‰. This discrepancy between expected and observed Δ17O(NO3-) values suggests the existence of an unexpected process that contributes significantly to the atmospheric nitrate budget over Dome C. The relative merits of different potential explanations for this puzzling result will be discussed in the context of oxidation chemistry, air mass transport, and snow/atmosphere exchange.

Triple oxygen isotope composition of photosynthetic oxygen

NASA Astrophysics Data System (ADS)

van der Meer, Anne; Kaiser, Jan

2013-04-01

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

Magnesium Isotopes as a Tracer of Crustal Materials in Volcanic Arc Magmas in the Northern Cascade Arc

NASA Astrophysics Data System (ADS)

Brewer, Aaron W.; Teng, Fang-Zhen; Mullen, Emily

2018-03-01

Fifteen North Cascade Arc basalts and andesites were analyzed for Mg isotopes to investigate the extent and manner of crustal contributions to this magmatic system. The δ26Mg of these samples vary from within the range of ocean island basalts (the lightest being -0.33 ± 0.07‰) to heavier compositions (as heavy as -0.15 ± 0.06‰). The observed range in chemical and isotopic composition is similar to that of other volcanic arcs that have been assessed to date in the circum-pacific subduction zones and in the Caribbean. The heavy Mg isotope compositions are best explained by assimilation and fractional crystallization within the deep continental crust with a possible minor contribution from the addition of subducting slab-derived fluids to the primitive magma. The bulk mixing of sediment into the primitive magma or mantle source and the partial melting of garnet-rich peridotite are unlikely to have produced the observed range of Mg isotope compositions. The results show that Mg isotopes may be a useful tracer of crustal input into a magma, supplementing traditional methods such as radiogenic isotopic and trace element data, particularly in cases in which a high fraction of crustal material has been added.

Chemical, isotopic, and gas compositions of selected thermal springs in Arizona, New Mexico, and Utah

USGS Publications Warehouse

Mariner, R.H.; Presser, T.S.; Evans, William C.

1977-01-01

Twenty-seven thermal springs in Arizona, New Mexico, and Utah were sampled for detailed chemical and isotopic analysis. The springs issue sodium chloride, sodium bicarbonate, or sodium mixed-anion waters of near neutral (6.2) to alkaline (9.2) pH. High concentrations of fluoride, more than 8 milligrams per liter, occur in Arizona in waters from Gillard Hot Springs, Castle Hot Springs, and the unnamed spring of Eagle Creek, and in New Mexico from springs along the Gila River. Deuterium compositions of the thermal waters cover the same range as those expected for meteoric waters in the respective areas. The chemical compositions of the thermal waters indicate that Thermo Hot Springs in Utah and Gillard Hot Springs in Arizona represent hydrothermal systems which are at temperatures higher than 125 deg C. Estimates of subsurface temperature based on the quartz and Na-K-Ca geothermometer differ by up to 60 deg C for Monroe, Joseph, Red Hill, and Crater hot springs in Utah. Similar conflicting estimates of aquifer temperature occur for Verde Hot Springs, the springs near Clifton and Coolidge Dam, in Arizona; and the warm springs near San Ysidro, Radium Hot Springs, and San Francisco Hot Springs, in New Mexico. Such disparities could result from mixing, precipitation of calcium carbonate, or perhaps appreciable concentrations of magnesium. (Woodard-USGS)

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

Planetary and meteoritic Mg/Si and δ30 Si variations inherited from solar nebula chemistry

NASA Astrophysics Data System (ADS)

Dauphas, Nicolas; Poitrasson, Franck; Burkhardt, Christoph; Kobayashi, Hiroshi; Kurosawa, Kosuke

2015-10-01

The bulk chemical compositions of planets are uncertain, even for major elements such as Mg and Si. This is due to the fact that the samples available for study all originate from relatively shallow depths. Comparison of the stable isotope compositions of planets and meteorites can help overcome this limitation. Specifically, the non-chondritic Si isotope composition of the Earth's mantle was interpreted to reflect the presence of Si in the core, which can also explain its low density relative to pure Fe-Ni alloy. However, we have found that angrite meteorites display a heavy Si isotope composition similar to the lunar and terrestrial mantles. Because core formation in the angrite parent-body (APB) occurred under oxidizing conditions at relatively low pressure and temperature, significant incorporation of Si in the core is ruled out as an explanation for this heavy Si isotope signature. Instead, we show that equilibrium isotopic fractionation between gaseous SiO and solid forsterite at ∼1370 K in the solar nebula could have produced the observed Si isotope variations. Nebular fractionation of forsterite should be accompanied by correlated variations between the Si isotopic composition and Mg/Si ratio following a slope of ∼1, which is observed in meteorites. Consideration of this nebular process leads to a revised Si concentration in the Earth's core of 3.6 (+ 6.0 / - 3.6) wt% and provides estimates of Mg/Si ratios of bulk planetary bodies.

Stable water isotopic composition of the Antarctic subglacial Lake Vostok: implications for understanding the lake's hydrology.

PubMed

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

2016-01-01

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

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

Interactions between surface waters in King George Island, Antarctica - a stable isotope perspective

NASA Astrophysics Data System (ADS)

Perşoiu, Aurel; Bădăluşă, Carmen

2017-04-01

In this paper we present a first study of the isotopic composition of surface waters in the southern peninsulas (Barton, Fildes, Weaver and Potter) of King George Island, Antarctica. We have collected > 200 samples of snow and snowmelt, water (lake, river and spring), ice (glacier ice and permafrost) from the four peninsulas in February 2016 and analyzed them for their oxygen and hydrogen stable isotopic composition. Samples from lake water (50+) indicate a clear west-east depletion trend, suggesting a rain-out process as air masses are moving westward (and are progressively depleted in heavy isotopes) from their origin in the Drake Passage. In both Fildes and Barton Peninsulas, permafrost samples have the heaviest isotopic composition, most probably due to preferential incorporation of heavy isotopes in the ice during freezing (and no fractionation during melting). As permafrost melts, the resulting water mixes with isotopically lighter infiltrated snowmelt, and thus the groundwater has a lower isotopic composition. Further, lake and river (the later fed by lakes) water has the lightest isotopic composition, being derived mostly from the melting of light snow and glacier ice. It seems feasible to separate isotopically water in lakes/rivers (largely fed by melting multi-year glaciers and snow) and water from melting of snow/ground ice This preliminary study suggests that it is possible to separate various water sources in the southern peninsulas of King George Island, and this separation could be used to study permafrost degradation, as well as feeding and migration patterns in the bird fauna, with implications for protection purposes. Acknowledgments. The National Institute of Research and Development for Biological Sciences (Bucharest, Romania) and the Korean polar institute financially supported fieldwork in King George Island. We thank the personal at King Sejong (South Korea), Belingshaussen (Russia) and Carlini (Argentina) stations in King George Island for logistic supports.

PALOMA : an isotope analyzer using static mass spectrometry, coupled with cryogenic and chemical trapping, for the MSL mission to Mars

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Goulpeau, G.; Leblanc, F.; Montmessin, F.; Sarda, P.; Agrinier, P.; Fouchet, T.; Waite, H.

The technique of GCMS analysis has to be completed by static mass spectrometry for precise in-situ measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation and gettering, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. Such an instrument (PALOMA) is presently developed in our laboratories, and it will be coupled with a Pyr-GCMS analyzer (MACE), built by a US consortium of science laboratories and industrials (University of Michigan, Southwest Research Institute, JPL, Ball Aerospace). The MACE/PALOMA experiment will be proposed on the NASA Mars Science Laboratory mission, planned to be launched in 2009. The scientific objectives of PALOMA, coupled with MACE, may be listed as follows : (i) search for isotopic signatures of past life in atmosphere, rock, dust and ice samples, with emphasis on carbon, nitrogen and hydrogen; (ii) accurately measure isotopic composition of atmospheric noble gases, and stable isotopes, in order to better constrain past escape, surface interaction, outgassing history and climate evolution; (iii) precisely measure diurnal/ seasonal variations of isotopic ratios of H2O, CO2, and N2, for improving our understanding of present and past climate, and of the role of water cycle. Main measurement objectives are : (i) C, H, O, N isotopic composition in both organic evolved samples (provided by MACE pyrolysis system) and atmosphere with high accuracy (a few per mil at 1-s level); (ii) noble gas (He, Ne, Ar, Kr, Xe) and stable (C, H, O, N) isotope composition in atmosphere with high accuracy (a few per mil at 1-s level); (iii) molecular and isotopic composition of inorganic evolved samples (salts, hydrates, nitrates, {ldots}), including ices; (iv) diurnal and seasonal monitoring of D/H in water vapor, and water ice.

Spatiotemporal patterns of plant water isotope values from a continental-scale sample network in Europe as a tool to improve hydroclimate proxies

NASA Astrophysics Data System (ADS)

Nelson, D. B.; Kahmen, A.

2016-12-01

The hydrogen and oxygen isotopic composition of water available for biosynthetic processes in vascular plants plays an important role in shaping the isotopic composition of organic compounds that these organisms produce, including leaf waxes and cellulose in leaves and tree rings. Characterizing changes in large scale spatial patterns of precipitation, soil water, stem water, and leaf water isotope values over time is therefore useful for evaluating how plants reflect changes in the isotopic composition of these source waters in different environments. This information can, in turn, provide improved calibration targets for understanding the environmental signals that plants preserve. The pathway of water through this continuum can include several isotopic fractionations, but the extent to which the isotopic composition of each of these water pools varies under normal field conditions and over space and time has not been systematically and concurrently evaluated at large spatial scales. Two season-long sampling campaigns were conducted at nineteen sites throughout Europe over the 2014 and 2015 growing seasons to track changes in the isotopic composition of plant-relevant waters. Samples of precipitation, soil water, stem water, and leaf water were collected over more than 200 field days and include more than 500 samples from each water pool. Measurements were used to validate continent-wide gridded estimates of leaf water isotope values derived from a combination of mechanistic and statistical modeling conducted with temperature, precipitation, and relative humidity data. Data-model comparison shows good agreement for summer leaf waters, and substantiates the incorporation of modeled leaf waters in evaluating how plants respond to hydroclimate changes at large spatial scales. These results also suggest that modeled leaf water isotope values might be used in future studies in similar ecosystems to improve the coverage density of spatial or temporal data.

The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Mass dependent fractionation of stable chromium isotopes in mare basalts: Implications for the formation and the differentiation of the Moon

NASA Astrophysics Data System (ADS)

Bonnand, Pierre; Parkinson, Ian J.; Anand, Mahesh

2016-02-01

We present the first stable chromium isotopic data from mare basalts in order to investigate the similarity between the Moon and the Earth's mantle. A double spike technique coupled with MC-ICP-MS measurements was used to analyse 19 mare basalts, comprising high-Ti, low-Ti and KREEP-rich varieties. Chromium isotope ratios (δ53Cr) for mare basalts are positively correlated with indices of magmatic differentiation such as Mg# and Cr concentration which suggests that Cr isotopes were fractionated during magmatic differentiation. Modelling of the results provides evidence that spinel and pyroxene are the main phases controlling the Cr isotopic composition during fractional crystallisation. The most evolved samples have the lightest isotopic compositions, complemented by cumulates that are isotopically heavy. Two hypotheses are proposed to explain this fractionation: (i) equilibrium fractionation where heavy isotopes are preferentially incorporated into the spinel lattice and (ii) a difference in isotopic composition between Cr2+ and Cr3+ in the melt. However, both processes require magmatic temperatures below 1200 °C for appreciable Cr3+ to be present at the low oxygen fugacities found in the Moon (IW -1 to -2 log units). There is no isotopic difference between the most primitive high-Ti, low-Ti and KREEP basalts, which suggest that the sources of these basalts were homogeneous in terms of stable Cr isotopes. The least differentiated sample in our sample set is the low-Ti basalt 12016, characterised by a Cr isotopic composition of -0.222 ± 0.025‰, which is within error of the current BSE value (-0.124 ± 0.101‰). The similarity between the mantles of the Moon and Earth is consistent with a terrestrial origin for a major fraction of the lunar Cr. This similarity also suggests that Cr isotopes were not fractionated by core formation on the Moon.

Using semi-continuous, in-situ measurements of nitrous oxide isotopic composition at a suburban site to track emission processes

NASA Astrophysics Data System (ADS)

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

2017-04-01

Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance emitted this century. The atmospheric N2O mole fraction has been increasing at a rate of 0.2-0.3% per year over the past decades due to anthropogenic emissions; in addition, recent results suggest that the rate of increase is rising - therefore effective mitigation of N2O emissions is a critical point for environmental policy. However, N2O sources are poorly defined and disperse, complicating the development of targeted mitigation strategies. Online isotopic measurements using preconcentration and laser spectroscopy [1,2,3] have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of trace gases such as N2O. Semi-continuous, real-time measurements of N2O isotopic composition (δ18O, site preference [SP = 14N15N16O - 15N14N16O] and δ15Nbulk) were performed at the suburban site of Dübendorf, Switzerland, for 19 months between July 2014 and February 2016. The data precision reached 0.1‰ in the final months, thus the results could clearly identify nocturnal build-up of N2O, with a corresponding decrease in δ18O, SP and δ15Nbulk due to isotopically depleted anthropogenic sources. Daily mean source isotopic composition was calculated by considering the measured and the background mole fraction and isotopic composition. Delta values of the mean emission source were highest in winter, with a seasonal cycle of 12, 8 and 5‰ for δ18O, SP and δ15Nbulk respectively. The chemical and meteorological parameters controlling source isotopic composition were considered using data from the Swiss National Air Pollution Monitoring Network (NABEL) as well as a transport regime cluster analysis. A clear spatial distribution for source isotopic composition was observed for δ18O, as well as a significant relationship with the level of urban pollution, indicating δ18O may be a strong indicator of combustion/industrial vs. agricultural N2O. In contrast, δ15Nbulk and particularly SP appear to vary too strongly in response to other factors affecting emission processes to provide a useful distinction between source categories on a regional scale - these isotopocules may however be useful to distinguish emission pathways on a local scale. For comparison, FLEXPART-COSMO transport simulations [4] were combined with emissions from the EDGAR inventory and estimates of source isotopic composition from literature, to simulate N2O isotopic composition at the sampling site. The model was able to capture variability in N2O mole fraction adequately (R2 = 0.34; p <<0.01). However, the measured variability in source isotopic composition was 1-2 orders of magnitude larger than simulated, illustrating that our knowledge of isotopic source signatures - in particular technical N2O sources - is still too limited to successfully model variations in ambient N2O isotopic composition. [1] Mohn et al. (2012) Atmospheric Measurement Techniques, doi:10.5194/amt-5-1601-2012 [2] Harris et al. (2014) Analytical Chemistry, doi: 10.1021/ac403606u. [3] Röckmann et al. (2016) Atmospheric Chemistry and Physics, doi:10.5194/acp-16-10469-2016. [4] Henne et al. (2016) Atmospheric Chemistry and Physics, doi:10.5194/acp-16-3683-2016.

Evidence for a nonmagmatic component in potassic hydrothermal fluids of porphyry cu-Au-Mo systems, Yukon, Canada

NASA Astrophysics Data System (ADS)

Selby, David; Nesbitt, Bruce E.; Creaser, Robert A.; Reynolds, Peter H.; Muehlenbachs, Karlis

2001-02-01

Isotopic (H, Sr, Pb, Ar) and fluid inclusion data for hydrothermal fluids associated with potassic alteration from three Late Cretaceous porphyry Cu occurrences, west central Yukon, suggest a nonmagmatic fluid component was present in these hydrothermal fluids. Potassic stage quartz veins contain a dominant assemblage of saline and vapor-rich fluid inclusions that have δD values between -120 and -180‰. Phyllic stage quartz veins are dominated by vapor-rich fluid inclusions and have δD values that overlap with but are, on average, heavier (-117 to -132‰) than those in potassic stage quartz veins. These δD values are significantly lower than those from plutonic quartz phenocrysts (-91 to -113‰), and from values typically reported for primary fluids from porphyry-style mineralization (-40 to -100‰). The initial Sr ( 87Sr/ 86Sr i) isotopic values for the plutons are 0.7055 (Casino), 0.7048 (Mt. Nansen), and 0.7055 (Cash). The 87Sr/ 86Sr i compositions of hydrothermal K-feldspar ranges from magmatic Sr i values to more radiogenic compositions (Casino: 0.70551-0.70834, n = 8; Mt. Nansen: 0.7063-0.7070, n = 4; Cash: 0.7058, n = 1). The fluid inclusion waters from potassic quartz veins have 87Sr/ 86Sr i values that are similar to those of co-existing hydrothermal K-feldspar. The Pb isotopic compositions of hydrothermal K-feldspar show a weak positive correlation with Sr i for identical samples. Fluid inclusion waters of phyllic quartz veins also have Sr i compositions more radiogenic than the plutons. The Pb isotopic composition of pyrite and bornite from phyllic alteration veins are similar to, or more radiogenic than, hydrothermal K-feldspar Pb isotopic values. Hydrothermal K-feldspar samples yield 40Ar/ 39Ar ages (Casino = 71.9 ± 0.7 to 73.4 ± 0.8 Ma; Mt. Nansen = 68.2 ± 0.7 and 69.5 ± 0.6 Ma; Cash = 68.3 ± 0.8 Ma) similar to the U-Pb zircon, K-Ar biotite and Re-Os molybdenite ages of the Late Cretaceous plutons, with the age spectra indicating no excess 40Ar or disturbance. The 40Ar/ 36Ar values (285-292) of the K-feldspar samples are similar to the atmospheric compositions (295 ± 5) during Late Cretaceous time. The H, Sr, Pb, and Ar isotopic compositions of hydrothermal K-feldspar and quartz vein fluid inclusion waters that characterize the potassic hydrothermal fluids show evidence for an exotic component in addition to magmatic water (fluid). This component has a low δD, radiogenic Sr and Pb, and an atmospheric Ar composition. The inheritance of pre-existing isotope compositions from the host rocks, postpotassic alteration isotope exchange, or the replenishment of the magma chamber with magma of different isotopic composition cannot explain the isotope data. We suggest that to generate the observed H, Sr, Pb, and Ar isotope compositions, crustal fluids must be a component (15-94%) of potassic hydrothermal fluids in porphyry mineralization in the deposits studied.

Osmium uptake, distribution, and 187Os/188Os and 187Re/188Os compositions in Phaeophyceae macroalgae, Fucus vesiculosus: Implications for determining the 187Os/188Os composition of seawater

NASA Astrophysics Data System (ADS)

Racionero-Gómez, B.; Sproson, A. D.; Selby, D.; Gannoun, A.; Gröcke, D. R.; Greenwell, H. C.; Burton, K. W.

2017-02-01

The osmium isotopic composition (187Os/188Os) of seawater reflects the balance of input from mantle-, continental- and anthropogenic-derived sources. This study utilizes the Phaeophyceae, Fucus vesiculosus, to analyse its Os abundance and uptake, as well as to assess if macroalgae records the Os isotope composition of the seawater in which it lives. The data demonstrates that Os is not located in one specific biological structure within macroalgae, but is found throughout the organism. Osmium uptake was measured by culturing F. vesiculosus non-fertile tips with different concentrations of Os with a known 187Os/188Os composition (∼0.16), which is significantly different from the background isotopic composition of local seawater (∼0.94). The Os abundance of cultured non-fertile tips show a positive correlation to the concentration of the Os doped seawater. Moreover, the 187Os/188Os composition of the seaweed equalled that of the culture medium, strongly confirming the possible use of macroalgae as a biological proxy for the Os isotopic composition of the seawater.

