Bromine isotopic signature facilitates de novo sequencing of peptides in free-radical-initiated peptide sequencing (FRIPS) mass spectrometry.

PubMed

Nam, Jungjoo; Kwon, Hyuksu; Jang, Inae; Jeon, Aeran; Moon, Jingyu; Lee, Sun Young; Kang, Dukjin; Han, Sang Yun; Moon, Bongjin; Oh, Han Bin

2015-02-01

We recently showed that free-radical-initiated peptide sequencing mass spectrometry (FRIPS MS) assisted by the remarkable thermochemical stability of (2,2,6,6-tetramethyl-piperidin-1-yl)oxyl (TEMPO) is another attractive radical-driven peptide fragmentation MS tool. Facile homolytic cleavage of the bond between the benzylic carbon and the oxygen of the TEMPO moiety in o-TEMPO-Bz-C(O)-peptide and the high reactivity of the benzylic radical species generated in •Bz-C(O)-peptide are key elements leading to extensive radical-driven peptide backbone fragmentation. In the present study, we demonstrate that the incorporation of bromine into the benzene ring, i.e. o-TEMPO-Bz(Br)-C(O)-peptide, allows unambiguous distinction of the N-terminal peptide fragments from the C-terminal fragments through the unique bromine doublet isotopic signature. Furthermore, bromine substitution does not alter the overall radical-driven peptide backbone dissociation pathways of o-TEMPO-Bz-C(O)-peptide. From a practical perspective, the presence of the bromine isotopic signature in the N-terminal peptide fragments in TEMPO-assisted FRIPS MS represents a useful and cost-effective opportunity for de novo peptide sequencing. Copyright © 2015 John Wiley & Sons, Ltd.

Riverine dissolved lithium isotopic signatures in low-relief central Africa and their link to weathering regimes

NASA Astrophysics Data System (ADS)

Henchiri, Soufian; Gaillardet, Jérôme; Dellinger, Mathieu; Bouchez, Julien; Spencer, Robert G. M.

2016-05-01

The isotopic composition of dissolved lithium (δ7Li) near the Congo River mouth varied from 14‰ to 22‰ in 2010 and was negatively correlated to discharge. From the relationship between dissolved δ7Li and strontium isotopes, we suggest that this large variation is due to mixing of waters from two contrasting continental weathering regimes. One end-member (high δ7Li ≈ 25‰) represents waters sourced from active lateritic soils covering the periphery of the basin (Li highly sequestered into secondary mineral products) and another representing blackwater rivers (low δ7Li ≈ 5.7‰) derived from the swampy central depression where high organic matter content in water leads to congruent dissolution of the Tertiary sedimentary bedrock. This suggests that the lithium isotopic signature of tropical low-relief surfaces is not unique and traces the long-term, large-scale vertical motions of the continental crust that control geomorphological settings. This evolution should be recorded in the oceanic secular δ7Li curve.

Oxygen Isotope Signatures of Biogenic Manganese(III/IV) Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Hansel, C. M.; Wankel, S. D.

2015-12-01

Manganese (Mn) oxide minerals are pervasive throughout a number of surface earth environments as rock varnishes, ferromanganese nodules, crusts around deep-sea vents, and cave deposits among many other marine, freshwater, and terrestrial deposits. Mn(III,IV) oxides are also among the strongest sorbents and oxidants in surface earth environments and are crucial to understanding the fate of organic matter in sedimentary environments. The precipitation of Mn oxide minerals proceeds via both abiotic and biotic oxidation pathways, the latter due to the indirect or direct activity of Mn(II)- oxidizing microorganisms, including bacteria and fungi. Although the precipitation of Mn oxides is believed to be primarily controlled by Mn(II)-oxidizing organisms in most surface earth environments, confirmation of this generally held notion has remained illusive and limits our understanding of their formation on Earth and beyond (e.g., Mars). Previous work provided evidence that O atom incorporation by specific Mn oxidation pathways may exhibit unique and predictable isotopic fractionation. In this study, we expand upon this evidence by measuring the oxygen isotope signature of several biogenic and abiogenic Mn oxide minerals synthesized under a range of oxygen-18 labeled water. These results allow us to determine the relative amount oxygen atoms derived from water and molecular oxygen that are incorporated in the oxide and shed light on corresponding isotope fractionation factors. Additionally, we show that, once precipitated, Mn oxide isotope signatures are robust with respect to aqueous oxygen isotope exchange. The study provides a foundation on which to study and interpret Mn oxides in natural environments and determine which environmental controls may govern Mn(II) oxidation.

Isotopic source signatures: Impact of regional variability on the δ13CH4 trend and spatial distribution

NASA Astrophysics Data System (ADS)

Feinberg, Aryeh I.; Coulon, Ancelin; Stenke, Andrea; Schwietzke, Stefan; Peter, Thomas

2018-02-01

The atmospheric methane growth rate has fluctuated over the past three decades, signifying variations in methane sources and sinks. Methane isotopic ratios (δ13CH4) differ between emission categories, and can therefore be used to distinguish which methane sources have changed. However, isotopic modelling studies have mainly focused on uncertainties in methane emissions rather than uncertainties in isotopic source signatures. We simulated atmospheric δ13CH4 for the period 1990-2010 using the global chemistry-climate model SOCOL. Empirically-derived regional variability in the isotopic signatures was introduced in a suite of sensitivity simulations. These simulations were compared to a baseline simulation with commonly used global mean isotopic signatures. We investigated coal, natural gas/oil, wetland, livestock, and biomass burning source signatures to determine whether regional variations impact the observed isotopic trend and spatial distribution. Based on recently published source signature datasets, our calculated global mean isotopic signatures are in general lighter than the commonly used values. Trends in several isotopic signatures were also apparent during the period 1990-2010. Tropical livestock emissions grew during the 2000s, introducing isotopically heavier livestock emissions since tropical livestock consume more C4 vegetation than midlatitude livestock. Chinese coal emissions, which are isotopically heavy compared to other coals, increase during the 2000s leading to higher global values of δ13CH4 for coal emissions. EDGAR v4.2 emissions disagree with the observed atmospheric isotopic trend for almost all simulations, confirming past doubts about this emissions inventory. The agreement between the modelled and observed δ13CH4 interhemispheric differences improves when regional source signatures are used. Even though the simulated results are highly dependent on the choice of methane emission inventories, they emphasize that the commonly used global mean signatures are inadequate. Regional isotopic signatures should be employed in modelling studies that try to constrain methane emission inventories.

Spatially Resolved Genomic, Stable Isotopic, and Lipid Analyses of a Modern Freshwater Microbialite from Cuatro Ciénegas, Mexico

PubMed Central

Nitti, Anthony; Daniels, Camille A.; Siefert, Janet; Souza, Valeria; Hollander, David

2012-01-01

Abstract Microbialites are biologically mediated carbonate deposits found in diverse environments worldwide. To explore the organisms and processes involved in microbialite formation, this study integrated genomic, lipid, and both organic and inorganic stable isotopic analyses to examine five discrete depth horizons spanning the surface 25 mm of a modern freshwater microbialite from Cuatro Ciénegas, Mexico. Distinct bacterial communities and geochemical signatures were observed in each microbialite layer. Photoautotrophic organisms accounted for approximately 65% of the sequences in the surface community and produced biomass with distinctive lipid biomarker and isotopic (δ13C) signatures. This photoautotrophic biomass was efficiently degraded in the deeper layers by heterotrophic organisms, primarily sulfate-reducing proteobacteria. Two spatially distinct zones of carbonate precipitation were observed within the microbialite, with the first zone corresponding to the phototroph-dominated portion of the microbialite and the second zone associated with the presence of sulfate-reducing heterotrophs. The coupling of photoautotrophic production, heterotrophic decomposition, and remineralization of organic matter led to the incorporation of a characteristic biogenic signature into the inorganic CaCO3 matrix. Overall, spatially resolved multidisciplinary analyses of the microbialite enabled correlations to be made between the distribution of specific organisms, precipitation of carbonate, and preservation of unique lipid and isotopic geochemical signatures. These findings are critical for understanding the formation of modern microbialites and have implications for the interpretation of ancient microbialite records. Key Words: Microbial ecology—Microbe-mineral interactions—Microbial mats—Stromatolites—Genomics. Astrobiology 12, 685–698. PMID:22882001

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

NASA Astrophysics Data System (ADS)

Nowak-Lovato, K.

2014-12-01

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

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.

All fats are not equal: Considerations when using fatty acid biomarkers in compound-specific stable isotope soil and sediment tracing

NASA Astrophysics Data System (ADS)

Reiffarth, Dominic; Petticrew, Ellen; Owens, Philip; Lobb, David

2013-04-01

The development of cost-effective, convenient and reliable methods for tracing sediment movement will help establish water security. The use of compound-specific stable isotopes (CSSIs) has seen limited, small-scale applications, often in watersheds exhibiting exotic and highly diverse vegetation types. The CSSI tracing technique relies on the detection and transport of naturally occurring organics of plant origin (biomarkers); the biomarkers of interest are produced by flora, deposited on the soil and potentially mobilized along with soil particles. In part, the uniqueness of a biomarker is dependent on its biological pathway. As a plant fixes CO2-its primary source of carbon for building larger organic molecules-discrimination against the heavier 13C isotope leads to an enrichment of 12C. The more complex the biological pathway the biomarker has been subjected to, the more discrimination and unique isotopic signature the biomarker exhibits. Successfully implementing CSSI tracing requires recognizing: (i) factors contributing to the natural variability of the isotopic signature (ii) the suitability of a biomarker and (iii) factors affecting sensitivity during analysis. Considering the relatively low input of suitable organic biomarkers into the soil and degree of signal dispersion, care must be taken to isolate and correctly identify biomarkers, particularly where vegetation types show low variability and where long-range transport occurs. Research is currently being conducted in the Horsefly River (British Columbia, Canada) and South Tobacco Creek (Manitoba, Canada) watersheds; the research seeks to address some of these concerns, particularly in a temperate climate where exotic vegetation types are not common and variability is expected to be low.

Isotope tracing of Hg pollution from artisanal small scale gold mining in an aquatic ecosystem of Amapá, Brazil

NASA Astrophysics Data System (ADS)

Adler Miserendino, R.; Silbergeld, E. K.; Guimarães, J. D.; Ghosh, S.; Bergquist, B. A.

2010-12-01

Artisinal small scale gold mining (ASGM) is a central economic activity throughout the developing world. It is both a poverty driven and poverty alleviating process; however, ASGM leads to extensive pollution of waterways through the use of Hg to extract gold from deposits. There have been many studies conducted in the Amazon showing elevated levels of Hg in fish and sediment downstream of ASGM sites; however, the debate continues about the contribution of Hg from ASGM versus other potential sources of Hg. In this study, we investigate whether Hg stable isotope analysis can be used to trace mercury pollution from an ASGM site through an aquatic ecosystem in Amapá, Brazil. We measured the Hg isotopic composition of sediment cores from two lakes, only one of which was heavily impacted by the use of elemental Hg in ASGM, as well as from grab samples at the AGSM site and upstream and downstream from the AGSM site along the river which connects the polluted lake to the ASGM site. Hg from all samples were trapped via combustion using the Leeman Labs Hydra-C mercury analyzer and analyzed for both mass-independent and mass-dependent signatures using cold vapor multi-collector inductively coupled plasma mass spectrometry (CV-MC-ICP-MS). Detectable variations in the Hg isotopic signatures were apparent across our field sites, suggesting stable isotopic analysis has great potential to trace contamination pathways in waterways. Preliminary data demonstrate Hg from the ASGM site has unique isotopic signatures that are seen downstream. However, the impacted lake sediments do not have the mining signature despite having three times more Hg than the non-impacted lake. Based on this data, it may be possible to trace Hg from ASGM and assess whether it is impacting local ecosystems and food webs. Hair and soil samples will also be discussed. This demonstration is essential for the broader application of these tools for understanding and applying Hg isotopic analysis in other contexts. This information may also be useful to help reduce Hg exposure of highly vulnerable populations exposed to Hg from ASGM through these aquatic networks in Amapá, Brazil.

A dual origin for water in carbonaceous asteroids revealed by CM chondrites

NASA Astrophysics Data System (ADS)

Piani, Laurette; Yurimoto, Hisayoshi; Remusat, Laurent

2018-04-01

Carbonaceous asteroids represent the principal source of water in the inner Solar System and might correspond to the main contributors for the delivery of water to Earth. Hydrogen isotopes in water-bearing primitive meteorites, for example carbonaceous chondrites, constitute a unique tool for deciphering the sources of water reservoirs at the time of asteroid formation. However, fine-scale isotopic measurements are required to unravel the effects of parent-body processes on the pre-accretion isotopic distributions. Here, we report in situ micrometre-scale analyses of hydrogen isotopes in six CM-type carbonaceous chondrites, revealing a dominant deuterium-poor water component (δD = -350 ± 40‰) mixed with deuterium-rich organic matter. We suggest that this deuterium-poor water corresponds to a ubiquitous water reservoir in the inner protoplanetary disk. A deuterium-rich water signature has been preserved in the least altered part of the Paris chondrite (δDParis ≥ -69 ± 163‰) in hydrated phases possibly present in the CM rock before alteration. The presence of the deuterium-enriched water signature in Paris might indicate that transfers of ice from the outer to the inner Solar System were significant within the first million years of the history of the Solar System.

Recharge processes in an alluvial aquifer riparian zone, Norman Landfill, Norman, Oklahoma, 1998-2000

USGS Publications Warehouse

Scholl, Martha; Christenson, Scott; Cozzarelli, Isabelle; Ferree, Dale; Jaeshke, Jeanne

2005-01-01

Analyses of stable isotope profiles (d2H and d18O) in the saturated zone, combined with water-table fluctuations, gave a comprehensive picture of recharge processes in an alluvial aquifer riparian zone. At the Norman Landfill U.S. Geological Survey Toxic Substances Hydrology research site in Norman, Oklahoma, recharge to the aquifer appears to drive biodegradation, contributing fresh supplies of electron acceptors for the attenuation of leachate compounds from the landfill. Quantifying recharge is a first step in studying this process in detail. Both chemical and physical methods were used to estimate recharge. Chemical methods included measuring the increase in recharge water in the saturated zone, as defined by isotopic signature, specific conductance or chloride measurements; and infiltration rate estimates using storm event isotopic signatures. Physical methods included measurement of water-table rise after individual rain events and on an approximately monthly time scale. Evapotranspiration rates were estimated using diurnal watertable fluctuations; outflux of water from the alluvial aquifer during the growing season had a large effect on net recharge at the site. Evaporation and methanogenesis gave unique isotopic signatures to different sources of water at the site, allowing the distinction of recharge using the offset of the isotopic signature from the local meteoric water line. The downward movement of water from large, isotopically depleted rain events in the saturated zone yielded recharge rate estimates (2.2 - 3.3 mm/day), and rates also were determined by observing changes in thickness of the layer of infiltrated recharge water at the top of the saturated zone (1.5 - 1.6 mm/day). Recharge measured over 2 years (1998-2000) in two locations at the site averaged 37 percent of rainfall, however, part of this water had only a short residence time in the aquifer. Isotopes showed recharge water entering the ground-water system in winter and spring, then being removed during the growing season by phreatophyte transpiration. Recharge timing was variable over the course of the study; July and August were the only months that had no recharge in both years. Recharge to the aquifer from the slough (wetland pond) was estimated at one location using the isotopic signature of water affected by evaporation. Recharge was correlated with the rainfall amount over the period of estimation, suggesting that recharge from the slough to the downgradient aquifer was an episodic process, corresponding to elevated water levels in the slough after large rain events.

The stable isotopes of site wide waters at an oil sands mine in northern Alberta, Canada

NASA Astrophysics Data System (ADS)

Baer, Thomas; Barbour, S. Lee; Gibson, John J.

2016-10-01

Oil sands mines have large disturbance footprints and contain a range of new landforms constructed from mine waste such as shale overburden and the byproducts of bitumen extraction such as sand and fluid fine tailings. Each of these landforms are a potential source of water and chemical release to adjacent surface and groundwater, and consequently, the development of methods to track water migration through these landforms is of importance. The stable isotopes of water (i.e. 2H and 18O) have been widely used in hydrology and hydrogeology to characterize surface water/groundwater interactions but have not been extensively applied in mining applications, or specifically to oil sands mining in northern Alberta. A prerequisite for applying these techniques is the establishment of a Local Meteoric Water Line (LMWL) to characterize precipitation at the mine sites as well as the development of a 'catalogue' of the stable water isotope signatures of various mine site waters. This study was undertaken at the Mildred Lake Mine Site, owned and operated by Syncrude Canada Ltd. The LMWL developed from 2 years (2009/2012) of sample collection is shown to be consistent with other LMWLs in western Canada. The results of the study highlight the unique stable water isotope signatures associated with hydraulically placed tailings (sand or fluid fine tailings) and overburden shale dumps relative to natural surface water and groundwater. The signature associated with the snow melt water on reclaimed landscapes was found to be similar to ground water recharge in the region. The isotopic composition of the shale overburden deposits are also distinct and consistent with observations made by other researchers in western Canada on undisturbed shales. The process water associated with the fine and coarse tailings streams has highly enriched 2H and 18O signatures. These signatures are developed through the non-equilibrium fractionation of imported fresh river water during evaporation from cooling towers used within the raw water process circuit. This highly fractionated surface water eventually becomes part of the recycled tailings water circuit, and as a consequence it undergoes further non-equilibrium fractionation as a result of surface evaporation, leading to additional enrichment along local evaporation lines.

Stellar Origins of C-13 and N-15-Enriched Presolar SiC Grains

NASA Technical Reports Server (NTRS)

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.; Wang, Jianhua; Pignatari, Marco; Jose, Jordi; Nguyen, Ann

2016-01-01

Extreme excesses of 13 C ( C (12 C/ 13 C<10) and 15 N ( N (14 N/ 15 N< 20) in rare presolar SiC 20) in rare presolar SiClar SiC grains have been considered diagnostic of an origin in classical novae [1], though an origin in core-collapse supernovae (CCSNe) has also been proposed [2]. We report multi-element isotopic data for 19 13 C- and 15 N-enriched presolar SiC grains(12 C/13 C<16 and 14 N/ 15 N<150) from an acid resistant residue of the Murchison meteorite. These grains are enriched in 13 C and15 N, but with quite diverse Si isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures.

Latitudinal Trends in Stable Isotope Signatures of Northeast Atlantic Rhodoliths

NASA Astrophysics Data System (ADS)

Hofmann, Laurie

2017-04-01

Rhodoliths are free-living calcifying red algae that form extensive beds in shallow marine benthic environments (< 200 m) that provide important habitats and nurseries for marine organisms and contribute to carbonate sediment accumulation. There is growing concern that these organisms are sensitive to global climate change, which will have important consequences for coastal productivity and stability. Despite their significance and sensitivity, their basic photosynthetic and calcification mechanisms are not well understood. The goal of this study was to determine the plasticity of dissolved inorganic carbon (DIC) uptake mechanisms of rhodoliths along a latitudinal gradient in the Northeast (NE) Atlantic using natural stable isotope signatures. The delta 13C signature of macroalgae can be used to provide an indication of the preferred inorganic carbon source (CO2 vs. HCO3-). Here we present the total and organic delta 13C signatures of NE Atlantic rhodoliths with respect to changing temperature and light along the latitudinal gradient from the Canary Islands to Spitsbergen. A decreasing trend in delta 13C signatures with increasing latitude suggests that rhodoliths rely solely on CO2 as an inorganic carbon source at mid latitudes, while those at low latitudes may be able to utilize HCO3-. Polar rhodoliths deviate from this trend, suggesting they may have unique physiological mechanisms related to inorganic carbon acquisition and assimilation, which may have important implications for calcification in an environment undergoing rapid changing ocean chemistry.

146Sm-142Nd systematics measured in enstatite chondrites reveals a heterogeneous distribution of 142Nd in the solar nebula.

PubMed

Gannoun, Abdelmouhcine; Boyet, Maud; Rizo, Hanika; El Goresy, Ahmed

2011-05-10

The short-lived (146)Sm-(142)Nd chronometer (T(1/2) = 103 Ma) is used to constrain the early silicate evolution of planetary bodies. The composition of bulk terrestrial planets is then considered to be similar to that of primitive chondrites that represent the building blocks of rocky planets. However for many elements chondrites preserve small isotope differences. In this case it is not always clear to what extent these variations reflect the isotope heterogeneity of the protosolar nebula rather than being produced by the decay of parent isotopes. Here we present Sm-Nd isotopes data measured in a comprehensive suite of enstatite chondrites (EC). The EC preserve (142)Nd/(144)Nd ratios that range from those of ordinary chondrites to values similar to terrestrial samples. The EC having terrestrial (142)Nd/(144)Nd ratios are also characterized by small (144)Sm excesses, which is a pure p-process nuclide. The correlation between (144)Sm and (142)Nd for chondrites may indicate a heterogeneous distribution in the solar nebula of p-process matter synthesized in supernovae. However to explain the difference in (142)Nd/(144)Nd ratios, 20% of the p-process contribution to (142)Nd is required, at odds with the value of 4% currently proposed in stellar models. This study highlights the necessity of obtaining high-precision (144)Sm measurements to interpret properly measured (142)Nd signatures. Another explanation could be that the chondrites sample material formed in different pulses of the lifetime of asymptotic giant branch stars. Then the isotope signature measured in SiC presolar would not represent the unique s-process signature of the material present in the solar nebula during accretion.

146Sm–142Nd systematics measured in enstatite chondrites reveals a heterogeneous distribution of 142Nd in the solar nebula

PubMed Central

Gannoun, Abdelmouhcine; Boyet, Maud; Rizo, Hanika; El Goresy, Ahmed

2011-01-01

The short-lived 146Sm–142Nd chronometer (T1/2 = 103 Ma) is used to constrain the early silicate evolution of planetary bodies. The composition of bulk terrestrial planets is then considered to be similar to that of primitive chondrites that represent the building blocks of rocky planets. However for many elements chondrites preserve small isotope differences. In this case it is not always clear to what extent these variations reflect the isotope heterogeneity of the protosolar nebula rather than being produced by the decay of parent isotopes. Here we present Sm–Nd isotopes data measured in a comprehensive suite of enstatite chondrites (EC). The EC preserve 142Nd/144Nd ratios that range from those of ordinary chondrites to values similar to terrestrial samples. The EC having terrestrial 142Nd/144Nd ratios are also characterized by small 144Sm excesses, which is a pure p-process nuclide. The correlation between 144Sm and 142Nd for chondrites may indicate a heterogeneous distribution in the solar nebula of p-process matter synthesized in supernovae. However to explain the difference in 142Nd/144Nd ratios, 20% of the p-process contribution to 142Nd is required, at odds with the value of 4% currently proposed in stellar models. This study highlights the necessity of obtaining high-precision 144Sm measurements to interpret properly measured 142Nd signatures. Another explanation could be that the chondrites sample material formed in different pulses of the lifetime of asymptotic giant branch stars. Then the isotope signature measured in SiC presolar would not represent the unique s-process signature of the material present in the solar nebula during accretion. PMID:21515828

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

USGS Publications Warehouse

Borrok, D.M.; Nimick, D.A.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles. Average ??66Zn and ??65Cu values for streams varied from +0.02??? to +0.46??? and -0.7??? to +1.4???, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ???0.3??? (66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.

Evaluation of Crayfish Growth and Assimilation on Animal and Detrital Food Sources: Are Stable Isotopes Telling the Whole Story?

NASA Astrophysics Data System (ADS)

Warren, L. L.; Wotton, R. S.; Wharton, G.; Fortino, K.; Ulseth, A. J.; Hershey, A. E.

2005-05-01

Crayfish are the dominant omnivores of many ecosystems and have strong direct and indirect effects through predation and organic matter processing. Despite this, the importance of detritus for crayfish production is poorly understood. We conducted a laboratory experiment where we fed crayfish an ad. lib. diet of only detritus, only fish tissue, or a mixture the above. The crayfish grew more on a diet which contained meat but growth was highly correlated with the amount of food consumed. The least amount of food was consumed in the detritus treatment, an intermediate amount of food in the meat treatment, and the most food in the mix treatment, suggesting that consumption of detritus by crayfish is related to more than simply the abundance of detritus. Nonetheless, isotopic evidence indicated that the crayfish were not assimilating leaf C and N. Additionally, crayfish in the meat containing treatments never exceeded the del 15N signature of their source by the approximately 3 units expected following fractionation, despite coming to isotopic equilibrium with their source. These findings suggest that crayfish may fractionate C and N uniquely. This difference may have to do with gut microbial activity and may have implications for the interpretation crayfish isotopic signatures.

East Asian origin of central Greenland last glacial dust: just one possible scenario?

NASA Astrophysics Data System (ADS)

Újvári, Gábor; Stevens, Thomas; Svensson, Anders; Klötzli, Urs Stephan; Manning, Christina; Németh, Tibor; Kovács, János

2016-04-01

Dust in Greenland ice cores is used to reconstruct the activity of dust emitting regions and atmospheric circulation for the last glacial period. However, the source dust material to Greenland over this period is the subject of considerable uncertainty. Here we use new clay mineral and Sr-Nd isotopic data from eleven loess samples collected around the Northern Hemisphere and compare the 87Sr/86Sr and 143Nd/144Nd isotopic signatures of fine (<10 μm) separates to existing Greenland ice core dust data (GISP2, GRIP; [1]; [2]). Smectite contents and kaolinite/chlorite (K/C) ratios allow exclusion of continental US dust emitting regions as potential sources, because of the very high (>3.6) K/C ratios and extremely high (>~70%) smectite contents. At the same time, Sr-Nd isotopic compositions demonstrate that ice core dust isotopic compositions can be explained by East Asian (Chinese loess) and/or Central/East Central European dust contributions. Central/East Central European loess Sr-Nd isotopic compositions overlap most with ice core dust, while the Sr isotopic signature of Chinese loess is slightly more radiogenic. Nevertheless, an admixture of 90‒10 % from Chinese loess and circum-Pacific volcanic material would also account for the Sr‒Nd isotopic ratios of central Greenland LGM dust. At the same time, sourcing of ice core dust from Alaska, continental US and NE Siberia seems less likely based on Sr and Nd isotopic signatures. The data demonstrate that currently no unique source discrimination for Greenland dust is possible using both published and our new data [3]. Thus, there is a need to identify more diagnostic tracers. Based on initial Hf isotope analyses of fine separates of three loess samples (continental US, Central Europe, China), an apparent dependence of Hf isotopic signatures on the relative proportions of radiogenic clay minerals (primarily illite) was found, as these fine dust fractions are apparently zircon-free. The observed difference between major potential source regions in 176Hf/177Hf that reach several ɛHf units and the first order clay mineralogy dependence of Hf isotopic signatures means there is strong potential for distinguishing between the two hypothesized Greenland dust sources using Hf isotopes [3]. [1] Biscaye P.E., Grousset F.E., Revel M., Van der Gaast S., Zielinski G.A., Vaars A., Kukla G. (1997). Asian provenance of glacial dust (stage 2) in the Greenland Ice Sheet Project 2 Ice Core, Summit, Greenland. Journal of Geophysical Research 102, 26765-26781. [2] Svensson A., Biscaye P.E., Grousset F.E. (2000) Characterization of late glacial continental dust in the Greenland Ice Core Project ice core. Journal of Geophysical Research 105, 4637-4656. [3] Újvári G., Stevens T., Svensson A., Klötzli U.S., Manning, C., Németh T., Kovács J., Sweeney M.R., Gocke M., Wiesenberg G.L.B., Markovic S.B., Zech M. (in press). Two possible source regions for Central Greenland last glacial dust. Geophysical Research Letters, doi: 10.1002/2015GL066153.

Using Nd and Sr isotopes to trace dust and volcanic inputs to soils on French Guadeloupe Island

NASA Astrophysics Data System (ADS)

Guo, J.; Pereyra, Y.; Ma, L.; Gaillardet, J.; Sak, P. B.; Bouchez, J.

2017-12-01

Soil is at the central part of the Critical Zone for its important roles in sustaining ecosystems and agriculture. At French Guadeloupe, a tropical humid volcanic island, previous studies have shown that the mineral nutrient elements such as K, Na, Ca, and Mg are highly depleted in the surface soil. And mineral nutrients introduced by dusts are an important mineral nutrient source for vegetation growth in this area. It is important to understand and quantify the sources of the mineral dust added to surface soils. Nd isotope ratios, due to their distinct signatures between two unique end-members in soils for this area: the young volcanic areas like Guadeloupe and the dust source region from the old continental shields like Sahara Desert, can be a robust tracer to understand this critical process. Nevertheless, Sr isotope ratios can trace the inputs of marine aerosols. Here we present a new Nd isotope study on Guadeloupe soil depth profiles, combined with previous Sr isotope data, to fingerprint the sources of dust and volcanic inputs into soils. Soil samples from three surface profiles (0 - 1000cm deep) at different locations of the Guadeloupe Island were systematically analyzed. The results show distinct depth variations for Nd isotope signature along profiles. For all profiles, deep soils are relatively consisted with bedrock value (ɛNd: 5.05). But in surface soils (0-600cm), unlike Sr isotope ratios that are significantly modified by marine aerosol input, Nd isotope ratios show similar decrease (to ɛNd:-10) and frequent fluctuations toward the surface, suggesting dust is the dominant source of Nd in these soils. This conclusion is further supported by REE and other trace element data. Thus, with a simplified two end-member model, Sahara dust contributes the Nd percentages in soils varying from 10.7% at the deepest profiles to 69.5% on surface, showing a significant amount of Nd on the surface soil came from dust source. The deep soil profiles are also characterized by the presence of Nd isotope spikes with negative values, suggesting dust signatures at depth. Such a feature could be related to the presence of a paleo-soil surface at the spike depth that was buried by later volcanic eruption. Both Nd and Sr isotopes hence show dust and volcanic inputs are important factors for soil developments on French Guadeloupe Island.