Optimizing isotope substitution in graphene for thermal conductivity minimization by genetic algorithm driven molecular simulations

NASA Astrophysics Data System (ADS)

Davies, Michael; Ganapathysubramanian, Baskar; Balasubramanian, Ganesh

2017-03-01

We present results from a computational framework integrating genetic algorithm and molecular dynamics simulations to systematically design isotope engineered graphene structures for reduced thermal conductivity. In addition to the effect of mass disorder, our results reveal the importance of atomic distribution on thermal conductivity for the same isotopic concentration. Distinct groups of isotope-substituted graphene sheets are identified based on the atomic composition and distribution. Our results show that in structures with equiatomic compositions, the enhanced scattering by lattice vibrations results in lower thermal conductivities due to the absence of isotopic clusters.

Transport-Induced Spatial Patterns of Sulfur Isotopes (δ34S) as Biosignatures

NASA Astrophysics Data System (ADS)

Mansor, Muammar; Harouaka, Khadouja; Gonzales, Matthew S.; Macalady, Jennifer L.; Fantle, Matthew S.

2018-01-01

Cave minerals deposited in the presence of microbes may host geochemical biosignatures that can be utilized to detect subsurface life on Earth, Mars, or other habitable worlds. The sulfur isotopic composition of gypsum (CaSO4·2H2O) formed in the presence of sulfur-oxidizing microbes in the Frasassi cave system, Italy, was evaluated as a biosignature. Sulfur isotopic compositions (δ34SV-CDT) of gypsum sampled from cave rooms with sulfidic air varied from -11 to -24‰, with minor deposits of elemental sulfur having δ34S values between -17 and -19‰. Over centimeter-length scales, the δ34S values of gypsum varied by up to 8.5‰. Complementary laboratory experiments showed negligible fractionation during the oxidation of elemental sulfur to sulfate by Acidithiobacillus thiooxidans isolated from the caves. Additionally, gypsum precipitated in the presence and absence of microbes at acidic pH characteristic of the sulfidic cave walls has δ34S values that are on average 1‰ higher than sulfate. We therefore interpret the 8.5‰ variation in cave gypsum δ34S (toward more negative values) to reflect the isotopic effect of microbial sulfide oxidation directly to sulfate or via elemental sulfur intermediate. This range is similar to that expected by abiotic sulfide oxidation with oxygen, thus complicating the use of sulfur isotopes as a biosignature at centimeter-length scales. However, at the cave room (meter-length) scale, reactive transport modeling suggests that the overall ˜13‰ variability in gypsum δ34S reflects isotopic distillation of circulating H2S gas due to microbial sulfide oxidation occurring along the cave wall-atmosphere interface. Systematic variations of gypsum δ34S along gas flow paths can thus be interpreted as biogenic given that slow, abiotic oxidation cannot produce the same spatial patterns over similar length scales. The expression and preservation potential of this biosignature is dependent on gas flow parameters and diagenetic processes that modify gypsum δ34S values over geological timescales.

Revising Estimates of the Methane Production Pathway in Peatland Porewater Using Intramolecular Isotopic Analyses of Acetate

NASA Astrophysics Data System (ADS)

Thomas, B.; Arthur, M. A.; Freeman, K. H.

2007-12-01

Stable isotopic measurements of methane and carbon dioxide are routinely applied to environmental samples to assess the relative importance of methane production by either aceticlastic or hydrogenotrophic methanogenesis. Such estimates rely upon assumptions about isotopic fractionation during methane production and oxidation. Rigorous isotope-based pathway estimates require knowledge of the carbon isotopic composition of both carbon dioxide and acetate. In practice, technical barriers have limited measurements of the isotopic composition of whole acetate in natural samples. Yet, the estimate of whole acetate isotopic values, even when available, may not represent accurately the composition of the methyl carbon, which is, in fact, the precursor to methane. It is exceedingly rare to find carbon isotopic measurements of acetate-methyl in the literature, and, to our knowledge, the d13C of the acetate-methyl precursor to methane has never before been reported from peatland porewater samples. Extremely 13C-depleted methane, -70 permil VPDB, and 13C-enriched carbon dioxide from acidic northern peat bogs are typically interpreted as signatures of hydrogenotrophic methanogenesis. The hypothesized dominance of methane production from hydrogen in acidic bogs contrasts with the vast majority of freshwater wetlands in which aceticlastic methanogenesis dominates. Using a new technique for the online analysis of the intramolecular carbon isotopic composition of acetate in natural samples, we find the acetate-methyl in peat porewaters can be significantly depleted relative to bulk organic matter. In porewater profiles from both winter and summer, acetate is as much as 15 permil depleted relative to bulk carbon. We hypothesize that acetate- methyl isotopic depletion results from conditions that favor autotrophic acetogenesis and subsequent acetate consumption by aceticlastic methanogens. Porewater depth profiles during winter and summer illustrate depth- dependent increases in the fraction of methane derived from carbon dioxide, with deeper peat dominated by hydrogenotrophic methanogenesis, but shallow peat dominated by aceticlastic methanogens. Significant aceticlastic methane production from autotrophically produced acetate challenges the ability of hydrogen isotopic measurements of methane to represent the pathway of methanogenesis. Supplementing our field observations, intramolecular acetate measurements of incubation experiments confirm that an aceticlastic methanogen can facilitate significant acetate-carboxyl exchange with DIC. This novel technique confirms two caveats associated with whole acetate carbon isotopic data: 1, the carboxyl carbon isotopic composition may not accurately reflect the composition of the parent molecule, and 2, the acetate methyl may be derived from inorganic carbon or the fractionation effect of fermentation in acidic porewaters may be significant.

Methane clumped isotopes: Progress and potential for a new isotopic tracer

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

Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here wemore » present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.« less

Oxygen-isotope, X-ray-diffraction and scanning-electron-microscope examinations of authigenic-layer-silicate minerals from Mississippian and Pennsylvanian sandstones in the Michigan Basin

USGS Publications Warehouse

Zacharias, K.F.; Sibley, D.F.; Westjohn, D.B.; Weaver, T. L.

1993-01-01

Oxygen-isotope compositions of authigenic-layer silicates (<2-micrometer fraction) extracted from Mississippian and Pennsylvanian sandstones in the Lower Peninsula of Michigan were determined. Petrographic and scanning-electron-microscope examinations, and X-ray diffractograms show that chlorite and kaolinite are the most common authigenic-layer silicates in Mississippian sandstones. The range of oxygen-isotope compositions of chlorite and kaolinite are +10.3 to +11.9 and +12.9 to +19.3 pars per thousand (per mil) (relative to Standard Mean Ocean Water), respectively. Kaolinite is the only authigenic-isotopic compositions of kaolinite range from +16.8 to +19.0 per mil.

Development of particle induced gamma-ray emission methods for nondestructive determination of isotopic composition of boron and its total concentration in natural and enriched samples.

PubMed

Chhillar, Sumit; Acharya, Raghunath; Sodaye, Suparna; Pujari, Pradeep K

2014-11-18

We report simple particle induced gamma-ray emission (PIGE) methods using a 4 MeV proton beam for simultaneous and nondestructive determination of the isotopic composition of boron ((10)B/(11)B atom ratio) and total boron concentrations in various solid samples with natural isotopic composition and enriched with (10)B. It involves measurement of prompt gamma-rays at 429, 718, and 2125 keV from (10)B(p,αγ)(7)Be, (10)B(p, p'γ)(10)B, and (11)B(p, p'γ)(11)B reactions, respectively. The isotopic composition of boron in natural and enriched samples was determined by comparing peak area ratios corresponding to (10)B and (11)B of samples to natural boric acid standard. An in situ current normalized PIGE method, using F or Al, was standardized for total B concentration determination. The methods were validated by analyzing stoichiometric boron compounds and applied to samples such as boron carbide, boric acid, carborane, and borosilicate glass. Isotopic compositions of boron in the range of 0.247-2.0 corresponding to (10)B in the range of 19.8-67.0 atom % and total B concentrations in the range of 5-78 wt % were determined. It has been demonstrated that PIGE offers a simple and alternate method for total boron as well as isotopic composition determination in boron based solid samples, including neutron absorbers that are important in nuclear technology.

Stalagmite geochemistry and the timing of the last interglacial-glacial transition in Central Europe (NE Hungary)

NASA Astrophysics Data System (ADS)

Siklosy, Z.; Demeny, A.; Pilet, S.; Leel-Ossy, Sz.; Lin, K.; Shen, C.-C.

2009-04-01

Speleothems can provide accurate chronologies for reconstructions of climate change by combination of U/Th dating and climate-related geochemical compositions. Geochemical studies of speleothems from Central Europe are mostly based on stable C and O isotope analyses, thus, complex geochemical studies combining isotope and trace element measurements are needed for more reliable climate models for this transitional area between oceanic and continental regions. We present stable H-C-O isotope and trace element records obtained on speleothems covering the Last Interglacial (MIS 5e) and the transition to MIS 5d. A stalagmite from Baradla Cave grew from 127.5 to 110 ka. Accelerated growth rates have been detected by U/Th age data in the 127 to 126 ka and 119 to 117 ka parts. Trace element compositions and 230Th/232Th ratios suggest changes in the hydrological regime, whereby early calcite precipitates formed in fissures during the dry and cold glacial period were dissolved by the starting flux of infiltrating meteoric water (producing elevated dissolved ion concentration but low detrital Th component), then the increasing amount of dripwater during the interglacial period resulted in trace element dilution. Temperature and precipitation amount variations are also reflected by the stable isotope compositions. Oxygen isotope composition shows a continuous increase from 127.5 ka until about 118 ka most probably related to temperature rise, whereas C isotope values are shifted in negative direction suggesting increasing humidity in accordance with trace element contents. The presumably warmest period at ca. 118 ka is associated with rather arid climate as indicated by peak d18O values coinciding with the highest dD values of fluid inclusion water. This is followed by a pronounced negative shift in both O and H isotope values, similarly to recent Alpine studies (Meyer et al., 2008), most probably related to cooling. Hydrogen isotope compositions of fluid inclusion water evaluated together with calculated oxygen isotope compositions of water indicate warming and increasing significance of summer precipitation at the latest period of the last interglacial, then increasing importance of winter precipitation and/or changes in oceanic source composition during the cooling phase. The good agreement with other (Alpine and marine) records indicate a synchronous climate change. However, after a negative shift in the wet/warm phase (increasing soil activity), C isotope values start to increase already at about 119 ky BP, warning to the use of the two isotope systems as event correlation tools. In conclusion, our combined isotope and trace element study indicate a complex pattern of temperature and humidity variations during and right after the Last Interglacial. Acknowledgements — This study was financially supported by the Hungarian Scientific Research Fund (OTKA T 049713). Measurements of U-Th isotopic compositions and and 230Th dates were supported by the National Science Council grants (94-2116-M002-012, 97-2752-M002-004-PAE & -005-PAE to C.C.S.). [Meyer, M.; Spötl, C.; Mangini, A. (2008): The demise of the Last Interglacial recorded in isotopically dated speleothems from the Alps. Quaternary Science Reviews, 27, 476-496.

Carbon isotope geochemistry and geobiology

NASA Technical Reports Server (NTRS)

Desmarais, D.

1985-01-01

Carbon isotope fractionation values were used to understand the history of the biosphere. For example, plankton analyses confirmed that marine extinctions at the end of the Cretaceous period were indeed severe (see Hsu's article in Sundquist and Broeker, 1984). Variations in the isotopic compositions of carbonates and evaporitic sulfates during the Paleozoic reflect the relative abundances of euxinic (anoxic) marine environments and organic deposits from terrestrial flora. The carbon isotopic composition of Precambrian sediments suggest that the enzyme ribulose bisphosphate carboxylase has existed for perhaps 3.5 billion years.

Albanian ophiolites as probes of a mantle heterogeneity study

NASA Astrophysics Data System (ADS)

Meisel, Thomas; Ginley, Stephen; Koller, Friedrich; Walker, Richard J.

2013-04-01

Most ophiolites are believed to be tectonically obducted slivers of oceanic lithosphere. As such they can provide information not only about the history of crust formation, but also about the composition of the chemical composition of the recent and ancient mantle composition. The occurrence of the well preserved Albanian Ophiolite Complex covers the length of Albania (ca. 150 km) is an ideal object not only for the study of the history of Jurassic tectonic event, but also for the study of the heterogeneity of the upper oceanic mantle from a millimeter to a 100 km scale. The occurrence of two almost parallel ophiolite chains, which have been described to be of different petrography presenting different parts of the upper mantle (MOR vs. SSZ type), allows the investigation of additional aspects of mantle heterogeneity. In this study we want to take advantage of the geochemical characteristics of platinum group elements (PGE) and of lithophile elements to estimate the extant of mantle melting, metasomatic and mixing events of a large portion of mantle obducted contemporaneously. In a first step only peridotites from the mantle sections of the ophiolite complexes are studied for the PGE content and the osmium isotopic composition. Together with major and trace element compositional data, following tasks will be addressed: development of a strategy for field and lab sampling, identification of processes that happened before and after obduction such as melt depletion, metasomatism, serpentinisation etc. and the determination of the size of modified and "pristine" domains. Samples from the western Albanian Ophiolite belt have been studied so far. Although the locations spread over the entire belt a remarkable similarity of PGE abundances is observed. In detail deviations from a correlation of Lu and TiO2 concentration data are also reflected in aberrant mantle normalized PGE patterns. Interestingly enough, this behavior is not manifested in a trend in the 187Os/188Os distribution. As a result the Os isotopic compositions of the entire belt represent the range to be expected from a post Archean upper mantle. The observed heterogeneous distribution of osmium isotopic compositions is most likely an image of the long depletion and incomplete remixing history of the upper Earth's mantle which was not significantly modified through event leading to the formation of ophiolite belts.

Calcium and Titanium Isotope Fractionation in CAIS: Tracers of Condensation and Inheritance in the Early Solar Protoplanetary Disk

NASA Technical Reports Server (NTRS)

Simon, J. I.; Jordan, M. K.; Tappa, M. J.; Kohl, I. E.; Young, E. D.

2016-01-01

The chemical and isotopic compositions of calcium-aluminum-rich inclusions (CAIs) can be used to understand the conditions present in the protoplantary disk where they formed. The isotopic compositions of these early-formed nebular materials are largely controlled by chemical volatility. The isotopic effects of evaporation/sublimation, which are well explained by both theory and experimental work, lead to enrichments of the heavy isotopes that are often exhibited by the moderately refractory elements Mg and Si. Less well understood are the isotopic effects of condensation, which limits our ability to determine whether a CAI is a primary condensate and/or retains any evidence of its primordial formation history.

Spatial, seasonal, and source variability in the stable oxygen and hydrogen isotopic composition of tap waters throughout the USA

USGS Publications Warehouse

Landwehr, Jurate M.; Coplen, Tyler B.; Stewart, David W.

2013-01-01

To assess spatial, seasonal, and source variability in stable isotopic composition of human drinking waters throughout the entire USA, we have constructed a database of δ18O and δ2H of US tap waters. An additional purpose was to create a publicly available dataset useful for evaluating the forensic applicability of these isotopes for human tissue source geolocation. Samples were obtained at 349 sites, from diverse population centres, grouped by surface hydrologic units for regional comparisons. Samples were taken concurrently during two contrasting seasons, summer and winter. Source supply (surface, groundwater, mixed, and cistern) and system (public and private) types were noted. The isotopic composition of tap waters exhibits large spatial and regional variation within each season as well as significant at-site differences between seasons at many locations, consistent with patterns found in environmental (river and precipitation) waters deriving from hydrologic processes influenced by geographic factors. However, anthropogenic factors, such as the population of a tap’s surrounding community and local availability from diverse sources, also influence the isotopic composition of tap waters. Even within a locale as small as a single metropolitan area, tap waters with greatly differing isotopic compositions can be found, so that tap water within a region may not exhibit the spatial or temporal coherence predicted for environmental water. Such heterogeneities can be confounding factors when attempting forensic inference of source water location, and they underscore the necessity of measurements, not just predictions, with which to characterize the isotopic composition of regional tap waters. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

On the origin and composition of Theia: Constraints from new models of the Giant Impact

NASA Astrophysics Data System (ADS)

Meier, M. M. M.; Reufer, A.; Wieler, R.

2014-11-01

Knowing the isotopic composition of Theia, the proto-planet which collided with the Earth in the Giant Impact that formed the Moon, could provide interesting insights on the state of homogenization of the inner Solar System at the late stages of terrestrial planet formation. We use the known isotopic and modeled chemical compositions of the bulk silicate mantles of Earth and Moon and combine them with different Giant Impact models, to calculate the possible ranges of isotopic composition of Theia in O, Si, Ti, Cr, Zr and W in each model. We compare these ranges to the isotopic composition of carbonaceous chondrites, Mars, and other Solar System materials. In the absence of post-impact isotopic re-equilibration, the recently proposed high angular momentum models of the Giant Impact ("impact-fission", Cúk, M., Stewart, S.T. [2012]. Science 338, 1047; and "merger", Canup, R.M. [2012]. Science 338, 1052) allow - by a narrow margin - for a Theia similar to CI-chondrites, and Mars. The "hit-and-run" model (Reufer, A., Meier, M.M.M., Benz, W., Wieler, R. [2012]. Icarus 221, 296-299) allows for a Theia similar to enstatite-chondrites and other Earth-like materials. If the Earth and Moon inherited their different mantle FeO contents from the bulk mantles of the proto-Earth and Theia, the high angular momentum models cannot explain the observed difference. However, both the hit-and-run as well as the classical or "canonical" Giant Impact model naturally explain this difference as the consequence of a simple mixture of two mantles with different FeO. Therefore, the simplest way to reconcile the isotopic similarity, and FeO dissimilarity, of Earth and Moon is a Theia with an Earth-like isotopic composition and a higher (∼20%) mantle FeO content.

Multiple enrichment of the Carpathian-Pannonian mantle: Pb-Sr-Nd isotope and trace element constraints

NASA Astrophysics Data System (ADS)

Rosenbaum, Jeffrey M.; Wilson, Marjorie; Downes, Hilary

1997-07-01

Pb isotope compositions of acid-leached clinopyroxene and amphibole mineral separates from spinel peridotite mantle xenoliths entrained in Tertiary-Quaternary alkali basalts from the Carpathian-Pannonian Region of eastern Europe provide important constraints on the processes of metasomatic enrichment of the mantle lithosphere in an extensional tectonic setting associated with recent subduction. Principal component analysis of Pb-Sr-Nd isotope and rare earth element compositions of the pyroxenes is used to identify the geochemical characteristics of the original lithospheric mantle protolith and a spectrum of infiltrating metasomatic agents including subduction-related aqueous fluids and silicate melts derived from a subduction-modified mantle wedge which contains a St. Helena-type (HIMU) plume component. The mantle protolith is highly depleted relative to mid-ocean ridge basalt-source mantle with Pb-Nd-Sr isotope compositions consistent with an ancient depletion event. Silicate melt infiltration into the protolith accounts for the primary variance in the Pb-Sr-Nd isotope compositions of the xenoliths and has locally generated metasomatic amphibole. Infiltration of aqueous fluids has introduced radiogenic Pb and Sr without significantly perturbing the rare earth element signature of the protolith. The Pb isotope compositions of the fluid-modified xenoliths suggest that they reacted with aqueous fluids released from a subduction zone which had equilibrated with sediment derived from an ancient basement terrain. We propose a model for mantle lithosphere evolution consistent with available textural and geochemical data for the xenolith population. The Pb-Sr-Nd isotope compositions of both alkaline mafic magmas and rare, subduction-related, calc-alkaline basaltic andesites from the region provide important constraints for the nature of the asthenospheric mantle wedge and confirm the presence of a HIMU plume component. These silicate melts contribute to the metasomatism of the mantle lithosphere rather than being derived therefrom.

Stable Isotopes as Indicators of Groundwater Recharge Mechanisms in Arid and Semi-arid Australia

NASA Astrophysics Data System (ADS)

Harrington, G. A.; Herczeg, A. L.

2001-05-01

The isotopic compositions of soil water and groundwaters in arid and semi-arid zones are always different from the mean composition of rainfall. Although evaporative processes always remove the lighter isotopes (1H and 16O) to the vapour phase, arid zone groundwaters are invariably depleted in the heavy isotopes (2H and 18O) relative to mean present day rainfall. We compare two sites, one in semi-arid South Australia and the other in arid Central Australia that have a similar mean annual rainfall (250 to 300 mm/a), very high potential evapotranspiration (2500 and 3500 mm/a respectively) but very different rainfall patterns (winter dominated versus summer monsoonal). We aim to evaluate whether inferences from groundwater \\delta2H and \\delta18O reveal information about palaeorecharge, or recharge mechanisms or a combination of both. Recharge to the unconfined limestone aquifer in the Mallee area of South Australia occurs annually via widespread (diffuse) infiltration of winter dominant rainfall. This process is reflected in soil and groundwater isotopic compositions that plot relatively close to both the Local Meteoric Water Line and the volume-weighted mean composition of winter rainfall, and have a deuterium excess (\\delta2H-8.\\delta18O) of between +2 and +8 for the freshest samples. Groundwater recharge to the arid Ti-Tree Basin occurs predominantly by inputs of partially-evaporated surface water from ephemeral rivers and flood-plains following rare, high-intensity storms that are derived from monsoonal activity to the north of Australia. These extreme events result in groundwater and soil water stable isotope compositions being significantly depleted in the heavy isotopes relative to the mean composition of rainfall and a deuterium excess of between minus 8 and +3 in the freshest groundwaters.

Large-scale drivers of Caucasus climate variability in meteorological records and Mt El'brus ice cores

NASA Astrophysics Data System (ADS)

Kozachek, Anna; Mikhalenko, Vladimir; Masson-Delmotte, Valérie; Ekaykin, Alexey; Ginot, Patrick; Kutuzov, Stanislav; Legrand, Michel; Lipenkov, Vladimir; Preunkert, Susanne

2017-05-01

A 181.8 m ice core was recovered from a borehole drilled into bedrock on the western plateau of Mt El'brus (43°20'53.9'' N, 42°25'36.0'' E; 5115 m a.s.l.) in the Caucasus, Russia, in 2009 (Mikhalenko et al., 2015). Here, we report on the results of the water stable isotope composition from this ice core with additional data from the shallow cores. The distinct seasonal cycle of the isotopic composition allows dating by annual layer counting. Dating has been performed for the upper 126 m of the deep core combined with 20 m from the shallow cores. The whole record covers 100 years, from 2013 back to 1914. Due to the high accumulation rate (1380 mm w.e. year-1) and limited melting, we obtained isotopic composition and accumulation rate records with seasonal resolution. These values were compared with available meteorological data from 13 weather stations in the region and also with atmosphere circulation indices, back-trajectory calculations, and Global Network of Isotopes in Precipitation (GNIP) data in order to decipher the drivers of accumulation and ice core isotopic composition in the Caucasus region. In the warm season (May-October) the isotopic composition depends on local temperatures, but the correlation is not persistent over time, while in the cold season (November-April), atmospheric circulation is the predominant driver of the ice core's isotopic composition. The snow accumulation rate correlates well with the precipitation rate in the region all year round, which made it possible to reconstruct and expand the precipitation record at the Caucasus highlands from 1914 until 1966, when reliable meteorological observations of precipitation at high elevation began.

[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.

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.

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

NASA Astrophysics Data System (ADS)

Sakthi Saravanan, C.; Mishra, B.

2009-07-01

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

The first investigation of Wilms' tumour atomic structure-nitrogen and carbon isotopic composition as a novel biomarker for the most individual approach in cancer disease

PubMed Central

Taran, Katarzyna; Frączek, Tomasz; Sikora-Szubert, Anita; Sitkiewicz, Anna; Młynarski, Wojciech; Kobos, Józef; Paneth, Piotr

2016-01-01

The paper describes a novel approach to investigating Wilms' tumour (nephroblastoma) biology at the atomic level. Isotope Ratio Mass Spectrometry (IRMS) was used to directly assess the isotope ratios of nitrogen and carbon in 84 Wilms' tumour tissue samples from 28 cases representing the histological spectrum of nephroblastoma. Marked differences in nitrogen and carbon isotope ratios were found between nephroblastoma histological types and along the course of cancer disease, with a breakout in isotope ratio of the examined elements in tumour tissue found between stages 2 and 3. Different isotopic compositions with regard to nitrogen and carbon content were observed in blastemal Wilms' tumour, with and without focal anaplasia, and in poorly- and well-differentiated epithelial nephroblastoma. This first assessment of nitrogen and carbon isotope ratio reveals the previously unknown part of Wilms' tumour biology and represents a potential novel biomarker, allowing for a highly individual approach to treating cancer. Furthermore, this method of estimating isotopic composition appears to be the most sensitive tool yet for cancer tissue evaluation, and a valuable complement to established cancer study methods with prospective clinical impact. PMID:27732932

Photosynthetic Fractionation of the Stable Isotopes of Oxygen and Carbon.

PubMed Central

Guy, R. D.; Fogel, M. L.; Berry, J. A.

1993-01-01

Isotope discrimination during photosynthetic exchange of O2 and CO2 was measured using enzyme, thylakoid, and whole cell preparations. Evolved oxygen from isolated spinach thylakoids was isotopically identical (within analytical error) to its source water. Similar results were obtained with Anacystis nidulans Richter and Phaeodactylum tricornutum Bohlin cultures purged with helium. For consumptive reactions, discrimination ([delta], where 1 + [delta]/1000 equals the isotope effect, k16/k18 or k12/k13) was determined by analysis of residual substrate (O2 or CO2). The [delta] for the Mehler reaction, mediated by ferredoxin or methylviologen, was 15.3[per mille (thousand) sign]. Oxygen isotope discrimination during oxygenation of ribulose-1,5-bisphosphate (RuBP) catalyzed by RuBP carboxylase/oxygenase (Rubisco) was 21.3[per mille (thousand) sign] and independent of enzyme source, unlike carbon isotope discrimination: 30.3[per mille (thousand) sign] for spinach enzyme and 19.6 to 23[per mille (thousand) sign] for Rhodospirillum rubrum and A. nidulans enzymes, depending on reaction conditions. The [delta] for O2 consumption catalyzed by glycolate oxidase was 22.7[per mille (thousand) sign]. The expected overall [delta] for photorespiration is about 21.7[per mille (thousand) sign]. Consistent with this, when Asparagus sprengeri Regel mesophyll cells approached the compensation point within a sealed vessel, the [delta]18O of dissolved O2 came to a steady-state value of about 21.5[per mille (thousand) sign] relative to the source water. The results provide improved estimates of discrimination factors in several reactions prominent in the global O cycle and indicate that photorespiration plays a significant part in determining the isotopic composition of atmospheric oxygen. PMID:12231663

Compound-specific carbon, nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

NASA Astrophysics Data System (ADS)

Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

2012-09-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ13C, and δ15N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ13C and increasing δD with increasing carbon number in the α-H, α-NH2 amino acids that correspond to predictions made for formation via Strecker-cyanohydrin synthesis. We also observe light δ13C signatures for β-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ω-amino acids). Higher deuterium enrichments are observed in α-methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent-body chemistry.

Compound-Specific Carbon, Nitrogen, and Hydrogen Isotopic Ratios for Amino Acids in CM and CR Chondrites and their use in Evaluating Potential Formation Pathways

NASA Technical Reports Server (NTRS)

Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

2012-01-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (oD, 013C, and olSN) of organic compounds can revcal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1I2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CRZ Graves Nunataks (GRA) 95229, CRZ Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing ODC and increasing oD with increasing carbon number in the aH, (l-NH2 amino acids that correspond to predictions made for formation via Streckercyanohydrin synthesis. We also observe light ODC signatures for -alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ro-amino acids). Higher deuterium enrichments are observed in amethyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than CM chondrites, reflecting different parent-body chemistry.

Prospects and Challenges in tropical isotope dendroclimatology

NASA Astrophysics Data System (ADS)

Evans, M. N.; Anchukaitis, K. J.; White, S. R.; Ektvedt, T. M.; Penniston, R. C.; Rheaume, M. M.; Bowman, D. M.

2008-12-01

We review a stable isotope-based approach to the development, modeling, interpretation, and analysis of hydrometeorological estimates from tropical trees. The strategy overcomes the common problem of missing, intermittent or non-annual ring structure in tropical trees by relying instead on the observation of the annual wet-dry seasonality typical to tropical environments as mirrored in the oxygen isotopic composition of wood-derived α-cellulose. We explore regions for which forward modeling of the proxy system would expect us to resolve hydrometeorological variations associated with the El Niño-Southern Oscillation (ENSO) phenomenon, rather than being limited to regions with tree species or environments producing verifiable annual ring chronologies. A modified protocol allows for rapid, simple and non-toxic micro-extraction of pure α-cellulose, which is isotopically indistinguishable from that produced by more classical means. We describe a new reactor for the pyrolysis of α-cellulose in an induction heater, which permits isotopic analysis of α-cellulose samples as small as 30μg, and as many as 100 automated sample analyses per day. A forward model adapted for tropical environments can be used to test and refine the interpretation of the isotopic data, and to predict locales for which we should be able to maximize the paleoclimatic potential of future sample collections. We have found the modeled isotopic chronometer and raingage in agreement with independent chronological controls in a variety of environments and tree species in Costa Rica, Indonesia, Brazil, Peru and Australia. Development of long hydrometeorological records from the terrestrial tropics is underway not only by our group, but by a growing number of collaborators and colleagues. Together we should be able to build a network of paleoprecipitation records and better understand the linkages between tropical surface ocean temperatures and large-scale drought.

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.

Orthodontic archwire composition and phase analyses by neutron spectroscopy.

PubMed

Tian, Kun V; Festa, Giulia; Basoli, Francesco; Laganà, Giuseppina; Scherillo, Antonella; Andreani, Carla; Bollero, Patrizio; Licoccia, Silvia; Senesi, Roberto; Cozza, Paola

2017-05-31

Quantitative metallurgical and phase analyses employing neutron diffraction technique were conducted on two as-received commercial rectangular austenitic stainless steel orthodontic archwires, G&H and Azdent, 0.43×0.64 mm (0.017×0.025 inch). Results showed a bi-phase structure containing martensitic phase (45.67% for G&H and 6.62% for Azdent) in addition to the expected metastable austenite. The former may be a strain-induced phase-transformation arising during the cold working process of wire fabrication. Further neutron resonance capture analysis determinations provided atomic and isotopic compositions, including alloying elements in each sample, complementary to the results of traditional energy dispersive X-ray spectroscopy. Together, these results assist in relating commercial alloying recipes and processing histories with mechanical performance, strength and ductility in particular.

Equilibrium carbon and hydrogen isotope fractionation in iron

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2009-12-01

Recent theoretical and experimental studies (e.g., [1-3]) have suggested that Si- and Fe-isotopic signatures can be used to characterize the compositions and conditions of segregation of metallic cores in planetary interiors. This study expands the theoretical framework to include carbon and hydrogen, which may also be alloying elements. Hydrogen (D/H) and carbon (13C/12C) fractionations in iron-rich metallic melts are estimated by modeling analogous iron-rich crystals, i.e., dhcp-FeH and η-Fe2C. C- and H-atoms in these crystals are completely coordinated by iron. The driving energy for equilibrium fractionation is assumed to come from the reduction of vibrational frequencies when heavy isotopes are substituted for light ones; vibrations are assumed to be harmonic. This treatment is crude at high temperature, and for the relatively anharmonic vibrations typical of hydrogen-bearing substances, but may provide a reasonably accurate, semi-quantitative approximation of real fractionation behavior. Vibrational frequencies of all crystals are modeled with density functional theory, using gradient-corrected functionals and ultrasoft pseudopotentials. For both carbon and hydrogen, the models suggest that the metal phase will be strongly depleted in heavy isotopes. At 2000 K, 1 atm, η-Fe2C will have 3‰ lower 13C/12C than coexisting diamond. Combining this result with previous high-temperature theoretical and experimental studies (e.g., [4]), metal-graphite fractionation is expected to be very similar, while metal-CO2 fractionation will be almost twice as large, ca. -5‰. Deuterium/hydrogen fractionations are expected to be an order of magnitude larger, with 50-70‰ lower D/H in dhcp-FeH than in coexisting H2 gas at 2000 K, and approximately 100‰ lower D/H than water vapor. These fractionations are much larger than those inferred for silicon and iron, as expected given the differences in atomic mass. References: 1. Georg et al. (2007) Nature 447:1102; 2. Rustad & Yin (2009) Nature Geoscience doi:10.1038/ngeo546; 3. Polyakov (2009) Science 323:912; 4. Polyakov & Kharlashina (1995) GCA 59:2561.

Variability of isotope and major ion chemistry in the Allequash Basin, Wisconsin

USGS Publications Warehouse

Walker, John F.; Hunt, Randall J.; Bullen, Thomas D.; Krabbenhoft, David P.; Kendall, Carol

2003-01-01

As part of ongoing research conducted at one of the U.S. Geological Survey's Water, Energy, and Biogeochem-ical Budgets sites, work was undertaken to describe the spatial and temporal variability of stream and ground water isotopic composition and cation chemistry in the Trout Lake watershed, to relate the variability to the watershed flow system, and to identify the linkages of geochemical evolution and source of water in the watershed. The results are based on periodic sampling of sites at two scales along Allequash Creek, a small headwater stream in northern Wisconsin. Based on this sampling, there are distinct water isotopic and geochemical differences observed at a smaller hillslope scale and the larger Allequash Creek scale. The variability was larger than expected for this simple watershed, and is likely to be seen in more complex basins. Based on evidence from multiple isotopes and stream chemistry, the flow system arises from three main source waters (terrestrial-, lake-, or wetland-derived recharge) that can be identified along any flowpath using water isotopes together with geochemical characteristics such as iron concentrations. The ground water chemistry demonstrates considerable spatial variability that depends mainly on the flow-path length and water mobility through the aquifer. Calcium concentrations increase with increasing flowpath length, whereas strontium isotope ratios increase with increasing extent of stagnation in either the unsaturated or saturated zones as waters move from source to sink. The flowpath distribution we identify provides important constraints on the calibration of ground water flow models such as that undertaken by Pint et al. (this issue).

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al Foil Impacts

NASA Technical Reports Server (NTRS)

Stadermann, Frank J.; Hoppe, Peter; Floss, Christine; Heck, Philipp R.; Hoerz, Friedrich; Huth, Joachim; Kearsley, Anton T.; Leitner, Jan; Marhas, Kuljeet K.; McKeegan, Kevin D.;

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al foil Impacts

NASA Technical Reports Server (NTRS)

Stadermann, Frank J.; Hoppe, Peter; Floss, Christine; Hoerz, Friedrich; Huth, Joachim; Kearsley, Anton T.; Leitner, Jan; Marhas, Kuljeet K.; McKeegan, Kevin D.; Stephan, Thomas;

Using nitrate dual isotopic composition (δ15N and δ18O) as a tool for exploring sources and cycling of nitrate in an estuarine system: Elkhorn Slough, California

USGS Publications Warehouse

Wankel, Scott D.; Kendall, Carol; Paytan, Adina

2009-01-01

Nitrate (NO-3 concentrations and dual isotopic composition (??15N and ??18O) were measured during various seasons and tidal conditions in Elkhorn Slough to evaluate mixing of sources of NO-3 within this California estuary. We found the isotopic composition of NO-3 was influenced most heavily by mixing of two primary sources with unique isotopic signatures, a marine (Monterey Bay) and terrestrial agricultural runoff source (Old Salinas River). However, our attempt to use a simple two end-member mixing model to calculate the relative contribution of these two NO-3 sources to the Slough was complicated by periods of nonconservative behavior and/or the presence of additional sources, particularly during the dry season when NO-3 concentrations were low. Although multiple linear regression generally yielded good fits to the observed data, deviations from conservative mixing were still evident. After consideration of potential alternative sources, we concluded that deviations from two end-member mixing were most likely derived from interactions with marsh sediments in regions of the Slough where high rates of NO-3 uptake and nitrification result in NO-3 with low ?? 15N and high ??18O values. A simple steady state dual isotope model is used to illustrate the impact of cycling processes in an estuarine setting which may play a primary role in controlling NO -3 isotopic composition when and where cycling rates and water residence times are high. This work expands our understanding of nitrogen and oxygen isotopes as biogeochemical tools for investigating NO -3 sources and cycling in estuaries, emphasizing the role that cycling processes may play in altering isotopic composition. Copyright 2009 by the American Geophysical Union.

Isotopic Effects in Nuclear Fragmentation and GCR Transport Problems

NASA Technical Reports Server (NTRS)

Cucinotta, Francis A.

2002-01-01

Improving the accuracy of the galactic cosmic ray (GCR) environment and transport models is an important goal in preparing for studies of the projected risks and the efficiency of potential mitigations methods for space exploration. In this paper we consider the effects of the isotopic composition of the primary cosmic rays and the isotopic dependence of nuclear fragmentation cross sections on GCR transport models. Measurements are used to describe the isotopic composition of the GCR including their modulation throughout the solar cycle. The quantum multiple-scattering approach to nuclear fragmentation (QMSFRG) is used as the data base generator in order to accurately describe the odd-even effect in fragment production. Using the Badhwar and O'Neill GCR model, the QMSFRG model and the HZETRN transport code, the effects of the isotopic dependence of the primary GCR composition and on fragment production for transport problems is described for a complete GCR isotopic-grid. The principle finding of this study is that large errors ( 100%) will occur in the mass-flux spectra when comparing the complete isotopic-grid (141 ions) to a reduced isotopic-grid (59 ions), however less significant errors 30%) occur in the elemental-flux spectra. Because the full isotopic-grid is readily handled on small computer work-stations, it is recommended that they be used for future GCR studies.

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

USGS Publications Warehouse

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

2013-01-01

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

Analysis of the interdecadal variability of summer precipitation in central Japan using a reconstructed 106 year long oxygen isotope record from tree ring cellulose

NASA Astrophysics Data System (ADS)

Kurita, Naoyuki; Nakatsuka, Takeshi; Ohnishi, Keiko; Mitsutani, Takumi; Kumagai, Tomo'omi

2016-10-01

We present a unique proxy for reconstructing the interannual variability of summer precipitation associated with the quasi-stationary front (Baiu front) in central Japan. The rainfall from the Baiu front has a relatively lower oxygen isotopic composition than other types of nonfrontal precipitation. The variability in the oxygen isotopes in summer rainfall is closely related to the Baiu frontal activity. In this study we used a mechanistic tree ring isotope model to reconstruct a 106 year long oxygen isotopic composition of precipitation during the early rainy season (June) based on the oxygen isotopic compositions of the annual rings of Chamaecyparis obtusa Endl trees from central Japan. The year-to-year variations of the isotopes over the most recent 25 years are associated with several teleconnection patterns that often lead to the Baiu precipitation anomalies in central Japan (such as the Pacific-Japan (PJ) pattern, Silk Road pattern, and wave train pattern along the polar jet). Yet none of these external forcing mechanisms apply further back in time. From the 1950s to 1980s, the interannual isotopic variability is predominantly related to local factors such as anomalous intensification/weakening of the Bonin High. Before the 1950s, the variability of the oxygen isotopic composition of precipitation is mainly associated with a wave train pattern along the polar jet. The isotopic variability is predominantly linked to the PJ pattern, while the PJ index is correlated with El Niño-Southern Oscillation. These findings suggest that the teleconnection patterns influencing Baiu precipitation variability vary according to interdecadal time scales during the twentieth century.