MIXING MODELS IN ANALYSES OF DIET USING MULTIPLE STABLE ISOTOPES: A CRITIQUE

EPA Science Inventory

Stable isotopes have become widely used in ecology to quantify the importance of different sources based on their isotopic signature. One example of this has been the determination of food webs, where the isotopic signatures of a predator and various prey items can be used to de...

Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird

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

Pearson, Scott, F.; Levey, Douglas, J.; Greenberg, Catheryn, H.

2003-02-28

Pearson, S.F., D.J. Levey, C.H. Greenberg, and C.M. del Rio. 2003. Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird. Oecologia. 135:516-523. The use of stable isotopes to infer diet requires quantifying the relationship between diet and tissues and, in particular, knowing of how quickly isotopes turnover in different tissues and how isotopic concentrations of different food components change (discriminate) when incorporated into consumer tissues. We used feeding trials with wild-caught yellow-rumped warblers (Dendroica coronata) to determine d15N and d13C turnover rates for blood, d15N and d13C diet-tissue discrimination factors, andmore » diet-tissue relationships for blood and feathers. After 3 weeks on a common diet, 36 warblers were assigned to one of four diets differing in the relative proportion of fruit and insects. Plasma half-life estimates ranged from 0.4 to 0.7 days for d13C and from 0.5 to 1.7 days for d15N. Half-life did not differ among diets. Whole blood half-life for d13C ranged from 3.9 to 6.1 days. Yellow-rumped warbler tissues were enriched relative to diet by 1.7.3.6% for nitrogen isotopes and by 1.2 to 4.3% for carbon isotopes, depending on tissue and diet. Consistent with previous studies, feathers were the most enriched and whole blood and plasma were the least enriched or, in the case of carbon, slightly depleted relative to diet. In general, tissues were more enriched relative to diet for birds with high percentages of insects. For all tissues, carbon and nitrogen isotope discrimination factors increased with carbon and nitrogen concentrations of diets. The isotopic signature of plasma increased linearly with the sum of the isotopic signature of the diet and the discrimination factor. Because the isotopic signature of tissues depends on both elemental concentration and isotopic signature of the diet, attempts to reconstruct diet from stable isotope signatures require mixing models that incorporate elemental concentration.« less

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.

Coupling Stable Water Isotopes in Vapor and Precipitation to Raindrop Size Distributions at a Mid-latitude Tall-tower Site to Evaluate the Role of Rain Evaporation in Boundary Layer Moisture Recycling

NASA Astrophysics Data System (ADS)

Kaushik, A.; Noone, D.

2016-12-01

The continental boundary layer moisture balance plays an important role in regulating water and energy exchange between the surface and the atmosphere, yet the mechanisms associated with moistening and drying are both poorly observed and modeled. Stable water isotope ratio measurements can provide insights into air mass origins, convection dynamics and mechanisms dominating atmosphere-land surface water fluxes. Profiles can be exploited to improve estimates of boundary layer moistening associated with evaporation of falling precipitation and contributions from surface evapotranspiration. We present two years of in situ tower-based measurements of isotope ratios of water vapor and precipitation (δD and δ18O) and raindrop size distributions from the Boulder Atmospheric Observatory (BAO) tall-tower site in Erie, Colorado. Isotope vapor measurements were made at 1 Hz with a full cycle from the surface to 300 meters recorded every 80 minutes. At the surface and 300m, water samples were collected during precipitation events and raindrop sizes were measured continuously using Parsivel instruments. We use this unique suite of measurements and, in particular, exploit the differences between the surface and 300m observations to constrain the surface layer hydrological mass balance during and after rain events, and evaluate parameterization choices for rain evaporation and moisture recycling in current isotope-enabled climate models. Aggregate raindrop size measurements showed shifts from populations of smaller raindrops at 300m to larger raindrops at the surface, contrary to what is expected for rain evaporation. Convective storms resulted in more uniform signatures between the surface and 300m, as well as longer isotope equilibration and adjustment time scales, whereas low Dexcess signatures (<9 to negative) during stratiform drizzle events were indicative of a greater degree of rain evaporation. Our observational results suggest that water vapor-rain equilibration is rarely achieved, and modification of the kinetic fractionation factor is necessary to better capture drop-size related isotope changes. This has implications not only for refining current global climate models, but also for interpreting proxy records connected to rainfall signatures that aid in understanding past hydrology.

Successful application of lead isotopes in source apportionment, legal proceedings, remediation and monitoring.

PubMed

Gulson, Brian; Korsch, Michael; Winchester, Wayne; Devenish, Matthew; Hobbs, Thad; Main, Cleve; Smith, Gerard; Rosman, Kevin; Howearth, Lynette; Burn-Nunes, Laurie; Seow, Jimmy; Oxford, Cameron; Yun, Gracie; Gillam, Lindsay; Crisp, Michelle

2012-01-01

In late 2006, the seaside community in Esperance Western Australia was alerted to thousands of native bird species dying. The source of the lead (Pb) was determined by Pb isotopes to derive from the handling of Pb carbonate concentrate through the Port, which began in July 2005. Concern was expressed for the impact of this on the community. Our objectives were to employ Pb isotope ratios to evaluate the source of Pb in environmental samples for use in legal proceedings, and for use in remediation and monitoring. Isotope measurements were undertaken of bird livers, plants, drinking water, soil, harbour sediments, air, bulk ceiling dust, gutter sludge, surface swabs and blood. The unique lead isotopic signature of the contaminating Pb carbonate enabled diagnostic apportionment of lead in samples. Apart from some soil and water samples, the proportion of contaminating Pb was >95% in the environmental samples. Lead isotopes were critical in resolving legal proceedings, are being used in the remediation of premises, were used in monitoring of workers involved in the decontamination of the storage facility, and monitoring transport of the concentrate through another port facility. Air samples show the continued presence of contaminant Pb, more than one year after shipping of concentrate ceased, probably arising from dust resuspension. Brief details of the comprehensive testing and cleanup of the Esperance community are provided along with the role of the Community. Lead isotopic analyses can provide significant benefits to regulatory agencies, interested parties, and the community where the signature is able to be characterised with a high degree of certainty. Crown Copyright © 2011. Published by Elsevier Inc. All rights reserved.

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

PubMed

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

2016-09-20

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

Carbon Monoxide Stable Isotopes: Extraction Technique Development and Urban Atmospheric Analysis

NASA Astrophysics Data System (ADS)

Vimont, Isaac Josef

We have developed an extraction system to analyze isotopes of carbon monoxide (CO). We then analyzed CO isotopes for two years at Indianapolis, IN, USA. These measurements were done at three towers, one of which measured incoming, background air into the city. We quantitatively removed the background signal and determined the urban CO mole fraction and isotopic enhancements. During the winter months, we constrained the isotopic signature and concluded that the majority of CO produced during the winter was produced by fossil fuel combustion. We found that the Indianapolis fossil fuel signature differed from that of studies done in Europe. Further, we performed a limited traffic study to look at CO isotopes from traffic. While this was not conclusive, it did support our hypothesis that a larger fraction of the Indianapolis vehicle fleet may have malfunctioning catalytic systems, which biases the isotopic results, particularly for delta18O. We used the wintertime fossil fuel isotopic signature to help constrain the summertime budget. It was hypothesized that a second source of CO was significant during the summer months. Oxidation of biogenically produced volatile organic compounds (BVOC's) was one possible source. Oxidized BVOC's were consistent with the changes between our winter and summer isotopic source signatures. We then used the isotopic signatures to determine that between zero and sixty percent of the summertime CO budget was produced from oxidized VOC's. This provided the first direct evidence of a larger percentage of urban CO being produced by oxidized VOC's.

Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

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

Maggi, F.M.; Riley, W.J.

2009-06-01

The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O productionmore » and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.« less

Water isotope partitioning and ecohydrologic separation in mixed conifer forest explored with a centrifugation water extraction method

NASA Astrophysics Data System (ADS)

Bowers, W.; Mercer, J.; Pleasants, M.; Williams, D. G.

2017-12-01

Isotopic partitioning of water within soil into tightly and loosely bound fractions has been proposed to explain differences between isotopic water sources used by plants and those that contribute to streams and ground water, the basis for the "two water worlds" hypothesis. We examined the isotope ratio values of water in trees, bulk soil, mobile water collected from soil lysimeters, stream water, and GW at three different hillslopes in a mixed conifer forest in southeastern Wyoming, USA. Hillslopes differed in aspect and topographic position with corresponding differences in surface energy balance, snowmelt timing, and duration of soil moisture during the dry summer. The isotopic results support the partitioning of water within the soil; trees apparently used a different pool of water for transpiration than that recovered from soil lysimeters and the source was not resolved with the isotopic signature of the water that was extracted from bulk soil via cryogenic vacuum distillation. Separating and measuring the isotope ratios values in these pools would test the assumption that the tightly bound water within the soil has the same isotopic signature as the water transpired by the trees. We employed a centrifugation approach to separate water within the soil held at different tensions by applying stepwise increases in rotational velocity and pressures to the bulk soil samples. Effluent and the remaining water (cryogenically extracted) at each step were compared. We first applied the centrifugation method in a simple lab experiment using sandy loam soil and separate introductions of two isotopically distinct waters. We then applied the method to soil collected from the montane hillslopes. For the lab experiment, we predicted that effluents would have distinct isotopic signatures, with the last effluent and extracted water more closely representing the isotopic signature of the first water applied. For our field samples, we predicted that the isotopic signature of the water discharged in the last centrifuge step and final extraction would more closely represent the isotopic signature of water extracted from trees. Understanding the isotopic partitioning of water within soil is important for interpreting plant water isotope values within the context of the "two water worlds" hypothesis.

Technical Report on the Behavior of Trace Elements, Stable Isotopes, and Radiogenic Isotopes During the Processing of Uranium Ore to Uranium Ore Concentrate

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

Marks, N. E.; Borg, L. E.; Eppich, G. R.

2015-07-09

The goals of this SP-1 effort were to understand how isotopic and elemental signatures behave during mining, milling, and concentration and to identify analytes that might preserve geologic signatures of the protolith ores. The impurities that are preserved through the concentration process could provide useful forensic signatures and perhaps prove diagnostic of sample origin.

Transfer of marine mercury to mountain lakes.

PubMed

Hansson, Sophia V; Sonke, Jeroen; Galop, Didier; Bareille, Gilles; Jean, Séverine; Le Roux, Gaël

2017-10-05

Stocking is a worldwide activity on geographical and historical scales. The rate of non-native fish introductions have more than doubled over the last decades yet the effect on natural ecosystems, in the scope of biologically mediated transport and biomagnification of Hg and Hg-isotopes, is unknown. Using geochemistry (THg) and stable isotopes (N, Sr and Hg), we evaluate natal origin and trophic position of brown trout (Salmo trutta fario), as well as mercury biomagnification trends and potential pollution sources to three high-altitude lakes. Farmed trout show Hg-isotope signatures similar to marine biota whereas wild trout shows Hg-isotope signatures typical of fresh water lakes. Stocked trout initially show Hg-isotope signatures similar to marine biota. As the stocked trout age and shifts diet to a higher trophic level, THg concentrations increase and the marine Hg isotope signatures, induced via farm fish feed, shift to locally produced MeHg with lower δ 202 Hg and higher Δ 199 Hg. We conclude that stocking acts a humanly induced biovector that transfers marine Hg to freshwater ecosystems, which is seen in the Hg-isotopic signature up to five years after stocking events occurred. This points to the need of further investigations of the role of stocking in MeHg exposure to freshwater ecosystems.

Barium-isotopic fractionation in seawater mediated by barite cycling and oceanic circulation

NASA Astrophysics Data System (ADS)

Horner, Tristan J.; Kinsley, Christopher W.; Nielsen, Sune G.

2015-11-01

The marine biogeochemical cycle of Ba is thought to be controlled by particulate BaSO4 (barite) precipitation associated with the microbial oxidation of organic carbon and its subsequent dissolution in the BaSO4-undersaturated water column. Despite many of these processes being largely unique to Ba cycling, concentrations of Ba and Si in seawater exhibit a strong linear correlation. The reasons for this correlation are ambiguous, as are the depth ranges corresponding to the most active BaSO4 cycling and the intermediate sources of Ba to particulate BaSO4. Stable isotopic analyses of dissolved Ba in seawater should help address these issues, as Ba-isotopic compositions are predicted to be sensitive to the physical and biogeochemical process that cycle Ba. We report a new methodology for the determination of dissolved Ba-isotopic compositions in seawater and results from a 4500 m depth profile in the South Atlantic at 39.99° S, 0.92° E that exhibit oceanographically-consistent variation with depth. These data reveal that water masses obtain their [Ba] and Ba-isotopic signatures when at or near the surface, which relates to the cycling of marine BaSO4. The shallow origin of these signatures requires that the substantial Ba-isotopic variations in the bathypelagic zone were inherited from when those deep waters were last ventilated. Indeed, the water column below 600 m is well explained by conservative mixing of water masses with distinct [Ba] and Ba-isotopic compositions. This leads us to conclude that large scale oceanic circulation is important for sustaining the similar oceanographic distributions of Ba and Si in the South Atlantic, and possibly elsewhere. These data demonstrate that the processes of organic carbon oxidation, BaSO4 cycling, and Ba-isotopic fractionation in seawater are closely coupled, such that Ba-isotopic analyses harbor great potential as a tracer of the carbon cycle in the modern and paleo-oceans.

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.

Natural uranium and strontium isotope tracers of water sources and surface water-groundwater interactions in arid wetlands: Pahranagat Valley, Nevada, USA

USGS Publications Warehouse

Paces, James B.; Wurster, Frederic C.

2014-01-01

Near-surface physical and chemical process can strongly affect dissolved-ion concentrations and stable isotope compositions of water in wetland settings, especially under arid climate conditions. In contrast, heavy radiogenic isotopes of strontium (87Sr/86Sr) and uranium (234U/238U) remain largely unaffected and can be used to help identify unique signatures from different sources and quantify end-member mixing that would otherwise be difficult to determine. The utility of combined Sr and U isotopes are demonstrated in this study of wetland habitats on the Pahranagat National Wildlife Refuge, which depend on supply from large-volume springs north of the Refuge, and from small-volume springs and seeps within the Refuge. Water budgets from these sources have not been quantified previously. Evaporation, transpiration, seasonally variable surface flow, and water management practices complicate the use of conventional methods for determining source contributions and mixing relations. In contrast, 87Sr/86Sr and 234U/238U remain unfractionated under these conditions, and compositions at a given site remain constant. Differences in Sr- and U-isotopic signatures between individual sites can be related by simple two- or three-component mixing models. Results indicate that surface flow constituting the Refuge’s irrigation source consists of a 65:25:10 mixture of water from two distinct regionally sourced carbonate aquifer springs, and groundwater from locally sourced volcanic aquifers. Within the Refuge, contributions from the irrigation source and local groundwater are readily determined and depend on proximity to those sources as well as water management practices.

Natural uranium and strontium isotope tracers of water sources and surface water-groundwater interactions in arid wetlands - Pahranagat Valley, Nevada, USA

NASA Astrophysics Data System (ADS)

Paces, James B.; Wurster, Frederic C.

2014-09-01

Near-surface physical and chemical process can strongly affect dissolved-ion concentrations and stable-isotope compositions of water in wetland settings, especially under arid climate conditions. In contrast, heavy radiogenic isotopes of strontium (87Sr/86Sr) and uranium (234U/238U) remain largely unaffected and can be used to help identify unique signatures from different sources and quantify end-member mixing that would otherwise be difficult to determine. The utility of combined Sr and U isotopes are demonstrated in this study of wetland habitats on the Pahranagat National Wildlife Refuge, which depend on supply from large-volume springs north of the Refuge, and from small-volume springs and seeps within the Refuge. Water budgets from these sources have not been quantified previously. Evaporation, transpiration, seasonally variable surface flow, and water management practices complicate the use of conventional methods for determining source contributions and mixing relations. In contrast, 87Sr/86Sr and 234U/238U remain unfractionated under these conditions, and compositions at a given site remain constant. Differences in Sr- and U-isotopic signatures between individual sites can be related by simple two- or three-component mixing models. Results indicate that surface flow constituting the Refuge's irrigation source consists of a 65:25:10 mixture of water from two distinct regionally sourced carbonate-aquifer springs, and groundwater from locally sourced volcanic aquifers. Within the Refuge, contributions from the irrigation source and local groundwater are readily determined and depend on proximity to those sources as well as water management practices.

Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

NASA Technical Reports Server (NTRS)

Johnson, Natasha M; Elsila, Jamie E.; Kopstein, Mickey; Nuth, Joseph A., III

2012-01-01

Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

A quantum cascade laser infrared spectrometer for CO2 stable isotope analysis: Field implementation at a hydrocarbon contaminated site under bio-remediation.

PubMed

Guimbaud, Christophe; Noel, Cécile; Chartier, Michel; Catoire, Valéry; Blessing, Michaela; Gourry, Jean Christophe; Robert, Claude

2016-02-01

Real-time methods to monitor stable isotope ratios of CO2 are needed to identify biogeochemical origins of CO2 emissions from the soil-air interface. An isotope ratio infra-red spectrometer (IRIS) has been developed to measure CO2 mixing ratio with δ(13)C isotopic signature, in addition to mixing ratios of other greenhouse gases (CH4, N2O). The original aspects of the instrument as well as its precision and accuracy for the determination of the isotopic signature δ(13)C of CO2 are discussed. A first application to biodegradation of hydrocarbons is presented, tested on a hydrocarbon contaminated site under aerobic bio-treatment. CO2 flux measurements using closed chamber method is combined with the determination of the isotopic signature δ(13)C of the CO2 emission to propose a non-intrusive method to monitor in situ biodegradation of hydrocarbons. In the contaminated area, high CO2 emissions have been measured with an isotopic signature δ(13)C suggesting that CO2 comes from petroleum hydrocarbon biodegradation. This first field implementation shows that rapid and accurate measurement of isotopic signature of CO2 emissions is particularly useful in assessing the contribution of contaminant degradation to the measured CO2 efflux and is promising as a monitoring tool for aerobic bio-treatment. Copyright © 2016. Published by Elsevier B.V.

Nitrogen Isotopic Anomalies in a Hydrous Interplanetary Dust Particle

NASA Technical Reports Server (NTRS)

Smith, J. B.; Dai, Z. R.; Weber, P. K.; Graham, G. A.; Hutcheon, I. D.; Bajt, S.; Ishii, H.; Bradley, J. P.

2005-01-01

Interplanetary dust particles (IDPs) collected in the stratosphere are the fine-grained end member (5 - 50 microns in size) of the meteoritic material available for investigation in the laboratory. IDPs are derived from either cometary or asteroidal sources. Some IDPs contain cosmically primitive materials with isotopic signatures reflecting presolar origins. Recent detailed studies using the NanoSIMS have shown there is a wide variation of isotopic signatures within individual IDPs; grains with a presolar signature have been observed surrounded by material with a solar isotopic composition. The majority of IDPs studied have been anhydrous. We report here results from integrated NanoSIMS/FIB/TEM/Synchrotron IR studies of a hydrous IDP, focused on understanding the correlations between the isotopic, mineralogical and chemical compositions of IDPs.

Denitrification and inference of nitrogen sources in the karstic Floridan Aquifer

USGS Publications Warehouse

Heffernan, J.B.; Albertin, A.R.; Fork, M.L.; Katz, B.G.; Cohen, M.J.

2011-01-01

Aquifer denitrification is among the most poorly constrained fluxes in global and regional nitrogen budgets. The few direct measurements of denitrification in groundwaters provide limited information about its spatial and temporal variability, particularly at the scale of whole aquifers. Uncertainty in estimates of denitrification may also lead to underestimates of its effect on isotopic signatures of inorganic N, and thereby confound the inference of N source from these data. In this study, our objectives are to quantify the magnitude and variability of denitrification in the Upper Floridan Aquifer (UFA) and evaluate its effect on N isotopic signatures at the regional scale. Using dual noble gas tracers (Ne, Ar) to generate physical predictions of N2 gas concentrations for 112 observations from 61 UFA springs, we show that excess (i.e. denitrification-derived) N2 is highly variable in space and inversely correlated with dissolved oxygen (O2). Negative relationship between O2 and ??15NNO 3 across a larger dataset of 113 springs, well-constrained isotopic fractionation coefficients, and strong 15N: 18O covariation further support inferences of denitrification in this uniquely organic-matter-poor system. Despite relatively low average rates, denitrification accounted for 32% of estimated aquifer N inputs across all sampled UFA springs. Back-calculations of source ??15NNO 3 based on denitrification progression suggest that isotopically-enriched nitrate (NO3-) in many springs of the UFA reflects groundwater denitrification rather than urban- or animal-derived inputs. ?? Author(s) 2011.

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

Kreuzer-Martin, Helen W.; Hegg, Eric L.

The use of isotopic signatures for forensic analysis of biological materials is well-established, and the same general principles that apply to interpretation of stable isotope content of C, N, O, and H apply to the analysis of microorganisms. Heterotrophic microorganisms derive their isotopic content from their growth substrates, which are largely plant and animal products, and the water in their culture medium. Thus the isotope signatures of microbes are tied to their growth environment. The C, N, O, and H isotope ratios of spores have been demonstrated to constitute highly discriminating signatures for sample matching. They can rule out specificmore » samples of media and/or water as possible production media, and can predict isotope ratio ranges of the culture media and water used to produce a given sample. These applications have been developed and tested through analyses of approximately 250 samples of Bacillus subtilis spores and over 500 samples of culture media, providing a strong statistical basis for data interpretation. A Bayesian statistical framework for integrating stable isotope data with other types of signatures derived from microorganisms has been able to characterize the culture medium used to produce spores of various Bacillus species, leveraging isotopic differences in different medium types and demonstrating the power of data integration for forensic investigations.« less

Plume mapping and isotopic characterisation of anthropogenic methane sources

NASA Astrophysics Data System (ADS)

Zazzeri, G.; Lowry, D.; Fisher, R. E.; France, J. L.; Lanoisellé, M.; Nisbet, E. G.

2015-06-01

Methane stable isotope analysis, coupled with mole fraction measurement, has been used to link isotopic signature to methane emissions from landfill sites, coal mines and gas leaks in the United Kingdom. A mobile Picarro G2301 CRDS (Cavity Ring-Down Spectroscopy) analyser was installed on a vehicle, together with an anemometer and GPS receiver, to measure atmospheric methane mole fractions and their relative location while driving at speeds up to 80 kph. In targeted areas, when the methane plume was intercepted, air samples were collected in Tedlar bags, for δ13C-CH4 isotopic analysis by CF-GC-IRMS (Continuous Flow Gas Chromatography-Isotope Ratio Mass Spectrometry). This method provides high precision isotopic values, determining δ13C-CH4 to ±0.05 per mil. The bulk signature of the methane plume into the atmosphere from the whole source area was obtained by Keeling plot analysis, and a δ13C-CH4 signature, with the relative uncertainty, allocated to each methane source investigated. Both landfill and natural gas emissions in SE England have tightly constrained isotopic signatures. The averaged δ13C-CH4 for landfill sites is -58 ± 3‰. The δ13C-CH4 signature for gas leaks is also fairly constant around -36 ± 2‰, a value characteristic of homogenised North Sea supply. In contrast, signatures for coal mines in N. England and Wales fall in a range of -51.2 ± 0.3‰ to -30.9 ± 1.4‰, but can be tightly constrained by region. The study demonstrates that CRDS-based mobile methane measurement coupled with off-line high precision isotopic analysis of plume samples is an efficient way of characterising methane sources. It shows that isotopic measurements allow type identification, and possible location of previously unknown methane sources. In modelling studies this measurement provides an independent constraint to determine the contributions of different sources to the regional methane budget and in the verification of inventory source distribution.

Biogeochemical sulphur cycle in an extreme environment - Life beneath a high arctic glacier, Nunavut, Canada

USGS Publications Warehouse

Grasby, S.E.; Allen, C.C.; Longazo, T.G.; Lisle, J.T.; Griffin, Dale W.; Beauchamp, B.

2003-01-01

Unique springs discharge from the surface of a high arctic glacier, releasing H2S, and depositing native sulphur, gypsum, and calcite. A rare CaCO3 polymorph, vaterite, is also observed. Physical and chemical conditions of the spring water and surrounding environment, as well as mineralogical and isotopic signatures, argue for biologically mediated redox reactions controlling sulfur. Cell counts and DNA analyses, confirm bacteria are present in the spring system. ?? 2003 Elsevier Science B.V. All rights reserved.

Successful application of lead isotopes in source apportionment, legal proceedings, remediation and monitoring

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

Gulson, Brian, E-mail: brian.gulson@mq.edu.au; CSIRO Earth Science and Resource Engineering North Ryde, NSW 1670; Korsch, Michael

In late 2006, the seaside community in Esperance Western Australia was alerted to thousands of native bird species dying. The source of the lead (Pb) was determined by Pb isotopes to derive from the handling of Pb carbonate concentrate through the Port, which began in July 2005. Concern was expressed for the impact of this on the community. Our objectives were to employ Pb isotope ratios to evaluate the source of Pb in environmental samples for use in legal proceedings, and for use in remediation and monitoring. Isotope measurements were undertaken of bird livers, plants, drinking water, soil, harbour sediments,more » air, bulk ceiling dust, gutter sludge, surface swabs and blood. The unique lead isotopic signature of the contaminating Pb carbonate enabled diagnostic apportionment of lead in samples. Apart from some soil and water samples, the proportion of contaminating Pb was >95% in the environmental samples. Lead isotopes were critical in resolving legal proceedings, are being used in the remediation of premises, were used in monitoring of workers involved in the decontamination of the storage facility, and monitoring transport of the concentrate through another port facility. Air samples show the continued presence of contaminant Pb, more than one year after shipping of concentrate ceased, probably arising from dust resuspension. Brief details of the comprehensive testing and cleanup of the Esperance community are provided along with the role of the Community. Lead isotopic analyses can provide significant benefits to regulatory agencies, interested parties, and the community where the signature is able to be characterised with a high degree of certainty. - Highlights: Black-Right-Pointing-Triangle Lead carbonate concentrate. Black-Right-Pointing-Triangle Successful use of Pb isotopes in identifying sources of Pb arising from transport and shipping. Black-Right-Pointing-Triangle Use of Pb isotopes in legal proceedings and their use in cleanup of residences. Black-Right-Pointing-Triangle Use of Pb isotopes in cleanup of a residual 9000 tonnes of Pb carbonate and in ongoing monitoring.« less

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.

Osmium, tungsten, and chromium isotopes in sediments and in Ni-rich spinel at the K-T boundary: Signature of a chondritic impactor

NASA Astrophysics Data System (ADS)

Quitté, Ghylaine; Robin, Eric; Levasseur, Sylvain; Capmas, Françoise; Rocchia, Robert; Birck, Jean-Louis; Allègre, Claude Jean

It is now established that a large extraterrestrial object hit the Earth at the end of the Cretaceous period, about 65 Ma ago. We have investigated Re-Os, Hf-W, and Mn-Cr isotope systems in sediments from the Cretaceous and the Paleogene in order to characterize the type of impactor. Within the Cretaceous-Tertiary (K-T) boundary layer, extraterrestrial material is mixed with terrestrial material, causing a dilution of the extraterrestrial isotope signature that is difficult to quantify. A phase essentially composed of Ni-rich spinel, formed in the atmosphere mainly from melted projectile material, is likely to contain the extraterrestrial isotopic signature of the impactor. We show that the analysis of spinel is indeed the best approach to determine the initial isotope composition of the impactor, and that W and Cr isotopes confirm that the projectile was a carbonaceous chondrite.

A New Method to Quantify the Isotopic Signature of Leaf Transpiration: Implications for Landscape-Scale Evapotranspiration Partitioning Studies

NASA Astrophysics Data System (ADS)

Wang, L.; Good, S. P.; Caylor, K. K.

2010-12-01

Characterizing the constituent components of evapotranspiration is crucial to better understand ecosystem-level water budgets and water use dynamics. Isotope based evapotranspiration partitioning methods are promising but their utility lies in the accurate estimation of the isotopic composition of underlying transpiration and evaporation. Here we report a new method to quantify the isotopic signature of leaf transpiration under field conditions. This method utilizes a commercially available laser-based isotope analyzer and a transparent leaf chamber, modified from Licor conifer leaf chamber. The method is based on the water mass balance in ambient air and leaf transpired air. We verified the method using “artificial leaves” and glassline extracted samples. The method provides a new and direct way to estimate leaf transpiration isotopic signatures and it has wide applications in ecology, hydrology and plant physiology.

Tracing the Impact of Aviation on the Atmospheric Nitrate With Oxygen Triple Isotopes

NASA Astrophysics Data System (ADS)

Shaheen, R.; Jackson, T. L.; Chan, S.; Hill, A.; Chakraborty, S.; Thiemens, M. H.

2014-12-01

The aviation industry is responsible for ~ 5% of anthropogenic climate change. Jet emission affects ~ in 25 mile radii from airports produce fine particles and concomitant pulmonary and cardio-vascular diseases. These unregulated emissions are of particular concerns for the health of local residents and environment in general due to rapid increase in worldwide air travel in 21st century. The accurate measurement of emissions from airports therefore requires development of new tools that quantification of aviation related emissions against other road traffic and hence to assess its local and global impacts and provide deeper understanding of nitrate in the environment in general, including the stratosphere where contrails are inadequately detailed Triple oxygen isotopic analysis of particulate nitrate from a DC 8 engine during a controlled experiment in Palmdale, CA documented the emission of nitric acid (~31 ng.m-3) at ~ 1m. The oxygen triple isotopic composition of nitrate emitted directly from the jet had δ18O values (22±1‰) identical to air O2 (δ18O = 23.5‰) with a mass dependent isotopic signature (Δ17O = 0), thus providing a unique isotopic signature of jet nitrate. A year long sampling campaign at one of the world's busiest airports, the Los Angeles International airport showed the contribution of NO3 varies from 60 to 90% in summer and winter with variations largely attributed to the change in road traffic as air traffic remains fairly constant throughout the year at LAX. The next step in this is to detect these contributions at distal sites and use this as a signal carrier of atmospheric nitrate and its transport in general in the global biogeochemical system. These aspects will be discussed in the presentation.