Forest Fires as a Possible Source of Isotopically Light Marine Fe Aerosols

NASA Astrophysics Data System (ADS)

Tegler, L. A.; Sherry, A. M.; Romaniello, S. J.; Anbar, A. D.

2016-12-01

Iron (Fe) is an important limiting micronutrient for primary productivity in many high-nutrient, low-chlorophyll (HNLC) regions of the ocean. These marine systems receive a significant fraction of their Fe from atmospheric deposition, which is thought to be dominated by mineral dust with an Fe isotopic composition at or above 0‰. However, Mead et al. (2013) observed isotopically light Fe in marine aerosols smaller than 2.5 μm, which is difficult to reconcile with known sources of marine aerosols. Based on previous experimental work, we hypothesize that biomass burning is the source of isotopically light Fe in atmospheric particles and suggest that biomass burning might represent an underappreciated source of Fe to marine ecosystems. While Guelke et al (2007) demonstrated that Fe in agricultural plants is isotopically light, few studies have examined the Fe isotope composition of naturally occurring forests likely to be a significant source of Fe during forest fires. To address this question, we measured the isotopic composition of Ponderosa pine growing in northern Arizona. Ponderosa pine is one the most common forest types in the western US and thus representative of an important North American fire region. Pine needles were chosen because they are susceptible to complete combustion during biomass burning events. To determine the Fe isotopic composition of pine trees, pine needles were sampled at various tree heights. We found that these samples had δ56Fe values between -1.5 and 0‰, indicating that pine needles can be isotopically light compared to local grasses and soil. These results support the hypothesis that biomass burning may contribute isotopically light Fe to marine aerosols.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

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

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

Evidence for rapid climate change in North America during the latest Paleocene thermal maximum: oxygen isotope compositions of biogenic phosphate from the Bighorn Basin (Wyoming)

NASA Astrophysics Data System (ADS)

Fricke, Henry C.; Clyde, William C.; O'Neil, James R.; Gingerich, Philip D.

1998-07-01

Oxygen isotope records of Cenozoic sea water temperatures indicate that a rapid warming event known as the Latest Paleocene Thermal Maximum (LPTM) occurred during the otherwise gradual increase in world temperatures during the Late Paleocene and Early Eocene. Oxygen isotope analysis of the carbonate and phosphate components of hydroxyapatite found in mammalian tooth enamel and body scales of river-dwelling fish from the Bighorn Basin in Wyoming were made to investigate corresponding changes in the terrestrial climate. A comparison of carbonate and phosphate isotope data from modern and fossil material indicates that some diagenetic alteration of the fossil material has occurred, although systematically larger intra-tooth ranges in the oxygen isotope composition of carbonate indicate that it is more likely to have been affected than phosphate. Carbonate and phosphate from the ecologically diverse mammals and fishes both record a shift to higher oxygen isotope ratios at the same time and of the same duration as the LPTM. These shifts reflect a change in the isotopic composition of regional precipitation, which in turn provides the first evidence for continental climate change during the LPTM. Assuming the present-day relation between the oxygen isotope composition of precipitation and temperature applies to conditions in the past, and that animal physiology and behavior is relatively invariant over time, the isotopic shift is equivalent to an increase of surface temperature in western North America of several degrees. This result is consistent with the magnitude of high-latitude ocean warming, and provides a basis for relating marine and terrestrial oxygen isotope records to records of terrestrial biotic change.

Variation in the isotopic composition of striped weakfish Cynoscion guatucupa of the Southwest Atlantic Ocean in response to dietary shifts.

PubMed

Viola, M N Paso; Riccialdelli, L; Jaureguizar, A; Panarello, H O; Cappozzo, H L

2018-05-01

The aim of this study was to analyze the isotopic composition in muscle of striped weakfish Cynoscion guatucupa from Southwest Atlantic Ocean in order to evaluate a possible variation in δ13C and δ15N in response to dietary shifts that occur as animals grow. We also explored for isotopic evidence of differences between sample locations. The results showed an agreement between isotope analysis and previous conventional studies. Differences in the isotope composition between sampling location were not observed. A positive relation exists between isotope values and total body length of the animals. The Cluster analysis defined three groups of size classes, validated by the MDS. Differences in the relative consumption of prey species in each size class were also observed performing isotope mixing models (SIAR). Variation in δ15N among size classes would be associated with the consumption of a different type of prey as animals grow. Small striped weakfish feed on small crustaceans and progressively increase their consumption of fish (anchovy, Engraulis anchoita), increasing by this way their isotope values. On the other hand, differences in δ13C values seemed to be related to age-class specific spatial distribution patterns. Therefore, large and small striped weakfish remain specialized but feeding on different prey at different trophic levels. These results contribute to the study of the diet of striped weakfish, improve the isotopic ecology models and highlight on the importance of accounting for variation in the isotopic composition in response to dietary shifts with the size of one of the most important fishery resources in the region.

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.

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis

PubMed Central

Brennecka, Gregory A.; Borg, Lars E.; Wadhwa, Meenakshi

2013-01-01

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium–aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy. PMID:24101483

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis.

PubMed

Brennecka, Gregory A; Borg, Lars E; Wadhwa, Meenakshi

2013-10-22

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium-aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy.

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

PubMed

Tanoue, Masahiro; Ichiyanagi, Kimpei; Yoshimura, Kei

2016-01-01

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

Box-modeling of bone and tooth phosphate oxygen isotope compositions as a function of environmental and physiological parameters.

PubMed

Langlois, C; Simon, L; Lécuyer, Ch

2003-12-01

A time-dependent box model is developed to calculate oxygen isotope compositions of bone phosphate as a function of environmental and physiological parameters. Input and output oxygen fluxes related to body water and bone reservoirs are scaled to the body mass. The oxygen fluxes are evaluated by stoichiometric scaling to the calcium accretion and resorption rates, assuming a pure hydroxylapatite composition for the bone and tooth mineral. The model shows how the diet composition, body mass, ambient relative humidity and temperature may control the oxygen isotope composition of bone phosphate. The model also computes how bones and teeth record short-term variations in relative humidity, air temperature and delta18O of drinking water, depending on body mass. The documented diversity of oxygen isotope fractionation equations for vertebrates is accounted for by our model when for each specimen the physiological and diet parameters are adjusted in the living range of environmental conditions.

Influence of the balance of the intertropical front on seasonal variations of the isotopic composition in rainfall at Kisiba Masoko (Rungwe Volcanic Province, SW, Tanzania).

PubMed

Nivet, Fantine; Bergonzini, Laurent; Mathé, Pierre-Etienne; Noret, Aurélie; Monvoisin, Gaël; Majule, Amos; Williamson, David

2018-08-01

Tropical rainfall isotopic composition results from complex processes. The climatological and environmental variability in East Africa increases this complexity. Long rainfall isotope datasets are needed to fill the lack of observations in this region. At Kisiba Masoko, Tanzania, rainfall and rain isotopic composition have been monitored during 6 years. Mean year profiles allow to analyse the seasonal variations. The mean annual rainfall is 2099 mm with a rain-weighted mean composition of -3.2 ‰ for δ 18 O and -11.7 ‰ for δ 2 H. The results are consistent with available data although they present their own specificity. Thus, if the local meteoric water line is δ 2 H = 8.6 δ 18 O + 14.8, two seasonal lines are observed. The seasonality of the isotopic composition in rain and deuterium excess has been compared with precipitating air masses backtracking trajectories to characterize a simple scheme of vapour histories. The three major oceanic sources have two moisture signatures with their own trajectory histories: one originated from the tropical Indian Ocean at the beginning of the rainy season and one from the Austral Ocean at its end. The presented isotopic seasonality depends on the balance of the intertropical front and provides a useful dataset to improve the knowledge about local processes.

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

PubMed Central

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

2013-01-01

In order to identify the function of uncultured microorganisms in their environment, the SIMSISH method, combining in situ hybridization (ISH) and nanoscale secondary ion mass spectrometry (nanoSIMS) imaging, has been proposed to determine the quantitative uptake of specific labelled substrates by uncultured microbes at the single cell level. This technique requires the hybridization of rRNA targeted halogenated DNA probes on fixed and permeabilized microorganisms. Exogenous atoms are introduced into cells and endogenous atoms removed during the experimental procedures. Consequently differences between the original and the apparent isotopic composition of cells may occur. In the present study, the influence of the experimental procedures of SIMSISH on the isotopic composition of carbon in E. coli cells was evaluated with nanoSIMS and compared to elemental analyser-isotopic ratio mass spectrometer (EA-IRMS) measurements. Our results show that fixation and hybridization have a very limited, reproducible and homogeneous influence on the isotopic composition of cells. Thereby, the SIMSISH procedure minimizes the contamination of the sample by exogenous atoms, thus providing a means to detect the phylogenetic identity and to measure precisely the carbon isotopic composition at the single cell level. This technique was successfully applied to a complex sample with double bromine – iodine labelling targeting a large group of bacteria and a specific archaea to evaluate their specific 13C uptake during labelled methanol anaerobic degradation. PMID:24204855

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

NASA Astrophysics Data System (ADS)

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

2015-06-01

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

Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

NASA Astrophysics Data System (ADS)

Chen, Mengli; Boyle, Edward A.; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo

2016-11-01

Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Neodymium isotopes in biogenic carbonates: reliable archives of ɛNd

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Isotopic modeling of the sub-cloud evaporation effect in precipitation.

PubMed

Salamalikis, V; Argiriou, A A; Dotsika, E

2016-02-15

In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a 'heat capacity' model providing high correlation coefficients for both isotopes (R(2)>80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH=95%) sub-cloud evaporation is negligible and the isotopic composition hardly changes even at high temperatures while at drier and warm conditions the enrichment of (18)Ο reaches up to 20‰, depending on the raindrop size and the initial meteorological conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2015-11-01

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

Origins of GEMS Grains

NASA Technical Reports Server (NTRS)

Messenger, S.; Walker, R. M.

2012-01-01

Interplanetary dust particles (IDPs) collected in the Earth s stratosphere contain high abundances of submicrometer amorphous silicates known as GEMS grains. From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation. We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1-6% of GEMS grains are surviving circumstellar grains. The remaining 94-99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the chemical compositions of GEMS grains are extremely heterogeneous and seem to rule out this possibility. Based on their solar isotopic compositions and their non-solar elemental compositions we propose that most GEMS grains formed in the nebula as late-stage non-equilibrium condensates.

Stable Isotopic Constraints on Abiogenic Hydrocarbon gas Contributions to Thermogenic Natural gas Resources in the Northern Appalachian Basin, USA

NASA Astrophysics Data System (ADS)

Burruss, R. C.; Laughrey, C. D.

2006-05-01

The generation of abiogenic methane by serpentinization or by graphite-water reactions in high-grade metamorphic rocks is well documented by isotopic, fluid inclusion, and petrographic studies. However, geochemical evidence is equivocal for abiogenic generation of higher hydrocarbon gases (ethane through pentane) in economic resources. Thermogenic hydrocarbon gases, generated by thermal cracking of sedimentary organic matter of biological origin, are progressively enriched in 13C as a function of increasing number of carbon atoms in the molecule. The isotopic composition is controlled by the kinetic isotope effect (KIE) during carbon-carbon bond breaking with the largest KIE for methane. Published work on gases in Precambrian rocks in Canada and South Africa suggest that some were generated by abiogenic Fischer-Tropsch type reactions that produced gases with carbon isotopic compositions that are reversed from the thermogenic trend. We have documented reversed isotopic compositions in natural gas accumulations in lower Paleozoic reservoirs of the Appalachian basin regionally from West Virginia and eastern Ohio through Pennsylvania to central New York. The regional accumulation in lower Silurian age strata shows progressive enhancement of the isotopic reversal with increasing depth in the basin. Multivariate analysis of the molecular and isotopic data define an end-member in the deep basin with an approximate composition of 98 mol % CH4, 1-2 mol % C2H6, << 1 mol % C3H8, and δ13C (CH4) = -27 ‰, δ13C (C2H6) = -40 ‰, δ13C (C3H8) = - 41‰. The nominal similarity of isotopic reversals in the gases from Precambrian rocks to those in the lower Paleozoic rocks of the Appalachian basin suggests that abiogenic F-T reactions may have generated some fraction of the gases in the deep basin. Comparison of molecular and hydrogen isotopic compositions show that the gases of putative abiogenic F-T origin are significantly different from Appalachian basin gases. All the Precambrian gases have extremely light hydrogen isotopic compositions of CH4 (δ2H < -300‰) and are depleted in CH4 (Canada gases C1/C2+ < 10, S. Africa gases C1/C2+ < 60) compared to gases in lower Paleozoic reservoirs of the Appalachian basin (δ2H (CH4) > -150‰, C1/C2+ up to 220). New isotopic studies of gas accumulations, gases in fluid inclusions, and of sedimentary organic matter in the Appalachian basin are in progress to constrain the possible contribution of abiogenic hydrocarbon generation to gas accumulations in this basin.

Thermal and chemical evolution in the early Solar System as recorded by FUN CAIs: Part II - Laboratory evaporation of potential CMS-1 precursor material

NASA Astrophysics Data System (ADS)

Mendybaev, Ruslan A.; Williams, Curtis D.; Spicuzza, Michael J.; Richter, Frank M.; Valley, John W.; Fedkin, Alexei V.; Wadhwa, Meenakshi

2017-03-01

We present the results of laboratory experiments in which a forsterite-rich melt estimated to be a potential precursor of Allende CMS-1 FUN CAI was evaporated into vacuum for different lengths of time at 1900 °C. The evaporation of this melt resulted in residues that define trajectories in chemical as well as magnesium, silicon and oxygen isotopic composition space and come very close to the measured properties of CMS-1. The isotopic composition of the evaporation residues was also used to determine the kinetic isotopic fractionation factors [α2,1 (vapor-melt) defined as the ratio of isotopes 2 and 1 of a given element in the evaporating gas divided by their ratio in the evaporating source] for evaporation of magnesium (α25,24 for 25Mg/24Mg), silicon (α29,28 for 29Si/28Si) and oxygen (α18,16 for 18O/16O) from the forsterite-rich melt at 1900 °C. The values of α25,24 = 0.98383 ± 0.00033 and α29,28 = 0.99010 ± 0.00038 are essentially independent of change in the melt composition as evaporation proceeds. In contrast, α18,16 changes from 0.9815 ± 0.0016 to ∼0.9911 when the residual melt composition changes from forsteritic to melilitic. Using the determined values of α25,24 and α29,28 and present-day bulk chemical composition of the CMS-1, the composition of the precursor of the inclusion was estimated to be close to the clinopyroxene + spinel + forsterite assemblage condensed from a solar composition gas. The correspondence between the chemical composition and isotopic fractionation of experimental evaporation residues and the present-day bulk chemical and isotopic compositions of CMS-1 is evidence that evaporation played a major role in the chemical evolution of CMS-1.

Osmium isotope variations in the oceans recorded by Fe-Mn crusts

USGS Publications Warehouse

Burton, K.W.; Bourdon, B.; Birck, J.-L.; Allegre, C.J.; Hein, J.R.

1999-01-01

This study presents osmium (Os) isotope data for recent growth surfaces of hydrogenetic ferromanganese (Fe-Mn) crusts from the Pacific, Atlantic and Indian Oceans. In general, these data indicate a relatively uniform Os isotopic composition for modern seawater, but suggest that North Atlantic seawater is slightly more radiogenic than that of the Pacific and Indian Oceans. The systematic difference in the Os isotopic composition between the major oceans probably reflects a greater input of old continental material with a high Re/Os ratio in the North Atlantic Ocean, consistent with the distribution of Nd and Pb isotopes. This spatial variation in the Os isotope composition in seawater is consistent with a residence time for Os of between 2 and 60 kyr. Indian Ocean samples show no evidence of a local source of radiogenic Os, which suggests that the present-day riverine input from the Himalaya-Tibet region is not a major source for Os. Recently formed Fe-Mn crusts from the TAG hydrothermal field in the North Atlantic yield an Os isotopic composition close to that of modern seawater, which indicates that, in this area, the input of unradiogenic Os from the hydrothermal alteration of oceanic crust is small. However, some samples from the deep Pacific (???4 km) possess a remarkably unradiogenic Os isotope composition (187Os/186Os ratios as low as 4.3). The compositional control of Os incorporation into the crusts and mixing relationships suggest that this unradiogenic composition is most likely due to the direct incorporation of micrometeoritic or abyssal peridotite particles, rather than indicating the presence of an unradiogenic deep-water mass. Moreover, this unradiogenic signal appears to be temporary, and local, and has had little apparent effect on the overall evolution of seawater. These results confirm that input of continental material through erosion is the dominant source of Os in seawater, but it is not clear whether global Os variations are due to the input of mantle or meteoritic material, or simply indicate that the continental source itself is not uniform.

Stable Isotope Analysis of Chlorate

NASA Astrophysics Data System (ADS)

Brundrett, M.; Jackson, W. A.; Sturchio, N. C.; Bohlke, J. K.; Hatzinger, P.

2016-12-01

Studies have confirmed the presence of chlorate (ClO3-) throughout terrestrial and extraterrestrial systems generally in excess of perchlorate (ClO4-) [1, 2]. ClO3- occurrence, production, and post depositional transformation has significant implications to our understanding of atmospheric Cl cycling and potential biogeochemical reactions on Earth and Mars. The isotopic composition of oxyanions can be used to evaluate their production mechanisms and post-depositional alteration [3, 4]. However, no information is available on the natural isotopic composition of ClO3-. The objective of this study was to develop a method to measure the stable isotope composition (δ18O, δ17O and δ37Cl) of ClO3- and to determine the isotopic composition of ClO3- in natural desert salt accumulations that have been studied previously for NO3- and ClO4- isotopic composition. The process of ClO3- purification and analysis of δ18O, δ 17O and δ37Cl is problematic but has recently been resolved by adapting previously published methods for ClO4-. Competitive anions (e.g. NO3-, Cl-, ClO4-, and SO4-2) are removed through a series of processes including biological reduction, solid phase extraction, and anion or cation exchange. Initial results for control samples treated with the above method have a maximum variation of ± 2 ‰. These methods are being applied to representative samples to determine if various sources of natural and synthetic ClO3- have distinctive isotopic compositions, as reported previously for ClO4- [3, 4]. Establishing the range of isotopic composition of natural ClO3- also could provide information about atmospheric ClO3- production mechanisms and post-depositional processing, with implications for the atmospheric chemistry of oxychlorine compounds and the global biogeochemical cycling of Cl. [1] Jackson et al. (2015) EPSL 430, 470-476. [2] Rao et al. (2010) ES&T 44, 8429-8434. [3] Jackson et al. (2010) ES&T 44, 4869-4876. [4] Bao and Gu (2004) ES&T 38, 5073-5077.

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

USGS Publications Warehouse

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

2000-01-01

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

A new geochemical instrument for the precise measurement of isotopic ratios and trace species in planetary atmospheres

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Sarda, Ph.; Agrinier, P.