Simultaneous determination of the quantity and isotopic signature of dissolved organic matter from soil water using high-performance liquid chromatography/isotope ratio mass spectrometry.

PubMed

Scheibe, Andrea; Krantz, Lars; Gleixner, Gerd

2012-01-30

We assessed the accuracy and utility of a modified high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS) system for measuring the amount and stable carbon isotope signature of dissolved organic matter (DOM) <1 µm. Using a range of standard compounds as well as soil solutions sampled in the field, we compared the results of the HPLC/IRMS analysis with those from other methods for determining carbon and (13)C content. The conversion efficiency of the in-line wet oxidation of the HPLC/IRMS averaged 99.3% for a range of standard compounds. The agreement between HPLC/IRMS and other methods in the amount and isotopic signature of both standard compounds and soil water samples was excellent. For DOM concentrations below 10 mg C L(-1) (250 ng C total) pre-concentration or large volume injections are recommended in order to prevent background interferences. We were able to detect large differences in the (13)C signatures of soil solution DOM sampled in 10 cm depth of plots with either C3 or C4 vegetation and in two different parent materials. These measurements also demonstrated changes in the (13)C signature that demonstrate rapid loss of plant-derived C with depth. Overall the modified HLPC/IRMS system has the advantages of rapid sample preparation, small required sample volume and high sample throughput, while showing comparable performance with other methods for measuring the amount and isotopic signature of DOM. Copyright © 2011 John Wiley & Sons, Ltd.

On the palaeobiology of the extinct cave bear Ursus spelaeus ROSENMÜLLER. Insights from stable isotope analysis

NASA Astrophysics Data System (ADS)

Grandal-D'Anglade, Aurora; Pérez-Rama, Marta; Fernández-Mosquera, Daniel

2010-05-01

Isotopic signatures (δ13C, δ15N) of bone collagen are used more and more to obtain the paleobiological data of fossil species. By means of these signatures, for example, the diet type of an extint species may be inferred. Also, the climate in which this species developed may greatly influence on the isotopic signature of its bone collagen. This influence is firstly produced in the initial material of the trophic chain but also may produce variations due to physiological changes caused by climatic changes in the species involved in this trophic chain. The cave bear (Ursus spelaeus ROSENMÜLLER) is a species of broad distribution in the European Pleistocene sites that has been studied from the isotopic point of view, trying to establish its diet type. For the moment, the results vary: though in most cases the isotopic values indicate a preferably herbivore diet type, differences exist between sites of different geographic zones and chronologies. Taking into account that climate influences on the cave bear's physiology through the physiological mechanism of hibernation, it is expected that in bears that lived in different climatic phases, the isotopic signatures will be also different. During hibernation a recycling of nitrogenised compounds is produced for protein synthesis, including bone collagen, so it is expected that the isotopic signature, at least of Nitrogen, will be altered with respect to the synthesized collagen when the bear is active and feeds normally. However, it is difficult to establish up to what extent the isotopic signatures due to hibernation or diet are overlapped. To study the physiological effect of hibernation on isotopic signatures we have selected bone remains of cave bears from populations whose chronologies correspond to different climatic moments, and in different ontogenetic stages, coming from Galician caves (NW of the Iberian Peninsula). Adult individuals show different isotopic signatures depending on their chronology. Juvenile individuals show differences originated by the effect of a greater or less contribution of maternal milk in their diets. Finally, the neonate individuals or still in foetal stage show isotopic values that directly reflect their mother's physiology in the hibernation, during which foetal development is produced. Interestingly, all the individuals of this age class present similar isotopic values in spite of belonging to populations with different values in the adults. This indicates, on one hand, that there exists a physiological effect on the isotopic signals produced by hibernation, effect that is similar in all the studied populations, and on the other, that this physiological effect of hibernation only appears in adult individuals of populations corresponding to cold moments, in which the hibernation period is longer. According to the results, we suggest the use of isotopic values of adult cave bears as climatic proxy for European Pleistocene sites. This work is part of the Ph.D. Thesis of M.P.R. and is a contribution to the research project BTE-CGL-2006-08996 of the Education and Science Ministry of Spain.

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

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

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

An isotopic view of water and nitrate transport through the vadose zone in Oregon's southern Willamette Valley's Groundwater Management Area

NASA Astrophysics Data System (ADS)

Brooks, J. R.; Pearlstein, S.; Hutchins, S.; Faulkner, B. R.; Rugh, W.; Willard, K.; Coulombe, R.; Compton, J.

2017-12-01

Groundwater nitrate contamination affects thousands of households in Oregon's southern Willamette Valley and many more across the USA. The southern Willamette Valley Groundwater Management Area (GWMA) was established in 2004 due to nitrate levels in the groundwater exceeding the human health standard of 10 mg nitrate-N L-1. Much of the nitrogen (N) inputs to the GWMA comes from agricultural fertilizers, and thus efforts to reduce N inputs to groundwater are focused upon improving N management. However, the effectiveness of these improvements on groundwater quality is unclear because of the complexity of nutrient transport through the vadose zone and long groundwater residence times. Our objective was to focus on vadose zone transport and understand the dynamics and timing of N and water movement below the rooting zone in relation to N management and water inputs. Stable isotopes are a powerful tool for tracking water movement, and understanding N transformations. In partnership with local farmers and state agencies, we established lysimeters and groundwater wells in multiple agricultural fields in the GWMA, and have monitored nitrate, nitrate isotopes, and water isotopes weekly for multiple years. Our results indicate that vadose zone transport is highly complex, and the residence time of water collected in lysimeters was much longer than expected. While input precipitation water isotopes were highly variable over time, lysimeter water isotopes were surprisingly consistent, more closely resembling long-term precipitation isotope means rather than recent precipitation isotopic signatures. However, some particularly large precipitation events with unique isotopic signatures revealed high spatial variability in transport, with some lysimeters showing greater proportions of recent precipitation inputs than others. In one installation where we have groundwater wells and lysimeters at multiple depths, nitrate/nitrite concentrations decreased with depth. N concentrations and δ15N values indicated leaching at 1 m and denitrification at 3 m depth. However, these relationships showed spatial and temporal complexity. We are exploring how these vadose zone complexities can be incorporated into practical understanding of the impacts of N management on groundwater inputs.

Annual Fossil-Fuel CO2 Emissions: Global Stable Carbon Isotope Signature (DB1013, V. 2016)

DOE Data Explorer

Andres, R. J. [CDIAC, Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (USA); Boden, T. A. [CDIAC, Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (USA); Marland, G. [Appalachian State University, Boone, NC (USA)

2016-01-01

The 2016 revision of this database contains estimates of the annual, global mean value of δ 13C of CO2 emissions from fossil-fuel consumption and cement manufacture for 1751-2013. These estimates of the carbon isotopic signature account for the changing mix of coal, petroleum, and natural gas being consumed and for the changing mix of petroleum from various producing areas with characteristic isotopic signatures. This time series of global fossil-fuel del 13C signature provides an additional constraint for balancing the sources and sinks of the global carbon cycle and complements the atmospheric δ 13C measurements that are used to partition the uptake of fossil carbon emissions among the ocean, atmosphere, and terrestrial biosphere reservoirs.

Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

NASA Technical Reports Server (NTRS)

Martens, C. S.; Green, C. D.; Blair, N. E.; Des Marais, D. J.

1986-01-01

Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95 percent. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.

Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

USGS Publications Warehouse

Gulson, B.L.; Church, S.E.; Mizon, K.J.; Meier, A.L.

1992-01-01

Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206Pb/204Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206Pb/ 204Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects. ?? 1992.

Stable carbon and nitrogen isotope ratios of sodium and potassium cyanide as a forensic signature.

PubMed

Kreuzer, Helen W; Horita, Juske; Moran, James J; Tomkins, Bruce A; Janszen, Derek B; Carman, April

2012-01-01

Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. Upon analysis, a few of the cyanide samples displayed nonhomogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Most samples had highly reproducible isotope content. Of the 65 cyanide samples, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples. © 2011 American Academy of Forensic Sciences.

Stable Carbon and Nitrogen Isotope Ratios of Sodium and Potassium Cyanide as a Forensic Signature

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

Kruzer, Helen W; Horita, Juske; Moran, James J

2012-01-01

Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a future chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. A few of these samples displayed non-homogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Mostmore » samples had highly reproducible isotope content. Of these, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples.« less

Isotopic signatures of anthropogenic CH4 sources in Alberta, Canada

NASA Astrophysics Data System (ADS)

Lopez, M.; Sherwood, O. A.; Dlugokencky, E. J.; Kessler, R.; Giroux, L.; Worthy, D. E. J.

2017-09-01

A mobile system was used for continuous ambient measurements of stable CH4 isotopes (12CH4 and 13CH4) and ethane (C2H6). This system was used during a winter mobile campaign to investigate the CH4 isotopic signatures and the C2H6/CH4 ratios of the main anthropogenic sources of CH4 in the Canadian province of Alberta. Individual signatures were derived from δ13CH4 and C2H6 measurements in plumes arriving from identifiable single sources. Methane emissions from beef cattle feedlots (n = 2) and landfill (n = 1) had δ13CH4 signatures of -66.7 ± 2.4‰ and -55.3 ± 0.2‰, respectively. The CH4 emissions associated with the oil or gas industry had distinct δ13CH4 signatures, depending on the formation process. Emissions from oil storage tanks (n = 5) had δ13CH4 signatures ranging from -54.9 ± 2.9‰ to -60.6 ± 0.6‰ and non-detectable C2H6, characteristic of secondary microbial methanogenesis in oil-bearing reservoirs. In contrast, CH4 emissions associated with natural gas facilities (n = 8) had δ13CH4 signatures ranging from -41.7 ± 0.7‰ to -49.7 ± 0.7‰ and C2H6/CH4 molar ratios of 0.10 for raw natural gas to 0.04 for processed/refined natural gas, consistent with thermogenic origins. These isotopic signatures and C2H6/CH4 ratios have been used for source discrimination in the weekly atmospheric measurements of stable CH4 isotopes over a two-month winter period at the Lac La Biche (LLB) measurement station, located in Alberta, approximately 200 km northeast of Edmonton. The average signature of -59.5 ± 1.4‰ observed at LLB is likely associated with transport of air after passing over oil industry sources located south of the station.

Variation in the mobilization of mercury into Black-winged Stilt Himantopus himantopus chicks in coastal saltpans, as revealed by stable isotopes

NASA Astrophysics Data System (ADS)

Tavares, P. C.; Kelly, A.; Maia, R.; Lopes, R. J.; Serrão Santos, R.; Pereira, M. E.; Duarte, A. C.; Furness, R. W.

2008-03-01

Causes of variation in mobilization of mercury into Black-winged Stilt Himantopus himantopus chicks were studied through analysis of stable isotope ratios of carbon and nitrogen. Blood and breast feathers were collected from chicks in coastal saltpans during successive breeding seasons. Detritus samples and potential prey (macroinvertebrates) were also collected. Total mercury concentrations and stable isotope signatures were measured using atomic absorption spectroscopy and isotope ratio mass spectrometry respectively. Mercury levels in Chironomidae, Corixidae and Hydrophilidae correlated with mercury levels in chick feathers. Differences of δ 15N signatures between macroinvertebrate groups indicated that they belong to different trophic levels. δ 15N signatures of invertebrates correlated with mercury levels in invertebrates and chicks, but not with δ 15N signatures in chicks. Between-group and between-site differences of δ 15N signatures and mercury levels in invertebrates suggested that they contribute differently to mercury mobilization into chicks, and their relative contribution depends on prey availability in each site. Inter-site differences in the biomagnification factor reinforced that idea. δ 13C signatures in invertebrates marked a larger range of carbon sources than just detritus. Variation of water inflow regime and prey availability may cause between-group and between-site differences of δ 13C signatures in prey. Discrepancies between feather and blood for δ 13C signatures in Praias-Sado and Vaia suggested that temporal variation of prey availability may be the main factor affecting mercury mobilization into chicks in both those cases, since their water inflow regimes are the same. The lowest levels of δ 13C signatures in Vau suggested that water inflow regime may be the main factor in this case, since no discrepancy existed in δ 13C signatures between blood and feather.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars.

PubMed

Shaheen, R; Abramian, A; Horn, J; Dominguez, G; Sullivan, R; Thiemens, Mark H

2010-11-23

The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess (17)O (0.4-3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O(3) reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars

PubMed Central

Shaheen, R.; Abramian, A.; Horn, J.; Dominguez, G.; Sullivan, R.; Thiemens, Mark H.

2010-01-01

The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess 17O (0.4–3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O3 reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth. PMID:21059939

The influence of lithology on surface water sources | Science ...

EPA Pesticide Factsheets

Understanding the temporal and spatial variability of surface water sources within a basin is vital to our ability to manage the impacts of climate variability and land cover change. Water stable isotopes can be used as a tool to determine geographic and seasonal sources of water at the basin scale. Previous studies in the Coastal Range of Oregon reported that the variation in the isotopic signatures of surface water does not conform to the commonly observed “rainout effect”, which exhibits a trend of increasing isotopic depletion with rising elevation. The primary purpose of this research is to investigate the mechanisms governing seasonal and spatial variations in the isotopic signature of surface waters within the Marys River Basin, located in the leeward side of the Oregon Coastal Range. Surface water and precipitation samples were collected every 2-3 weeks for isotopic analysis of δ18O and δ2H for one year. Results indicate a significant difference in isotopic signature between watersheds underlain by basalt and sandstone. The degree of separation was the most distinct during the summer when low flows reflect deeper groundwater sources, whereas isotopic signatures during the rainy season (fall and winter) showed a greater degree of similarity between the two lithologies. This indicates that baseflow within streams drained by sandstone versus basalt is being supplied from two distinctly separate water sources. In addition, Marys River flow at the outle

Annual Fossil-Fuel CO2 Emissions: Global Stable Carbon Isotopic Signature (1751-2008) (DB1013 V.2011)

DOE Data Explorer

Andres, R. J. [CDIAC, Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (USA); Boden, T. A. [CDIAC, Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (USA); Marland, G. [CDIAC, Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (USA)

1996-01-01

The 2011 revision of this database contains estimates of the annual, global mean value of del 13C of CO2 emissions from fossil-fuel consumption and cement manufacture for 1751-2008. These estimates of the carbon isotopic signature account for the changing mix of coal, petroleum, and natural gas being consumed and for the changing mix of petroleum from various producing areas with characteristic isotopic signatures. This time series of global fossil-fuel del 13C signature provides an additional constraint for balancing the sources and sinks of the global carbon cycle and complements the atmospheric del 13C measurements that are used to partition the uptake of fossil carbon emissions among the ocean, atmosphere, and terrestrial biosphere reservoirs.

Small-scale studies of roasted ore waste reveal extreme ranges of stable mercury isotope signatures

NASA Astrophysics Data System (ADS)

Smith, Robin S.; Wiederhold, Jan G.; Jew, Adam D.; Brown, Gordon E.; Bourdon, Bernard; Kretzschmar, Ruben

2014-07-01

Active and closed Hg mines are significant sources of Hg contamination to the environment, mainly due to large volumes of mine waste material disposed of on-site. The application of Hg isotopes as source tracer from such contaminated sites requires knowledge of the Hg isotope signatures of different materials potentially released to the environment. Previous work has shown that calcine, the waste residue of the on-site ore roasting process, can exhibit distinct Hg isotope signatures compared with the primary ore. Here, we report results from a detailed small-scale study of Hg isotope variations in calcine collected from the closed New Idria Hg mine, San Benito County, CA, USA. The calcine samples exhibited different internal layering features which were investigated using optical microscopy, micro X-ray fluorescence, micro X-ray absorption spectroscopy (μ-XAS), and stable Hg isotope analysis. Significant Fe, S, and Hg concentration gradients were found across the different internal layers. Isotopic analyses revealed an extreme variation with pronounced isotopic gradients across the internal layered features. Overall, δ202Hg (±0.10‰, 2 SD) describing mass-dependent fractionation (MDF) ranged from -5.96 to 14.49‰, which is by far the largest range of δ202Hg values reported for any environmental sample. In addition, Δ199Hg (±0.06‰, 2 SD) describing mass-independent fractionation (MIF) ranged from -0.17 to 0.21‰. The μ-XAS analyses suggested that cinnabar and metacinnabar are the dominant Hg-bearing phases in the calcine. Our results demonstrate that the incomplete roasting of HgS ores in Hg mines can cause extreme mass-dependent Hg isotope fractionations at the scale of individual calcine pieces with enrichments in both light and heavy Hg isotopes relative to the primary ore signatures. This finding has important implications for the application of Hg isotopes as potential source tracers for Hg released to the environment from closed Hg mines and highlights the need for detailed source signature identification.

Source tracing of natural organic matter bound mercury in boreal forest runoff with mercury stable isotopes.

PubMed

Jiskra, Martin; Wiederhold, Jan G; Skyllberg, Ulf; Kronberg, Rose-Marie; Kretzschmar, Ruben

2017-10-18

Terrestrial runoff represents a major source of mercury (Hg) to aquatic ecosystems. In boreal forest catchments, such as the one in northern Sweden studied here, mercury bound to natural organic matter (NOM) represents a large fraction of mercury in the runoff. We present a method to measure Hg stable isotope signatures of colloidal Hg, mainly complexed by high molecular weight or colloidal natural organic matter (NOM) in natural waters based on pre-enrichment by ultrafiltration, followed by freeze-drying and combustion. We report that Hg associated with high molecular weight NOM in the boreal forest runoff has very similar Hg isotope signatures as compared to the organic soil horizons of the catchment area. The mass-independent fractionation (MIF) signatures (Δ 199 Hg and Δ 200 Hg) measured in soils and runoff were in agreement with typical values reported for atmospheric gaseous elemental mercury (Hg 0 ) and distinctly different from reported Hg isotope signatures in precipitation. We therefore suggest that most Hg in the boreal terrestrial ecosystem originated from the deposition of Hg 0 through foliar uptake rather than precipitation. Using a mixing model we calculated the contribution of soil horizons to the Hg in the runoff. At moderate to high flow runoff conditions, that prevailed during sampling, the uppermost part of the organic horizon (Oe/He) contributed 50-70% of the Hg in the runoff, while the underlying more humified organic Oa/Ha and the mineral soil horizons displayed a lower mobility of Hg. The good agreement of the Hg isotope results with other source tracing approaches using radiocarbon signatures and Hg : C ratios provides additional support for the strong coupling between Hg and NOM. The exploratory results from this study illustrate the potential of Hg stable isotopes to trace the source of Hg from atmospheric deposition through the terrestrial ecosystem to soil runoff, and provide a basis for more in-depth studies investigating the mobility of Hg in terrestrial ecosystems using Hg isotope signatures.

Long-Term Species, Sexual and Individual Variations in Foraging Strategies of Fur Seals Revealed by Stable Isotopes in Whiskers

PubMed Central

Kernaléguen, Laëtitia; Cazelles, Bernard; Arnould, John P. Y.; Richard, Pierre; Guinet, Christophe; Cherel, Yves

2012-01-01

Background Individual variations in the use of the species niche are an important component of diversity in trophic interactions. A challenge in testing consistency of individual foraging strategy is the repeated collection of information on the same individuals. Methodology/Principal Findings The foraging strategies of sympatric fur seals (Arctocephalus gazella and A. tropicalis) were examined using the stable isotope signature of serially sampled whiskers. Most whiskers exhibited synchronous δ13C and δ15N oscillations that correspond to the seal annual movements over the long term (up to 8 years). δ13C and δ15N values were spread over large ranges, with differences between species, sexes and individuals. The main segregating mechanism operates at the spatial scale. Most seals favored foraging in subantarctic waters (where the Crozet Islands are located) where they fed on myctophids. However, A. gazella dispersed in the Antarctic Zone and A. tropicalis more in the subtropics. Gender differences in annual time budget shape the seal movements. Males that do not perform any parental care exhibited large isotopic oscillations reflecting broad annual migrations, while isotopic values of females confined to a limited foraging range during lactation exhibited smaller changes. Limited inter-individual isotopic variations occurred in female seals and in male A. tropicalis. In contrast, male A. gazella showed large inter-individual variations, with some males migrating repeatedly to high-Antarctic waters where they fed on krill, thus meaning that individual specialization occurred over years. Conclusions/Significance Whisker isotopic signature yields unique long-term information on individual behaviour that integrates the spatial, trophic and temporal dimensions of the ecological niche. The method allows depicting the entire realized niche of the species, including some of its less well-known components such as age-, sex-, individual- and migration-related changes. It highlights intrapopulation heterogeneity in foraging strategies that could have important implications for likely demographic responses to environmental variability. PMID:22431988

Degradation and Volatilization of Chlorofluorocarbons in Contaminated Groundwater Explored by Stable Carbon Isotope Analysis

NASA Astrophysics Data System (ADS)

Horst, A.; Lacrampe-Couloume, G.; Sherwood Lollar, B.

2015-12-01

Chlorofluorocarbons (CFCs) are ozone depleting compounds whose production was phased out by the regulations of the Montreal Protocol (1987). Accidental release and disposal also led to contamination of groundwater at many locations, however, and this legacy persists. Although very stable, CFCs may degrade via abiotic and biotic pathways. Quantification of the degree of transformation of CFCs has been challenging due to other processes such as dilution, sorption and volatilization. Compound specific stable carbon isotope analysis (CSIA) has been successfully applied for a variety of priority pollutants to distinguish degradation from other processes and to quantify transformation rates. A Purge & Trap - CSIA method developed in our lab was applied to determine the stable carbon isotopic signature of CFCs and HCFCs (hydrochlorofluorocarbons) in groundwater samples from a contaminated site. Preliminary results suggest that degradation of CFCs and HCFCs may result in enriched δ13C values, consistent with fractionation during bond breakage as has been reported for many other hydrocarbon pollutants. The effect of volatile loss during sampling on the isotopic signatures of CFCs was examined in laboratory experiments. Volatilization from pure phase CFCs showed a small inverse isotope effect during open system volatilization, opposite to the normal isotope effect generally observed during biodegradation. For volatilization of CFCs dissolved in water a much smaller isotope effect was observed. An important result from this work is that any volatile loss may introduce only a small change in CFC isotopic signatures in groundwater, and importantly, due to the opposite direction of isotope effects associated with volatilization versus degradation, any effects of volatile loss on the isotopic signatures cannot be confused with transformation of CFCs. At most, volatilization might contribute to a conservative estimate of the extent of degradation.

Alpha and conversion electron spectroscopy of 238,239Pu and 241Am and alpha-conversion electron coincidence measurements

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

Dion, Michael P.; Miller, Brian W.; Warren, Glen A.

2016-09-01

A technique to determine the isotopics of a mixed actinide sample has been proposed by measuring the coincidence of the alpha particle during radioactive decay with the conversion electron (or Auger) emitted during the relaxation of the daughter isotope. This presents a unique signature to allow the deconvolution of isotopes that possess overlapping alpha particle energy. The work presented here are results of conversion electron spectroscopy of 241Am, 238Pu and 239Pu using a dual-stage peltier-cooled 25 mm2 silicon drift detector. A passivated ion implanted planar silicon detector provided measurements of alpha spectroscopy. The conversion electron spectra were evaluated from 20–55more » keV based on fits to the dominant conversion electron emissions, which allowed the relative conversion electron emission intensities to be determined. These measurements provide crucial singles spectral information to aid in the coincident measurement approach.« less

Vehicle NOx emission plume isotopic signatures: Spatial variability across the eastern United States

NASA Astrophysics Data System (ADS)

Miller, David J.; Wojtal, Paul K.; Clark, Sydney C.; Hastings, Meredith G.

2017-04-01

On-road vehicle nitrogen oxide (NOx) sources currently dominate the U.S. anthropogenic emission budgets, yet vehicle NOx emissions have uncertain contributions to oxidized nitrogen (N) deposition patterns. Isotopic signatures serve as a potentially valuable observational tool to trace source contributions to NOx chemistry and N deposition, yet in situ emission signatures are underconstrained. We characterize the spatiotemporal variability of vehicle NOx emission isotopic signatures (δ15N-NOx) representative of U.S. vehicle fleet-integrated emission plumes. A novel combination of on-road mobile and stationary urban measurements is performed using a field and laboratory-verified technique for actively capturing NOx in solution to quantify δ15N-NOx at hourly resolution. On-road δ15N-NOx upwind of Providence, RI, ranged from -7 to -3‰. Simultaneous urban background δ15N-NOx observations showed comparable range and variations with on-road measurements, suggesting that vehicles dominate NOx emissions in the Providence area. On-road spatial δ15N-NOx variations of -9 to -2‰ were observed under various driving conditions in six urban metropolitan areas and rural interstate highways during summer and autumn in the U.S. Northeast and Midwest. Although isotopic signatures were insensitive to on-road driving mode variations, statistically significant correlations were found between δ15N-NOx and NOx emission factor extremes associated with heavy diesel emitter contributions. Overall, these results constrain an isotopic signature of fleet-integrated roadway NOx emission plumes, which have important implications for distinguishing vehicle NOx from other sources and tracking emission contributions to NOx chemistry and N deposition.

Earth's Coming of Age: Isotopically Tracking the Global Transformation from the Hadean to the Geologically Modern Earth

NASA Astrophysics Data System (ADS)

Bennett, V. C.; Nutman, A. P.

2017-12-01

Some of the strongest direct evidence that documents fundamental changes in the chemistry and organisation of Earth's interior derives from radiogenic isotopic compositions that include both long-lived (particularly 176Lu-176Hf and 147Sm-143Nd) and short-lived, i.e., now extinct parent isotope, systems (182Hf-182W, 146Sm-142Nd). Changes in patterns of isotopic evolution are linked to changes in mantle dynamics such that tracking these signatures in geologically well-characterised rocks can be used to discover the the nature and evolution of tectonic processes. Over the past decade, intensive geochemical investigations by various groups focussing on the oldest (> 4.0 Ga to 3.6 Ga) rock record, as preserved in several localities, have revealed isotopic distinctions in the early Earth compared with those in Proterozoic and younger rocks. For example, whilst the major and trace element compositions of Eoarchean gneisses have analogs in younger rocks in accord with a continuum of crust formation processes, radiogenic isotopic signatures from both long and short half-life decay schemes record an image of the Earth in transition from early differentiation processes, likely associated with planetary accretion and formation, to more modern style characterised by plate tectonics. The emerging image is that many Eoarchean rocks possess extinct nuclide anomalies in the form of 142Nd and 182Hf isotopic signatures that are absent in modern terrestrial samples; these signatures are evidence of chemical fractionation processes occuring within the first ca. 10-300 million years of Solar System history. In addition, viewing the global database, patterns of long-half life isotope signatures i.e., 143Nd and 176Hf differ from those seen in younger (<3.6 Ga) rocks, again providing a tracer of mantle dynamics and reflecting the influence of early processes. It is becoming increasingly apparent that the well demonstrated "coupled" 176Hf-143Nd isotopic evolution generated by plate tectonic processes and characterizing Phanerozoic and Proterozoic mantle derived rocks is absent in the Eoarchean record. Here, we track this isotopic transition in key regions and demonstrate how this places limits on the timing and style of transition from early to modern Earth.

From Mars Meteorites to Laboratory Investigations: Understanding Heterogeneous Photochemical Transformations Using Oxygen Triple Isotope Anomalies of Carbonates

NASA Astrophysics Data System (ADS)

Shaheen, R.; Smirnova, V.; Jackson, T. L.; Mang, L.; Thiemens, M. H.

2016-12-01

The planet Mars is unique in our solar system with a positive O-isotope anomaly observed in its bulk silicate and carbonates minerals ranging from 0.3 to 0.6 ‰. The carbonate isotopic signature can be used to reveal its origin, past history and atmosphere-hydrosphere-geosphere-interactions. Ozone is a powerful natural tracer of photochemical processes in Earth's atmosphere. It possess the highest enrichment in heavy isotopes δ17O ≈ δ18O (70-150‰) and oxygen isotopic anomaly (Δ17O = 30-40‰). The oxygen isotopic anomaly from ozone is transferred to other oxygen carrying molecules in the atmosphere through different mechanisms. Laboratory experiments were conducted with the JSC-Mars Simulant and iron oxide to investigate how this anomaly can be transferred to water and minerals under conditions similar to present day Mars. Three sets of laboratory experiments (O3-H2O-UV-minerals; O2-H2O-UV-minerals; O3-H2O-minerals) were performed. The oxygen triple isotopic analysis of product mineral carbonates formed from adsorbed CO2 reaction showed an oxygen isotopic anomaly (Δ17O = 0.4-3‰). The oxygen triple isotopic composition of water at photochemical equilibrium shifted towards ozone with Δ17O = 9‰ indicating reaction of ozone with water vapor via electronically excited oxygen atoms and transfer of the anomaly via hydroxyl radicals. HOx (HO, HO2) are extremely reactive and have very short life time (< μs), however, our data indicate that its signature is preserved through surficial interactions with adsorbed CO2 on mineral surfaces. Hydroxyl radicals may have played a significant role in heterogeneous photochemical transformations on mineral dust in the atmosphere of Mars and transfer of ozone anomaly to water and other oxygen bearing minerals through surficial reactions. Series of experiments were performed to constrain the amount of H2O required to preserve the oxygen isotope anomaly observed in carbonate minerals in the Martian meteorites. These observation will help refine Mars photochemistry models and also to constrain the past hydrological cycle and its coupling with the regolith. The observed inverse correlation between ozone and water vapor also suggests a dynamic role of hydroxyl radical chemistry in the atmosphere of Mars.

Isotopic decoupling during porous melt flow: A case-study in the Lherz peridotite

NASA Astrophysics Data System (ADS)

Le Roux, V.; Bodinier, J.-L.; Alard, O.; O'Reilly, S. Y.; Griffin, W. L.

2009-03-01

Most peridotite massifs and mantle xenoliths show a wide range of isotopic variations, often involving significant decoupling between Hf, Nd and Sr isotopes. These variations are generally ascribed either to mingling of individual components of contrasted isotopic compositions or to time integration of parent-element enrichment by percolating melts/fluids, superimposed onto previous depletion event(s). However, strong isotopic decoupling may also arise during porous flow as a result of daughter-elements fractionation during solid-liquid interaction. Although porous flow is recognized as an important process in mantle rocks, its effects on mantle isotopic variability have been barely investigated so far. The peridotites of the Lherz massif (French Pyrenees) display a frozen melt percolation front separating highly refractory harzburgites from refertilized lherzolites. Isotopic signatures observed at the melt percolation front show a strong decoupling of Hf from Nd and Sr isotopes that cannot be accounted for by simple mixing involving the harzburgite protolith and the percolating melt. Using one dimensional percolation-diffusion and percolation-reaction modeling, we show that these signatures represent transient isotopic compositions generated by porous flow. These signatures are governed by a few critical parameters such as daughter element concentrations in melt and peridotite, element diffusivity, and efficiency of isotopic homogenization rather than by the chromatographic effect of melt transport and the refertilization reaction. Subtle variations in these parameters may generate significant inter-isotopic decoupling and wide isotopic variations in mantle rocks.

Effect of baking and fermentation on the stable carbon and nitrogen isotope ratios of grain-based food.

PubMed

Bostic, Joshua N; Palafox, Sherilyn J; Rottmueller, Marina E; Jahren, A Hope

2015-05-30

Isotope ratio mass spectrometry (IRMS) is used extensively to reconstruct general attributes of prehistoric and modern diets in both humans and animals. In order to apply these methods to the accurate determination of specific intakes of foods/nutrients of interest, the isotopic signature of individually consumed foods must be constrained. For example, 86% of the calories consumed in the USA are derived from processed and prepared foods, but the relationship between the stable isotope composition of raw ingredients and the resulting products has not been characterized. To examine the effect of common cooking techniques on the stable isotope composition of grain-based food items, we prepared yeast buns and sugar cookies from standardized recipes and measured bulk δ(13) C and δ(15) N values of samples collected throughout a 75 min fermentation process (buns) and before and after baking at 190°C (buns and cookies). Simple isotope mixing models were used to determine if the isotopic signatures of 13 multi-ingredient foods could be estimated from the isotopic signatures of their constituent raw ingredients. No variations in δ(13) C or δ(15) N values were detected between pre- and post-baked yeast buns (pre: -24.78‰/2.61‰, post: -24.75‰/2.74‰), beet-sugar cookies (pre: -24.48‰/3.84‰, post: -24.47‰/3.57‰), and cane-sugar cookies (pre: -19.07‰/2.97‰, post: -19.02‰/3.21‰), or throughout a 75 min fermentation process in yeast buns. Using isotopic mass balance equations, the δ(13) C/δ(15) N values of multi-ingredient foods were estimated from the isotopic composition of constituent raw ingredients to within 0.14 ± 0.13‰/0.24 ± 0.17‰ for gravimetrically measured recipes and 0.40 ± 0.38‰/0.58 ± 0.53‰ for volumetrically measured recipes. Two common food preparation techniques, baking and fermentation, do not substantially affect the carbon or nitrogen isotopic signature of grain-based foods. Mass-balance equations can be used to accurately estimate the isotopic signature of multi-ingredient food items for which quantitative ingredient information is available. Copyright © 2015 John Wiley & Sons, Ltd.

Compound-Specific Isotope Analysis of Amino Acids for Stardust-Returned Samples

NASA Technical Reports Server (NTRS)

Cook, Jamie; Elsila, Jamie E.; Stern J. C.; Glavin, D. P.; Dworkin, J. P.

2008-01-01

Significant portions of the early Earth's prebiotic organic inventory , including amino acids, could have been delivered to the Earth's sur face by comets and their fragments. Analysis of comets via spectrosc opic observations has identified many organic molecules, including me thane, ethane, arnmonia, cyanic acid, formaldehyde, formamide, acetal ehyde, acetonitrile, and methanol. Reactions between these identifie d molecules could allow the formation of more complex organics such a s amino acids. Isotopic analysis could reveal whether an extraterrest rial signature is present in the Stardust-exposed amines and amino ac ids. Although bulk isotopic analysis would be dominated by the EACA contaminant's terrestrial signature, compoundspecific isotope analysi s (CSIA) could determine the signature of each of the other individua l amines. Here, we report on progress made towards CSIA of the amino acids glycine and EACA in Stardustreturned samples.

Isotope investigation on groundwater recharge and dynamics in shallow and deep alluvial aquifers of southwest Punjab.

PubMed

Keesari, Tirumalesh; Sharma, Diana A; Rishi, Madhuri S; Pant, Diksha; Mohokar, Hemant V; Jaryal, Ajay Kumar; Sinha, U K

2017-11-01

Groundwater samples collected from the alluvial aquifers of southwest Punjab, both shallow and deep zones were measured for environmental tritium ( 3 H) and stable isotopes ( 2 H and 18 O) to evaluate the source of recharge and aquifer dynamics. The shallow groundwater shows wide variation in isotopic signature (δ 18 O: -11.3 to -5.0‰) reflecting multiple sources of recharge. The average isotopic signature of shallow groundwaters (δ 18 O: -6.73 ± 1.03‰) is similar to that of local precipitation (-6.98 ± 1.66‰) indicating local precipitation contributes to a large extent compared to other sources. Other sources have isotopically distinct signatures due to either high altitude recharge (canal sources) or evaporative enrichment (irrigation return flow). Deep groundwater shows relatively depleted isotopic signature (δ 18 O: -8.6‰) and doesn't show any evaporation effect as compared to shallow zone indicating recharge from precipitation occurring at relatively higher altitudes. Environmental tritium indicates that both shallow ( 3 H: 5 - 10 T.U.) and deeper zone ( 3 H: 1.5 - 2.5 T.U.) groundwaters are modern. In general the inter-aquifer connections seem to be unlikely except a few places. Environmental isotope data suggests that shallow groundwater is dynamic, local and prone to changes in land use patterns while deep zone water is derived from distant sources, less dynamic and not impacted by surface manifestations. A conceptual groundwater flow diagram is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA

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

Sharma, Shikha; Sack, Andrea; Adams, James P.

Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ{sup 13}C{sub DIC}) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in {sup 13}C due to enhanced carbonate dissolution associated with the release of H{sub 2}SO{sub 4} from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional minemore » waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ{sup 34}S{sub SO4} and δ{sup 18}O{sub SO4} isotopic signatures of the mine drainage and the presence of presumptive SO{sub 4}-reducing bacteria suggest that SO{sub 4} reduction activity also contributes C depleted in {sup 13}C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H{sub 2}SO{sub 4} dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO{sub 2} outgassing.« less

Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

PubMed

Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

2016-06-01

The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental data presented in the two-dimensional plot of hydrogen versus carbon stable isotope signatures.

Investigating isotopic signatures of atmospheric nitrous acid (HONO)

NASA Astrophysics Data System (ADS)

Chai, J.; Miller, D. J.; Hastings, M. G.

2016-12-01

Nitrous acid (HONO) is an important reactive nitrogen species that can be easily photolyzed to nitrogen oxide and hydroxyl radical in the troposphere. HONO greatly influences atmospheric oxidation capacity, affecting the formation of tropospheric ozone (O3) and secondary aerosol. Recent studies have indicated that in addition to heterogeneous NOx reactions, biomass burning, soil emission and photolysis of nitric acid (HNO3) on surfaces (e.g. aerosol particles and soot) are also important sources of HONO. However, these sources have not yet been well constrained. The stable isotope ratios in nitrate have been successfully used to trace NOx sources and oxidation chemistry in the atmosphere. Can the isotopic signatures of HONO be used to trace NOx oxidation and renoxification pathways? For this purpose, we have built an annular denuder HONO collection system for the stable isotope study of HONO. Preliminary tests show successful collection and recovery of HONO synthesized in our lab. Nitrogen and oxygen isotopic analysis of the recovered HONO also shows consistent isotopic signatures. Results from field applications of this method in near road and on road environments, agricultural settings, and laboratory based biomass burns will be presented.

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

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

Wimmer, Bernhard, E-mail: bernhard.wimmer@ait.ac.at; Hrad, Marlies; Huber-Humer, Marion

Highlights: ► The isotopic signature of δ{sup 13}C-DIC of leachates is linked to the reactivity of MSW. ► Isotopic signatures of leachates depend on aerobic/anaerobic conditions in landfills. ► In situ aeration of landfills can be monitored by isotope analysis in leachate. ► The isotopic analysis of leachates can be used for assessing the stability of MSW. ► δ{sup 13}C-DIC of leachates helps to define the duration of landfill aftercare. - Abstract: Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated themore » isotopic signatures of δ{sup 13}C, δ{sup 2}H and δ{sup 18}O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ{sup 13}C-value of the dissolved inorganic carbon (δ{sup 13}C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ{sup 13}C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ{sup 13}C-DIC of −20‰ to −25‰. The production of methane under anaerobic conditions caused an increase in δ{sup 13}C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ{sup 13}C-DIC of about −20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation–reduction status of MSW landfills. Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration.« less

Linking stable isotopes and biochemical responses in Balanus glandula under sewage influence.

PubMed

Laitano, M V; Díaz-Jaramillo, M; Rodriguez, Y E; Ducós, E; Panarello, H O; Fernández-Gimenez, A V

2018-02-01

In the present study, we analyzed the influence of untreated sewage exposure on carbon (δ13C) and nitrogen (δ15N) isotopic composition and several biochemical responses in the barnacle Balanus glandula. The main objective was to evaluate whether changes in stable isotopes signature do reflect biochemical sub-lethal effects in a sewage influence gradient. Stable isotopes analysis showed differences in isotope signatures between close sewage influence and distant sites, being δ13C signatures stronger than that of δ15N. Regarding biochemical effects, although organisms close to the effluent would be clearly exposed to contaminants (increased GST activity) the oxidative stress would not be too evident (peroxidases and ACAP not affected). The most affected physiological aspect was the digestive one, reflected in increased alkaline proteases and lipases activities. A clear relation between δ15N and GST activity was found, showing to δ15N as an indicator of potential exposure to chemical contaminants.

Changing sources of strontium to soils and ecosystems across the Hawaiian Islands

USGS Publications Warehouse

Chadwick, O.A.; Derry, L.A.; Bern, C.R.; Vitousek, P.M.

2009-01-01

Strontium isotope ratios assist ecosystem scientists in constraining the sources of alkaline earth elements, but their interpretation can be difficult because of complexities in mineral weathering and in the geographical and environmental controls on elemental additions and losses. Hawaii is a "natural laboratory" where a number of important biogeochemical variables have either limited ranges or vary in systematic ways, providing a unique opportunity to understand the impact of time, climate, and atmospheric inputs on the evolution of base cation sources to ecosystems. There are three major sources of strontium (Sr) to these ecosystems, each with distinct isotopic compositions: basalt lava, Asian dust, and rainfall. We present Sr isotope and concentration data on both bulk soil digests and NH4Ac extracts from soil profiles covering a wide range of environments and substrate ages. Bulk soil material from dry climates and/or young substrate ages with > 80????g g- 1 Sr retain basalt-like Sr isotopic signatures, whereas those with Sr concentrations < 80????g g- 1 can have isotope signatures that range from basalt-like values to the more radiogenic values associated with continental dust. Although both dust accumulation and lava weathering are time- and rainfall-dependent, the overall concentration of Sr drops with increasing leaching even as quartz and mica derived from continental dust sources increase to > 40% by mass. At elevated dust levels, lava-derived Sr is low and dust-derived Sr is the dominant control of 87Sr/86Sr in bulk soils; however, 87Sr/86Sr of NH4Ac-extractable Sr largely reflects atmospheric deposition of marine aerosol in these situations. Overall, whole-soil Sr isotope values are controlled by complex interactions between Sr provided by lava weathering but partially lost by leaching, and Sr provided by dust but held in more resistant minerals. The isotopic composition of NH4Ac-extractable Sr and of the biota is controlled by lava weathering and rainfall contribution of Sr with only minor contributions from radiogenic dust sources. ?? 2009 Elsevier B.V.

Isotopic constraints on global atmospheric methane sources and sinks: a critical assessment of recent findings and new data

NASA Astrophysics Data System (ADS)

Schwietzke, S.; Sherwood, O.; Michel, S. E.; Bruhwiler, L.; Dlugokencky, E. J.; Tans, P. P.

2017-12-01

Methane isotopic data have increasingly been used in recent studies to help constrain global atmospheric methane sources and sinks. The added scientific contributions to this field include (i) careful comparisons and merging of atmospheric isotope measurement datasets to increase spatial coverage, (ii) in-depth analyses of observed isotopic spatial gradients and seasonal patterns, and (iii) improved datasets of isotopic source signatures. Different interpretations have been made regarding the utility of the isotopic data on the diagnosis of methane sources and sinks. Some studies have found isotopic evidence of a largely microbial source causing the renewed growth in global atmospheric methane since 2007, and underestimated global fossil fuel methane emissions compared to most previous studies. However, other studies have challenged these conclusions by pointing out substantial spatial variability in isotopic source signatures as well as open questions in atmospheric sinks and biomass burning trends. This presentation will review and contrast the main arguments and evidence for the different conclusions. The analysis will distinguish among the different research objectives including (i) global methane budget source attribution in steady-state, (ii) source attribution of recent global methane trends, and (iii) identifying specific methane sources in individual plumes during field campaigns. Additional comparisons of model experiments with atmospheric measurements and updates on isotopic source signature data will complement the analysis.

Statistical clumped isotope signatures

PubMed Central

Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.

2016-01-01

High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

Exploring water cycle dynamics by sampling multiple stable water isotope pools in a developed landscape in Germany

NASA Astrophysics Data System (ADS)

Orlowski, Natalie; Kraft, Philipp; Pferdmenges, Jakob; Breuer, Lutz

2016-09-01

A dual stable water isotope (δ2H and δ18O) study was conducted in the developed (managed) landscape of the Schwingbach catchment (Germany). The 2-year weekly to biweekly measurements of precipitation, stream, and groundwater isotopes revealed that surface and groundwater are isotopically disconnected from the annual precipitation cycle but showed bidirectional interactions between each other. Apparently, snowmelt played a fundamental role for groundwater recharge explaining the observed differences to precipitation δ values. A spatially distributed snapshot sampling of soil water isotopes at two soil depths at 52 sampling points across different land uses (arable land, forest, and grassland) revealed that topsoil isotopic signatures were similar to the precipitation input signal. Preferential water flow paths occurred under forested soils, explaining the isotopic similarities between top- and subsoil isotopic signatures. Due to human-impacted agricultural land use (tilling and compression) of arable and grassland soils, water delivery to the deeper soil layers was reduced, resulting in significant different isotopic signatures. However, the land use influence became less pronounced with depth and soil water approached groundwater δ values. Seasonally tracing stable water isotopes through soil profiles showed that the influence of new percolating soil water decreased with depth as no remarkable seasonality in soil isotopic signatures was obvious at depths > 0.9 m and constant values were observed through space and time. Since classic isotope evaluation methods such as transfer-function-based mean transit time calculations did not provide a good fit between the observed and calculated data, we established a hydrological model to estimate spatially distributed groundwater ages and flow directions within the Vollnkirchener Bach subcatchment. Our model revealed that complex age dynamics exist within the subcatchment and that much of the runoff must has been stored for much longer than event water (average water age is 16 years). Tracing stable water isotopes through the water cycle in combination with our hydrological model was valuable for determining interactions between different water cycle components and unravelling age dynamics within the study area. This knowledge can further improve catchment-specific process understanding of developed, human-impacted landscapes.

Principles and limitations of stable isotopes in differentiating organic and conventional foodstuffs: 2. Animal products.

PubMed

Inácio, Caio T; Chalk, Phillip M

2017-01-02

In this review, we examine the variation in stable isotope signatures of the lighter elements (δ 2 H, δ 13 C, δ 15 N, δ 18 O, and δ 34 S) of tissues and excreta of domesticated animals, the factors affecting the isotopic composition of animal tissues, and whether stable isotopes may be used to differentiate organic and conventional modes of animal husbandry. The main factors affecting the δ 13 C signatures of livestock are the C3/C4 composition of the diet, the relative digestibility of the diet components, metabolic turnover, tissue and compound specificity, growth rate, and animal age. δ 15 N signatures of sheep and cattle products have been related mainly to diet signatures, which are quite variable among farms and between years. Although few data exist, a minor influence in δ 15 N signatures of animal products was attributed to N losses at the farm level, whereas stocking rate showed divergent findings. Correlations between mode of production and δ 2 H and δ 18 O have not been established, and only in one case of an animal product was δ 34 S a satisfactory marker for mode of production. While many data exist on diet-tissue isotopic discrimination values among domesticated animals, there is a paucity of data that allow a direct and statistically verifiable comparison of the differences in the isotopic signatures of organically and conventionally grown animal products. The few comparisons are confined to beef, milk, and egg yolk, with no data for swine or lamb products. δ 13 C appears to be the most promising isotopic marker to differentiate organic and conventional production systems when maize (C4) is present in the conventional animal diet. However, δ 13 C may be unsuitable under tropical conditions, where C4 grasses are abundant, and where grass-based husbandry is predominant in both conventional and organic systems. Presently, there is no universal analytical method that can be applied to differentiate organic and conventional animal products.

Growth versus metabolic tissue replacement in mouse tissues determined by stable carbon and nitrogen isotope analysis

NASA Astrophysics Data System (ADS)

Macavoy, S. E.; Jamil, T.; Macko, S. A.; Arneson, L. S.

2003-12-01

Stable isotope analysis is becoming an extensively used tool in animal ecology. The isotopes most commonly used for analysis in terrestrial systems are those of carbon and nitrogen, due to differential carbon fractionation in C3 and C4 plants, and the approximately 3‰ enrichment in 15N per trophic level. Although isotope signatures in animal tissues presumably reflect the local food web, analysis is often complicated by differential nutrient routing and fractionation by tissues, and by the possibility that large organisms are not in isotopic equilibrium with the foods available in their immediate environment. Additionally, the rate at which organisms incorporate the isotope signature of a food through both growth and metabolic tissue replacement is largely unknown. In this study we have assessed the rate of carbon and nitrogen isotopic turnover in liver, muscle and blood in mice following a diet change. By determining growth rates, we were able to determine the proportion of tissue turnover caused by growth versus that caused by metabolic tissue replacement. Growth was found to account for approximately 10% of observed tissue turnover in sexually mature mice (Mus musculus). Blood carbon was found to have the shortest half-life (16.9 days), followed by muscle (24.7 days). Liver carbon turnover was not as well described by the exponential decay equations as other tissues. However, substantial liver carbon turnover was observed by the 28th day after diet switch. Surprisingly, these tissues primarily reflect the carbon signature of the protein, rather than carbohydrate, source in their diet. The nitrogen signature in all tissues was enriched by 3 - 5‰ over their dietary protein source, depending on tissue type, and the isotopic turnover rates were comparable to those observed in carbon.

Differential soil water sourcing of managed Loblolly Pine and Sweet Gum revealed by stable isotopes in the Upper Coastal Plain, USA

NASA Astrophysics Data System (ADS)

Brockman, L. E.; Younger, S. E.; Jackson, C. R.; McDonnell, J.; Janzen, K. F.

2017-12-01

Stable isotope signatures of stem water can illuminate where in the soil profile different types of trees are accessing soil water and thereby contribute to our understanding of water movement through the soil plant atmosphere continuum. The objective of this study was to use 2H and 18O isotopes to characterize water sources of fourteen-year-old intensively managed Loblolly Pine and Sweet Gum stands in replicated (n=3) paired plots. In order to differentiate the isotopic signatures of tree and soil water, both species and five soil depths were sampled monthly for one year. Tree sap and soil water were extracted cryogenically and their isotopic signatures were determined. Although plant water uptake is generally considered a non-fractionating process, our dataset suggests a source of fractionation in 2H signatures in both species and during most of the thirteen sampling events. As a result, only the 18O isotopic data were used to determine the vertical distribution of soil water contributions to stem water. Statistically, we grouped the five soil sampling depths into three isotopic horizons. Shallow, intermediate and deep soil represent sampling depths of 0-10cm, 30-70cm and 100-125cm, respectively. These isotopic horizons were used in a direct inference approach and Bayesian mixing model analysis to determine the origin of stem water. In this study, Loblolly Pine used more water from intermediate and deep soil while Sweet Gum used more water from shallow and intermediate soil. In the winter months, January through March, Loblolly Pine transpired primarily deep soil where as Sweet Gum mainly utilized shallow soil for transpiration. These results indicate that both species have opportunistic water use patterns with seasonal variation.

Carbon isotope analyses of n-alkanes released from rapid pyrolysis of oil asphaltenes in a closed system.

PubMed

Chen, Shasha; Jia, Wanglu; Peng, Ping'an

2016-08-15

Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Supraglacial sulfur springs and associated biological activity in the Canadian high arctic - signs of life beneath the ice

USGS Publications Warehouse

Grasby, Stephen E.; Allen, Carlton C.; Longazo, Teresa G.; Lisle, John T.; Griffin, Dale W.; Beauchamp, Benoit

2003-01-01

Unique springs, discharging from the surface of an arctic glacier, release H2S and deposit native sulfur, gypsum, and calcite. The presence of sulfur in three oxidation states indicates a complex series of redox reactions. Physical and chemical conditions of the spring water and surrounding environment, as well as mineralogical and isotopic signatures, suggest biologically mediated reactions. Cell counts and DNA analyses confirm bacteria are present in the spring system, and a limited number of sequenced isolates suggests that complex communities of bacteria live within the glacial system.

Uniform deposition of uranium hexafluoride (UF6): Standardized mass deposits and controlled isotopic ratios using a thermal fluorination method

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

McNamara, Bruce K.; O’Hara, Matthew J.; Casella, Andrew M.

2016-07-01

Abstract: We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other uranium compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within the chamber to a highly predictable degree. We demonstrate the preparation of uranium deposits that range between ~0.01 and 470±34 ng∙cm-2. The data suggest the method can be extended to creating depositions at the sub-picogram∙cm-2 level. Additionally, the isotopic composition of the deposits can be customized by selection of the uranium source materials. Wemore » demonstrate a layering technique whereby two uranium solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit of UF6 that bears an isotopic signature that is a composite of the two uranium sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics.« less

Geological controls on isotopic signatures of streamflow: results from a nested catchment experiment in Luxembourg (Europe)

NASA Astrophysics Data System (ADS)

Pfister, Laurent; McDonnell, Jeffrey J.; Hissler, Christophe; Martinez-Carreras, Nuria; Gourdol, Laurent; Klaus, Julian; François Iffly, Jean; Barnich, François; Stewart, Mike K.

2014-05-01

Controls of geology and topography on hydrological metrics, like summer low flow (Grant and Tague, 2004) or dynamic storage (Sayama et al., 2011), have been identified in nested catchment experiments. However, most tracer-based studies on streamflow generation have been carried out in small (10 km2) homogenous catchments (Klaus and McDonnell, 2013). The controlling effects of catchment physiography on how catchments store and release water, and how this eventually controls stream isotope behaviour over a large range of scale are poorly understood. Here, we present results from a nested catchment analysis in the Alzette River basin (Luxembourg, Europe). Our hydro-climatological network consists of 16 recording streamgauges and 21 pluviographs. Catchment areas range from 0.47 to 285 km2, with clean and mixed combinations of distinct geologies ranging from schists to marls, sandstone, dolomite and limestone. Our objective was to identify geological controls on (i) winter runoff ratios, (ii) maximum storage and (iii) isotopic signatures in streamflow. For each catchment we determined average runoff ratios from winter season precipitation-discharge double-mass curves. Maximum catchment storage was based on the dynamic storage change approach of Sayama et al. (2011). Changes in isotopic signatures of streamflow were documented along individual catchment flow duration curves. We found strong correlations between average winter runoff ratios, maximum storage and the prevailing geological settings. Catchments with impermeable bedrock (e.g. marls or schists) were characterised by small storage potential and high average filling ratios. As a consequence, these catchments also exhibited the highest average runoff ratios. In catchments underlain by permeable bedrock (e.g. sandstone), storage potential was significantly higher and runoff ratios were considerably smaller. The isotopic signatures of streamflow showed large differences between catchments. In catchments dominated by permeable bedrock, isotopic signatures of streamflow remained stable throughout the entire flow duration curve consistent with a large storage and mixing potential. On less permeable bedrock substrate, we have observed that isotopic signatures in streamflow were much more variable, due to reduced storage volume and comparatively smaller mixing potential. Other metrics such as catchment size and flowpath length exerted a smaller secondary control on isotopic signatures of streamflow in the Alzette River sub-basins. Tague, C., Grant, G.E., 2004. A geological framework for interpreting the low-flow regimes of Cascade streams, Willamette River Basin, Oregon. Water Resources Research, 40(4), doi:10.1029/2003WR002629 Sayama, T., McDonnell, J.J., Dhakal, A., Sullivan, K., 2011. How much water can a watershed store ? Hydrological Processes 25, 3899-3908. Klaus, J., McDonnell, J.J., 2013. Hydrograph separation using stable isotopes: Review and evaluation. Journal of Hydrology 505, 47-64.

Correlations Between Surficial Sulfur and a REE Crustal Assimilation Signature in Martian Shergottites

NASA Technical Reports Server (NTRS)

Jones, J. H.; Franz, H. B.

2015-01-01

Compared to terrestrial basalts, the Martian shergottite meteorites have an extraordinary range of Sr and Nd isotopic signatures. In addition, the S isotopic compositions of many shergottites show evidence of interaction with the Martian surface/ atmosphere through mass-independent isotopic fractionations (MIF, positive, non-zero delta(exp 33)S) that must have originated in the Martian atmosphere, yet ultimately were incorporated into igneous sulfides (AVS - acid-volatile sulfur). These positive delta(exp 33)S signatures are thought to be governed by solar UV photochemical processes. And to the extent that S is bound to Mars and not lost to space from the upper atmosphere, a positive delta(exp 33)S reservoir must be mass balanced by a complementary negative reservoir.

Methane Emissions in the London Region: Deciphering Regional Sources with Mobile Measurements

NASA Astrophysics Data System (ADS)

Zazzeri, G.; Lowry, D.; Fisher, R. E.; France, J. L.; Lanoisellé, M.; Bjorkegren, A.; Nisbet, E. G.

2014-12-01

Methane stable isotope analysis, coupled with mole fraction measurement, has been used to link isotopic signature to methane emissions from the leading methane sources in the London region, such as landfills and gas leaks. A mobile Picarro G2301 CRDS analyser was installed in a vehicle, together with an anemometer and a Hemisphere GPS receiver, to measure atmospheric methane mole fractions and their relative location. When methane plumes were located and intercepted, air samples were collected in Tedlar bags, for δ13C-CH4 isotopic analysis by CF-GC-IRMS (Continous Flow-Gas Chromatography-Isotopic Ratio Mass Spectroscopy). This method provides high precision isotopic values, determining δ13C-CH4 to ±0.05 per mil. The bulk signature of the methane plume into the atmosphere from the whole source area was obtained by Keeling plot analysis, and a δ13C-CH4 signature, with the relative uncertainty, allocated to each methane source investigated. The averaged δ13C-CH4 signature for landfill sites around the London region is - 58 ± 3 ‰, whereas the δ13C-CH4 signature for gas leaks is fairly constant at -36 ± 2 ‰, a value characteristic of North Sea supply. The Picarro G2301 analyser was installed also on the roof of King's College London, located in the centre of the city, and connected to an air inlet located 7 meters above roof height. An auto-sampler was connected to the same air inlet and launched remotely when a high nocturnal build up was expected, allowing up to twenty air bags to be collected for methane isotopic analysis over a 24 hour period. The main source contributing to overnight methane build up in central London is fugitive gas, in agreement with inventories. From the isotopic characterisation of urban methane sources and the source mix in London, the contribution to the urban methane budget and the local distribution of the methane sources given in inventories can be validated.

Estimation of lake water - groundwater interactions in meromictic mining lakes by modelling isotope signatures of lake water.

PubMed

Seebach, Anne; Dietz, Severine; Lessmann, Dieter; Knoeller, Kay

2008-03-01

A method is presented to assess lake water-groundwater interactions by modelling isotope signatures of lake water using meteorological parameters and field data. The modelling of delta(18)O and deltaD variations offers information about the groundwater influx into a meromictic Lusatian mining lake. Therefore, a water balance model is combined with an isotope water balance model to estimate analogies between simulated and measured isotope signatures within the lake water body. The model is operated with different evaporation rates to predict delta(18)O and deltaD values in a lake that is only controlled by weather conditions with neither groundwater inflow nor outflow. Comparisons between modelled and measured isotope values show whether the lake is fed by the groundwater or not. Furthermore, our investigations show that an adaptation of the Craig and Gordon model [H. Craig, L.I. Gordon. Deuterium and oxygen-18 variations in the ocean and the marine atmosphere. In Stable Isotopes in Oceanographic Studies and Paleotemperature, Spoleto, E. Tongiorgi (Ed.), pp. 9-130, Consiglio Nazionale delle Ricerche, Laboratorio di Geologia Nucleare, Pisa (1965).] to specific conditions in temperate regions seems necessary.