2003-04-01

The technique of GCMS analysis, which has been used with a great success on several past planetary missions, is not adapted for precise measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation, and chemical trapping, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. This technique allows to reach a precision on isotopic ratios of the order of a few 0.1 ppm for a typical amount of gas of a few micromoles. We are presently studying an instrument based on the same principle for space exploration applications. The PALOMA instrument (PAyload for Local Observation of Mars Atmosphere) will be proposed in response to the AO for the instrumentation of the NASA Mars Smart Lander mission, planned to be launched in 2009. It might be part as well of the EXOMARS mission presently studied at ESA in the frame of the Aurora program. The miniaturization of major key elements, like the cryogenic device, the mass spectrometer, the line and its ensemble of valves, is presently led in our laboratories under CNES funding. The instrument consists of : (i) a gas purification and separation line, using techniques of cryogenic and chemical trapping, and possibly membrane permeation for molecular hydrogen analysis, (ii) a mass spectrometer working in static mode, without carrier gas (both time-of-flight and magnetic solutions are studied), (iii) a turbo-molecular pump that provides the required level of vacuum in the separation line and in the spectrometer. In the specific case of Mars, it is designed to work during typically 2 years (about 1000 measurement cycles), in order to perform accurate measurements of molecular, elemental and isotopic composition and of their diurnal/seasonal variations. The gas is sampled directly from the ambient atmosphere, without need for an external sample distribution system. The general characteristics of the instrument are as following . The mass is 6 kg, for a size of 30 x 30 x 20 cm. The required power, averaged over a complete measurement cycle, is 20 W (peak value : 30 W). The total energy required for one sequence is 100 Wh. This number must be considered as an upper limit, and corresponds to the most complex sequence (noble gas isotope analysis). Sequences used for stable isotopes measurement, and atmospheric molecular composition (trace gases of geological and/or astrobiological interest), are expected to be simpler, and less power-consuming. The anticipated volume of data produced by one observation sequence is estimated to be in the 3-6 kb range. The gas is sampled directly from the ambient atmosphere.

Fontinalis antipyretica as a bioindicator of environmental conditions in freshwater ecosystem from Sava River watershed and Cerknişko Lake, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Mechora, Špela; Stibilj, Vekoslava

2014-05-01

Polluted waters recharging from agriculture water systems into watersheds have influence on water quality and living habitat. Stable isotopes of carbon and nitrogen in combination with other minor and trace elements are often used to trace biogeochemical processes and contamination of water systems. The aim of the study was to assess state of environment with minor and trace elements and stable isotopes of C and N in selected Slovenian streams. Ten locations in Notranjska region, Slovenia, with different land use in the catchment (town, village, agricultural areas, farms, dairy farms), including reference point considered as non-polluted site, were sampled. Samples of water and aquatic moss F. antipyretica in Slovenian fresh waters were taken in all four seasons during years 2010 and 2012, but for stable isotope analyses of C and N only in three seasons during years 2010 and 2011. The water chemistry of investigated locations is dominated by hydrogen carbonate - calcium - magnesium, concentrations of nitrate seasonally range from 2.07 mg/l to 6.4 mg/l and at reference site does not exceed 1.3 mg/l. Total alkalinity of water at investigated locations ranges from 2.9 to 6.02 mM. The pH of investigated water range from 7.2 to 8.5, waters are saturated with oxygen (up to 134%) and conductivity ranges from 295 to 525 mikroS/cm, while at reference site conductivity is up to 180 mikroS/cm. The content of minor and trace elements in F. antipyretica ranged for Ni 4-38 mikrog/g, Zn 17-105 mikrog/g, Pb 2-28 mikrog/g, Cd 220-1953 ng/g, Cu 4-27 mikrog/g, Cr 4-49 mikrog/g, As 1-6 mikrog/g and Se 0.33-3.24 mikrog/g. The most polluted watershed was Pšata stream (agricultural areas, cattle farm) with highest values for Ni, Cr, Pb, Zn and As. The highest content of Se, was found in village (dairy farms) in Žerovniščica stream. The highest values were measured in February and October. Isotopic composition of dissolved inorganic carbon seasonally range from -13.3 to -8.1‰, and indicate waters dominated by degradation of organic matter and dissolution of carbonates. At the reference point average measured isotopic composition of dissolved inorganic carbon value is -2.7‰ which confirmed that this is a non-polluted site. Isotopic composition of carbon of F. antipyretica seasonally ranges from -45 to -32.9‰ and isotopic composition of nitrogen from -0.2‰ to 6.5‰, respectively. In comparison to C3 terrestrial plants F. antipyretica has more negative isotopic composition of carbon value, which is probably related with the difference in CO2 plant fixation and depends on isotopic composition of dissolved inorganic carbon in water, which is primarily controlled by geological composition and soil thickness in the watershed. Higher isotopic composition of nitrogen value found in F. antipyretica is related to agricultural activity in watershed, while at the reference site measured isotopic composition of nitrogen value is -4.1 ‰. From our study it is evident that isotopic composition of carbon and nitrogen is useful tracer of natural and anthropogenic inputs from terrestrial (fertilizing, sewage sludge) to water system.

Bioavailability and uptake of smelter emissions in freshwater zooplankton in northeastern Washington, USA lakes using Pb isotope analysis and trace metal concentrations.

PubMed

Child, A W; Moore, B C; Vervoort, J D; Beutel, M W

2018-07-01

The upper Columbia River and associated valley systems are highly contaminated with metal wastes from nearby smelting operations in Trail, British Columbia, Canada (Teck smelter), and to a lesser extent, Northport, Washington, USA (Le Roi smelter). Previous studies have investigated depositional patterns of airborne emissions from these smelters, and documented the Teck smelter as the primary metal contamination source. However, there is limited research directed at whether these contaminants are bioavailable to aquatic organisms. This study investigates whether smelter derived contaminants are bioavailable to freshwater zooplankton. Trace metal (Zn, Cd, As, Sb, Pb and Hg) concentrations and Pb isotope compositions of zooplankton and sediment were measured in lakes ranging from 17 to 144 km downwind of the Teck smelter. Pb isotopic compositions of historic ores used by both smelters are uniquely less radiogenic than local geologic formations, so when zooplankton assimilate substantial amounts of smelter derived metals their compositions deviate from local baseline compositions toward ore compositions. Sediment metal concentrations and Pb isotope compositions in sediment follow significant (p < 0.001) negative exponential and sigmoidal patterns, respectively, as distance from the Teck smelting operation increases. Zooplankton As, Cd, and Sb contents were related to distance from the Teck smelter (p < 0.05), and zooplankton Pb isotope compositions suggest As, Cd, Sb and Pb from historic and current smelter emissions are biologically available to zooplankton. Zooplankton from lakes within 86 km of the Teck facility display isotopic evidence that legacy ore pollution is biologically available for assimilation. However, without water column data our study is unable to determine if legacy contaminants are remobilized from lake sediments, or erosional pathways from the watershed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Predicting animal δ18O: Accounting for diet and physiological adaptation

NASA Astrophysics Data System (ADS)

Kohn, Matthew J.

1996-12-01

Theoretical predictions and measured isotope variations indicate that diet and physiological adaptation have a significant impact on animals δ18O and cannot be ignored. A generalized model is therefore developed for the prediction of animal body water and phosphate δ18O to incorporate these factors quantitatively. Application of the model reproduces most published compositions and compositional trends for mammals and birds. A moderate dependence of animal δ18O on humidity is predicted for drought-tolerant animals, and the correlation between humidity and North American deer bone composition as corrected for local meteoric water is predicted within the scatter of the data. In contrast to an observed strong correlation between kangaroo δ18O and humidity (Δδ18O/Δh ∼ 2.5± 0.4‰/10%r.h.), the predicted humidity dependence is only 1.3 - 1.7‰/10% r.h., and it is inferred that drinking water in hot dry areas of Australia is enriched in 18O over rainwater. Differences in physiology and water turnover readily explain the observed differences in δ18O for several herbivore genera in East Africa, excepting antelopes. Antelope models are more sensitive to biological fractionations, and adjustments to the flux of transcutaneous water vapor within experimentally measured ranges allows their δ18O values to be matched. Models of the seasonal changes of forage composition for two regions with dissimilar climates show that significant seasonal variations in animal isotope composition are expected, and that animals with different physiologies and diets track climate differently. Analysis of different genera with disparate sensitivities to surface water and humidity will allow the most accurate quantification of past climate changes.

Nature of diamonds in Yakutian eclogites: views from eclogite tomography and mineral inclusions in diamonds

NASA Astrophysics Data System (ADS)

Anand, Mahesh; Taylor, Lawrence A.; Misra, Kula C.; Carlson, William D.; Sobolev, Nikolai V.

2004-09-01

We have performed dissections of two diamondiferous eclogites (UX-1 and U33/1) from the Udachnaya kimberlite, Yakutia in order to understand the nature of diamond formation and the relationship between the diamonds, their mineral inclusions, and host eclogite minerals. Diamonds were carefully recovered from each xenolith, based upon high-resolution X-ray tomography images and three-dimensional models. The nature and physical properties of minerals, in direct contact with diamonds, were investigated at the time of diamond extraction. Polished sections of the eclogites were made, containing the mould areas of the diamonds, to further investigate the chemical compositions of the host minerals and the phases that were in contact with diamonds. Major- and minor-element compositions of silicate and sulfide mineral inclusions in diamonds show variations among each other, and from those in the host eclogites. Oxygen isotope compositions of one garnet and five clinopyroxene inclusions in diamonds from another Udachnaya eclogite (U51) span the entire range recorded for eclogite xenoliths from Udachnaya. In addition, the reported compositions of almost all clinopyroxene inclusions in U51 diamonds exhibit positive Eu anomaly. This feature, together with the oxygen isotopic characteristics, is consistent with the well-established hypothesis of subduction origin for Udachnaya eclogite xenoliths. It is intuitive to expect that all eclogite xenoliths in a particular kimberlite should have common heritage, at least with respect to their included diamonds. However, the variation in the composition of multiple inclusions within diamonds, and among diamonds, from the same eclogite indicates the involvement of complex processes in diamond genesis, at least in the eclogite xenoliths from Yakutia that we have studied.

Surface water mass composition changes captured by cores of Arctic land-fast sea ice

NASA Astrophysics Data System (ADS)

Smith, I. J.; Eicken, H.; Mahoney, A. R.; Van Hale, R.; Gough, A. J.; Fukamachi, Y.; Jones, J.

2016-04-01

In the Arctic, land-fast sea ice growth can be influenced by fresher water from rivers and residual summer melt. This paper examines a method to reconstruct changes in water masses using oxygen isotope measurements of sea ice cores. To determine changes in sea water isotope composition over the course of the ice growth period, the output of a sea ice thermodynamic model (driven with reanalysis data, observations of snow depth, and freeze-up dates) is used along with sea ice oxygen isotope measurements and an isotopic fractionation model. Direct measurements of sea ice growth rates are used to validate the output of the sea ice growth model. It is shown that for sea ice formed during the 2011/2012 ice growth season at Barrow, Alaska, large changes in isotopic composition of the ocean waters were captured by the sea ice isotopic composition. Salinity anomalies in the ocean were also tracked by moored instruments. These data indicate episodic advection of meteoric water, having both lower salinity and lower oxygen isotopic composition, during the winter sea ice growth season. Such advection of meteoric water during winter is surprising, as no surface meltwater and no local river discharge should be occurring at this time of year in that area. How accurately changes in water masses as indicated by oxygen isotope composition can be reconstructed using oxygen isotope analysis of sea ice cores is addressed, along with methods/strategies that could be used to further optimize the results. The method described will be useful for winter detection of meteoric water presence in Arctic fast ice regions, which is important for climate studies in a rapidly changing Arctic. Land-fast sea ice effective fractionation coefficients were derived, with a range of +1.82‰ to +2.52‰. Those derived effective fractionation coefficients will be useful for future water mass component proportion calculations. In particular, the equations given can be used to inform choices made when engaging in end member determination for working out the component proportions of water masses.

Hafnium and neodymium isotopes and REY distribution in the truly dissolved, nanoparticulate/colloidal and suspended loads of rivers in the Amazon Basin, Brazil

NASA Astrophysics Data System (ADS)

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

2017-09-01

Radiogenic isotopes in river sediments and river waters have been widely used in provenance studies, as these samples naturally integrate the geology/chemistry of the entire catchment. While the Hf and Nd isotope systems are coupled during igneous processes, they are decoupled during supergene processes at the Earth's surface, which is reflected by the isotope composition of riverine sediments. We present the first data for both Hf and Nd isotope compositions of the dissolved (0.2 μm-filtrates rich in nanoparticles and colloids, NPCs) and the truly dissolved (1 kDa-ultrafiltrates) load of rivers. Hafnium and Nd isotope compositions and concentrations of the Rare Earths and Yttrium (REY) and Hf were determined for suspended particles (>0.2 μm) as well as for the dissolved and the truly dissolved load of the Rio Solimões, the Amazon's largest tributary draining the Andes, and of the Rio Negro, an organic NPC- and particle-rich river draining the rainforest of northern Amazonia. We also analyzed the Nd isotope compositions of suspended sediments and 0.2 μm-filtered water samples from the Amazon River and its tributaries Rio Tapajos, Rio Xingu and Rio Jari. Our novel results clearly show that the decoupling of the Hf and Nd isotope systems is related to incongruent weathering processes on the continent, as this decoupling can already be observed in the different Hf and Nd pools, i.e. in the particulate, the NPC-dominated dissolved and the truly dissolved load of rivers. In the Rio Negro and Rio Solimões, a strong particle size-dependent difference in Hf isotope composition is observed. Values of εHf become more radiogenic as filter poresize decreases, which can be related to the density- and size-dependent distribution of Hf-rich minerals, e.g. zircons, and their absence from the truly dissolved pool. In contrast, the Nd isotope composition of Amazonian river waters reflects that of their catchment geology. Tributaries draining the Precambrian Brazilian and Guyana shields show very unradiogenic εNd values of -19 to -25 in their dissolved load, whereas the Rio Solimões draining the Andes yields a more radiogenic εNd signal of only -7. The dissolved Nd isotope composition of the Amazon is dominated by its Andean tributaries and averages at -8. Although Nd isotope compositions are thought to not being fractionated by Earth surface processes, significant differences of 1.3-1.9 ε-units can be observed between the dissolved and suspended loads in the Amazon River and its main tributary, the Rio Solimões. In these rivers, the dissolved load is more radiogenic than the suspended sediment, which is likely due to incongruent weathering and related mineral sorting in the Andean headwaters. In contrast, the organic-rich and mineral-poor shield rivers do not show a difference between the truly dissolved, dissolved and suspended load, as the Nd in all these pools is controlled by surface- and solution-complexation and hence isotopically homogenized by continuous exchange and re-equilibration.

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

Local equilibrium of mafic enclaves and granitoids of the Turtle pluton, southeast California: Mineral, chemical, and isotopic evidence

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

Allen, C.M.

Major element and trace element compositions of whole rocks, mineral compositions, and Rb-Sr isotopic compositions of enclave and host granitoid pairs from the Early Cretaceous, calc-alkaline Turtle pluton of southeastern California suggest that the local environmental profoundly affects some enclave types. In the Turtle pluton, where the source of fine-grained, mafic enclaves can be deduced to be magmatic by the presence of partially disaggregated basaltic dikes, mineral chemistry suggests partial or complete local equilibrium among mineral species in the enclave and its host granitoid. Because of local Rb-Sr isotopic equilibration between fine-grained enclaves and host granitoid, one cannot use Srmore » isotopes to distinguish an enclave source independent of its host rocks from an enclave source related to the enclosing pluton. However, preliminary Nd isotopic data suggest an independent, mantle source for enclaves.« less

The record of mantle heterogeneity preserved in Earth's oceanic crust

NASA Astrophysics Data System (ADS)

Burton, K. W.; Parkinson, I. J.; Schiano, P.; Gannoun, A.; Laubier, M.

2017-12-01

Earth's oceanic crust is produced by melting of the upper mantle where it upwells beneath mid-ocean ridges, and provides a geographically widespread elemental and isotopic `sample' of Earth's mantle. The chemistry of mid-ocean ridge basalts (MORB), therefore, holds key information on the compositional diversity of the upper mantle, but the problem remains that mixing and reaction during melt ascent acts to homogenise the chemical variations they acquire. Nearly all isotope and elemental data obtained thus far are for measurements of MORB glass, and this represents the final melt to crystallise, evolving in an open system. However, the crystals that are present are often not in equilibrium with their glass host. Melts trapped in these minerals indicate that they crystallised from primitive magmas that possess diverse compositions compared to the glass. Therefore, these melt inclusions preserve information on the true extent of the mantle that sources MORB, but are rarely amenable to precise isotope measurement. An alternative approach is to measure the isotope composition of the primitive minerals themselves. Our new isotope data indicates that these minerals crystallised from melts with significantly different isotope compositions to their glass host, pointing to a mantle source that has experienced extreme melt depletion. These primitive minerals largely crystallised in the lower oceanic crust, and our preliminary data for lower crustal rocks and minerals shows that they preserve a remarkable range of isotope compositions. Taken together, these results indicate that the upper mantle sampled by MORB is extremely heterogeneous, reflecting depletion and enrichment over much of Earth's geological history.

Helium-oxygen-osmium isotopic and elemental constraints on the mantle sources of the Deccan Traps

NASA Astrophysics Data System (ADS)

Peters, Bradley J.; Day, James M. D.; Greenwood, Richard C.; Hilton, David R.; Gibson, Jennifer; Franchi, Ian A.

2017-11-01

The Deccan Traps, a 65 million-year-old continental flood basalt province located in western India, is the result of one of the largest short-lived magmatic events to have occurred on Earth. The nature and composition of its mantle source(s), however, have been difficult to resolve due to extensive assimilation of continental crust into the ascending Traps magmas. To circumvent this issue, using high-precision electron microprobe analysis, we have analyzed olivine grains from MgO-rich (up to 15.7 wt.%) lavas that likely erupted before substantial crustal assimilation occurred. We compare olivine, pyroxene and plagioclase mineral chemistry and He-O-Os isotope compositions with bulk rock major- and trace-element abundances and 187Os/188Os for both bulk-rocks and mineral separates. Helium isotope compositions for the olivine grains generally show strong influence from crustal assimilation (<3 RA), but one ankaramite from the Pavagadh volcanic complex has a 3He/4He ratio of 10.7 RA, which is slightly lower than the range of 3He/4He measured for present-day Réunion Island volcanism (∼12-14 RA). Olivine-dominated mineral separates span a more restricted range in 187Os/188Os (0.1267 to 0.1443) compared with their host lavas (0.1186 to 0.5010), with the separates reflecting a parental magma composition less affected by lithospheric or crustal interaction than for the bulk-rocks. Despite significant He-Os isotopic variations, Δ17O is relatively invariant (- 0.008 ± 0.014 ‰) and indistinguishable from the bulk mantle, consistent with high-3He/4He hotspots measured to-date. Compositions of olivine grains indicate the presence of up to 25% of a pyroxenite source for Deccan parental magmas, in good agreement with ∼20% predicted from isotopic data for the same samples. Modeled pyroxenite signatures are similar to geochemical signatures expected to arise due to other types of mantle differentiation or due to assimilation of continental crust; however, we show that crustal assimilation cannot account for all of the compositional features of the olivine. Weak correlations exist between a global compilation of Xpx (Deccan: 0.2-0.7) and 3He/4He, δ18O (Deccan olivine: 4.9-5.2‰) and 187Os/188Os. Robust relationships between these parameters may be precluded due to a lack of two-reservoir source mixing, instead involving multiple mantle domains with distinct compositions, or because Xpx may reflect both source features and crustal assimilation. Notwithstanding, geochemical similarities exist between Deccan Traps olivine (3He/4He = 10.7 RA; 187Os/188Osi = 0.1313 ± 45, 2σ) and Réunion igneous rocks (3He/4He = 12-14 RA; 187Os/188Osi = 0.1324 ± 14). These relationships imply that a characteristic geochemical 'fingerprint' may have persisted in the mantle plume that fed the Deccan Traps, since its inception at 65 Ma, to ongoing eruptions occurring on Réunion up to the present-day.