The Mg isotopic systematics of granitoids in continental arcs and implications for the role of chemical weathering in crust formation

PubMed Central

Shen, Bing; Jacobsen, Benjamin; Lee, Cin-Ty A.; Yin, Qing-Zhu; Morton, Douglas M.

2009-01-01

Continental crust is too Si-rich and Mg-poor to derive directly from mantle melting, which generates basaltic rather than felsic magmas. Converting basalt to more felsic compositions requires a second step involving Mg loss, which is thought to be dominated by internal igneous differentiation. However, igneous differentiation alone may not be able to generate granites, the most silicic endmember making up the upper continental crust. Here, we show that granites from the eastern Peninsular Ranges Batholith (PRB) in southern California are isotopically heavy in Mg compared with PRB granodiorites and canonical mantle. Specifically, Mg isotopes correlate positively with Si content and O, Sr, and Pb isotopes and negatively with Mg content. The elevated Sr and Pb isotopes require that a component in the source of the granitic magmas to be ancient preexisting crust making up the prebatholithic crustal basement, but the accompanying O and Mg isotope fractionations suggest that this prebatholithic crust preserved a signature of low-temperature alteration. The protolith of this basement rock may have been the residue of chemical weathering, which progressively leached Mg from the residue, leaving the remaining Mg highly fractionated in terms of its isotopic signature. Our observations indicate that ancient continental crust preserves the isotopic signature of compositional modification by chemical weathering. PMID:19920171

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.

Metal isotope coded profiling of organic ligands by mass spectrometry in aquatic environments

NASA Astrophysics Data System (ADS)

Wichard, Thomas; Deicke, Michael; Frieder Mohr, Jan; Klein, Martin

2017-04-01

Metal isotope coded profiling (MICP) introduces a universal discovery platform for metal chelating natural products that act as metallophores, ion buffers or sequestering agents. The detection of cation and oxoanion complexing ligands is facilitated by the identification of unique isotopic signatures created by the application of isotopically pure metals. We present a targeted analysis of low-molecular-weight organic ligands based on fast UHPLC-ESI-MS measurements. Replacement of, for example, natural iron or molybdenum with isotopically pure 54Fe/58Fe (ratio 1:1) or 95Mo/98Mo (ratio 1:1) causes easily detectable unique isotopic signatures in the mass spectra of potential metal-complexing ligands. This can be achieved under laboratory conditions not only in growth media, but also by spiking directly aqueous samples or solid-phase extracts. Importantly, as the relative affinity of the metallophores for e.g., Mo or Fe is dependent on the pH, all experiments needs to be conducted under pH-controlled conditions. The improved ionization efficiency of some metal complexes helps to enhance the signal-to-noise ratio compared to the free ligand at the same chromatographic conditions. The methodology does not necessarily depend on HR-ESI-MS measurements (e.g., Q-Exactive Orbitrap) and can be applied to any mass spectrometer. With MICP, two birds can be killed with one stone: (i) the identification of metallophores (e.g., siderophores, molybdophores) for metal uptake by any organism and (ii) organic ligands which solely work as metal buffer in dissolved organic matter (DOM). We currently address following two main research lines: First, DOM has often been used as a proxy for bio-productivity in terms of a carbon source; however, the specific impact of DOM as a "metal buffer" for biological processes is still under-investigated. Upon the administration of individual isotopes or isotopic pairs, for example, 54Fe/58Fe, 63Cu/65Cu, 66Zn/68Zn, or 95Mo/98Mo and subsequent measurements by mass spectrometry, organic ligands can be identified that contribute potentially to the regulation of bioavailability and toxicity of metals in the water column. Secondly, metal acquisition by ligand exchange processes is vital for macroalgae-bacteria interactions. Both alga and bacteria contribute to the "soup of organic ligands" which potentially increases the bioavailability of metals due to various ligand exchanges with DOM. In particular, we will outline the analytical process resulting in the identification of ligands in the chemosphere of the marine macroalga Ulva (Chlorophyta) and its associated bacteria. In summary, the identification of metal organic ligands in natural samples will pave the way for understanding the organic ligand-mediated metal acquisition shuttled from DOM to alga. (References: Wichard T. (2016) Front. Mar. Sci. 3:131; Deicke M., Mohr J.M., Wichard T. (2014) Analyst, 139, 6096-6099)

Trawling disturbance on the isotopic signature of a structure-building species, the sea urchin Gracilechinus acutus (Lamarck, 1816)

NASA Astrophysics Data System (ADS)

González-Irusta, José M.; Preciado, Izaskun; López-López, Lucia; Punzón, Antonio; Cartes, Joan E.; Serrano, Alberto

2014-08-01

Bottom trawling is one of the main sources of anthropogenic disturbance in benthic habitats with important direct and indirect effects on the ecosystem functional diversity. In this study, the effect of this impact on a structure-building species, the sea urchin Gracilechinus acutus, was studied in the Central Cantabrian Sea (southern Bay of Biscay) comparing its isotopic signature and additional population descriptors across different trawling pressures. Trawling disturbance had a significant effect on the studied descriptors. In trawling areas, this urchin showed significantly lower values of biomass and mean size and significantly higher values of fullness index. Moreover, the trawling disturbance effect was also significant in the isotopic signature of G. acutus. Urchins inhabiting untrawled areas showed significant lower values of δ15N than urchins dwelling areas under trawling pressure. The urchins' isotopic enrichment increased along the species ontogeny regardless of the trawling effort level. Stable isotope analyses are a suitable tool to detect trawling disturbance on the trophic pathways but do not suffice to explain these changes, especially if there is a lack of baseline information.

Lead isotope database of unpublished results from sulfide mineral occurrences-California, Idaho, Oregon, and Washington

USGS Publications Warehouse

Church, S.E.

2010-01-01

The Pb isotope database for sulfide deposits and occurrences in the Western United States was funded by the Mineral Resources Program, U.S. Geological Survey (USGS). Reports on Pb isotope data from Alaska were published in Church and others (1987a) and Gaccetta and Church (1989). The primary objectives of the project were three-fold: * To utilize Pb isotope signatures, in conjunction with the regional mapping, to assess the relative ages and to categorize the types of deposits studied, * To relate the Pb isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and * To use the Pb isotope data to correlate lithotectonic terranes within the northern Cordillera. The report by Church and others (1987b) shows how this fingerprinting methodology can be applied to trace the offset of lithostratigraphic terranes

Stable isotopes in juvenile marine fishes and their invertebrate prey from the Thames Estuary, UK, and adjacent coastal regions

NASA Astrophysics Data System (ADS)

Leakey, Chris D. B.; Attrill, Martin J.; Jennings, Simon; Fitzsimons, Mark F.

2008-04-01

Estuaries are regarded as valuable nursery habitats for many commercially important marine fishes, potentially providing a thermal resource, refuge from predators and a source of abundant prey. Stable isotope analysis may be used to assess relative resource use from isotopically distinct sources. This study comprised two major components: (1) development of a spatial map and discriminant function model of stable isotope variation in selected invertebrate groups inhabiting the Thames Estuary and adjacent coastal regions; and (2) analysis of stable isotope signatures of juvenile bass ( Dicentrarchus labrax), sole ( Solea solea) and whiting ( Merlangius merlangus) for assessment of resource use and feeding strategies. The data were also used to consider anthropogenic enrichment of the estuary and potential energetic benefits of feeding in estuarine nursery habitat. Analysis of carbon (δ 13C), nitrogen (δ 15N) and sulphur (δ 34S) isotope data identified significant differences in the 'baseline' isotopic signatures between estuarine and coastal invertebrates, and discriminant function analysis allowed samples to be re-classified to estuarine and coastal regions with 98.8% accuracy. Using invertebrate signatures as source indicators, stable isotope data classified juvenile fishes to the region in which they fed. Feeding signals appear to reflect physiological (freshwater tolerance) and functional (mobility) differences between species. Juvenile sole were found to exist as two isotopically-discrete sub-populations, with no evidence of mixing between the two. An apparent energetic benefit of estuarine feeding was only found for sole.

Variation in nitrate isotopic signatures in sewage for source apportionment with urbanization: a case study in Beijing, China.

PubMed

Xian, Chaofan; Ouyang, Zhiyun; Li, Yanmin; Xiao, Yang; Ren, Yufen

2016-11-01

Nitrate (NO 3 - ) pollution is a severe problem in urban aquatic systems especially within megacity undergoing rapid urbanization, and mostly, sewage is supposed as the prevailing NO 3 - source. A dual isotope approach (δ 15 N-NO 3 - and δ 18 O-NO 3 - ) was applied to explore the variation in NO 3 - isotopic signatures in sewage processed by wastewater treatment plants (WWTPs) in Beijing from 2014 to 2015. We found that the raw and treated sewage owned the different NO 3 - isotopic signatures, including δ 15 N from 1.1 to 24.7 ‰ and δ 18 O from 1.6 to 22.8 ‰ in raw sewage, as well as δ 15 N from 6.1 to 22.8 ‰ and δ 18 O from 1.6 to 13.2 ‰ in treated effluents. The WWTP processing would result in the enrichment of NO 3 - isotopic compositions in discharged effluents with NO 3 - concentrations increasing. Besides, advanced sewage treatment technology with more pollutant N reduction may raise the heavier NO 3 - isotopic compositions further. The NO 3 - isotope value ranges of urban sewage and manure should be separated, and the seasonal and tighter NO 3 - isotope value ranges are supposed to improve the accuracy of source apportionment. The NO 3 - isotope value ranges conducted in this study might provide useful information for tracing NO 3 - sources towards the implementation of efficient water pollution control in Beijing.

Using Oxygen and Carbon Isotopic Signatures in Order to Infer Climatic and Dietary Information in Roman Edessa, Greece

NASA Astrophysics Data System (ADS)

Michael, Dimitra-Ermioni; Dotsika, Elissavet

2017-12-01

Even though many isotopic studies have been conducted on ancient populations from Greece for the purpose of dietary reconstruction; mostly through carbon and nitrogen isotopic signals of bone collagen, less attention has been given to the utility of apatite signatures (oxygen and carbon) as dietary and palaeoenvironmental tools. Moreover, until recently the isotopic signal of tooth enamel for both the purposes of environmental and dietary reconstructions has been rarely assessed in ancient Greek societies. Therefore, the present study aims to provide with novel isotopic information regarding Edessa; a town in Northern Greece, during the Roman period. The current study primarily aims to explore the possible differentiation between the present climatic conditions in Edessa in relation to those occurring at the Roman period. Secondly, this study aims to reveal the significant utility of enamel isotopic signatures (carbon and oxygen) in palaeoenvironmental and palaeodietary studies regarding ancient human remains. The isotopic analyses have been conducted at the Stable Isotope and Radiocarbon Unit of INN, NCSR “Demokritos”. The population of Roman Edessa (2nd-4th c. AD) consists of 22 individuals, providing with 19 bone samples and 16 enamel ones. The mean enamel oxygen value is at -7.7 ±1.1 %0, the bone apatite mean oxygen value at -9.2 ±1.9 %0, and finally the mean carbon enamel value is at -11.7 ±1.2 %0. Oxygen values probably indicate that Edessa had a cooler climate during the Roman times in relation to present conditions, even though more research should be carried out in order to be more certain. In addition, the possible existence of non-local individuals has been revealed through the oxygen teeth enamel-bone apatite spacing. Finally, the carbon enamel signature has pointed out possible differentiations between the adult and the juvenile diet. Based on Edessa’s findings, the stated study strongly encourages the enamel oxygen and carbon isotopic signals as palaeoclimatological and palaeodietary tools respectively.

Isotopic variability of cave bears (δ15N, δ13C) across Europe during MIS 3

NASA Astrophysics Data System (ADS)

Krajcarz, Magdalena; Pacher, Martina; Krajcarz, Maciej T.; Laughlan, Lana; Rabeder, Gernot; Sabol, Martin; Wojtal, Piotr; Bocherens, Hervé

2016-01-01

Collagen, the organic fraction of bone, records the isotopic parameters of consumed food for carbon (δ13C) and nitrogen (δ15N). This relationship of isotopic signature between diet and tissue is an important tool for the study of dietary preferences of modern and fossil animal species. Since the first information on the isotopic signature of cave bear was reported, numerous data from Europe have become available. The goal of this work is to track the geographical variation of cave bear collagen isotopic values in Europe during Marine Isotopic Stage 3 (about 60,000-25,000 yr BP). In this study the results of new δ13C and δ15N isotopic analyses of cave bear collagen from four Central-Eastern European sites are presented, as well as a review of all published isotopic data for cave bears of the same period. The main conclusion is a lack of geographical East-West pattern in the variations of δ13C and δ15N values of cave bear collagen. Moreover, no relationship was found between cave bear taxonomy and isotopic composition. The cave bears from Central-Eastern Europe exhibit δ13C and δ15N values near the average of the range of Central, Western and Southern European cave bears. Despite the fact that most cave bear sites follow an altitudinal gradient, separate groups of sites exhibit shift in absolute values of δ13C, what disturbs an altitude-related isotopic pattern. The most distinct groups are: high Alpine sites situated over 1500 m a.s.l. - in terms of δ13C; and two Romanian sites Peştera cu Oase and Urşilor - in case of δ15N. Although the cave bear isotopic signature is driven by altitude, the altitudinal adjustment of isotopic data is not enough to explain the isotopic dissimilarity of these cave bears. The unusually high δ15N signature of mentioned Romanian sites is an isolated case in Europe. Cave bears from relatively closely situated Central-Eastern European sites and other Romanian sites are more similar to Western European than to Romanian populations in terms of isotopic composition, and probably ecology.

Assessment of the Interstellar Processes Leading to Deuterium Enrichment in Meteoritic Organics

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Bernstein, Max P.; Dworkin, Jason P.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low temperature gas phase ion-molecule reactions, low temperature gas-grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D-enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, 0, and N in the same compounds.

Stable isotope patterns in micronekton from the Mozambique Channel

NASA Astrophysics Data System (ADS)

Ménard, Frédéric; Benivary, Hermann Doris; Bodin, Nathalie; Coffineau, Nathalie; Le Loc'h, François; Mison, Thomas; Richard, Pierre; Potier, Michel

2014-02-01

We measured the stable carbon (δ13C) and nitrogen (δ15N) isotopic composition of tissues of micronektonic organisms (fishes, squids, crustaceans and gelatinous organisms) collected in the Mozambique Channel during two scientific cruises in 2008 and 2009. The oceanic circulation in the Mozambique Channel is dominated by mesoscale cyclonic and anticyclonic eddies which play a key role in biological processes of less-productive deep-sea ecosystems. We investigated the potential impact of mesoscale features on the δ13C and δ15N values of 32 taxa of micronekton. Fishes, squids, crustaceans and gelatinous organisms encompassed a wide range of isotopic niches, with large overlaps among species. Our results showed that mesoscale features did not really influence the isotopic signatures of the sampled organisms, although cyclonic eddies can occasionally impact the nitrogen signatures of micronekton. We show that δ13C values were intermediate between standard offshore and nearshore signatures, suggesting that pelagic production in the Mozambique Channel could be partly supported by the transport and export of inorganic and organic particles from the Mozambican coast toward the offshore area. Trophic levels calculated from δ15N values ranged from 2.6 to 4.2, showing that micronekton taxa can be tertiary consumers in the Mozambique Channel. Our findings evidenced clusters of micronektonic organisms according to their δ15N or δ13C isotopic signatures, but variations in stable isotope values reflect a complex set of embedded processes linked to physical mesoscale dynamics (rotational dynamics of eddies) and basic biology and ecology of micronektonic organisms (vertical habitat, migration pattern, dietary habits, body length) that are discussed with regard to the stable isotope method based on time-integrated assimilated food.

Assessing ecohydrological controls on catchment water storage, flux and age dynamics using tracers in a physically-based, spatially distributed model

NASA Astrophysics Data System (ADS)

Kuppel, S.; Tetzlaff, D.; Maneta, M. P.; Soulsby, C.

2017-12-01

Stable water isotope tracing has been extensively used in a wide range of geographical environments as a means to understand the sources, flow paths and ages of water stored and exiting a landscape via evapotranspiration, surface runoff and/or stream flow. Comparisons of isotopic signatures of precipitation and water in streams, soils, groundwater and plant xylem facilitates the assessment of how plant water use may affect preferential hydrologic pathways, storage dynamics and transit times in the critical zone. While tracers are also invaluable for testing model structure and accuracy, in most cases the measured isotopic signatures have been used to guide the calibration of conceptual runoff models with simplified vegetation and energy balance representation, which lacks sufficient detail to constrain key ecohydrological controls on flow paths and water ages. Here, we use a physically-based, distributed ecohydrological model (EcH2O) which we have extended to track 2H and 18O (including fractionation processes), and water age. This work is part of the "VeWa" project which aims at understanding ecohydrological couplings across climatic gradients in the wider North, where the hydrological implications of projected environmental change are essentially unknown though expected to be high. EcH2O combines a hydrologic scheme with an explicit representation of plant growth and phenology while resolving the energy balance across the soil-vegetation-atmosphere continuum. We focus on a montane catchment in Scotland, where unique long-term, high resolution hydrometric, ecohydrological and isotopic data allows for extensive model testing and projections. Results show the importance of incorporating soil fractionation processes to explain stream isotope dynamics, particularly seasonal enrichment in this humid, energy-limited catchment. This generic process-based approach facilitates analysis of dynamics in isotopes, storage and ages for the different hydrological compartments (canopy to groundwater) and, in particular, the explicit partitioning between soil evaporation and plant transpiration. Our study clearly advances our understanding of dynamics in water storage, flux and age in northern ecosystems, integrating ecohydrology, unsaturated zone, surface water, and groundwater hydrology.

Analysis of dissolved organic carbon concentration and 13C isotopic signature by TOC-IRMS - assessment of analytical performance

NASA Astrophysics Data System (ADS)

Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

2013-04-01

Stable carbon isotopes provide a powerful tool to assess carbon pools and their dynamics. Dissolved organic carbon (DOC) has been recognized to play an important role in ecosystem functioning and carbon cycling and has therefore gained increased research interest. However, direct measurement of 13C isotopic signature of carbon in the dissolved phase is technically challenging particularly using high temperature combustion. Until recently, mainly custom-made systems existed which were modified for coupling of TOC instruments with IRMS for simultaneous assessment of C content and isotopic signature. The variety of coupled systems showed differences in their analytical performances. For analysis of DOC high temperature combustion is recognized as best performing method, owing to its high efficiency of conversion to CO2 also for highly refractory components (e.g. humic, fulvic acids) present in DOC and soil extracts. Therefore, we tested high temperature combustion TOC coupled to IRMS (developed by Elementar Group) for bulk measurements of DOC concentration and 13C signature. The instruments are coupled via an Interface to exchange the carrier gas from O2 to He and to concentrate the derived CO2 for the isotope measurement. Analytical performance of the system was assessed for a variety of organic compounds characterized by different stability and complexity, including humic acid and DOM. We tested injection volumes between 0.2-3 ml, thereby enabling measurement of broad concentration ranges. With an injection volume of 0.5 ml (n=3, preceded by 1 discarded injection), DOC and 13C signatures for concentrations between 5-150 mg C/L were analyzed with high precision (standard deviation (SD) predominantly <0.1‰), good accuracy and linearity (overall SD <0.9‰). For the same settings, slightly higher variation in precision was observed among the lower concentration range and depending upon specific system conditions. Differences in 13C signatures of about 50‰ among samples did not affect the precision of the analysis of natural abundance and labeled samples. Natural DOM, derived from different soils and assessed at various concentrations, was measured with similar good analytical performance, and also tested for the effect of freezing and re-dissolving. We found good performance of TOC-IRMS in comparison with other systems capable of determining C concentration and isotopic signatures. We recognize the advantages of this system providing: - High sample throughput, short measurement time (15 minutes), flexible sample volume - Easy maintenance, handling, rapid sample preparation (no pretreatment) This preliminary assessment highlights wide-ranging opportunities for further research on concentrations and isotopic signatures by TOC-IRMS to elucidate the role of dissolved carbon in terrestrial and aquatic systems.

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

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

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

Seabird satellite tracking validates the use of latitudinal isoscapes to depict predators' foraging areas in the Southern Ocean.

PubMed

Jaeger, Audrey; Lecomte, Vincent J; Weimerskirch, Henri; Richard, Pierre; Cherel, Yves

2010-12-15

Stable isotopes are increasingly being used to trace wildlife movements. A fundamental prerequisite of animal isotopic tracking is a good knowledge of spatial isotopic variations in the environment. Few accessible reference maps of the isotopic landscape ("isoscapes") are available for marine predators. Here, we validate for the first time an isotopic gradient for higher trophic levels by using a unique combination of a large number of satellite-tracks and subsequent blood plasma isotopic signatures from a wide-ranging oceanic predator. The plasma δ(13)C and δ(15)N values of wandering albatrosses (n = 45) were highly and positively correlated to the Southern Ocean latitudes at which the satellite-tracked individuals foraged. The well-defined latitudinal baseline carbon isoscapes in the Southern Ocean is thus reflected in the tissue of consumers, but with a positive shift due to the cumulative effect of a slight (13)C-enrichment at each trophic level. The data allowed us to estimate the carbon isotopic position of the main oceanic fronts in the area, and thus to delineate robust isoscapes of the main foraging zones for top predators. The plasma δ(13)C and δ(15)N values were positively and linearly correlated, thus suggesting that latitudinal isoscapes also occur for δ(15)N at the base of the food web in oceanic waters of the Southern Ocean. The combination of device deployments with sampling of relevant tissues for isotopic analysis appears to be a powerful tool for investigating consumers' isoscapes at various spatio-temporal scales. Copyright © 2010 John Wiley & Sons, Ltd.

Carbon Isotopes Profiles of Human Whole Blood, Plasma, Red Blood Cells, Urine and Feces for Biological/Biomedical 14C-Accelerator Mass Spectrometry Applications

PubMed Central

Kim, Seung-Hyun; Chuang, Jennifer C.; Kelly, Peter B.; Clifford, Andrew J.

2011-01-01

Radiocarbon (14C) is an ideal tracer for in vivo human ADME (absorption, distribution, metabolism, elimination) and PBPK (physiological-based pharmacokinetic) studies. Living plants preferentially incorporate atmospheric 14CO2, vs 13CO2, vs 12CO2, which result in unique signature. Furthermore, plants and the food chains they support also have unique carbon isotope signatures. Humans, at the top of the food chain, consequently acquire isotopic concentrations in the tissues and body fluids depending on their dietary habits. In preparation of ADME and PBPK studies, 12 healthy subjects were recruited. The human baseline (specific to each individual and their diet) total carbon (TC) and carbon isotope 13C (δ13C) and 14C (Fm) were quantified in whole blood (WB), plasma, washed red blood cell (RBC), urine, and feces. TC (mg of C/100μL) in WB, plasma, RBC, urine, and feces were 11.0, 4.37, 7.57, 0.53, and 1.90, respectively. TC in WB, RBC, and feces was higher in men over women, P < 0.05. Mean δ13C were ranked low to high as follows, feces < WB = plasma = RBC = urine, P < 0.0001. δ13C was not affected by gender. Our analytic method shifted δ13C by only ± 1.0 ‰ ensuring our Fm measurements were accurate and precise. Mean Fm were ranked low to high as follows, plasma = urine < WB = RBC = feces, P < 0.05. Fm in feces was higher for men over women, P < 0.05. Only in WB, 14C levels (Fm) and TC were correlated with one another (r = 0.746, P < 0.01). Considering the lag time to incorporate atmospheric 14C into plant foods (vegetarian) and or then into animal foods (non-vegetarian), the measured Fm of WB in our population (recruited April 2009) was 1.0468 ± 0.0022 (mean±SD), the Fm of WB matched the (extrapolated) atmospheric Fm of 1.0477 in 2008. This study is important in presenting a procedure to determine a baseline for a study group for human ADME and PBPK studies using 14C as a tracer. PMID:21452856

INCORPORATING CONCENTRATION DEPENDENCE IN STABLE ISOTOPE MIXING MODELS

EPA Science Inventory

Stable isotopes are frequently used to quantify the contributions of multiple sources to a mixture; e.g., C and N isotopic signatures can be used to determine the fraction of three food sources in a consumer's diet. The standard dual isotope, three source linear mixing model ass...

INCORPORATING CONCENTRATION DEPENDENCE IN STABLE ISOTOPE MIXING MODELS

EPA Science Inventory

Stable isotopes are often used as natural labels to quantify the contributions of multiple sources to a mixture. For example, C and N isotopic signatures can be used to determine the fraction of three food sources in a consumer's diet. The standard dual isotope, three source li...

Comparative isotope ecology of African great apes.

PubMed

Oelze, Vicky M; Fahy, Geraldine; Hohmann, Gottfried; Robbins, Martha M; Leinert, Vera; Lee, Kevin; Eshuis, Henk; Seiler, Nicole; Wessling, Erin G; Head, Josephine; Boesch, Christophe; Kühl, Hjalmar S

2016-12-01

The isotope ecology of great apes is a useful reference for palaeodietary reconstructions in fossil hominins. As extant apes live in C 3 -dominated habitats, variation in isotope signatures is assumed to be low compared to hominoids exploiting C 4 -plant resources. However, isotopic differences between sites and between and within individuals are poorly understood due to the lack of vegetation baseline data. In this comparative study, we included all species of free-ranging African great apes (Pan troglodytes, Pan paniscus, Gorilla sp.). First, we explore differences in isotope baselines across different habitats and whether isotopic signatures in apes can be related to feeding niches (faunivory and folivory). Secondly, we illustrate how stable isotopic variations within African ape populations compare to other extant and extinct primates and discuss possible implications for dietary flexibility. Using 701 carbon and nitrogen isotope data points resulting from 148 sectioned hair samples and an additional collection of 189 fruit samples, we compare six different great ape sites. We investigate the relationship between vegetation baselines and climatic variables, and subsequently correct great ape isotope data to a standardized plant baseline from the respective sites. We obtained temporal isotopic profiles of individual animals by sectioning hair along its growth trajectory. Isotopic signatures of great apes differed between sites, mainly as vegetation isotope baselines were correlated with site-specific climatic conditions. We show that controlling for plant isotopic characteristics at a given site is essential for faunal data interpretation. While accounting for plant baseline effects, we found distinct isotopic profiles for each great ape population. Based on evidence from habituated groups and sympatric great ape species, these differences could possibly be related to faunivory and folivory. Dietary flexibility in apes varied, but temporal variation was overall lower than in fossil hominins and extant baboons, shifting from C 3 to C 4 -resources, providing new perspectives on comparisons between extinct and extant primates. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrochemically controlled iron isotope fractionation

NASA Astrophysics Data System (ADS)

Black, Jay R.; Young, Edward D.; Kavner, Abby

2010-02-01

Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

Thermal equilibration of iron meteorite and pallasite parent bodies recorded at the mineral scale by Fe and Ni isotope systematics

NASA Astrophysics Data System (ADS)

Chernonozhkin, Stepan M.; Weyrauch, Mona; Goderis, Steven; Oeser, Martin; McKibbin, Seann J.; Horn, Ingo; Hecht, Lutz; Weyer, Stefan; Claeys, Philippe; Vanhaecke, Frank

2017-11-01

In this work, a femtosecond laser ablation (LA) system coupled to a multi-collector inductively coupled plasma-mass spectrometer (fs-LA-MC-ICP-MS) was used to obtain laterally resolved (30-80 μm), high-precision combined Ni and Fe stable isotope ratio data for a variety of mineral phases (olivine, kamacite, taenite, schreibersite and troilite) composing main group pallasites (PMG) and iron meteorites. The stable isotopic signatures of Fe and Ni at the mineral scale, in combination with the factors governing the kinetic or equilibrium isotope fractionation processes, are used to interpret the thermal histories of small differentiated asteroidal bodies. As Fe isotopic zoning is only barely resolvable within the internal precision level of the isotope ratio measurements within a single olivine in Esquel PMG, the isotopically lighter olivine core relative to the rim (Δ56/54Ferim-core = 0.059‰) suggests that the olivines were largely thermally equilibrated. The observed hint of an isotopic and concentration gradient for Fe of crudely similar width is interpreted here to reflect Fe loss from olivine in the process of partial reduction of the olivine rim. The ranges of the determined Fe and Ni isotopic signatures of troilite (δ56/54Fe of -0.66 to -0.09‰) and schreibersite (δ56/54Fe of -0.48 to -0.09‰, and δ62/60Ni of -0.64 to +0.29‰) may result from thermal equilibration. Schreibersite and troilite likely remained in equilibrium with their enclosing metal to temperatures significantly below their point of crystallization. The Ni isotopic signatures of bulk metal and schreibersite correlate negatively, with isotopically lighter Ni in the metal of PMGs and isotopically heavier Ni in the metal of the iron meteorites analyzed. As such, the light Ni isotopic signatures previously observed in PMG metal relative to chondrites may not result from heterogeneity in the Solar Nebula, but rather reflect fractionation in the metal-schreibersite system. Comparison between the isotope ratio profiles of Fe and Ni determined across kamacite-taenite interfaces (Δ56/54Fekam-tae = -0.51 to -0.69‰ and Δ62/60Nikam-tae = +1.59 to +2.50‰) and theoretical taenite sub-solidus diffusive isotopic zoning broadly constrain the cooling rates of Esquel, CMS 04071 PMGs and Udei Station IAB to between ∼25 and 500 °C/Myr.

Argon Isotopes Provide Robust Signature of Atmospheric Loss

NASA Image and Video Library

2013-04-08

This image, made by the quadrupole mass spectrometer in the SAM suite of instruments in NASA Curiosity Mars rover. shows the ratio of the argon isotope argon-36 to the heavier argon isotope argon-38, in various measurements.

Isotopic signatures suggest important contributions from recycled gasoline, road dust and non-exhaust traffic sources for copper, zinc and lead in PM10 in London, United Kingdom

NASA Astrophysics Data System (ADS)

Dong, Shuofei; Ochoa Gonzalez, Raquel; Harrison, Roy M.; Green, David; North, Robin; Fowler, Geoff; Weiss, Dominik

2017-09-01

The aim of this study was to improve our understanding of what controls the isotope composition of Cu, Zn and Pb in particulate matter (PM) in the urban environment and to develop these isotope systems as possible source tracers. To this end, isotope ratios (Cu, Zn and Pb) and trace element concentrations (Fe, Al, Cu, Zn, Sb, Ba, Pb, Cr, Ni and V) were determined in PM10 collected at two road sites with contrasting traffic densities in central London, UK, during two weeks in summer 2010, and in potential sources, including non-combustion traffic emissions (tires and brakes), road furniture (road paint, manhole cover and road tarmac surface) and road dust. Iron, Ba and Sb were used as proxies for emissions derived from brake pads, and Ni, and V for emissions derived from fossil fuel oil. The isotopic composition of Pb (expressed using 206Pb/207Pb) ranged between 1.1137 and 1.1364. The isotope ratios of Cu and Zn expressed as δ65CuNIST976 and δ66ZnLyon ranged between -0.01‰ and +0.51‰ and between -0.21‰ and +0.33‰, respectively. We did not find significant differences in the isotope signatures in PM10 over the two weeks sampling period and between the two sites, suggesting similar sources for each metal at both sites despite their different traffic densities. The stable isotope composition of Pb suggests significant contribution from road dust resuspension and from recycled leaded gasoline. The Cu and Zn isotope signatures of tires, brakes and road dust overlap with those of PM10. The correlation between the enrichments of Sb, Cu, Ba and Fe in PM10 support the previously established hypothesis that Cu isotope ratios are controlled by non-exhaust traffic emission sources in urban environments (Ochoa Gonzalez et al., 2016). Analysis of the Zn isotope signatures in PM10 and possible sources at the two sites suggests significant contribution from tire wear. However, temporary additional sources, likely high temperature industrial emissions, need to be invoked to explain the isotopically light Zn found in 3 out of 18 samples of PM10.

Two mantle domains and the time scales of fluid transfer beneath the Vanuatu arc

NASA Astrophysics Data System (ADS)

Turner, Simon P.; Peate, David W.; Hawkesworth, Chris J.; Eggins, Stephen M.; Crawford, Anthony J.

1999-11-01

U-Th isotope disequilibria can provide constraints on the time elapsed since fluid addition to the mantle wedge beneath island arcs. The Vanuatu arc offers new insights into these processes because Pb isotopes there are not dominated by components from the subducting plate and so preserve the signatures of the mantle wedge. The Pb isotope data document the presence of separate Pacific and Indian mantle domains beneath the arc volcanoes. The Indian mantle was brought beneath the central part of the arc from the backarc by collision with the D'Entrecasteaux Ridge, resulting in a slowing of subduction there. The distinction in the mantle wedge composition is also uniquely apparent in U-Th isotope data, which define two subparallel arrays on the U-Th equiline diagram, one anchored to high U/Th Pacific mantle and the other to lower U/Th Indian mantle. These data provide clear evidence of the effects of variable mantle composition on U-Th isotope disequilibria. We argue that such arrays faithfully record the time elapsed since fluid release from the subducting plate. The data indicate that this occurred ca. 16 ka in the area of collision and slow subduction, but ca. 60 ka where the rate of subduction is substantially faster. This suggests a link between the rate of subduction and the time elapsed since fluid release.

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

NASA Astrophysics Data System (ADS)

Helliker, B.

2007-12-01

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

Individual-specific transgenerational marking of fish populations based on a barium dual-isotope procedure.

PubMed

Huelga-Suarez, Gonzalo; Moldovan, Mariella; Garcia-Valiente, America; Garcia-Vazquez, Eva; Alonso, J Ignacio Garcia

2012-01-03

The present study focuses on the development and evaluation of an individual-specific transgenerational marking procedure using two enriched barium isotopes, (135)Ba and (137)Ba, mixed at a given and selectable molar ratio. The method is based on the deconvolution of the isotope patterns found in the sample into four molar contribution factors: natural xenon (Xe nat), natural barium (Ba nat), Ba135, and Ba137. The ratio of molar contributions between Ba137 and Ba135 is constant and independent of the contribution of natural barium in the sample. This procedure was tested in brown trout ( Salmo trutta ) kept in captivity. Trout were injected with three different Ba137/Ba135 isotopic signatures ca. 7 months and 7 days before spawning to compare the efficiency of the marking procedure at long and short term, respectively. The barium isotopic profiles were measured in the offspring by means of inductively coupled plasma mass spectrometry. Each of the three different isotopic signatures was unequivocally identified in the offspring in both whole eggs and larvae. For 9 month old offspring, the characteristic barium isotope signatures could also be detected in the otoliths even in the presence of a high and variable amount of barium of natural isotope abundance. In conclusion, it can be stated that the proposed dual-isotope marking is inheritable and can be detected after both long-term and short-term marking. Furthermore, the dual-isotope marking can be made individual-specific, so that it allows identification of offspring from a single individual or a group of individuals within a given fish group. © 2011 American Chemical Society

Global Isotopic Signatures of Oceanic Island Basalts.

DTIC Science & Technology

1991-08-01

and the__ WOODS HOLE OCEANOGRAPHIC INSTITUTION August 1991 ©Lynn A. Oschmann 1991 The author hereby grants to MIT, WHOI, and the U.S. Government...Massachusetts Institute of Technology! Woods Hole Oceanographic Institution Certified 1W ___ ____________________ Dr. Staidlc\\ R. I L, rt Senior Scientik, Woods ...Institute of T’echnology! Woods Hole Oceanographic Institution 3 GLOBAL ISOTOPIC SIGNATURES OF OCEANIC ISLAND BASALTS by LYNN A. OSCHMANN Submitted to the

Lead isotope evolution across the Neoproterozoic boundary between craton and juvenile crust, Bayuda Desert, Sudan

NASA Astrophysics Data System (ADS)

Evuk, David; Lucassen, Friedrich; Franz, Gerhard

2017-11-01

Metaigneous mafic and ultramafic rocks from the juvenile Neoproterozoic Arabian Nubian Shield (ANS) and the Proterozoic, reworked Saharan Metacraton (SMC) have been analysed for major- and trace elements and Sr, Nd, and Pb isotopes. Most of the rocks are amphibolites metamorphosed at amphibolite facies conditions, some with relicts of a granulite facies stage. The other rocks are metapyroxenites, metagabbros, and some ultramafic rocks. Trace element compositions of the metabasaltic (dominantly tholeiitic) rocks resemble the patterns of island arcs and primitive lavas from continental arcs. Variable Sr and Nd isotope ratios indicate depleted mantle dominance for most of the samples. 207Pb/204Pb signatures distinguish between the influence of high 207Pb/204Pb old SMC crust and depleted mantle signatures of the juvenile ANS crust. The Pb isotope signatures for most metabasaltic rocks, metapyroxenites and metagabbros from SMC indicate an autochthonous formation. The interpretation of the new data together with published evidence from mafic xenoliths on SMC and ophiolite from ANS allows an extrapolation of mantle evolution in time. There are two lines of evolution in the regional mantle, one, which incorporates potential upper crust material during Neoproterozoic, and a second one with a depleted mantle signature since pre-Neoproterozoic that still is present in the Red Sea and Gulf of Aden spreading centres.

Identifying sources of nitrogen to Hanalei Bay, Kauai, utilizing the nitrogen isotope signature of macroalgae

USGS Publications Warehouse

Derse, E.; Knee, K.L.; Wankel, Scott D.; Kendall, C.; Berg, C.J.; Paytan, A.

2007-01-01

Sewage effluent, storm runoff, discharge from polluted rivers, and inputs of groundwater have all been suggested as potential sources of land derived nutrients into Hanalei Bay, Kauai. We determined the nitrogen isotopic signatures (??15N) of different nitrate sources to Hanalei Bay along with the isotopic signature recorded by 11 species of macroalgal collected in the Bay. The macroalgae integrate the isotopic signatures of the nitrate sources over time, thus these data along with the nitrate to dissolved inorganic phosphate molar ratios (N:P) of the macroalgae were used to determine the major nitrate source to the bay ecosystem and which of the macro-nutrients is limiting algae growth, respectively. Relatively low ??15N values (average -0.5???) were observed in all algae collected throughout the Bay; implicating fertilizer, rather than domestic sewage, as an important external source of nitrogen to the coastal water around Hanalei. The N:P ratio in the algae compared to the ratio in the Bay waters imply that the Hanalei Bay coastal ecosystem is nitrogen limited and thus, increased nitrogen input may potentially impactthis coastal ecosystem and specifically the coral reefs in the Bay. Identifying the major source of nutrient loading to the Bay is important for risk assessment and potential remediation plans. ?? 2007 American Chemical Society.

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

DOE PAGES

Rolison, John M.; Stirling, Claudine H.; Middag, Rob; ...

2018-02-19

We present that the chemical response of the Precambrian oceans to rising atmospheric O 2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shiftmore » in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS 2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the ‘Great Oxidation Event’ around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.« less

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

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

Rolison, John M.; Stirling, Claudine H.; Middag, Rob

We present that the chemical response of the Precambrian oceans to rising atmospheric O 2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shiftmore » in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS 2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the ‘Great Oxidation Event’ around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.« less

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

NASA Astrophysics Data System (ADS)

Rolison, John M.; Stirling, Claudine H.; Middag, Rob; Gault-Ringold, Melanie; George, Ejin; Rijkenberg, Micha J. A.

2018-04-01

The chemical response of the Precambrian oceans to rising atmospheric O2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shift in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the 'Great Oxidation Event' around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.

Ecologically and Geologically Relevant Isotope Signatures of C, N, and S in Okenone Producing Purple Sulfur Bacteria

NASA Astrophysics Data System (ADS)

Smith, D.; Steele, A.; Bowden, R.; Fogel, M. L.

2013-12-01

The carbon (C), nitrogen (N), and sulfur (S) cycles are linked in euxinic environments by purple sulfur bacteria (PSB). PSB could be responsible for the isotopic enrichments that have been observed in both fresh and marine anoxic basins. Okenane, the only recognized molecular fossil unique to PSB, is derived from okenone, a carotenoid pigment unique to Chromatiaceae. Since PSB have this exclusive molecular fossil and are fundamental components in the overall ecology of euxinic environments, a comprehensive study was undertaken to assess the C, N, and S metabolisms PSB carryout under precise laboratory conditions. The consequential isotopic fractionations that may be documented in modern environments and geologic record were examined. Autotrophic cultures of Marichromatium purpuratum DSMZ 1591 (Mpurp1591) were observed to have a fractionation between CO2 and biomass (Δ13Cbiomass - CO2), ranging from -16.1 to -37.6‰, dependent on growth stage. This rather large range of CO2 fractionation expands previously reported values for RuBisCO in PSB. Ammonium assimilation, controlled by glutamate dehydrogenase, was shown to have a fractionation (Δ15Nbiomass - NH4) of -15‰ in autotrophic cultures of Mpurp1591 and Thiocapsa marina 5653, documented for the first time in PSB. While it has been previously shown that phototrophic sulfur oxidizing bacteria connect sulfur and carbon cycling in euxinic ecosystems, the percentage of elemental sulfur and bulk biomass δ34S values of Mpurp1591 cells were contingent upon their carbon metabolisms. Here we show that the isotopic enrichments of S and N observed in freshwater and marine anoxic basins could be explained by the prevalence of PSB.

Helium Isotopes and Noble Gas Abundances of Cave Dripping Water in Three Caves in East Asia

NASA Astrophysics Data System (ADS)

Chen, A. T.; Shen, C. C.; Tan, M.; Li, T.; Uemura, R.; Asami, R.

2015-12-01

Paleo-temperature recorded in nature archives is a critical parameter to understand climate change in the past. With advantages of unique inert chemical characteristics and sensitive solubilities with temperature, dissolved noble gases in speleothem inclusion water were recently proposed to retrieve terrestrial temperature history. In order to accurately apply this newly-developed speleothem noble gas temperature (NGT) as a reliable proxy, a fundamental issue about behaviors of noble gases in the karst should be first clarified. In this study, we measured noble gas contents in air and dripping water to evaluate any ratio deviation between noble gases. Cave dripping water samples was collected from three selected caves, Shihua Cave in northern China, Furong Cave in southwestern, and Gyukusen Cave in an island located in the western Pacific. For these caves are characterized by a thorough mixing and long-term storage of waters in a karst aquifer by the absence of seasonal oxygen isotope shifts. Ratios of dripping water noble gases are statistically insignificant from air data. Helium isotopic ratios in the dripping water samples match air value. The results indicate that elemental and isotopic signatures of noble gases from air can be frankly preserved in the epikarst and support the fidelity of NGT techniques.

Ca isotopic geochemistry of an Antarctic aquatic system

USGS Publications Warehouse

Lyons, W. Berry; Bullen, Thomas D.; Welch, Kathleen A.

2017-01-01

The McMurdo Dry Valleys, Antarctica, are a polar desert ecosystem. The hydrologic system of the dry valleys is linked to climate with ephemeral streams that flow from glacial melt during the austral summer. Past climate variations have strongly influenced the closed-basin, chemically stratified lakes on the valley floor. Results of previous work point to important roles for both in-stream processes (e.g., mineral weathering, precipitation and dissolution of salts) and in-lake processes (e.g., mixing with paleo-seawater and calcite precipitation) in determining the geochemistry of these lakes. These processes have a significant influence on calcium (Ca) biogeochemistry in this aquatic ecosystem, and thus variations in Ca stable isotope compositions of the waters can aid in validating the importance of these processes. We have analyzed the Ca stable isotope compositions of streams and lakes in the McMurdo Dry Valleys. The results validate the important roles of weathering of aluminosilicate minerals and/or CaCO3 in the hyporheic zone of the streams, and mixing of lake surface water with paleo-seawater and precipitation of Ca-salts during cryo-concentration events to form the deep lake waters. The lakes in the McMurdo Dry Valleys evolved following different geochemical pathways, evidenced by their unique, nonsystematic Ca isotope signatures.

Uniform deposition of uranium hexafluoride (UF6): Standardized mass deposits and controlled isotopic ratios using a thermal fluorination method.

PubMed

McNamara, Bruce K; O'Hara, Matthew J; Casella, Andrew M; Carter, Jennifer C; Addleman, R Shane; MacFarlan, Paul J

2016-07-01

We report a convenient method for the generation of volatile uranium hexafluoride (UF6) from solid uranium oxides and other U compounds, followed by uniform deposition of low levels of UF6 onto sampling coupons. Under laminar flow conditions, UF6 is shown to interact with surfaces within a fixed reactor geometry to a highly predictable degree. We demonstrate the preparation of U deposits that range between approximately 0.01 and 500ngcm(-2). The data suggest the method can be extended to creating depositions at the sub-picogramcm(-2) level. The isotopic composition of the deposits can be customized by selection of the U source materials and we demonstrate a layering technique whereby two U solids, each with a different isotopic composition, are employed to form successive layers of UF6 on a surface. The result is an ultra-thin deposit that bears an isotopic signature that is a composite of the two U sources. The reported deposition method has direct application to the development of unique analytical standards for nuclear safeguards and forensics. Further, the method allows access to very low atomic or molecular coverages of surfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

Mobile mapping of methane emissions and isoscapes

NASA Astrophysics Data System (ADS)

Takriti, Mounir; Ward, Sue; Wynn, Peter; Elias, Dafydd; McNamara, Niall

2017-04-01

Methane (CH4) is a potent greenhouse gas emitted from a variety of natural and anthropogenic sources. It is crucial to accurately and efficiently detect CH4 emissions and identify their sources to improve our understanding of changing emission patterns as well as to identify ways to curtail their release into the atmosphere. However, using established methods this can be challenging as well as time and resource intensive due to the temporal and spatial heterogeneity of many sources. To address this problem, we have developed a vehicle mounted mobile system that combines high precision CH4 measurements with isotopic mapping and dual isotope source characterisation. We here present details of the development and testing of a unique system for the detection and isotopic analysis of CH4 plumes built around a Picarro isotopic (13C/12C) gas analyser and a high precision Los Gatos greenhouse gas analyser. Combined with micrometeorological measurements and a mechanism for collecting discrete samples for high precision dual isotope (13C/12C, 2H/1H) analysis the system enables mapping of concentrations as well as directional and isotope based source verification. We then present findings from our mobile methane surveys around the North West of England. This area includes a variety of natural and anthropogenic methane sources within a relatively small geographical area, including livestock farming, urban and industrial gas infrastructure, landfills and waste water treatment facilities, and wetlands. We show that the system was successfully able to locate leaks from natural gas infrastructure and emissions from agricultural activities and to distinguish isotope signatures from these sources.

Temporal Variations in the Mantle Source of MORB near the Vema Fracture Zone (Central Atlantic): Nd and Sr Isotopes in Peridotites and Basaltic Glasses

NASA Astrophysics Data System (ADS)

Cipriani, A.; Cipriani, A.; Brunelli, D.; Brueckner, H. K.; Brueckner, H. K.; Bonatti, E.; Bonatti, E.

2001-12-01

Sr-Nd-Pb isotopic ratios of zero age basalts sampled along Mid-Ocean Ridges (MOR) have demonstrated that the mantle is heterogeneous at a regional scale. However, how the mantle evolves through time below a single segment of MOR it is still matter of debate. Peridotites and basaltic glasses were collected along a lithospheric section uplifted and exposed on the southern side of the Vema transform (10o North, Atlantic Ocean) along a seafloor spreading flow line for a stretch of almost 200 km (corresponding to roughly 10 my). This set of samples offers a unique opportunity to detect changes through time of the mantle signature in a segment of Mid Atlantic Ridge, by analyzing radiogenic isotopes in the clinopyroxenes (cpx) from peridotites and glasses from the overlying basalts. Work is in progress; initial Sr and Nd measurements from cpxs within peridotites indicate several things. First, the cpxs display "depleted" mantle signatures. Second, there is a considerable variation of the isotopic ratios along the exposed section (143Nd/144Nd varies from 0.51293 to 0.51345, 87Sr/86Sr varies from 0.70228 to 0.70422) and these variations occur over a short time scale (some occur within an interval of one million year). Next, the Sr and Nd ratios are inversely correlated and fall along the mantle array. Finally, cpx Nd ratios are inversely correlated with the Cr/Al ratio of the spinel and ortopyroxene (opx) from the peridotites while Sr ratios are positively correlated. Thus, the chemically most depleted peridotite with high Cr/Al ratios show the most enriched isotopic signatures, a pattern that has also been observed in alpine-type peridotites and peridotite nodules and that is generally interpreted as metasomatism by enriched fluids affecting depleted peridotite more extensively than less depleted peridotite. This may indicate that the temporal variations in the extent of melting detected by Cr/Al ratio in spinel and opx (Bonatti et al., Variations with age of mantle ultramafic composition near the Vema Fracture Zone, Central Atlantic. EOS, Vol.79, No.45, F919) are related to rapid changes in the degree of depletion of the upwelling mantle sources and that the degree of depletion of these mantle sources is an inherited feature from earlier processes rather than the result of melting at the MOR.

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

NASA Astrophysics Data System (ADS)

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-10-01

;Clumped-isotope; thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope ;clumps;). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium. Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral-solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3-) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

The new high-resolution IRMS MAT253 ULTRA at Utrecht University

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; Hofmann, Magdalena; Paul, Dipayan; Popa, Elena; Adnew, Getachew

2017-04-01

In 2016, the new high-resolution, multi-collector isotope ratio mass spectrometer MAT253 ULTRA [1] was installed at Utrecht University. This instrument is designed to reach a mass resolving power of 20,000 to 40,000 (M/ΔM). The ion currents are detected with a variable multi-collector unit that allows to register up to 9 ion currents simultaneously with Faraday cups and ion counters. The width of the entrance slit can be varied between 5 and 250μm so that the instrument can be operated under low, medium and high mass resolution, and an optimum balance between resolution and sensitivity can be selected for the respective applications. The central field of application of the new IRMS at Utrecht University is the measurement of multiply substituted isotopologues (clumped isotopes) in atmospheric trace compounds (e.g. 13CDH3, 13C18O16O, 18O18O, 15N14N18O) [1-7]. It is known from thermodynamics that the zero point energy of a chemical bond usually decreases when multiple heavy isotopes clump together in a molecule, and this effect depends on temperature [7]. Therefore, the abundance of clumped isotopes can be used as temperature indicator under thermodynamical equilibrium conditions. However, in the atmosphere, many reactions are controlled kinetically. It has been shown recently for a few examples that negative clumping signatures (anti-clumping) can be produced under non-equilibrium conditions [3,4]. In addition, based on purely statistical reasons, anti-clumping signatures will be produced in any molecule that contains indistinguishable atoms, which originate from isotopically distinct reservoir [5,6]. Thus, the investigation of multiply substituted isotopologues is expected to generate novel isotope signatures that can complement conventional stable isotope analysis in atmospheric science. We will present data on the performance of the MAT 253 ULTRA instrument and first scientific applications to atmospheric research. 1. Eiler, J.M., et al., A high-resolution gas-source isotope ratio mass spectrometer, Int. J. Mass Spect., 2013. 335: 45- 56. 2. Young, E.D., et al., A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases, Int. J. Mass Spect., 2016. 401: 1-10. 3. Wang, D.T., et al., Nonequilibrium clumped isotope signals in microbial methane, Science, 2015. 348: 428-431. 4. Yeung, L.Y., et al., Biological signatures in clumped isotopes of O2, Science, 2015. 348: 431-434. 5. Yeung, L.Y., Combinatorial effects on clumped isotopes and their significance in biogeochemistry, Geochim. Cosmochim. Act., 2016: doi:10.1016/j.gca.2015.09.020. 6. Röckmann, T., et al., Statistical clumped isotope signatures Scientific reports, 2016. 6: 31947; doi: 10.1038/srep31947. 7. Wang, Z.G., et al., Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases, Geochim. Cosmochim. Act., 2004. 68: 4779-4797.

Isotopic niches of fishes in coastal, neritic and oceanic waters off Adélie land, Antarctica

NASA Astrophysics Data System (ADS)

Cherel, Yves; Koubbi, Philippe; Giraldo, Carolina; Penot, Florian; Tavernier, Eric; Moteki, Masato; Ozouf-Costaz, Catherine; Causse, Romain; Chartier, Amélie; Hosie, Graham

2011-08-01

We used the stable isotope method to investigate the ecological niches of Antarctic fishes, with δ 13C and δ 15N as proxies of fish habitats and dietary habits, respectively. Muscle isotopic signature was measured for each of 237 delipidated tissue samples from 27 fish species collected offshore Adélie Land, East Antarctica. Overall, δ 13C values ranged from -25.3‰ to -18.2‰, thus allowing characterizing of the fish habitats, with inshore/benthic species having more positive δ 13C signatures than offshore/pelagic ones. No clear difference in the δ 13C values of pelagic fishes was found between species living in neritic and oceanic waters. Overall, the δ 15N signatures of neritic pelagic and epibenthic fishes encompassed ˜1.0 trophic level (3.1‰), a higher difference than that (1.4‰) found within the oceanic assemblage. Fishes with the lowest and highest δ 15N values are primarily invertebrate- and fish-eaters, respectively. The isotopic niches of fishes illustrate the different mechanisms allowing coexistence, with most fishes segregating at least by one of the two niche axes (δ 13C and δ 15N). Muscle isotopic values also document interindividual foraging specialization over the long-term in coastal benthic fishes, but not in more offshore pelagic species. Finally, the δ 15N signatures of fishes overlap with those of penguins and seals, indicating that seabirds and marine mammals share the upper levels of the Antarctic pelagic ecosystem with some large fish species. In conclusion, the concept of isotopic niche is a powerful tool to investigate various aspects of the ecological niche of Antarctic fishes, thus complementing the use of other conventional and non-conventional approaches.

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.

Comparing spatial and temporal patterns of river water isotopes across networks

EPA Science Inventory

A detailed understanding of the spatial and temporal dynamics of water sources across river networks is central to managing the impacts of climate change. Because the stable isotope composition of precipitation varies geographically, variation in surface-water isotope signatures ...

Advances in Methane Isotope Measurements via Direct Absorption Spectroscopy with Applications to Oil and Gas Source Characterization

NASA Astrophysics Data System (ADS)

Yacovitch, T. I.; Herndon, S. C.; Roscioli, J. R.; Petron, G.; Shorter, J. H.; Jervis, D.; McManus, J. B.; Nelson, D. D.; Zahniser, M. S.; Kolb, C. E., Jr.

2015-12-01

Instrumental developments in the measurement of multiple isotopes of methane (12CH4, 13CH4 and 12CH3D) are presented. A first generation 8-micron instrument quantifies 12CH4 and 13CH4 at a 1-second rate via tunable infrared direct absorption spectroscopy (TILDAS). A second generation instrument uses two 3-micron intraband cascade lasers in an Aerodyne dual laser chassis for simultaneous measurement of 12CH4, 13CH4 and 12CH3D. Sensitivity and noise performance improvements are examined. The isotopic signature of methane provides valuable information for emission source identification of this greenhouse gas. A first generation spectrometer has been deployed in the field on a mobile laboratory along with a sophisticated 4-tank calibration system. Calibrations are done on an agressive schedule, allowing for the correction of measured isotope ratios to an absolute isotope scale. Distinct isotopic signatures are found for a number of emission sources in the Denver-Julesburg Basin: oil and gas gathering stations, compressor stations and processing plants; a municipal landfill, and dairy/cattle operations. The isotopic signatures are compared with measured ethane/methane ratios. These direct absorption measurements have larger uncertainties than samples measured via gas chromatography-mass spectrometry, but have several advantages over canister sampling methods: individual sources of short duration are easier to isolate; calibrated isotope ratio results are available immediately; replicate measurements on a single source are easily performed; and the number of sources sampled is not limited by canister availability and processing time.

Isotopic signatures: An important tool in today`s world

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

Rokop, D.J.; Efurd, D.W.; Benjamin, T.M.

1995-12-01

High-sensitivity/high-accuracy actinide measurement techniques developed to support weapons diagnostic capabilities at the Los Alamos National Laboratory are now being used for environmental monitoring. The measurement techniques used are Thermal Ionization Mass Spectrometry (TIMS), Alpha Spectrometry(AS), and High Resolution Gamma Spectrometry(HRGS). These techniques are used to address a wide variety of actinide inventory issues: Environmental surveillance, site characterizations, food chain member determination, sedimentary records of activities, and treaty compliance concerns. As little as 10 femtograms of plutonium can be detected in samples and isotopic signatures determined on samples containing sub-100 femtogram amounts. Uranium, present in all environmental samples, can generally yieldmore » isotopic signatures of anthropogenic origin when present at the 40 picogam/gram level. Solid samples (soils, sediments, fauna, and tissue) can range from a few particles to several kilograms in size. Water samples can range from a few milliliters to as much as 200 liters.« less

In search of the noble gas 3.52 Ga atmospheric signatures

NASA Astrophysics Data System (ADS)

Pujol, M.; Marty, B.; Philippot, P.

2008-12-01

The isotopic signatures of noble gases in the Present-day mantle and in the atmosphere permit exceptional insight into the evolution of these reservoirs through time ([1]). However, related exchange models are under- constrained and would require direct measurements of the atmospheric composition long ago, e.g., in the Archaean. Drilling in the the 3.52 Ga chert-barite ([2]) of the Dresser formation(Pilbara Drilling Project) , North Pole, Pilbara craton (Western Australia), led to recovery of exceptionally fresh samples preserving primary fluid inclusions unaffected by surface weathering. The whole formation is considered to be an already established basin when hydrothermal processes started. The chemical composition of primary fluid inclusions trapped in hydrothermal quartz from vacuolar komatiitic basalt from 110 m depth were determined by synchrotron X-ray microfluorescence (ESRF, Grenoble,France). Data show that fluids are relatively homogenous, consisting of a Ba-rich fluid and a Fe (+Ba)-rich fluid of hydrothermal origin as concluded by Foriel et al.([3]). The isotopic compositions of xenon and argon trapped in these fluids were measured by mass spectrometry following vacuum crushing. The three argon isotopes show a homogeneous signature quite different from present-day Earth atmosphere but we cannot exclude the possibility that secondary nuclear reactions produced these anomalies. Despite this, the Xe isotopic trends indicate a less radiogenic signature than the Present-day atmosphere, and probably represent a remnant of the Archaean atmosphere. If this xenon composition is primitive then it implies that there is no cosmogenic production through time. However, argon ratios could be explained by cosmogenic production which implies significant surface exposure times. Cosmogenic production will produce correlated argon and xenon isotope signatures. Therefore it is necessary to differentiate primary from secondary composition. To investigate the effects of these nuclear reactions on Xe isotope production, barite from 30m shallower depth in the same core were analyzed. Variable excesses can be linked to spallogenic and cosmogenic reactions ([4] [5] [6]) which allow the primitive Xe isotopic signature to be isolated from subsequent secondary production. Models of the archaean atmospheric noble gas signature can thereby be compared with different theories on primitive atmospheric composition. [1] Staudacher T. Allègre C.J. (1982) EPSL 60, p 389-406 [2] Van Kranendonk MJ., Hickman A.H., Williams I.R. and Nijman W. (2001) Rec.-Geol. Surv. West. Aust. 2001/9, 134 [3] Foriel J., Philippot P., Rey P., Somogyi A., Banks D. and Ménez B. (2004) EPSL, 228, 451-463 [4]Srinivasan B. (1976) EPSL, 31, 129-141 [5]Charalambus S. (1971) Nuclear Physics, A166, 145 [6]Meshik A. P., Hohenberg C. M., Pravdivtseva O. V. and Kapusta Y. (2001) Phys. Rev., C 64, 035205-1 035205-6

Low-resolution gamma-ray spectrometry for an information barrier based on a multi-criteria template-matching approach

NASA Astrophysics Data System (ADS)

Göttsche, Malte; Schirm, Janet; Glaser, Alexander

2016-12-01

Gamma-ray spectrometry has been successfully employed to identify unique items containing special nuclear materials. Template information barriers have been developed in the past to confirm items as warheads by comparing their gamma signature to the signature of true warheads. Their development has, however, not been fully transparent, and they may not be sensitive to some relevant evasion scenarios. We develop a fully open template information barrier concept, based on low-resolution measurements, which, by design, reduces the extent of revealed sensitive information. The concept is based on three signatures of an item to be compared to a recorded template. The similarity of the spectrum is assessed by a modification of the Kolmogorov-Smirnov test to confirm the isotopic composition. The total gamma count rate must agree with the template as a measure of the projected surface of the object. In order to detect the diversion of fissile material from the interior of an item, a polyethylene mask is placed in front of the detector. Neutrons from spontaneous and induced fission events in the item produce 2.223 MeV gamma rays from neutron capture by hydrogen-1 in the mask. This peak is detected and its intensity scales with the item's fissile mass. The analysis based on MCNP Monte Carlo simulations of various plutonium configurations suggests that this concept can distinguish a valid item from a variety of invalid ones. The concept intentionally avoids any assumptions about specific spectral features, such as looking for specific gamma peaks of specific isotopes, thereby facilitating a fully unclassified discussion. By making all aspects public and allowing interested participants to contribute to the development and benchmarking, we enable a more open and inclusive discourse on this matter.