Clues on Acid-Sulfate Alteration and Hematite Formation on Earth and Mars From Iron Isotopic Analyses of Terrestrial Analogues From Hawaii

NASA Technical Reports Server (NTRS)

Nie, N. X.; Dauphas, N.; Morris, R. V

2017-01-01

The Mars Exploration Rover mission revealed the presence of rocks and minerals indicative of water-rock interactions on Mars. A range of mineralogies have been identified, including hematite spherules (i.e., blueberries), jarosite, Mg-, Ca-sulfates, silica-rich materials and silicate relics from basaltic rocks. The mineral assemblages have been interpreted to be derived from acid-sulfate alteration of basaltic materials. Indeed, the chemical compositions of rocks and soils at Home Plate in Gusev Crater follow the trends expected for acid-sulfate alteration.

Compound-specific isotopes of fatty acids as indicators of trophic interactions in the East China Sea ecosystem

NASA Astrophysics Data System (ADS)

Wu, Ying; Wang, Na; Zhang, Jing; Wan, Ruijing; Dai, Fangqun; Jin, Xianshi

2016-09-01

The composition and compound-specific isotopes of fatty acids were studied within food webs in the East China Sea. Lipid-normalized stable carbon isotopes of total organic carbon had a good correlation with trophic level. Variations in fatty acid compositions among diff erent species were observed but were unclear. Diff erent dietary structures could be traced from molecular isotopes of selected fatty acids in the Shiba shrimp ( Matapenaeus joyneri), the coastal mud shrimp ( Solenocera crassicornis) and the northern Maoxia shrimp ( Acetes chinensis). Both M. joyneri and S. crassicornis are mainly benthos feeders, while A. chinensis is a pelagic species, although they have a similar fatty acid composition. There was a good correlation for isotopes of arachidonic acid (C20:4n6; ARA) and docosahexaenoic acid (C22:6n3; DHA) among pelagic species from higher trophic levels. The isotopic compositions of DHA in benthic species were more negative than those of pelagic species at the same trophic level. The fact that the diet of benthic species contains more degraded items, the carbon isotopes of which are derived from a large biochemical fraction, may be the reason for this variation. A comparative study of benthic and pelagic species demonstrated the diff erent carbon sources in potential food items and the presence of a more complex system at the water-sediment interface.

The carbon isotopic composition of ecosystem breath

NASA Astrophysics Data System (ADS)

Ehleringer, J.

2008-05-01

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

Understanding the Marine Chromium Isotope Record from Modern and Ancient Carbonates

NASA Astrophysics Data System (ADS)

Parkinson, I. J.; Bonnand, P.; James, R. H.; Fairchild, I. J.; Dixon, S.

2011-12-01

Chromium isotopes may provide a powerful tool for reconstructing the redox state of ancient seawater because Cr isotope fractionation is large (up to 7% in δ53Cr) during the reduction of Cr(VI) to Cr(III) in natural waters [1]. Recent studies have demonstrated that although Cr(VI) is predicted to be the thermodynamically stable form in seawater (as CrO42-), significant amounts (5-20%) of Cr(III) may also be present in surface waters [2]. Therefore the δ53Cr of seawater could vary by up to 2%. Marine carbonates potentially provide a means to extracting information about the Cr isotopic composition of seawater in the geological past and we have developed a high-precision double-spike technique for analysing Cr isotopes in carbonates [3]. The δ53Cr of modern Bahamas Bank carbonates (+0.76%) is broadly consistent with these carbonates recording a seawater Cr signature. Moreover, these pure carbonates contain significant amounts of Cr (1-4 ppm), which indicates that Cr is strongly partitioned into calcium carbonate. Therefore carbonates are likely to provide a faithful record of the δ53Cr composition of seawater. Shallow marine carbonates from the Phanerozoic range in δ53Cr from +0.76 to +1.8%, and some Neoproterozoic carbonates also have heavy Cr isotopic compositions of +0.5 to +1.0 %. Such compositions may reflect changes in the inputs of Cr to the oceans and/or changes in the redox state of the oceans. However, to interpret Cr isotopic compositions in ancient carbonates additionally requires a careful assessment of their trace element contents. This study aims to demonstrate how a combination of redox sensitive trace elements, such as Ce, and Cr isotopes allow an assessment of the marine chromium isotope record. [1] Ellis et al., 2002, Science, 295, 2060-2062. [2] Connolly et al., 2006, Deep Sea Res. Part I, 2006 53, 1975-1988. [3] P. Bonnand, et al., 2011, J. Anal. At. Spectr., 26, 528-535.

Relationship between the trajectory of mid-latitude cyclones in the eastern Pacific Ocean and the isotopic composition of snowfall in the Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Vasquez, K. T.; Sickman, J. O.; Lucero, D. M.; Heard, A. M.

2014-12-01

Climate change has caused a change in the Sierra Nevada snowpack and the timing of its snowmelt, threatening a valuable water resource that provides for 25 million people and 5 million hectares of irrigated land. Understanding past and future variations in the snowpack is crucial in order to plan future water management. Of particular importance would be an archive of the variability of past snowfall, which can be recorded through the isotopic records found in local paleoproxies (e.g., diatoms). We propose to quantify the relationship between sources of atmospheric moisture in the Sierra Nevada and the isotopic composition of its snowpack to uncover whether isotopic variations recorded in paloearchives are a result of the isotopic composition of the precipitation, thereby showing whether these archives could serve as a reliable source of atmospheric moisture. Preliminary analysis conducted from December 2012 to March 2013 at Sequoia National Park resulted in statistically significant correlations between the isotopic composition of the winter snowfall and storm track trajectories. It was observed that storms originating from more northern latitudes had predominantly lighter isotopes (more negative δ 2H and δ18O) and sub-tropical/tropical Pacific storms showed more positive δ 2H and δ18O. This pattern reflects the isotopic gradient of the Pacific Ocean and can prove useful when interpreting the climatic significance of the δ2H and δ18O values in analyzed proxies. While our initial investigation was promising, the winter of 2012 -2013 was abnormally dry compared to long-term averages. Before directing our investigation to known paleoproxies, we aim to determine if the correlation between storm tracks and isotopic composition of precipitation holds in years with average and above average precipitation through analysis of archived samples from calendar years 2007 - 2011 from Giant Forest in Sequoia National Park (southern sierra) and Manzanita Lake in Lassen Volcanic National Park (northern sierra).

Secular variations of iron isotopes in ferromanganese crusts: evidences for deeply sourced iron in the Pacific Ocean?

NASA Astrophysics Data System (ADS)

Rouxel, O. J.; Gueguen, B.

2016-12-01

Ferromanganese (Fe-Mn) crusts are potential archive of the Fe isotope composition of deep seawater through time. Here, we report Fe isotope composition of two pairs of Fe-Mn crusts collected on two volcanic seamounts from the Northern Pacific Ocean (Apuupuu Seamount, Hawaii) and the Southern Pacific Ocean (near Rurutu Island, Austral archipelago of French Polynesia). This approach allows (a) a direct comparison of the Fe isotope record in Fe-Mn crusts from the same seamount in order to address local effects, and (b) a comparison of geochemical composition of crusts between North and South Pacific in order to address the effect of more global geochemical processes. The results show that, despite different growth rates, diagenetic history, textures and geochemical patterns, Fe-Mn crusts from both North and South Pacific Oceans have fairly homogenous Fe isotope compositions over the last 17 Ma, yielding average δ56Fe values of -0.22 ± 0.20‰ (1sd, n = 54). The results also show striking correlations between Fe and Pb isotope ratios, indicating that local mixing between water masses is the main factor controlling Fe isotope composition in FeMn crusts. Recently, Horner et al. (2015) reported a range of δ56Fe values from -1.12‰ to 1.54‰ along a 76 Ma-old FeMn crust from the central pacific. However, secular variations of Fe isotopes inferred from other FeMn crusts in the Central North Pacific and Western Pacific (Yang and Rouxel, unpublished) show different patterns over the last 40 Ma, with δ56Fe ranging from -0.07 to -0.61‰ (n=81). Hence, the application of Fe isotopes as paleoceanographic proxies to trace deeply sourced iron at the scale of oceanic basins should be used with caution, prompting for an integrative approach combining diverse yet complimentary geochemical proxies.

Hf-Nd isotope decoupling in the oceanic lithosphere: constraints from spinel peridotites from Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Bizimis, Michael; Sen, Gautam; Salters, Vincent J. M.

2004-01-01

We present a detailed geochemical investigation on the Hf, Nd and Sr isotope compositions and trace and major element contents of clinopyroxene mineral separates from spinel lherzolite xenoliths from the island of Oahu, Hawaii. These peridotites are believed to represent the depleted oceanic lithosphere beneath Oahu, which is a residue of a MORB-related melting event some 80-100 Ma ago at a mid-ocean ridge. Clinopyroxenes from peridotites from the Salt Lake Crater (SLC) show a large range of Hf isotopic compositions, from ɛHf=12.2 (similar to the Honolulu volcanics series) to extremely radiogenic, ɛHf=65, at nearly constant 143Nd/ 144Nd ratios ( ɛNd=7-8). None of these samples show any isotopic evidence for interaction with Koolau-type melts. A single xenolith from the Pali vent is the only sample with Hf and Nd isotopic compositions that falls within the MORB field. The Hf isotopes correlate positively with the degree of depletion in the clinopyroxene (e.g. increasing Mg#, Cr#, decreasing Ti and heavy REE contents), but also with increasing Zr and Hf depletions relative to the adjacent REE in a compatibility diagram. The Lu/Hf isotope systematics of the SLC clinopyroxenes define apparent ages of 500 Ma or older and these compositions cannot be explained by mixing between any type of Hawaiian melts and the depleted Pacific lithosphere. Metasomatism of an ancient (e.g. 1 Ga or older) depleted peridotite protolith can, in principle, explain these apparent ages and the Nd-Hf isotope decoupling, but requires that the most depleted samples were subject to the least amount of metasomatism. Alternatively, the combined isotope, trace and major element compositions of these clinopyroxenes are best described by metasomatism of the 80-100 Ma depleted oceanic lithosphere by melts products of extensive mantle-melt interaction between Honolulu Volcanics-type melts and the depleted lithosphere.

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.

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

Chemical Imaging and Stable Isotope Analysis of Atmospheric Particles by NanoSIMS (Invited)

NASA Astrophysics Data System (ADS)

Sinha, B.; Harris, E. J.; Pöhlker, C.; Wiedemann, K. T.; van Pinxteren, D.; Tilgner, A.; Fomba, K. W.; Schneider, J.; Roth, A.; Gnauk, T.; Fahlbusch, B.; Mertes, S.; Lee, T.; Collett, J. L.; Shiraiwa, M.; Gunthe, S. S.; Smith, M.; Artaxo, P. P.; Gilles, M.; Kilcoyne, A. L.; Moffet, R.; Weigand, M.; Martin, S. T.; Poeschl, U.; Andreae, M. O.; Hoppe, P.; Herrmann, H.; Borrmann, S.

2013-12-01

Chemical imaging analysis of the internal distribution of chemical compounds by a combination of SEM-EDX, and NanoSIMS allows investigating the physico-chemical properties and isotopic composition of individual aerosol particles. Stable sulphur isotope analysis provides insight into the sources, sinks and oxidation pathways of SO2 in the environment. Oxidation by OH radicals, O3 and H2O2 enriches the heavier isotope in the product sulphate, whereas oxidation by transition metal ions (TMI), hypohalites and hypohalous acids depletes the heavier isotope in the product sulphate. The isotope fractionation during SO2 oxidation by stabilized Criegee Intermediate radicals is unknown. We studied the relationship between aerosol chemical composition and predominant sulphate formation pathways in continental clouds in Central Europe and during the wet season in the Amazon rain forest. Sulphate formation in continental clouds in Central Europe was studied during HCCT-2010, a lagrangian-type field experiment, during which an orographic cloud was used as a natural flow-through reactor to study in-cloud aerosol processing (Harris et al. 2013). Sulphur isotopic compositions in SO2 and H2SO4 gas and particulate sulphate were measured and changes in the sulphur isotope composition of SO2 between the upwind and downwind measurement sites were used to determine the dominant SO2 chemical removal process occurring in the cloud. Changes in the isotopic composition of particulate sulphate revealed that transition metal catalysis pathway was the dominant SO2 oxidation pathway. This reaction occurred primarily on coarse mineral dust particles. Thus, sulphate produced due to in-cloud SO2 oxidation is removed relatively quickly from the atmosphere and has a minor climatic effect. The aerosol samples from the Amazonian rainforest, a pristine tropical environment, were collected during the rainy season. The samples were found to be dominated by SOA particles in the fine mode and primary biological aerosol particles in the coarse mode (Pöhlker et al. 2012). We applied STXM-NEXAFS analysis, SEM-EDX analysis and NanoSIMS analysis to investigate the morphology, chemical composition and isotopic composition of aerosol samples. Biogenic salt particles emitted from active biota in the rainforest were found to be enriched in the heavier sulphur isotope, whereas particles with a high organic mass fraction modified by condensation of VOC oxidation products and/or cloud processing were significantly depleted in the heavier sulphur isotope compared to the seed particles. This indicates either a depleted gas phase source of sulphur dioxide contributed to the sulphate formation via the H2O2, O3 or OH oxidation pathway or an unaccounted reaction pathway which depletes the heavier isotope in the product sulphate contributes to the secondary sulphate formation in the pristine Amazon rainforest. Harris, E., et al., Science 340, 727-730, 2013 Pöhlker, C., Science 337, 1075-1078, 2012

Sr isotopic composition of Afar volcanics and its implication for mantle evolution

NASA Astrophysics Data System (ADS)

Barberi, F.; Civetta, L.; Varet, J.

1980-10-01

Investigations of Rb-Sr systematics of basalts from the Afar depression (Ethiopia) indicate the presence of a heterogeneous mantle source region. The Sr isotopic compositions of the basalts from the Afar axial and transverse ranges identify source regions which are enriched in LIL elements and radiogenic Sr (axial ranges) and others which are relatively depleted (transverse ranges). Sr isotopic composition of basalts from the Red Sea, Gulf of Aden and Gulf of Tadjoura, which range from 0.70300 to 0.70340 are also reported and compared with the more radiogenic Afar region, which is characterized by 87Sr/ 86Sr ranging from 0.70328 to 0.70410. Available geochemical and isotopic data suggest that a relation exists between magma composition and the advancement of the rifting process through progressive lithosphere attenuation leading to continental break-up. However, the petrogenetic process is not simple and probably implies a vertically zoned mantle beneath the Afar region. Sr isotopic evidence suggests that the vertically zoned mantle is more radiogenic and enriched in LIL elements in its upper part.

Planetary Accretion, Oxygen Isotopes and the Central Limit Theorem

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Hill, Hugh G. M.; Vondrak, Richard R. (Technical Monitor)

2001-01-01

The accumulation of presolar dust into increasingly larger aggregates (CAIs and Chondrules, Asteroids, Planets) should result in a very drastic reduction in the numerical spread in oxygen isotopic composition between bodies of similar size, in accord with the Central Limit Theorem. Observed variations in oxygen isotopic composition are many orders of magnitude larger than would be predicted by a simple, random accumulation model that begins in a well-mixed nebula - no matter which size-scale objects are used as the beginning or end points of the calculation. This discrepancy implies either that some as yet unspecified process acted on the solids in the Solar Nebula to increase the spread in oxygen isotopic composition during each and every stage of accumulation or that the nebula was heterogeneous and maintained this heterogeneity throughout most of nebular history. Large-scale nebular heterogeneity would have significant consequences for many areas of cosmochemistry, including the application of some well-known isotopic systems to the dating of nebular events or the prediction of bulk compositions of planetary bodies on the basis of a uniform cosmic abundance.

Lead and strontium isotopic evidence for crustal interaction and compositional zonation in the source regions of Pleistocene basaltic and rhyolitic magmas of the Coso volcanic field, California

USGS Publications Warehouse

Bacon, C.R.; Kurasawa, H.; Delevaux, M.H.; Kistler, R.W.; Doe, B.R.

1984-01-01

The isotopic compositions of Pb and Sr in Pleistocene basalt, high-silica rhyolite, and andesitic inclusions in rhyolite of the Coso volcanic field indicate that these rocks were derived from different levels of compositionally zoned magmatic systems. The 2 earliest rhyolites probably were tapped from short-lived silicic reservoirs, in contrast to the other 36 rhyolite domes and lava flows which the isotopic data suggest may have been leaked from the top of a single, long-lived magmatic system. Most Coso basalts show isotopic, geochemical, and mineralogic evidence of interaction with crustal rocks, but one analyzed flow has isotopic ratios that may represent mantle values (87Sr/86Sr=0.7036,206Pb/204Pb=19.05,207Pb/204Pb=15.62,208Pb/204Pb= 38.63). The (initial) isotopic composition of typical rhyolite (87Sr/86Sr=0.7053,206Pb/204Pb=19.29,207Pb/204Pb= 15.68,208Pb/204Pb=39.00) is representative of the middle or upper crust. Andesitic inclusions in the rhyolites are evidently samples of hybrid magmas from the silicic/mafic interface in vertically zoned magma reservoirs. Silicic end-member compositions inferred for these mixed magmas, however, are not those of erupted rhyolite but reflect the zonation within the silicic part of the magma reservoir. The compositional contrast at the interface between mafic and silicic parts of these systems apparently was greater for the earlier, smaller reservoirs. ?? 1984 Springer-Verlag.

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

PubMed

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

1989-11-01

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

Laser ion source for isobaric heavy ion collider experiment.

PubMed

Kanesue, T; Kumaki, M; Ikeda, S; Okamura, M

2016-02-01

Heavy-ion collider experiment in isobaric system is under investigation at Relativistic Heavy Ion Collider. For this experiment, ion source is required to maximize the abundance of the intended isotope. The candidate of the experiment is (96)Ru + (96)Zr. Since the natural abundance of particular isotope is low and composition of isotope from ion source depends on the composites of the target, an isotope enriched material may be needed as a target. We studied the performance of the laser ion source required for the experiment for Zr ions.

Membrane inlet laser spectroscopy to measure H and O stable isotope compositions of soil and sediment pore water with high sample throughput

DOE PAGES

Oerter, Erik J.; Perelet, Alexei; Pardyjak, Eric; ...

2016-10-20

Here, the fast and accurate measurement of H and O stable isotope compositions (δ 2H and δ 18O values) of soil and sediment pore water remains an impediment to scaling-up the application of these isotopes in soil and vadose hydrology. Here we describe a method and its calibration to measuring soil and sediment pore water δ 2H and δ 18O values using a water vapor-permeable probe coupled to an isotope ratio infrared spectroscopy analyzer.

Implications of 187Os isotopic heterogeneities in a mantle plume: evidence from Gorgona Island and Curaçao

NASA Astrophysics Data System (ADS)

Walker, Richard J.; Storey, Michael; Kerr, Andrew C.; Tarney, John; Arndt, Nicholas T.