An Isotopic Map of Dust Source Areas in the McMurdo Sound Sector of Antarctica

NASA Astrophysics Data System (ADS)

Blakowski, M. A.; Aciego, S.; Delmonte, B.; Baroni, C.; Salvatore, M. C.

2014-12-01

The McMurdo Sound sector of Antarctica features a unique, polar desert ecosystem characterized by low temperatures, hyper-aridity, and high-speed winds. These climatic conditions result in limited water sources, sparse vegetation, underdeveloped soils, and abundant unconsolidated sediment easily influenced by wind-driven transport. Radiogenic isotopes (87Sr/86Sr, 143Nd/144Nd) provide constant signatures of dust from source- to sink-areas. Accordingly, aeolian dust derived from arid regions has been recognized in many studies as an important tracer of atmospheric circulation, as well as a tool for deciphering past climatic conditions in dust source regions. However, while major global dust sources (e.g. from South America, Africa, and Asia) are well studied and easily identifiable via distinct isotopic signatures when encountered in different depositional environments (e.g. Antarctic ice cores), local material from sources in and around the ice-free Dry Valleys and surrounding areas have remained in need of further documentation. We analyzed 40 samples of silt, sand, glacial drift, and weathered regolith material in both fine (<5μm) and coarse fractions collected from Victoria Land and the McMurdo Sound sector, including Cape Royds, Cape Bird, and the McMurdo Ice Shelf. Here we present an ArcGIS-generated, high-precision geochemical map of Antarctic PSAs synthesized from our data and combined with geomorphological and stratigraphic information on the studied sites. We believe that our expanded isotopic catalogue and map can be used to enhance and/or prompt regional studies in a variety of disciplines, such as by providing greater constraints on models of regional dust variability and transport pathways and of the melting history of the Antarctic ice sheet, and by determining the provenance of dust archived in ice cores, lake sediment, soil records, and impurities in Antarctic sea-ice.

Stable Carbon Isotopic Signatures of Abiotic Organics from Hydrothermal Synthesis Experiments

NASA Technical Reports Server (NTRS)

Stern, Jennifer C.; Summers, David P.; Kubo, Mike; Yassar, Saima

2006-01-01

Stable carbon isotopes can be powerful biogeochemical markers in the study of life's origins. Biogenic carbon fixation produces organics that are depleted in C-13 by about -20 to -30%0. Less attention has been paid to the isotopic signatures of abiotic processes. The possibility of abiotic processes producing organics with morphologies and isotopic signatures in the biogenic range has been at the center of recent debate over the Earth's earliest microfossils. The abiotic synthesis of organic compounds in hydrothermal environments is one possible source of endogenous organic matter to the prebiotic earth. Simulated hydrothermal settings have been shown to synthesize, among other things, single chain amphiphiles and simple lipids from a mix of CO, CO2, and H2. A key characteristic of these amphiphilic molecules is the ability to self-assemble in aqueous phases into more organized structures called vesicles, which form a selectively permeable boundary and serve the function of containing and concentrating other organic molecules. The ability to form cell like structures also makes these compounds more likely to be mistaken for biogenic. Hydrothermal simulation experiments were conducted from oxalic or formic acid in water at 175 C for 72 hr. The molecular and isotopic composition of the products of these reactions were determined and compared to biogenic fractionations . Preliminary results indicate isotopic fractionation during abiotic hydrocarbon synthesis in hydrothermal environments is on par with biological carbon fixation.

Possible Food Sources of Macrozoobenthos in the Manko Mangrove Ecosystem, Okinawa (Japan): A Stable Isotope Analysis Approach

PubMed Central

Wardiatno, Yusli; Mardiansyah; Prartono, Tri; Tsuchiya, Makoto

2015-01-01

Identifying potential food sources in mangrove ecosystems is complex because of the multifarious inputs from both land and sea. This study, which was conducted in the Manko mangrove ecosystem of Okinawa, Japan, determined the composition of the stable isotopes δ13C and δ15N in primary producers and macrozoobenthos to estimate the potential food sources assimilated and to elucidate the target trophic levels of the macrozoobenthos. We measured the two stable isotope signatures of three gastropods (Cerithidea sp., Cassidula mustelina, Peronia verruculata), two crabs (Grapsidae sp., Uca sp.), mangrove tree (Kandelia candel) leaves, and sediment from the mangrove ecosystem. The respective carbon and nitrogen isotope signature results were as follows: −22.4‰ and 8.6‰ for Cerithidea sp., −25.06‰ and 8‰ for C. mustelina, −22.58‰ and 8‰ for P. verruculata, −24.3‰ and 10.6‰ for unidentified Grapsidae, −21.87 ‰ and 11.5 ‰ for Uca sp., −29.81‰ and 11‰ for K. candel, and −24.23‰ and 7.2‰ for the sediment. The stable isotope assimilation signatures of the macrozoobenthos indicated sediment as their food source. Considering the trophic levels, the stable isotope values may also indicate that the five macrozoobenthos species were secondary or higher consumers. PMID:26019747

Evaluating Microstructure Preservation using Scanning Electron Microscopy in an Extinct Bivalve, Lahillia larseni

NASA Astrophysics Data System (ADS)

Mohr, R. C.; Tobin, T. S.

2017-12-01

Ontogenetic stable isotope (δ18O) sampling of accretionary carbonate shells can provide sub-annual records of environmental conditions, such as seawater temperature, during the life of an organism. These records of seasonal temperature variations can refine our understanding of ancient climates and past climate change. However, because original isotopic signatures can be altered by diagenesis, it is necessary to examine potential specimens for evidence of diagenetic alteration. Abundant aragonitic Lahillia larseni bivalves from the latest Cretaceous and Early Paleogene on Seymour Island, Antarctica, provide excellent opportunities for sclerochronological investigations. Shells of L. larseni preserve clear annual growth bands, which make them ideal candidates for high-resolution δ18O sampling to produce sub-annual records of seawater temperature variation. While the good visual condition of these shells and the preservation of original aragonitic material suggests a high level of preservation suitable for isotopic analysis, subtle alteration of the original shell microstructures can still compromise the original isotopic signatures. Scanning electron microscopy (SEM) can be used to evaluate the preservation of these microstructures. This study compares methods for imaging L. larseni bivalve shells with SEM and seeks a consistent way to evaluate their various microstructures for evidence of diagenetic alteration. High-resolution ontogenetic isotopic sampling will also be conducted on several L. larseni shells, as roughly sinusoidal δ18O profiles are often an indication that the original isotopic signatures have been preserved.

Assessing the hydraulic connection between fresh water aquifers and unconventional gas production using methane and stable isotopes

NASA Astrophysics Data System (ADS)

Iverach, Charlotte P.; Cendón, Dioni I.; Hankin, Stuart I.; Lowry, Dave; Fisher, Rebecca E.; France, James L.; Nisbet, Euan G.; Baker, Andy; Kelly, Bryce F. J.

2015-04-01

Unconventional gas developments pose a risk to groundwater quality and quantity in adjacent or overlying aquifers. To manage these risks there is a need to measure the background concentration of indicator groundwater chemicals and to map pathways of hydraulic connectivity between aquifers. This study presents methane (CH4) concentration and isotopic composition, dissolved organic carbon concentration ([DOC]) and tritium (3H) activity data from an area of expanding coal seam gas (CSG) exploration and production (Condamine Catchment, south-east Queensland, Australia). The target formation for gas production within the Condamine Catchment is the Walloon Coal Measures (WCM). This is a 700 m thick, low-rank CSG resource, which consists of numerous thin discontinuous lenses of coal separated by very fine-to medium-grained sandstone, siltstone, and mudstone, with minor calcareous sandstone, impure limestone and ironstone. The thickness of the coal makes up less than 10% of the total thickness of the unit. The WCM are overlain by sandstone formations, which form part of the Great Artesian Basin (GAB). The Condamine Alluvium fills a paleo-valley carved through the above formations. A combination of groundwater and degassing air samples were collected from irrigation bores and government groundwater monitoring boreholes. Degassing air samples were collected using an SKC 222-2301 air pump, which pumped the gas into 3 L Tedlar bags. The groundwater was analysed for 3H and [DOC]. A mobile CH4 survey was undertaken to continuously sample air in and around areas of agricultural and unconventional gas production. The isotopic signature of gas from the WCM was determined by sampling gas that was off-gassing from a co-produced water holding pond as it was the largest emission that could be directly linked to the WCM. This was used to determine the source signature of the CH4 from the WCM. We used Keeling plots to identify the source signature of the gas sampled. For the borehole samples these plots assume that there are only two sources of CH4, each with a unique isotopic signature. When the two sources mix in varying proportions they will plot along a straight line in the Keeling plot. Geometric mean displacement was used to fit a regression line and determine the intercept value. Within the Keeling plot, samples clustered according to their 3H and [DOC] values. One cluster is associated with near surface biological processes, while the other cluster can be attributed to gas sourced from the WCM. This indicates that in places there is hydraulic connectivity between the WCM and the overlying Condamine Alluvium. The results from this case study demonstrate that measuring 3H activity, [DOC] and CH4 concentrations in combination with CH4 isotopic analysis can provide an early indicator of hydraulic connectivity in areas of expanding unconventional gas development.

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.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

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

Kreuzer, Helen W.; Horita, Juske; Moran, James J.

Sodium and potassium cyanide are highly toxic, produced in large amounts by the chemical industry, and linked to numerous high-profile crimes. The U.S. Centers for Disease Control and Prevention has identified cyanide as one of the most probable agents to be used in a future chemical terrorism event. We investigated whether stable C and N isotopic content of sodium and potassium cyanide could serve as a forensic signature for sample matching, using a collection of 65 cyanide samples. A few of these samples displayed non-homogeneous isotopic content associated with degradation to a carbonate salt and loss of hydrogen cyanide. Mostmore » samples had highly reproducible isotope content. Of these, >95% could be properly matched based on C and N isotope ratios, with a false match rate <3%. These results suggest that stable C and N isotope ratios are a useful forensic signature for matching cyanide samples.« less

Assimilation of terrigenous organic matter via bacterial biomass as a food source for a brackish clam, Corbicula japonica (Mollusca: Bivalva)

NASA Astrophysics Data System (ADS)

Yamanaka, Toshiro; Mizota, Chitoshi; Maki, Yonosuke; Matsumasa, Masatoshi

2013-07-01

Corbicula japonica collected from the Kitakami River estuary, northeastern Japan, showed lower δ34S values in soft-body parts (+1.7 to +11.0‰) than the ambient seawater sulfate sulfur (+21‰), and this value gradually decreased at successive sites up to 15.8 km upstream from the river mouth. Previous study using carbon and nitrogen isotopes suggests that the bivalve nonselectively assimilates particulate organic matter of marine and terrestrial origin by filter feeding. This pattern in δ34S values may indicate a considerable contribution of a food source derived from terrigenous organic matter, which has low δ34S values close to 0‰, and the bivalve has been reported to have cellulase and hemicellulase activities. Unique fatty acids (iso 17:0 and anteiso 17:0 acids), both characteristic of sulfate-reducing bacteria, were observed in the salt-free, soft-body parts of the bivalve. The concentration of monounsaturated fatty acids, possibly derived from bacteria, was also high. Trace amounts of a polyunsaturated fatty acid (20:5ω3) specific to dinoflagellates were detected. In Corbicula habitats, reductive sandy layers with ample sulfides that were sporadically intercalated into the oxidative sandy sediment were often observed. The stable isotopic signatures of sediment sulfides (acid-volatile sulfide) and associated pore-water sulfates were -8.9 to +8.6‰ and +22.4 to +26.3‰, respectively, indicating the existence of bacterial sulfate-reducing activity and thiobios biomass. These isotopic signatures of the sediment, with the fatty acid composition of the bivalve, confirm the importance of a food source derived from bacteria belonging to the thiobios in the substrate sediments via pedal feeding, rather than direct digestion of terrigenous organic matter, in this estuarine ecosystem.

Can we use high precision metal isotope analysis to improve our understanding of cancer?

PubMed

Larner, Fiona

2016-01-01

High precision natural isotope analyses are widely used in geosciences to trace elemental transport pathways. The use of this analytical tool is increasing in nutritional and disease-related research. In recent months, a number of groups have shown the potential this technique has in providing new observations for various cancers when applied to trace metal metabolism. The deconvolution of isotopic signatures, however, relies on mathematical models and geochemical data, which are not representative of the system under investigation. In addition to relevant biochemical studies of protein-metal isotopic interactions, technological development both in terms of sample throughput and detection sensitivity of these elements is now needed to translate this novel approach into a mainstream analytical tool. Following this, essential background healthy population studies must be performed, alongside observational, cross-sectional disease-based studies. Only then can the sensitivity and specificity of isotopic analyses be tested alongside currently employed methods, and important questions such as the influence of cancer heterogeneity and disease stage on isotopic signatures be addressed.

Molybdenum isotope systematics in subduction zones

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Isotopic signature of atmospheric xenon released from light water reactors.

PubMed

Kalinowski, Martin B; Pistner, Christoph

2006-01-01

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

Differentiated stable isotopes signatures between pre- and post-flexion larvae of Atlantic bluefin tuna (Thunnus thynnus) and of its associated tuna species of the Balearic Sea (NW Mediterranean)

NASA Astrophysics Data System (ADS)

García, Alberto; Laiz-Carrión, Raúl; Uriarte, Amaya; Quintanilla, José M.; Morote, Elvira; Rodríguez, José M.; Alemany, Francisco

2017-06-01

The trophic ecology of bluefin tuna larvae (Thunnus thynnus) from the Balearic Sea, together with its co-existing tuna species such as albacore (T. alalunga), bullet (Auxis rochei) and little tunny (Euthynnus alletteratus) were examined by nitrogen and carbon stable isotope analyses. A total of 286 larvae were analyzed for this study, of which 72 larvae corresponded to bluefin, 57 to albacore, 81 to bullet tuna and 76 to little tunny. Tuna larvae were separated into the pre-flexion and post-flexion developmental stages. Within the size 3-9 mm standard length (SL), the stable isotope of nitrogen (δ15N) showed significant differences between species where bluefin tuna larvae ranked highest. Pre-flexion bluefin tuna and little tunny larvae showed significantly higher δ15N signatures than the post-flexion larvae. This effect is attributed to a biochemical trace of maternal δ15N signatures. However, neither albacore nor bullet tuna larvae showed this pattern in δ15N signatures, possibly owing to a compensation effect between lower maternal δ15N values transmitted to pre-flexion larvae and the early increase of δ15N values in post-flexion stages. One way ANOVA showed significant differences between species in the stable isotope ratio of carbon (δ13C) values, which suggests specific differences of carbon sources. Furthermore, a similar significant ontogenic effect between δ13C signatures of pre-flexion and post-flexion larvae is also evidenced in all four species. At pre-flexion stages, all species except bullet tuna larvae showed significant negative relationships between δ15N and larval standard length. At post-flexion stages, a significant linear relationship with larval size was only observed in albacore and bullet tuna larvae indicating a possible trophic shift towards early piscivory. With respect to δ13C values with larval size, all four species showed significant linear decreases. It may be explained by the metabolism of growth of somatic mass subject to modification of the relative carbon isotopic sources. In conclusion, the species' signatures of δ15N and δ13C indicate differentiated early life trophic niches. In addition, it is worth remarking the potential use of transgenerational isotopic transmission in future research applications.

Foraging ecology of an endemic shorebird, the African Black Oystercatcher ( Haematopus moquini) on the south-east coast of South Africa

NASA Astrophysics Data System (ADS)

Kohler, Sophie; Bonnevie, Bo; McQuaid, Christopher; Jaquemet, Sébastien

2009-09-01

We investigated small-medium (1-300 km) scale variation in the foraging ecology of the African Black Oystercatcher during its breeding season, using traditional diet analysis coupled with carbon and nitrogen stable isotope analysis. Fieldwork was conducted between January and March 2006 and 2007, on rocky shores on the south-east coast of South Africa at East London, Kenton and Port Elizabeth. Middens of shelled prey left by adults feeding their chicks were collected from five territories and the abundances of the collected prey on the foraging areas were estimated using quadrats. Blood samples from 45 birds (16 females, 10 males and 19 chicks) and tissues from the predominant prey species on the territory of each breeding pair were collected for isotope analysis. The Manly-Chesson selectivity index revealed that adults feed their chicks preferentially with the limpet Scutellastra cochlear and the Mediterranean mussel Mytilus galloprovincialis, if available. A slight enrichment in the 15N stable-carbon isotope signature was observed towards the west in both prey and oystercatchers. Differences in isotope signatures between males and females from the same breeding pair indicate sex-related differences in the diet. Both had signatures indicating a mixed diet, but with males exhibiting a signature closer to that of limpets and females closer to that of mussels. In the single case where mussels were rare on the feeding territory, the two members of a pair showed carbon signatures which were identical and very similar to that of limpets. These results indicate dietary partitioning between genders in breeding pairs.

Transport, biodegradation and isotopic fractionation of chlorinated ethenes: modeling and parameter estimation methods

NASA Astrophysics Data System (ADS)

Béranger, Sandra C.; Sleep, Brent E.; Lollar, Barbara Sherwood; Monteagudo, Fernando Perez

2005-01-01

An analytical, one-dimensional, multi-species, reactive transport model for simulating the concentrations and isotopic signatures of tetrachloroethylene (PCE) and its daughter products was developed. The simulation model was coupled to a genetic algorithm (GA) combined with a gradient-based (GB) method to estimate the first order decay coefficients and enrichment factors. In testing with synthetic data, the hybrid GA-GB method reduced the computational requirements for parameter estimation by a factor as great as 300. The isotopic signature profiles were observed to be more sensitive than the concentration profiles to estimates of both the first order decay constants and enrichment factors. Including isotopic data for parameter estimation significantly increased the GA convergence rate and slightly improved the accuracy of estimation of first order decay constants.

Investigation of sulphur isotope variation due to different processes applied during uranium ore concentrate production.

PubMed

Krajkó, Judit; Varga, Zsolt; Wallenius, Maria; Mayer, Klaus; Konings, Rudy

The applicability and limitations of sulphur isotope ratio as a nuclear forensic signature have been studied. The typically applied leaching methods in uranium mining processes were simulated for five uranium ore samples and the n ( 34 S)/ n ( 32 S) ratios were measured. The sulphur isotope ratio variation during uranium ore concentrate (UOC) production was also followed using two real-life sample sets obtained from industrial UOC production facilities. Once the major source of sulphur is revealed, its appropriate application for origin assessment can be established. Our results confirm the previous assumption that process reagents have a significant effect on the n ( 34 S)/ n ( 32 S) ratio, thus the sulphur isotope ratio is in most cases a process-related signature.

Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

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

Kimball, Justine; Eagle, Robert; Dunbar, Robert

Here, deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C 18O 16O 2 inmore » carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect high-Mg and aragonite crystals attaining nominal mineral equilibrium clumped isotope signatures due to conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological “vital effect” influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological vital effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO 2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ 47 is a subject that warrants further investigation.« less

Carbonate “clumped” isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

DOE PAGES

Kimball, Justine; Eagle, Robert; Dunbar, Robert

2016-12-12

Here, deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop “clumped” isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C 18O 16O 2 inmore » carbonate minerals, analyzed in CO 2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ 47 values. We analyzed Δ 47 in live-collected aragonitic scleractinian ( Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ 47 values were compared to in situ temperatures, and the relationship between Δ 47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ 47–temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ 47–temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO 2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect high-Mg and aragonite crystals attaining nominal mineral equilibrium clumped isotope signatures due to conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological “vital effect” influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological vital effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO 2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ 47 is a subject that warrants further investigation.« less

Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

USGS Publications Warehouse

Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

2015-01-01

“Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two types of experiments yielded statistically indistinguishable results, and these measurements yield a calibration that overlaps with our theoretical predictions for calcite at equilibrium. The slow-growing Devils Hole calcite exhibits Δ47 and δ18O values consistent with lattice equilibrium.Factors influencing DIC speciation (pH, salinity) and the timescale for DIC equilibration, as well as reactions at the mineral–solution interface, have the potential to influence clumped-isotope signatures and the δ18O of carbonate minerals. In fast-growing carbonate minerals, solution chemistry may be an important factor, particularly over extremes of pH and salinity. If a crystal grows too rapidly to reach an internal equilibrium (i.e., achieve the value for the temperature-dependent mineral lattice equilibrium), it may record the clumped-isotope signature of a DIC species (e.g., the temperature-dependent equilibrium of HCO3−) or a mixture of DIC species, and hence record a disequilibrium mineral composition. For extremely slow-growing crystals, and for rapidly-grown samples grown at a pH where HCO3- dominates the DIC pool at equilibrium, effects of solution chemistry are likely to be relatively small or negligible. In summary, growth environment, solution chemistry, surface equilibria, and precipitation rate may all play a role in dictating whether a crystal achieves equilibrium or disequilibrium clumped-isotope signatures.

Are recycled carbonates essential to explain light Mg isotopes in magmatic rocks? Insights from Late Cenozoic mantle-derived magmas in Iran

NASA Astrophysics Data System (ADS)

Pang, K. N.; Teng, F. Z.; Sun, Y.; Chung, S. L.; Zarrinkoub, M. H.

2016-12-01

Mantle-derived magmas at continental collision zones represent probes into the mantle that might have been variably metasomatized prior to collision. To address how and to what extent mantle metasomatism occurred, particularly for the role of recycled carbonates, we conducted a Mg isotopic study of two suites of Late Cenozoic mantle-derived magmas in Iran, part of the Arabia-Eurasia collision zone preceded by the long-lasting Tethyan subduction. The Qal'eh Hasan Ali high-Mg ultrapotassic rocks, low-degree partial melts from the metasomatized lithospheric mantle, have mantle-like δ26Mg (-0.23 to -0.28 ‰) despite high CaO/Al2O3 and Zr/Hf, low Ti/Eu and Hf/Sm, and presence of carbonate globules in devitrified glass indicative of carbonate or carbonatite involvement in their genesis. The absence of light Mg isotopic composition of these rocks indicates that either the recycled carbonates were in the form of calcitic rather than dolomitic melts, or the amount of Mg from the carbonatite was too little to appear in these rocks. The Lut-Sistan alkali basalts, sodic magmas suggested to have derived from low-degree melting of the asthenosphere followed by variable differentiation, display a range of δ26Mg from -0.17 to -0.26 ‰ with three outlying data at -0.37‰, -0.39‰ and -0.56 ‰. The samples with light Mg isotopes do not show greater influence by carbonate or carbonatite in terms of the elemental indices noted above. Instead, they are characterized by lower light and middle REE abundances and slightly lower initial 143Nd/144Nd than the majority of samples. The covariations can be explained by minor incorporation of lower crustal garnet during magma ascent through local thickened crust in the collision zone. We propose that thickened crust where garnet pyroxenites exist is capable of imparting a light Mg isotopic signature to mantle-derived magmas, and that such signature is not unique to the involvement of carbonate or carbonatite in the mantle source.

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.

Stable carbon isotopes as an indicator for soil degradation in an alpine environment (Urseren Valley, Switzerland).

PubMed

Schaub, Monika; Alewell, Christine

2009-05-01

Analyses of soil organic carbon (SOC) content and stable carbon isotope signatures (delta(13)C) of soils were assessed for their suitability to detect early stage soil erosion. We investigated the soils in the alpine Urseren Valley (southern central Switzerland) which are highly impacted by soil erosion. Hill slope transects from uplands (cambisols) to adjacent wetlands (histosols and histic to mollic gleysols) differing in their intensity of visible soil erosion, and reference wetlands without erosion influence were sampled. Carbon isotopic signature and SOC content of soil depth profiles were determined. A close correlation of delta(13)C and carbon content (r > 0.80) is found for upland soils not affected by soil erosion, indicating that depth profiles of delta(13)C of these upland soils mainly reflect decomposition of SOC. Long-term disturbance of an upland soil is indicated by decreasing correlation of delta(13)C and SOC (r

Long term atmospheric deposition as the source of nitrate and other salts in the Atacama Desert, Chile: New evidence from mass-independent oxygen isotopic compositions

USGS Publications Warehouse

Michalski, Greg; Böhlke, J.K.; Thiemens , Mark

2004-01-01

Isotopic analysis of nitrate and sulfate minerals from the nitrate ore fields of the Atacama Desert in northern Chile has shown anomalous 17O enrichments in both minerals. Δ17O values of 14–21 ‰ in nitrate and 0.4 to 4 ‰ in sulfate are the most positive found in terrestrial minerals to date. Modeling of atmospheric processes indicates that the Δ17O signatures are the result of photochemical reactions in the troposphere and stratosphere. We conclude that the bulk of the nitrate, sulfate and other soluble salts in some parts of the Atacama Desert must be the result of atmospheric deposition of particles produced by gas to particle conversion, with minor but varying amounts from sea spray and local terrestrial sources. Flux calculations indicate that the major salt deposits could have accumulated from atmospheric deposition in a period of 200,000 to 2.0 M years during hyper-arid conditions similar to those currently found in the Atacama Desert. Correlations between Δ17O and δ18O in nitrate salts from the Atacama Desert and Mojave Desert, California, indicate varying fractions of microbial and photochemical end-member sources. The photochemical nitrate isotope signature is well preserved in the driest surficial environments that are almost lifeless, whereas the microbial nitrate isotope signature becomes dominant rapidly with increasing moisture, biologic activity, and nitrogen cycling. These isotopic signatures have important implications for paleoclimate, astrobiology, and N cycling studies.

Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

NASA Astrophysics Data System (ADS)

Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

2013-09-01

In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb ppb-1 and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2 / ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

NASA Astrophysics Data System (ADS)

Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

2013-04-01

In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb/ppb and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2/ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

Origin of methane-rich natural gas at the West Pacific convergent plate boundary.

PubMed

Sano, Yuji; Kinoshita, Naoya; Kagoshima, Takanori; Takahata, Naoto; Sakata, Susumu; Toki, Tomohiro; Kawagucci, Shinsuke; Waseda, Amane; Lan, Tefang; Wen, Hsinyi; Chen, Ai-Ti; Lee, Hsiaofen; Yang, Tsanyao F; Zheng, Guodong; Tomonaga, Yama; Roulleau, Emilie; Pinti, Daniele L

2017-11-15

Methane emission from the geosphere is generally characterized by a radiocarbon-free signature and might preserve information on the deep carbon cycle on Earth. Here we report a clear relationship between the origin of methane-rich natural gases and the geodynamic setting of the West Pacific convergent plate boundary. Natural gases in the frontal arc basin (South Kanto gas fields, Northeast Japan) show a typical microbial signature with light carbon isotopes, high CH 4 /C 2 H 6 and CH 4 / 3 He ratios. In the Akita-Niigata region - which corresponds to the slope stretching from the volcanic-arc to the back-arc -a thermogenic signature characterize the gases, with prevalence of heavy carbon isotopes, low CH 4 /C 2 H 6 and CH 4 / 3 He ratios. Natural gases from mud volcanoes in South Taiwan at the collision zone show heavy carbon isotopes, middle CH 4 /C 2 H 6 ratios and low CH 4 / 3 He ratios. On the other hand, those from the Tokara Islands situated on the volcanic front of Southwest Japan show the heaviest carbon isotopes, middle CH 4 /C 2 H 6 ratios and the lowest CH 4 / 3 He ratios. The observed geochemical signatures of natural gases are clearly explained by a mixing of microbial, thermogenic and abiotic methane. An increasing contribution of abiotic methane towards more tectonically active regions of the plate boundary is suggested.

Stable isotope signatures reflect dietary diversity in European forest moths.