1999-03-01

Recent work has suggested that the mafic-ultramafic volcanism in evidence throughout portions of the Caribbean, Central America, and northern South America, including the islands of Gorgona and Curaçao, was generated as part of a middle-Cretaceous, large igneous province. New Re-Os isochron results for tholeiitic basalts from Gorgona and Curaçao indicate crystallization ages of 89.2 ± 5.2 and 85.6 ± 8.1 Ma, respectively, consistent with reported Ar ages. The Gorgona ultramafic suite shows a large range in initial Os isotopic composition, with γ Os values ranging from -0.5 to +12.4. This large range reflects isotopic heterogeneities in the mantle source similar to those observed for modern ocean island basalts. In contrast to ocean island basalts, however, Os isotopic compositions do not correlate with variations in Nd, Sr, or Pb isotopic compositions, which are within the range of depleted mid-ocean ridge basalts. The processes that produced these rocks evidently resulted in the decoupling of Os isotopes from the Nd, Sr, and Pb isotopic systems. Picrites from Curaçao have very uniform, chondritic initial Os isotopic compositions, with initial γ Os values ranging only from -0.4 to ±1.4. Basalts from Curaçao, however, define an isochron with a 187Os-enriched initial isotopic composition (γ Os = +9.5). In contrast to the 187Os-enriched ultramafic rocks from Gorgona, the enrichment in these basalts could have resulted from lithospheric contamination. If the Gorgona and Curaçao rocks were derived from the same plume, Os results, combined with Sr, Nd, and Pb data indicate a heterogeneous plume, with multiple compositionally and isotopically distinct domains. The Os isotopic results require derivation of Os from a minimum of two distinct reservoirs, one with a composition very similar to the chondritic average and one with long-term enriched Re/Os. Oceanic crustal recycling has been invoked to explain most of the 187Os enrichments that have been observed in ocean island basalt sources and could potentially apply to the Gorgona suite. Crustal recycling, however, requires large proportions of very ancient recycled basaltic crust in the sources of the 187Os-enriched ultramafic rocks to explain the magnitude of 187Os enrichments observed. For example, addition of 20% oceanic crust to fertile mantle, and nearly 3 billion years are necessary to generate a reservoir with the Os isotopic composition of the most radiogenic komatiites. If the recycled oceanic crust was added to basalt-depleted mantle, as may be indicated by ɛ Nd values for the komatiites averaging about +10, even larger proportions of older crust are required. Large proportions of oceanic mafic crust in the sources of the 187Os-enriched komatiites, although petrologically conceivable under certain melting conditions, is unlikely here given the limited trace element and lithophile isotope system variations. These results raise questions about the efficacy of using Os isotopes to constrain the proportion of recycled oceanic crust in other plumes. Other possible mechanisms for generating 187Os-enriched mantle include invoking the existence of a 187Os-enriched lower mantle, and minor outer core-lower mantle interactions.

The mineralogy, petrology, and composition of anomalous eucrite Emmaville

NASA Astrophysics Data System (ADS)

Barrett, T. J.; Mittlefehldt, D. W.; Greenwood, R. C.; Charlier, B. L. A.; Hammond, S. J.; Ross, D. K.; Anand, M.; Franchi, I. A.; Abernethy, F. A. J.; Grady, M. M.

2017-04-01

The Emmaville eucrite is a relatively poorly studied basaltic achondrite with an anomalous oxygen isotope signature. In this study, we report comprehensive mineralogical, petrographic, and geochemical data from Emmaville in order to understand its petrogenesis and relationship with the basaltic eucrites. Emmaville is an unusually fine-grained, hornfelsic-textured metabasalt with pervasive impact melt veins and mineral compositions similar to those of typical basaltic eucrites. The major and trace element bulk composition of Emmaville is also typical of a basaltic eucrite. Three separated individual lithologies were also analyzed for O isotopes; a dark gray fraction (E1), a shocked lithology (E2), and a lighter gray portion (E3). Fractions E1 and E2 shared similar O isotope compositions to the bulk sample (E-B), whereas the lighter gray portion (E3) is slightly elevated in Δ17O and significantly elevated in δ18O compared to bulk. No evidence for any exogenous material is observed in the thin sections, coupled with the striking compositional similarity to typical basaltic eucrites, appears to preclude a simple impact-mixing hypothesis. The O-isotopes of Emmaville are similar to those of Bunburra Rockhole, A-881394, and EET 92023, and thus distinct from the majority of the HEDs, despite having similarities in petrology, mineral, and bulk compositions. It would, therefore, seem plausible that all four of these samples are derived from a single HED-like parent body that is isotopically distinct from that of the HEDs (Vesta) but similar in composition.

The Chlorine Isotope Composition of Martian Meteorites

NASA Astrophysics Data System (ADS)

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

2014-11-01

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

Determination of the isotopic composition of evapotranspiration in a mature oil palm plantation in Jambi province, Indonesia.

NASA Astrophysics Data System (ADS)

Bonazza, Mattia; Meijide, Ana; Knohl, Alexander

2017-04-01

Evapotranspiration (ET) is defined as the sum of the water vapor fluxes from evaporation (E) and transpiration (T). The relative proportion between these two quantities depends on the species, on their age and on the structure of the stand and canopy. Evaporation represents the fraction of water that doesn't contribute to plants growth hence it often considered as "unused" water by the plants root system. For this reason, in a fast changing environment like Indonesia where, since almost 30 years, tropical rainforests are gradually converted into extensive oil palm plantation, it is important to quantify the amount of evaporated water to improve agricultural practices and water quality. As powerful tracers of the hydrological cycle, water stable isotopes represent an important tool to estimate the isotopic composition of the evapotranspiration flux and they can be used as a starting point for the determination of the T/ET ratio, which can be considered as a plant water uptake efficiency indicator. The isotopic composition (δDvand δ18Ov) and the mixing ratio (qv) of water vapor measured in a stand is the result of the isotopic mixing between two members; ecosystem evapotranspiration (δET) and background air (δa). With the implementation of laser-based isotopic analysers we are now able to improve the measurement frequency of δDvand δ18Ov that leads us to an improved estimation of δET. Here we present the results of a measurement campaign, performed with a Picarro L-2120i and conducted in a mature oil palm plantation in the province of Jambi, Indonesia. We measured the atmospheric water vapor mixing ratio and isotopic composition at 5 sampling heights (21 m, 16 m, 9 m, 3.5 and 0.3 m) along a flux tower throughout the oil palm canopy (average height 10 m). The range of the water vapor isotopic composition was between -19 and -11 and -134 and -82 ‰ for δ18Ov and δDvrespectively. A fairly open canopy structure resulted in small mixing ratio gradients along the vertical profile. We collected and analysed all rain event and estimated the variability of the water vapor isotopic composition. Micrometeorological measurements, provided by the tower's sensors, were used to calculate ET using the Bowen ratio energy balance. To determine the isotopic composition of the evapotranspiration flux we used and compared two different methods: Keeling plot and flux gradient approach.

Distribution and geochemical characterization of coalbed gases at excavation fields at natural analogue site area Velenje Basin, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Žigon, Stojan; Grassa, Fausto; Sedlar, Jerneja; Zadnik, Ivo; Zavšek, Simon

2016-04-01

Unconventional gas resources, including coal bed methane and shale gas, are a growing part of the global energy mix, which has changed the economic and strategic picture for gas consuming and producing countries, including the USA, China and Australia that, together are responsible for around half the currently recoverable unconventional gas resources. However, CBM production was often hindered by low permeability and mineralization in cleats and fractures, necessitating the development of cost effective horizontal drilling and completion techniques. Geochemical and isotopic monitoring of coalbed gases at excavation fields in Velenje Basin started in year 2000, with the aim to obtain better insights into the origin of coalbed gases. Results from active excavation fields in the mining areas Pesje and Preloge in the year period 2014-2015 are presented in this study. Composition and isotopic composition of coalbed gases were determined with mass - spectrometric methods. The chemical (methane, carbon dioxide, nitrogen) and isotopic composition of carbon in methane and carbon dioxide in the Velenje Basin vary and depend on the composition of the source of coalbed gas before excavation, advancement of the working face, depth of the longwall face, pre-mining activity and newly mined activity. The basic gas components determined in excavation fields are carbon dioxide and methane. Knowledge of the stable isotope geochemistry of coal bed and shale gas and the related production water is essential to determine not only gas origins but also the dominant methanogenic pathway in the case of microbial gas. Concentrations of methane at active excavation fields are changing from 1.8 to 63.9 %, concentrations of carbon dioxide are changing from 36.1 to 98.2% and CDMI (Carbon Dioxide Methane Index) index from 0.2 to 100 %. Isotopic composition of carbon dioxide is changing from -11.0 to -1.9‰ , isotopic composition of methane from -71.8 to -43.3‰ , isotopic composition of deuterium in methane from -343.9 to -223.1‰ , respectively. Further, these characteristics of methane have been compared with those observed in other coal sedimentary basins worldwide. The isotopic compositions of carbon and hydrogen in methane in the excavation fields show its biogenic origin, while a high Carbon Dioxide Methane Index (CDMI index) indicates the bacterial and endogenic origin of carbon dioxide.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

Around 1/3 of Earth's divergent ridge system is now classified as "slow" spreading [1], exposing ultramafic rocks (abyssal peridotites) at the seafloor. Such material is often highly altered by serpentinisation and steatisation (talc formation). It is crucial to understand such processes in order to access the original composition of the mantle, and to quantify any impact on ocean composition. Here we examine the effect of both serpentinisation and steatisation on Si, Mg and Zn isotopes. Hydrothermal alteration and seafloor weathering are both sources of oceanic Si [2] and weathering of abyssal peridotites is a source of oceanic Mg [3]; hence isotopic fractionation as a result of seafloor alteration could affect oceanic Si and Mg isotope composition. Zinc isotopes can provide complimentary information; the magnitude and direction of fractionation is highly dependent on complexing ligand [4] and can provide compositional information on the fluids driving metasomatism. For this study, two cores from the well-characterised abyssal peridotites recovered on ODP Leg 209 were examined [5]. Hole 1274a peridotites exhibit variable serpentinisation at ~200°C, whereas samples from Hole 1268a have been comprehensively serpentinised and then subsequently steatised to talc facies at ~350°C, by a low Mg/Si, low pH fluid. The Si, Mg and Zn isotope compositions of 1274a samples are extremely homogeneous, identical to that of pristine mantle rocks (BSE) i.e., serpentinisation at this locality was predominantly isochemical [5]. In contrast, samples from 1268a show greater isotopic variability. In all samples, Mg is enriched in the heavier isotopes relative to BSE, consistent with formation of isotopically heavy secondary phases [6]. For Si, serpentinised samples are slightly enriched in the lighter isotopes compared to BSE, again consistent with the behaviour of Si during formation of secondary phases [7]. Within the steatised samples, some exhibit enrichments in the lighter Si isotopes (similar to the serpentinites), however, some are isotopically heavy, relative to BSE. Such samples were found to have abundant chlorite, whose formation requires fluid with high Al activity, likely sourced from late-emplaced gabbroic dykes. The Zn of all 1268a samples are enriched in the lighter isotopes, implying the involvement of isotopically light sulfide precipitation during metasomatism [4]. The consistently heavy Mg isotope data suggest that seafloor alteration of peridotites can input an isotopically light Mg-bearing fluid to the ocean. Fluid composition is less easy to determine from the more complex behaviour observed in Si isotopes, although it is unlikely to substantially deviate from BSE, consistent with previous observations [8]. Finally, the strong enrichment in the lighter isotopes of Zn confirms that this isotope system could be used as a tracer of recycled serpentinised material at arc settings, as suggested in [4]. [1] Dick et al. (2003) Nature 426, 405-412; [2] Treguer and De La Rocha (2013) Ann. Rev. Mar. Sci. 5, 477-501; [3] Snow & Dick (1995) GCA, 59, 4219-4235; [4] Pons et al. (2011) PNAS 108(43) 17639-17643; [5] Bach et al., (2004) G3 5; [6] Tipper et al. (2006) EPSL 247, 267-279; [7] Opfergelt et al. (2012) Chem. Geol. 326, 113-122; [8] De La Rocha et al. (2000) GCA 64, 2467-2477.

Partitioning evapotranspiration fluxes with water stable isotopic measurements: from the lab to the field

NASA Astrophysics Data System (ADS)

Quade, M. E.; Brueggemann, N.; Graf, A.; Rothfuss, Y.

2017-12-01

Water stable isotopes are powerful tools for partitioning net into raw water fluxes such as evapotranspiration (ET) into soil evaporation (E) and plant transpiration (T). The isotopic methodology for ET partitioning is based on the fact that E and T have distinct water stable isotopic compositions, which in turn relies on the fact that each flux is differently affected by isotopic kinetic effects. An important work to be performed in parallel to field measurements is to better characterize these kinetic effects in the laboratory under controlled conditions. A soil evaporation laboratory experiment was conducted to retrieve characteristic values of the kinetic fractionation factor (αK) under varying soil and atmospheric water conditions. For this we used a combined soil and atmosphere column to monitor the soil and atmospheric water isotopic composition profiles at a high temporal and vertical resolution in a nondestructive manner by combining micro-porous membranes and laser spectroscopy. αK was calculated by using a well-known isotopic evaporation model in an inverse mode with the isotopic composition of E as one input variable, which was determined using a micro-Keeling regression plot. Knowledge on αK was further used in the field (Selhausen, North Rhine-Westphalia, Germany) to partition ET of catch crops and sugar beet (Beta vulgaris) during one growing season. Soil and atmospheric water isotopic profiles were measured automatically across depths and heights following a similar modus operandi as in the laboratory experiment. Additionally, a newly developed continuously moving elevator was used to obtain water vapor isotopic composition profiles with a high vertical resolution between soil surface, plant canopy and atmosphere. Finally, soil and plant samples were collected destructively to provide a comparison with the traditional isotopic methods. Our results illustrate the changing proportions of T and E along the growing season and demonstrate the applicability of our new non-destructive approach to field conditions.

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.

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

NASA Astrophysics Data System (ADS)

Pringle, E. A.; Moynier, F.

2016-12-01

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

Enrichment of 18O in the mantle sources of the Antarctic portion of the Karoo large igneous province

NASA Astrophysics Data System (ADS)

Heinonen, Jussi S.; Luttinen, Arto V.; Whitehouse, Martin J.

2018-03-01

Karoo continental flood basalt (CFB) province is known for its highly variable trace element and isotopic composition, often attributed to the involvement of continental lithospheric sources. Here, we report oxygen isotopic compositions measured with secondary ion mass spectrometry for hand-picked olivine phenocrysts from 190 to 180 Ma CFBs and intrusive rocks from Vestfjella, western Dronning Maud Land, that form an Antarctic extension of the Karoo province. The Vestfjella lavas exhibit heterogeneous trace element and radiogenic isotope compositions (e.g., ɛ Nd from - 16 to + 2 at 180 Ma) and the involvement of continental lithospheric mantle and/or crust in their petrogenesis has previously been suggested. Importantly, our sample set also includes rare primitive dikes that have been derived from depleted asthenospheric mantle sources ( ɛ Nd up to + 8 at 180 Ma). The majority of the oxygen isotopic compositions of the olivines from these dike rocks (δ18O = 4.4-5.2‰; Fo = 78-92 mol%) are also compatible with such sources. The olivine phenocrysts in the lavas, however, are characterized by notably higher δ18O (6.2-7.5‰; Fo = 70-88 mol%); and one of the dike samples gives intermediate compositions (5.2‒6.1‰, Fo = 83-87 mol%) between the other dikes and the CFBs. The oxygen isotopic compositions do not correlate with radiogenic isotope compositions susceptible to crustal assimilation (Sr, Nd, and Pb) or with geochemical indicators of pyroxene-rich mantle sources. Instead, δ18O correlates positively with enrichments in large-ion lithophile elements (especially K) and 187Os. We suggest that the oxygen isotopic compositions of the Vestfjella CFB olivines primarily record large-scale subduction-related metasomatism of the sub-Gondwanan mantle (base of the lithosphere or deeper) prior to Karoo magmatism. The overall influence of such sources to Karoo magmatism is not known, but, in addition to continental lithosphere, they may be responsible for some of the geochemical heterogeneity observed in the CFBs.

In search of the Earth-forming reservoir: Mineralogical, chemical, and isotopic characterizations of the ungrouped achondrite NWA 5363/NWA 5400 and selected chondrites

NASA Astrophysics Data System (ADS)

Burkhardt, Christoph; Dauphas, Nicolas; Tang, Haolan; Fischer-GöDde, Mario; Qin, Liping; Chen, James H.; Rout, Surya S.; Pack, Andreas; Heck, Philipp R.; Papanastassiou, Dimitri A.

2017-05-01

High-precision isotope data of meteorites show that the long-standing notion of a "chondritic uniform reservoir" is not always applicable for describing the isotopic composition of the bulk Earth and other planetary bodies. To mitigate the effects of this "isotopic crisis" and to better understand the genetic relations of meteorites and the Earth-forming reservoir, we performed a comprehensive petrographic, elemental, and multi-isotopic (O, Ca, Ti, Cr, Ni, Mo, Ru, and W) study of the ungrouped achondrites NWA 5363 and NWA 5400, for both of which terrestrial O isotope signatures were previously reported. Also, we obtained isotope data for the chondrites Pillistfer (EL6), Allegan (H6), and Allende (CV3), and compiled available anomaly data for undifferentiated and differentiated meteorites. The chemical compositions of NWA 5363 and NWA 5400 are strikingly similar, except for fluid mobile elements tracing desert weathering. We show that NWA 5363 and NWA 5400 are paired samples from a primitive achondrite parent-body and interpret these rocks as restite assemblages after silicate melt extraction and siderophile element addition. Hafnium-tungsten chronology yields a model age of 2.2 ± 0.8 Myr after CAI, which probably dates both of these events within uncertainty. We confirm the terrestrial O isotope signature of NWA 5363/NWA 5400; however, the discovery of nucleosynthetic anomalies in Ca, Ti, Cr, Mo, and Ru reveals that the NWA5363/NWA 5400 parent-body is not the "missing link" that could explain the composition of the Earth by the mixing of known meteorites. Until this "missing link" or a direct sample of the terrestrial reservoir is identified, guidelines are provided of how to use chondrites for estimating the isotopic composition of the bulk Earth.

Zn isotopic heterogeneity in the mantle: A melting control?

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

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.

Correlated silicon and titanium isotopic compositions of presolar SiC grains from the Murchison CM2 chondrite

NASA Astrophysics Data System (ADS)

Gyngard, Frank; Amari, Sachiko; Zinner, Ernst; Marhas, Kuljeet Kaur

2018-01-01

We report correlated Si, and Ti isotopic compositions and elemental concentrations of 238 presolar SiC grains from the Murchison CM2 meteorite. Combined with measurements of the C and N isotopic compositions of these 238 grains, 220 were determined to be of type mainstream, 10 type AB, 4 type Y and 4 type Z. SiC grains of diameter ≳2.5 μm, to ensure enough material to attempt Ti measurements, were randomly chosen without any other prejudice. The Ti isotopic compositions of the majority of the grains are characterized by enrichments in 46Ti, 47Ti, 49Ti, and 50Ti relative to 48Ti, and show linear isotopic correlations indicative of galactic chemical evolution and neutron capture of the grains parent stars. The variability in the observed Ti signal as a function of depth in most of the grains indicates the presence of distinct subgrains, likely TiC that have been previously observed in TEM studies. Vandium-51 concentrations correlate with those of Ti, indicating V substitutes for Ti in the TiC matrix in many of the grains. No isotopic anomalies in 52Cr/53Cr ratios were observed, and Cr concentrations did not correlate with those of either Ti or V.

Lead isotope compositions as guides to early gold mineralization: The North Amethyst vein system, Creede district, Colorado

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.

1994-01-01

Pb isotope compositions from the late stage of the North Amethyst vein system and from the Bondholder and central and southern Creede mining districts are more radiogenic than the host volcanic rocks of the central cluster of the San Juan volcanic field. Our Pb isotope results indicate that early Au mineralization of the North Amethyst area may represent the product of an older and relatively local hydrothermal system distinct from that of the younger base metal and Ag mineralization found throughout the region. Fluids that deposited Au minerals may have derived their Pb isotope composition by a greater degree of interaction with shallow, relatively less radiogenic volcanic wall rocks. The younger, base metal and Ag-rich mineralization that overprints the Au mineralization in the North Amethyst area clearly has a more radiogenic isotopic signature, which implies that the later mineralization derived a greater component of its Pb from Proterozoic source rocks, or sediments derived from them.Paragenetically early sulfide-rich vein assemblages have the least radiogenic galenas and generally also have the highest Au contents. Thus, identification of paragenetically early vein assemblages with relatively unradiogenic Pb isotope compositions similar to those of the North Amethyst area provides an additional exploration tool for Au in the central San Juan Mountains area.

Calcium Isotopic Composition of Bulk Silicate Earth

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Estimates of lake trout (Salvelinus namaycush) diet in Lake Ontario using two and three isotope mixing models

USGS Publications Warehouse

Colborne, Scott F.; Rush, Scott A.; Paterson, Gordon; Johnson, Timothy B.; Lantry, Brian F.; Fisk, Aaron T.

2016-01-01

Recent development of multi-dimensional stable isotope models for estimating both foraging patterns and niches have presented the analytical tools to further assess the food webs of freshwater populations. One approach to refine predictions from these analyses is to include a third isotope to the more common two-isotope carbon and nitrogen mixing models to increase the power to resolve different prey sources. We compared predictions made with two-isotope carbon and nitrogen mixing models and three-isotope models that also included sulphur (δ34S) for the diets of Lake Ontario lake trout (Salvelinus namaycush). We determined the isotopic compositions of lake trout and potential prey fishes sampled from Lake Ontario and then used quantitative estimates of resource use generated by two- and three-isotope Bayesian mixing models (SIAR) to infer feeding patterns of lake trout. Both two- and three-isotope models indicated that alewife (Alosa pseudoharengus) and round goby (Neogobius melanostomus) were the primary prey items, but the three-isotope models were more consistent with recent measures of prey fish abundances and lake trout diets. The lake trout sampled directly from the hatcheries had isotopic compositions derived from the hatchery food which were distinctively different from those derived from the natural prey sources. Those hatchery signals were retained for months after release, raising the possibility to distinguish hatchery-reared yearlings and similarly sized naturally reproduced lake trout based on isotopic compositions. Addition of a third-isotope resulted in mixing model results that confirmed round goby have become an important component of lake trout diet and may be overtaking alewife as a prey resource.

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.

Isotopically distinct reservoirs in the solar nebula: Isotope anomalies in Vigarano meteorite inclusions

NASA Technical Reports Server (NTRS)

Loss, R. D.; Lugmair, G. W.; Davis, A. M.; Macpherson, G. J.

1994-01-01

The isotopic compositions of Mg, Ca, Ti, Cr, Zn, Sr, Ba, Nd, and Sm were measured in four relatively unaltered refractory inclusions from the Vigarano carbonaceous chondrite meteorite. Three of the inclusions (USNM 1623-2, 1623-3, and 1623-8) show similar Mg, Ca, Ti, and Cr isotopic compositions to those found in most inclusions in the Allende carbonaceous chondrite. This indicates that these Vigarano inclusions sampled the same isotopic reservoirs as the majority of the Allende inclusions that isotope signatures in the latter were not significantly modified by the secondary alteration that permeates most Allende inclusions. In contrast, inclusion 1623-5 has large deficits in Mg-26, Ca-48, and Ti-50 and small but distinct Cr-54, Zn-66, Sr-84, Ba-135, Ba-137, and Sm-144 anomalies. The magnitudes of these unusual anomalies in the refractory elements are within analytical uncertainty of those found in the Allende 'FUN" inclusion C1, yet 1623-5 has a very different bulk chemical composition from C1. The fact that 1623-5 and C1 have identical isotopic anomalies yet have significantly distinct major and trace element contents provide convincing evidence for the presence of isotopically distinct reservoirs in the early solar system.

The role of stable isotopes in understanding rainfall ...

EPA Pesticide Factsheets

The isotopic composition of water transmitted by the canopy as throughfall or stemflow reflects important hydrologic processes occurring in the canopy. A synthesis of the literature shows that complex spatiotemporal variations of isotopic composition are created by canopy interception. As a whole, the studies suggest a set of controlling factors including fractionation, exchange among liquid and vapor phase water, and spatiotemporal redistribution along varying canopy flowpaths. However, our limited understanding of physical processes and water routing in the canopy limits the ability to discern all details for predicting interception isotope effects. We suggest that the isotopic composition of throughfall and stemflow may be the key to improve our understanding of water storage and transport in the canopy, similar to how isotopic analysis contributed to progress in our understanding of watershed runoff processes. While interception isotope effects have largely been studied under the premise that they are a source of error, previous works also indicate a wide range of possible interactions that intercepted water may have with the canopy and airspace. We identify new research questions that may be answered by stable isotopes as a path forward in examining and generalizing small-scale interception processes that could facilitate integration of interception into watershed ecohydrological concepts. Evaporation from forest canopies (interception loss) is a prominent

Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

NASA Astrophysics Data System (ADS)

Magdas, D. A.; Cristea, G.; Cordea, D. V.; Bot, A.; Puscas, R.; Radu, S.; Mirel, V.; Mihaiu, M.

2013-11-01

Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ18O and δ2H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ18O and δ2H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.

Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

NASA Astrophysics Data System (ADS)

Brookman, Tom H.; Ambrose, Stanley H.

2012-09-01

Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Partitioning evapotranspiration via continuous sampling of water vapor isotopes over common row crops and candidate biofuel crops.

NASA Astrophysics Data System (ADS)

Miller, J. N.; Black, C. K.; Bernacchi, C.

2014-12-01

Global demand for renewable energy is accelerating land conversion from common row crops such as maize and soybean to cellulosic biofuel crops such as miscanthus and switchgrass. This land conversion is expected to alter ecohydrology via changes in evapotranspiration (ET). However, the direction in which evapotranspiration will shift, either partitioning more moisture through soil evaporation (E) or through plant transpiration (T) is uncertain. To investigate how land conversion from maize to miscanthus affects ET partitioning we measured the isotopic composition of water vapor via continuous air sampling. We obtained continuous diurnal measurements of δ2H and δ18O for miscanthus and maize on multiple days over the course of the growing season. Water vapor isotopes drawn from two heights were measured at 2 Hz using a cavity ringdown spectrometer and partitioned into components of E and T using a simple mixing equation. A second approach to partitioning was accomplished by subtracting transpiration measurements, obtained through sap flow sensors, from total ET, measured via eddy covariance. Preliminary results reveal that both methods compare favorably and that transpiration dominates variations in ET in miscanthus fields more so than in fields of maize.

C, N, and O Isotopic Heterogeneities in Low-density Supernova Graphite Grains from Orgueil

NASA Astrophysics Data System (ADS)

Groopman, Evan; Bernatowicz, Thomas; Zinner, Ernst

2012-07-01

We report on the results of NanoSIMS isotope imaging of low-density supernova graphite grains from the Orgueil meteorite. 70 nm thick microtomed sections of three supernova graphite grains were deposited on Si wafers and isotopically imaged in the NanoSIMS. These sections contain hotspots of excesses in 18O and 15N, which are spatially well correlated, and are likely carried by internal TiC subgrains. These hotspots are considerably more enriched in 18O and 15N than the host graphite grain. Correlations between 18O and 15N excesses indicate that the grains incorporated material from the He/C supernova zone. Isotope images of the surfaces of some grains show heterogeneities in their N and O isotope compositions, with extreme excesses in 15N and 18O. In the microtome sections, we also observe two types of heterogeneities in the grains' C isotopic compositions: smooth, radial gradients in 12C/13C, with this ratio trending toward solar with increasing radius; and highly anomalous pockets up to 2 μm in size with 12C/13C Gt solar that are located near the centers of the grain sections. Partial isotopic equilibration does not likely explain the C isotopic heterogeneities. These grains and their constituent parts probably formed in a stellar environment with changing isotopic composition.

Correlated microanalysis of zircon: Trace element, δ 18O, and U-Th-Pb isotopic constraints on the igneous origin of complex >3900 Ma detrital grains

NASA Astrophysics Data System (ADS)

Cavosie, Aaron J.; Valley, John W.; Wilde, Simon A.; E. I. M. F.

2006-11-01

The origins of >3900 Ma detrital zircons from Western Australia are controversial, in part due to their complexity and long geologic histories. Conflicting interpretations for the genesis of these zircons propose magmatic, hydrothermal, or metamorphic origins. To test the hypothesis that these zircons preserve magmatic compositions, trace elements [rare earth elements (REE), Y, P, Th, U] were analyzed by ion microprobe from a suite of >3900 Ma zircons from Jack Hills, Western Australia, and include some of the oldest detrital zircons known (4400-4300 Ma). The same ˜20 μm domains previously characterized for U/Pb age, oxygen isotope composition (δ 18O), and cathodoluminescence (CL) zoning were specifically targeted for analysis. The zircons are classified into two types based on the light-REE (LREE) composition of the domain analyzed. Zircons with Type 1 domains form the largest group (37 of 42), consisting of grains that preserve evolved REE compositions typical of igneous zircon from crustal rocks. Grains with Type 1 domains display a wide range of CL zoning patterns, yield nearly concordant U/Pb ages from 4400 to 3900 Ma, and preserve a narrow range of δ 18O values from 4.7‰ to 7.3‰ that overlap or are slightly elevated relative to mantle oxygen isotope composition. Type 1 domains are interpreted to preserve magmatic compositions. Type 2 domains occur in six zircons that contain spots with enriched light-REE (LREE) compositions, here defined as having chondrite normalized values of La N > 1 and Pr N > 10. A subset of analyses in Type 2 domains appear to result from incorporation of sub-surface mineral inclusions in the analysis volume, as evidenced by positively correlated secondary ion beam intensities for LREE, P, and Y, which are anti-correlated to Si, although not all Type 2 analyses show these features. The LREE enrichment also occurs in areas with discordant U/Pb ages and/or high Th/U ratios, and is apparently associated with past or present radiation damage. The enrichment is not attributed to hydrothermal alteration, however, as oxygen isotope ratios in Type 2 domains overlap with magmatic values of Type 1 domains, and do not appear re-set as might be expected from dissolution or ion-exchange processes operating at variable temperatures. Thus, REE compositions in Type 2 domains where mineral inclusions are not suspected are best interpreted to result from localized enrichment of LREE in areas with past or present radiation damage, and with a very low fluid/rock ratio. Correlated in situ analyses allow magmatic compositions in these complex zircons to be distinguished from the effects of secondary processes. These results are additional evidence for preservation of magmatic compositions in Jack Hills zircons, and demonstrate the benefits of detailed imaging in studies of complicated detrital zircons of unknown origin. The data reported here support previous interpretations that the majority of >3900 Ma zircons from the Jack Hills have an origin in evolved granitic melts, and are evidence for the existence of continental crust very early in Earth's history.

Strontium isotopes reveal weathering processes in lateritic covers in southern China with implications for paleogeographic reconstructions

PubMed Central

Wei, Xiao; Wang, Shijie; Ji, Hongbing; Shi, Zhenhua

2018-01-01

The isotope ratios of Sr are useful tracers for studying parent material sources, weathering processes, and biogeochemical cycling. Mineralogical and geochemical investigations of two lateritic weathering covers, in an area close to the Tropic of Cancer (Guangxi Province, southern China), were undertaken to study the regional weathering processes and Sr isotopic sources. We found that weathering and decomposition of Rb- and Sr-bearing minerals change the Sr isotopic composition in weathering products (lateritic soils). Weathering of illite lowered the 87Sr/86Sr ratio whereas dissolving and leaching of carbonate minerals increased the 87Sr/86Sr ratio. An Fe nodular horizon is widely developed on the top of the weathering covers in the studied area and it differs from the lateritic soil horizon in mineral composition, construction, and elemental concentration. Furthermore, both Fe2O3 and P2O5 (concentrations) are negatively correlated with the 87Sr/86Sr ratios, suggesting fixation of apatite by Fe oxides is a controlling factor of the Sr isotopic composition in the Fe nodular horizon. The 87Sr/86Sr and Nb/Sr ratios imply the contents and proportions of Fe nodules and clay are critical in controlling the changes of Sr isotopic composition in the Fe nodular horizon. The two stages of the weathering process of carbonate rocks are revealed by the87Sr/86Sr versus Nb/Sr diagram. The 87Sr/86Sr and Rb/Sr ratios suggest that Sr isotopes in the weathering covers within the studied area are derived mainly from parent rock weathering and that the contributions from allothogenic Sr isotopes are limited. A comparison of Sr isotopic composition signatures in the weathering covers of the studied area and Guizhou Province provided insight into the Sr isotopic source and paleogeographic evolution of southern China. From the Permian to the Triassic, the continental fragment sources of the South China sedimentary basin changed significantly. In the Permian, Southern China presented the paleogeographic pattern that the north was higher (in elevation) than the south. PMID:29373592

Strontium isotopes reveal weathering processes in lateritic covers in southern China with implications for paleogeographic reconstructions.

PubMed

Wei, Xiao; Wang, Shijie; Ji, Hongbing; Shi, Zhenhua

2018-01-01

The isotope ratios of Sr are useful tracers for studying parent material sources, weathering processes, and biogeochemical cycling. Mineralogical and geochemical investigations of two lateritic weathering covers, in an area close to the Tropic of Cancer (Guangxi Province, southern China), were undertaken to study the regional weathering processes and Sr isotopic sources. We found that weathering and decomposition of Rb- and Sr-bearing minerals change the Sr isotopic composition in weathering products (lateritic soils). Weathering of illite lowered the 87Sr/86Sr ratio whereas dissolving and leaching of carbonate minerals increased the 87Sr/86Sr ratio. An Fe nodular horizon is widely developed on the top of the weathering covers in the studied area and it differs from the lateritic soil horizon in mineral composition, construction, and elemental concentration. Furthermore, both Fe2O3 and P2O5 (concentrations) are negatively correlated with the 87Sr/86Sr ratios, suggesting fixation of apatite by Fe oxides is a controlling factor of the Sr isotopic composition in the Fe nodular horizon. The 87Sr/86Sr and Nb/Sr ratios imply the contents and proportions of Fe nodules and clay are critical in controlling the changes of Sr isotopic composition in the Fe nodular horizon. The two stages of the weathering process of carbonate rocks are revealed by the87Sr/86Sr versus Nb/Sr diagram. The 87Sr/86Sr and Rb/Sr ratios suggest that Sr isotopes in the weathering covers within the studied area are derived mainly from parent rock weathering and that the contributions from allothogenic Sr isotopes are limited. A comparison of Sr isotopic composition signatures in the weathering covers of the studied area and Guizhou Province provided insight into the Sr isotopic source and paleogeographic evolution of southern China. From the Permian to the Triassic, the continental fragment sources of the South China sedimentary basin changed significantly. In the Permian, Southern China presented the paleogeographic pattern that the north was higher (in elevation) than the south.

Stable isotope compositions of waters in the Great Basin, United States 3. Comparison of groundwaters with modern precipitation

USGS Publications Warehouse

Smith, G.I.; Friedman, I.; Veronda, G.; Johnson, C.A.

2002-01-01

Groundwater samples from wells and springs, scattered over most of the Great Basin province, were collected and analyzed for their isotopic makeup. They were augmented by previously published isotopic data on groundwaters from southeast California and by several hundred unpublished isotopic analyses. The ratio of 2H (deuterium, D) to 1H, in water samples from valleys in parts of California, Idaho, Nevada, Oregon, and Utah, are here compared with the winter, summer, and annual isotopic compositions of precipitation falling in or near the sampled areas. The main goal of this study was to identify basins where the groundwaters have isotopic compositions that are "lighter" (depleted in the heavier isotope, D) relative to modern winter precipitation. Where these basins do not adjoin substantially higher terrain, we consider those light groundwaters to be of Pleistocene age and thus more than 10,000 years old. Where the groundwater is 10 to 19??? lighter than local winter precipitation, we consider it to be possibly an indication of Pleistocene water; where the ??D makeup is >20??? lighter, we consider it to be probably Pleistocene water. More than 80 sites underlain by waters of possible or probable Pleistocene age were identified.

Titanium and Oxygen Isotope Compositions of Individual Chondrules from Ordinary Chondrites

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Stable calcium isotope composition of a pedogenic carbonate in forested ecosystem: the case of the needle fibre calcite (NFC).

NASA Astrophysics Data System (ADS)

Milliere, Laure; Verrecchia, Eric; Gussone, Nikolaus

2014-05-01

Calcium (Ca), carbon (C) and oxygen (O) are important elements in terrestrial environment, as their biogeochemical cycles are directly related to the storage of atmospheric carbon. Nevertheless, contrarily to C and O, Ca isotope composition has been only poorly studied in the terrestrial carbonates. Needle Fibre Calcite (NFC) is one of the most common pedogenic carbonates, unless its origin is still under debate. Recent studies explain its formation by precipitation inside fungal hyphae. Due to this possible biogenic origin, NFC can be considered as a potential bridge between the biochemistry (precipitation inside organic structure) and geochemistry (pedogenic carbonate related to soil conditions) of the Ca. Thus, the study of the Ca isotope composition of NFC seem to be of first interest in order to shed light on the behaviour of Ca in terrestrial environment, especially when precipitation of secondary carbonates is involved. The sampling site is situated in the Swiss Jura Mountains and has been chosen due to a previous complete study of the C and O isotope composition of NFC in relation to the ecosystem, which represent a good precondition for the understanding of the NFC Ca isotope signatures in this context. In this study, the implication of the fungi in the origin of NFC is investigated, by comparing the Ca isotope composition of NFC and a purely physicochemical calcite cement (LCC), both precipitated in the same environment. The δ44Ca signature of NFC and LCC crystals were used to determine possible differences of the precipitation rate during their formation. NFC and LCC have similar δ18O composition and are supposed to precipitate at the same temperature (Milliere et al., 2011a). Thus the study of Ca isotope composition of NFC seems to demonstrate that the elongated shape of the calcite needle can be explained by different precipitation processes than the rhombohedric calcite crystals precipitated in the same environment; and more precisely, the specific shape of NFC could be ascribed to a growth related to fungal organic molecules or potentially inside fungal hyphae. Three microscopic morphologies of NFC, previously defined (Milliere et al., 2011a), have been also examined in order to trace the evolution of the NFC inside the soil porosity. The Ca isotope composition of the simple needles, which are supposed to be the original form of NFC are the less fractionated compared to the soil solution, whereas the Ca isotope composition of the two other microscopic morphologies, namely the simple needle with nanofibres and the simple needle with overgrowths, are more fractionated, like the LCC, indicating potentially the influence of biogenic processes in the formation of the simple needles. Milliere L, Hasinger O, Bindschedler S, Cailleau G, Spangenberg JE, Verrecchia EP. 2011a. Stable carbon and oxygen isotopic signatures of pedogenic needle fibre calcite. Geoderma 161, 74-87.