PubMed

Adams, Marc-Oliver; Seifert, Carlo Lutz; Lehner, Lisamarie; Truxa, Christine; Wanek, Wolfgang; Fiedler, Konrad

2016-01-01

Information on larval diet of many holometabolous insects remains incomplete. Carbon (C) and nitrogen (N) stable isotope analysis in adult wing tissue can provide an efficient tool to infer such trophic relationships. The present study examines whether moth feeding guild affiliations taken from literature are reflected in isotopic signatures. Non-metric multidimensional scaling and permutational analysis of variance indicate that centroids of dietary groups differ significantly. In particular, species whose larvae feed on mosses or aquatic plants deviated from those that consumed vascular land plants. Moth δ(15)N signatures spanned a broader range, and were less dependent on species identity than δ(13)C values. Comparison between moth samples and ostensible food sources revealed heterogeneity in the lichenivorous guild, indicating only Lithosia quadra as an obligate lichen feeder. Among root-feeding Agrotis segetum, some specimens appear to have developed on crop plants in forest-adjacent farm land. Reed-feeding stem-borers may partially rely on intermediary trophic levels such as fungal or bacterial growth. Diagnostic partitioning of moth dietary guilds based on isotopic signatures alone could not be achieved, but hypotheses on trophic relationships based on often vague literature records could be assessed with high resolution. Hence, the approach is well suited for basic categorization of moths where diet is unknown or notoriously difficult to observe (i.e. Microlepidoptera, lichen-feeders).

Authentication and dating of biomass components of industrial materials; links to sustainable technology

NASA Astrophysics Data System (ADS)

Currie, L. A.; Klinedinst, D. B.; Burch, R.; Feltham, N.; Dorsch, R.

2000-10-01

There are twin pressures mounting in US industry for increased utilization of biomass feedstocks and biotechnology in production. The more demanding pressure relates to economic sustainability, that is, because of increased competition globally, businesses will fail unless a minimum margin of profit is maintained while meeting the demands of consumers for less expensive products. The second pressure relates to "Green Technology" where environmental sustainability, linked for example to concerns about climate change and the preservation of natural resources, represents a worldwide driving force to reduce the consumption of fossil hydrocarbons. The resulting transition of biomass production in the industrial plant, as opposed to the agricultural plant, has resulted in an increasing need for isotopic methods of authenticating and dating feedstocks, intermediates and industrial products. The research described represents a prototypical case study leading to the definition of a unique dual isotopic ( 13C, 14C) signature or "fingerprint" for a new biomass-based commercial polymer, polypropylene terephthalate (3GT).

Iron isotope signatures within chondrules from Allende and Chainpur as indicators of thermal history.

NASA Astrophysics Data System (ADS)

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

2003-04-01

Introduction: We have studied the petrography and Fe-isotope composition of seven chondrules, four from Allende (CV3) and three from Chainpur (LL3.4). A range of textural-chemical chondrule types are represented, allowing us to examine the Fe-isotope signature in material with different thermal histories, with a view to constraing the chondrule forming process and elucidating the nature of chondrule precursor material. Analytical procedures are detailed elsewhere [1,2,3] Fe-isotope Fractionation: The overall variation in δ56Fe is 1.98 ppm and in δ57Fe is 2.87 ppm. EM-1 (non-porphyritic) is most isotopically heavy and EM-3 (porphyritic) is most isotopically light, with all other chondrules falling in a mass fractionation line between these two end-members. This line is defined by the equation δ57Fe = (1.450±0.050)δ56Fe - (0.009±0.016) (R^2 = 0.9995). Discussion: The Fe-fractionation exhibited here is less than would be expected during open system evaporation. This suggests that Rayleigh conditions were not fulfilled during chondrule melting. Chainpur chondrules exhibit less fractionation than Allende chondrules, a total of 0.46 ppm (δ56Fe) in contrast to 1.98 ppm (δ56Fe), respectively, suggesting that Chainpur may be more equilibrated than Allende. Chainpur Fe-isotopes may have been increasingly homogenised by later addition of Fe, either from the nebular reservoir or parent body alteration. Porphyritic and nonporphyritic chondrules have differing thermal histories. The former are a product of incomplete melting, whereas the latter derive from almost total/complete melting of precursor material. However, Fe-isotope fractionation does not appear to vary systematically with texture. We conclude that chondrule Fe-isotopic signatures represent that of the precursor material, with later equilibration of the Chainpur chondrules. Melting history may also influence the Fe-isotopic signature. The isotopically heaviest chondrules (e.g. EM-1 &EC-3) may derive from a melt which attained liquidus temperatures more than once. The precursor to EM-2 (isotopically lightest), may not have been subject to as many aggressive heating events. References: [1] Mullane et al. (2001) LPS XXXII, Abs. #1545. [2] Mullane et al. (2002) In: Plasma Source Mass Spec. Royal Soc. Chem. (in press). [3] Mullane et al. (2002) Met. Plan. Sci. 37, 105 Abs. [4] Alexander C.M.O'D. &Wang J. (2001) Met. Plan. Sci. 36, 419--428.

Evidencing lead deposition at the urban scale using "short-lived" isotopic signatures of the source term (Pb-Zn refinery)

NASA Astrophysics Data System (ADS)

Franssens, Matthias; Flament, Pascal; Deboudt, Karine; Weis, Dominique; Perdrix, Espéranza

2004-09-01

To demonstrate the ability of the lead isotope signature technique to evidence the spatial extent of an industrial Pb deposition plume at a local scale, dry deposition of lead in the urban environment of a Pb-Zn refinery was investigated, as a study case, using transient ("short-lived") isotopic signatures of the industrial source. Sampling campaigns were achieved in representative weather conditions, on an 8-h basis. Dry deposition rates measured downwind from refinery emissions (≈102-103 μg Pb m-2 h-1), cross-sectionally in a 3-5 km radius area around the plant, represent 10-100 times the urban background dry fallout, measured upwind, as well as fallout measured near other potential sources of anthropogenic Pb. The Pb-Zn refinery isotopic signature (approx. 1.100<206Pb/207Pb<1.135) is made identifiable, using the same set of Pb and Zn ores for 2 days before sampling and during field experiments, by agreement with the executive staff of the plant. This source signature is less radiogenic than signatures of urban background Pb aerosols (1.155<206Pb/207Pb<1.165) and minor sources of Pb aerosols (1.147<206Pb/207Pb<1.165). By a simple binary mixing model calculation, we established the extension of the industrial Pb deposition plume. Fifty to eighty percents of total lead settled by the dry deposition mode, 3-4 km away from the refinery, still have an industrial origin. That represents from 40 to 80 μg Pb m-2 h-1, in an area where the blood lead level exceeds 100 μg Pb l-1 for 30% of men and 12% of women living there. We demonstrate here that stable Pb isotope analysis is able to evidence the Pb dry deposition plume in stabilised aerodynamic conditions, using a short-lived source term, suggesting that this methodology is able to furnish valuable data to validate industrial Pb aerosols dispersion models, at the urban scale.

Stable isotopes of carbon and nitrogen in the study of avian and mammalian trophic ecology

Treesearch

Jeffrey F. Kelly

2000-01-01

Differential fractionation of stable isotopes of carbon during photosynthesis causes C4 plants and C3 plants to have distinct carbon-isotope signatures. In addition, marine C3 plants have stable-isotope ratios of carbon that are intermediate between C4 and terrestrial C3 plants. The direct incorporation of the carbon-isotope ratio (13C/12C) of plants into consumers...

STELLAR ORIGINS OF EXTREMELY {sup 13}C- AND {sup 15}N-ENRICHED PRESOLAR SIC GRAINS: NOVAE OR SUPERNOVAE?

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

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.

Extreme excesses of {sup 13}C ({sup 12}C/{sup 13}C < 10) and {sup 15}N ({sup 14}N/{sup 15}N < 20) in rare presolar SiC grains have been considered diagnostic of an origin in classical novae, though an origin in core collapse supernovae (CCSNe) has also been proposed. We report C, N, and Si isotope data for 14 submicron- to micron-sized {sup 13}C- and {sup 15}N-enriched presolar SiC grains ({sup 12}C/{sup 13}C < 16 and {sup 14}N/{sup 15}N < ∼100) from Murchison, and their correlated Mg–Al, S, and Ca–Ti isotope data when available. These grains are enriched in {sup 13}C and {sup 15}N,more » but with quite diverse Si isotopic signatures. Four grains with {sup 29,30}Si excesses similar to those of type C SiC grains likely came from CCSNe, which experienced explosive H burning occurred during explosions. The independent coexistence of proton- and neutron-capture isotopic signatures in these grains strongly supports heterogeneous H ingestion into the He shell in pre-supernovae. Two of the seven putative nova grains with {sup 30}Si excesses and {sup 29}Si depletions show lower-than-solar {sup 34}S/{sup 32}S ratios that cannot be explained by classical nova nucleosynthetic models. We discuss these signatures within the CCSN scenario. For the remaining five putative nova grains, both nova and supernova origins are viable because explosive H burning in the two stellar sites could result in quite similar proton-capture isotopic signatures. Three of the grains are sub-type AB grains that are also {sup 13}C enriched, but have a range of higher {sup 14}N/{sup 15}N. We found that {sup 15}N-enriched AB grains (∼50 < {sup 14}N/{sup 15}N < ∼100) have distinctive isotopic signatures compared to putative nova grains, such as higher {sup 14}N/{sup 15}N, lower {sup 26}Al/{sup 27}Al, and lack of {sup 30}Si excess, indicating weaker proton-capture nucleosynthetic environments.« less

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste.

PubMed

Wimmer, Bernhard; Hrad, Marlies; Huber-Humer, Marion; Watzinger, Andrea; Wyhlidal, Stefan; Reichenauer, Thomas G

2013-10-01

Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ(13)C, δ(2)H and δ(18)O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ(13)C-value of the dissolved inorganic carbon (δ(13)C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ(13)C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ(13)C-DIC of -20‰ to -25‰. The production of methane under anaerobic conditions caused an increase in δ(13)C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ(13)C-DIC of about -20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation-reduction status of MSW landfills. Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration. Copyright © 2013 Elsevier Ltd. All rights reserved.

Arthropod food web restoration following removal of an invasive wetland plant.

PubMed

Gratton, Claudio; Denno, Robert F

2006-04-01

Restoration of habitats impacted by invasive plants is becoming an increasingly important tool in the management of native biodiversity, though most studies do not go beyond monitoring the abundance of particular taxonomic groups, such as the return of native vegetation. Yet, the reestablishment of trophic interactions among organisms in restored habitats is equally important if we are to monitor and understand how ecosystems recover. This study examined whether food web interactions among arthropods (as inferred by abundance of naturally occurring stable isotopes of C [delta13C] and N [delta15N]) were reestablished in the restoration of a coastal Spartina alterniflora salt marsh that had been invaded by Phragmites australis. From patterns of C and N stable isotopes we infer that trophic interactions among arthropods in the native salt marsh habitats are characterized by reliance on the dominant marsh plant Spartina as a basal resource. Herbivores such as delphacid planthoppers and mirid bugs have isotope signatures characteristic of Spartina, and predatory arthropods such as dolicopodid flies and spiders likewise have delta13C and delta15N signatures typical of Spartina-derived resources (approximately -13 per thousand and 10 per thousand, respectively). Stable isotope patterns also suggest that the invasion of Phragmites into salt marshes and displacement of Spartina significantly alter arthropod food web interactions. Arthropods in Phragmites-dominated sites have delta13C isotope values between -18 per thousand and -20 per thousand, suggesting reliance on detritus and/or benthic microalgae as basal resources and not on Phragmites, which has a delta13C approximately -26 per thousand. Since most Phragmites herbivores are either feeding internally or are rare transients from nearby Spartina, these resources do not provide significant prey resources for other arthropod consumers. Rather, predator isotope signatures in the invaded habitats indicate dependence on detritus/algae as basal resources instead of the dominant vegetation. The reestablishment of Spartina after removal of Phragmites, however, not only returned species assemblages typical of reference (uninvaded) Spartina, but stable isotope signatures suggest that the trophic interactions among the arthropods were also similar in reestablished habitats. Specifically, both herbivores and predators showed characteristic Spartina signatures, suggesting the return of the original grazer-based food web structure in the restored habitats.

Continual in situ monitoring of pore water stable isotopes in the subsurface

NASA Astrophysics Data System (ADS)

Volkmann, T. H. M.; Weiler, M.

2014-05-01

Stable isotope signatures provide an integral fingerprint of origin, flow paths, transport processes, and residence times of water in the environment. However, the full potential of stable isotopes to quantitatively characterize subsurface water dynamics is yet unfolded due to the difficulty in obtaining extensive, detailed, and repeated measurements of pore water in the unsaturated and saturated zone. This paper presents a functional and cost-efficient system for non-destructive continual in situ monitoring of pore water stable isotope signatures with high resolution. Automatic controllable valve arrays are used to continuously extract diluted water vapor in soil air via a branching network of small microporous probes into a commercial laser-based isotope analyzer. Normalized liquid-phase isotope signatures are then obtained based on a specific on-site calibration approach along with basic corrections for instrument bias and temperature dependent isotopic fractionation. The system was applied to sample depth profiles on three experimental plots with varied vegetation cover in southwest Germany. Two methods (i.e., based on advective versus diffusive vapor extraction) and two modes of sampling (i.e., using multiple permanently installed probes versus a single repeatedly inserted probe) were tested and compared. The results show that the isotope distribution along natural profiles could be resolved with sufficiently high accuracy and precision at sampling intervals of less than four minutes. The presented in situ approaches may thereby be used interchangeably with each other and with concurrent laboratory-based direct equilibration measurements of destructively collected samples. It is thus found that the introduced sampling techniques provide powerful tools towards a detailed quantitative understanding of dynamic and heterogeneous shallow subsurface and vadose zone processes.

Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird

Treesearch

Scott F. Pearson; Douglas J. Levey; Cathryn H. Greenberg; Carlos Martinez del Rio

2003-01-01

The use of stable isotopes to infer diet requires quantifying the relationship between diet and tissues and, in particular, knowing of how quickly isotopes turnover in different tissues and how isotopic concentrations of different food components change (discriminate) when incorporated into consumer tissues. We used feeding trials with wild-caught yellow-rumped...

A compact gas-filled avalanche counter for DANCE

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

Wu, C. Y.; Chyzh, A.; Kwan, E.

2012-08-04

A compact gas-filled avalanche counter for the detection of fission fragments was developed for a highly segmented 4π γ-ray calorimeter, namely the Detector for Advanced Neutron Capture Experiments located at the Lujan Center of the Los Alamos Neutron Science Center. It has been used successfully for experiments with 235U, 238Pu, 239Pu, and 241Pu isotopes to provide a unique signature to differentiate the fission from the competing neutron-capture reaction channel. We also used it to study the spontaneous fission in 252Cf. The design and performance of this avalanche counter for targets with extreme α-decay rate up to ~2.4×108/s are described.

The behavior of U- and Th-series nuclides in the estuarine environment

USGS Publications Warehouse

Swarzenski, P.W.; Porcelli, D.; Andersson, P.S.; Smoak, J.M.

2003-01-01

Rivers carry the products of continental weathering, and continuously supply the oceans with a broad range of chemical constituents. This erosional signature is, however, uniquely moderated by biogeochemical processing within estuaries. Estuaries are commonly described as complex filters at land-sea margins, where significant transformations can occur due to strong physico-chemical gradients. These changes differ for different classes of elements, and can vary widely depending on the geographic location. U- and Th-series nuclides include a range of elements with vastly different characteristics and behaviors within such environments, and the isotopic systematics provide methods for investigating the transport of these nuclides and other analog species across estuaries and into the coastal ocean.

Biogeochemistry Science and Education Part One: Using Non-Traditional Stable Isotopes as Environmental Tracers Part Two: Identifying and Measuring Undergraduate Misconceptions in Biogeochemistry

NASA Astrophysics Data System (ADS)

Mead, Chris

This dissertation is presented in two sections. First, I explore two methods of using stable isotope analysis to trace environmental and biogeochemical processes. Second, I present two related studies investigating student understanding of the biogeochemical concepts that underlie part one. Fe and Hg are each biogeochemically important elements in their own way. Fe is a critical nutrient for phytoplankton, while Hg is detrimental to nearly all forms of life. Fe is often a limiting factor in marine phytoplankton growth. The largest source, by mass, of Fe to the open ocean is windblown mineral dust, but other more soluble sources are more bioavailable. To look for evidence of these non-soil dust sources of Fe to the open ocean, I measured the isotopic composition of aerosol samples collected on Bermuda. I found clear evidence in the fine size fraction of a non-soil dust Fe source, which I conclude is most likely from biomass burning. Widespread adoption of compact fluorescent lamps (CFL) has increased their importance as a source of environmental Hg. Isotope analysis would be a useful tool in quantifying this impact if the isotopic composition of Hg from CFL were known. My measurements show that CFL-Hg is isotopically fractionated, in a unique pattern, during normal operation. This fractionation is large and has a distinctive, mass-independent signature, such that CFL Hg can be uniquely identified from other sources. Misconceptions research in geology has been a very active area of research, but student thinking regarding the related field of biogeochemistry has not yet been studied in detail. From interviews with 40 undergraduates, I identified over 150 specific misconceptions. I also designed a multiple-choice survey (concept inventory) to measure understanding of these same biogeochemistry concepts. I present statistical evidence, based on the Rasch model, for the reliability and validity of this instrument. This instrument will allow teachers and researchers to easily quantify learning outcomes in biogeochemistry and will complement existing concept inventories in geology, chemistry, and biology.

STABLE ISOTOPE SIGNATURES OF MUCUS OF STEELHEAD TROUT IN A CONTROLLED DIET SWITCH EXPERIMENT

EPA Science Inventory

Our work has shown that fish mucus can serve as a very rapid indicator of diet switching in fish. We performed diet switching studies of steelhead trout in a controlled hatchery setting using specially formulated low delta 15N signature and high delta 15N signature diets. To ou...

Stable Isotope Signatures of Middle Palaeozoic Ahermatypic Rugose Corals - Deciphering Secondary Alteration, Vital Fractionation Effects, and Palaeoecological Implications.

PubMed

Jakubowicz, Michal; Berkowski, Blazej; López Correa, Matthias; Jarochowska, Emilia; Joachimski, Michael; Belka, Zdzislaw

2015-01-01

This study investigates stable isotope signatures of five species of Silurian and Devonian deep-water, ahermatypic rugose corals, providing new insights into isotopic fractionation effects exhibited by Palaeozoic rugosans, and possible role of diagenetic processes in modifying their original isotopic signals. To minimize the influence of intraskeletal cements on the observed signatures, the analysed specimens included unusual species either devoid of large intraskeletal open spaces ('button corals': Microcyclus, Palaeocyclus), or typified by particularly thick corallite walls (Calceola). The corals were collected at four localities in the Holy Cross Mountains (Poland), Mader Basin (Morocco) and on Gotland (Sweden), representing distinct diagenetic histories and different styles of diagenetic alteration. To evaluate the resistance of the corallites to diagenesis, we applied various microscopic and trace element preservation tests. Distinct differences between isotopic compositions of the least-altered and most-altered skeleton portions emphasise a critical role of material selection for geochemical studies of Palaeozoic corals. The least-altered parts of the specimens show marine or near-marine stable isotope signals and lack positive correlation between δ13C and δ18O. In terms of isotopic fractionation mechanisms, Palaeozoic rugosans must have differed considerably from modern deep-water scleractinians, typified by significant depletion in both 18O and 13C, and pronounced δ13C-δ18O co-variance. The fractionation effects exhibited by rugosans seem similar rather to the minor isotopic effects typical of modern non-scleractinian corals (octocorals and hydrocorals). The results of the present study add to growing evidence for significant differences between Scleractinia and Rugosa, and agree with recent studies indicating that calcification mechanisms developed independently in these two groups of cnidarians. Consequently, particular caution is needed in using scleractinians as analogues in isotopic studies of extinct coral lineages. Answering some of the pertinent palaeoecological questions, such as that of the possibility of photosymbiosis in Palaeozoic corals, may not be possible based on stable isotope data.

The genetic link between the Azores Archipelago and the Southern Azores Seamount Chain (SASC): The elemental, isotopic and chronological evidences

NASA Astrophysics Data System (ADS)

Ribeiro, Luisa Pinto; Martins, Sofia; Hildenbrand, Anthony; Madureira, Pedro; Mata, João

2017-12-01

New geochemical, isotopic (Sr-Nd-Hf-Pb) and K-Ar data, are presented here on samples from the Southern Azores Seamount Chain (SASC) located south of the Azores Plateau. The SASC also includes the Great Meteor, Small Meteor and Closs seamounts, morphologically connected by a saddle at - 4100 m deep. We conclude that the SASC are characterized by a narrow isotopic variability that falls within the Azores isotopic field. Although each seamount has its own isotopic signature, their mantle source must comprise four local mantle end-members, three of which are common to the Azores, e.g. Plato isotopic signature results from the mixing between HIMU and N-MORB while Great Meteor signature results from this mix with the Azores Common Component (AzCC). A fourth end-member with high 208Pb/204Pb and decoupled Th/U ratios (Δ8/4 up to 59.2) is identified on Great Meteor northern flank. New K-Ar ages on Plato (33.4 ± 0.5 Ma) and Small Hyeres (31.6 ± 0.4 Ma) show nearly coeval volcanism, which is contemporaneous with the E-MORBs erupted at the MAR, drilled on oceanic crust with 30-34 Ma (DSDP82). This study endorses the genetic link between the Azores Archipelago and the SASC to the long-term activity of the Azores plume and the large-scale ridge-hotspot interaction, contributing to better constrain the temporal-spatial evolution of this region of the North Atlantic.

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Use of stable isotope signatures to determine mercury sources in the Great Lakes

USGS Publications Warehouse

Lepak, Ryan F.; Yin, Runsheng; Krabbenhoft, David P.; Ogorek, Jacob M.; DeWild, John F.; Holsen, Thomas M.; Hurley, James P.

2015-01-01

Sources of mercury (Hg) in Great Lakes sediments were assessed with stable Hg isotope ratios using multicollector inductively coupled plasma mass spectrometry. An isotopic mixing model based on mass-dependent (MDF) and mass-independent fractionation (MIF) (δ202Hg and Δ199Hg) identified three primary Hg sources for sediments: atmospheric, industrial, and watershed-derived. Results indicate atmospheric sources dominate in Lakes Huron, Superior, and Michigan sediments while watershed-derived and industrial sources dominate in Lakes Erie and Ontario sediments. Anomalous Δ200Hg signatures, also apparent in sediments, provided independent validation of the model. Comparison of Δ200Hg signatures in predatory fish from three lakes reveals that bioaccumulated Hg is more isotopically similar to atmospherically derived Hg than a lake’s sediment. Previous research suggests Δ200Hg is conserved during biogeochemical processing and odd mass-independent fractionation (MIF) is conserved during metabolic processing, so it is suspected even is similarly conserved. Given these assumptions, our data suggest that in some cases, atmospherically derived Hg may be a more important source of MeHg to higher trophic levels than legacy sediments in the Great Lakes.

Stable-isotope analysis of canvasback winter diet in upper Chesapeake Bay

USGS Publications Warehouse

Haramis, G.M.; Jorde, Dennis G.; Macko, S.A.; Walker, J.L.

2001-01-01

A major decline in submerged aquatic vegetation (SAV) in Chesapeake Bay has altered the diet of wintering Canvasbacks (Aythya valisineria) from historically plant to a combination of benthic animal foods, especially the ubiquitous Baltic clam (Macoma balthica), supplemented with anthropogenic corn (Zea mays). Because the isotopic signature of corn is readily discriminated from bay benthos, but not SAV, we used stable-isotope methodology to investigate the corn–SAV component of the winter diet of Canvasbacks. Feeding trials with penned Canvasbacks were conducted to establish turnover rates and fractionation end-point loci of δ13C and δ15N signatures of whole blood for individual ducks fed ad libitum diets of (1) Baltic clams, (2) Baltic clams and corn, and (3) tubers of wild celery (Vallisneria americana). Turnover time constants averaged 4.5 weeks, indicating that signatures of wild ducks would be representative of bay diets by late February. Isotopic signatures of wild Canvasbacks sampled in February fell on a continuum between end-point loci for the Baltic clam and the combination Baltic clam and corn diet. Although that finding verifies a clear dependence on corn–SAV for wintering Canvasbacks, it also reveals that not enough corn–SAV is available to establish ad libitum consumption for the 15,000+ Canvasbacks wintering in the upper bay. On the basis of mean δ13C signature of bay Canvasbacks (n = 59) and ingestion rates from feeding trials, we estimated that 258 kg corn per day would account for the observed δ13C enrichment and supply 18% of daily energetic needs for 15,000 Canvasbacks. That level of corn availability is so realistic that we conclude that SAV is likely of little dietary importance to Canvasbacks in that portion of the bay.

Microbial methane from in situ biodegradation of coal and shale: A review and reevaluation of hydrogen and carbon isotope signatures

USGS Publications Warehouse

Vinson, David S.; Blair, Neal E.; Martini, Anna M.; Larter, Steve; Orem, William H.; McIntosh, Jennifer C.

2017-01-01

Stable carbon and hydrogen isotope signatures of methane, water, and inorganic carbon are widely utilized in natural gas systems for distinguishing microbial and thermogenic methane and for delineating methanogenic pathways (acetoclastic, hydrogenotrophic, and/or methylotrophic methanogenesis). Recent studies of coal and shale gas systems have characterized in situ microbial communities and provided stable isotope data (δD-CH4, δD-H2O, δ13C-CH4, and δ13C-CO2) from a wider range of environments than available previously. Here we review the principal biogenic methane-yielding pathways in coal beds and shales and the isotope effects imparted on methane, document the uncertainties and inconsistencies in established isotopic fingerprinting techniques, and identify the knowledge gaps in understanding the subsurface processes that govern H and C isotope signatures of biogenic methane. We also compare established isotopic interpretations with recent microbial community characterization techniques, which reveal additional inconsistencies in the interpretation of microbial metabolic pathways in coal beds and shales. Collectively, the re-assessed data show that widely-utilized isotopic fingerprinting techniques neglect important complications in coal beds and shales.Isotopic fingerprinting techniques that combine δ13C-CH4 with δD-CH4 and/or δ13C-CO2have significant limitations: (1) The consistent ~ 160‰ offset between δD-H2O and δD-CH4 could imply that hydrogenotrophic methanogenesis is the dominant metabolic pathway in microbial gas systems. However, hydrogen isotopes can equilibrate between methane precursors and coexisting water, yielding a similar apparent H isotope signal as hydrogenotrophic methanogenesis, regardless of the actual methane formation pathway. (2) Non-methanogenic processes such as sulfate reduction, Fe oxide reduction, inputs of thermogenic methane, anaerobic methane oxidation, and/or formation water interaction can cause the apparent carbon isotope fractionation between δ13C-CH4 and δ13C-CO2(α13CCO2-CH4) to differ from the true methanogenic fractionation, complicating interpretation of methanogenic pathways. (3) Where little-fractionating non-methanogenic bacterial processes compete with highly-fractionating methanogenesis, the mass balance between CH4 and CO2 is affected. This has implications for δ13C values and provides an alternative interpretation for net C isotope signatures than solely the pathways used by active methanogens. (4) While most of the reviewed values of δD-H2O - δD-CH4 and α13CCO2-CH4 are apparently consistent with hydrogenotrophic methanogenesis as the dominant pathway in coal beds and shales, recent microbial community characterization techniques suggest a possible role for acetoclastic or methylotrophic methanogenesis in some basins.

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)].

Worldwide measurements of radioxenon background near isotope production facilities, a nuclear power plant and at remote sites: the ‘‘EU/JA-II’’ Project

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

Saey, P. R.J.; Ringbom, Anders; Bowyer, Ted W.

The Comprehensive Nuclear-Test-Ban Treaty (CTBT) specifies that radioxenon measurements should be performed at 40 or more stations worldwide within the International Monitoring System (IMS). Measuring radioxenon is one of the principle techniques to detect underground nuclear explosions. Specifically, presence and ratios of different radioxenon isotopes allows determining whether a detection event under consideration originated from a nuclear explosion or a civilian source. However, radioxenon monitoring on a global scale is a novel technology and the global civil background must be characterized sufficiently. This paper lays out a study, based on several unique measurement campaigns, of the worldwide concentrations and sourcesmore » of verification relevant xenon isotopes. It complements the experience already gathered with radioxenon measurements within the CTBT IMS programme and focuses on locations in Belgium, Germany, Kuwait, Thailand and South Africa where very little information was available on ambient xenon levels or interesting sites offered opportunities to learn more about emissions from known sources. The findings corroborate the hypothesis that a few major radioxenon sources contribute in great part to the global radioxenon background. Additionally, the existence of independent sources of 131mXe (the daughter of 131I) has been demonstrated, which has some potential to bias the isotopic signature of signals from nuclear explosions.« less

The use of stable isotope to evaluate water mixing and water use by flood plain trees along the Garonne valley

USGS Publications Warehouse

Lambs, L.; Loubiat, M.; Richardson, W.

2003-01-01

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (18O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. 18O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (??18O: -9.1??? to -9.0???, conductivity: 217-410??S/cm) was distinctly different from groundwater (??18O: -7.1??? to -6.6???, conductivity: 600-900??S/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (1m). Trees at both locations maintained sap with ionic charges much greater (2.3-3.7x) than that of source water. The combined use of 18O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.

Stable Isotope Systematics of Martian Perchlorate

NASA Astrophysics Data System (ADS)

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

2015-12-01

Chlorine isotopic compositions in HCl released during evolved gas analysis (EGA) runs have been detected by the Sample Analysis at Mars (SAM) instrument on the Curiosity rover ranging from approximately -9‰ to -50‰ δ37Cl, with two spatially and isotopically separated groups of samples averaging -15‰ and -45‰. These extremely low values are the first such detection of any known natural material; common terrestrial values very rarely exceed ±5‰, and the most extreme isotopic signature yet detected elsewhere in the solar system are values of around +24‰ on the Moon. The only other known location in the solar system with large negative chlorine isotopes is the Atacama Desert, where perchlorate with -14‰ δ37Cl has been detected. The Atacama perchlorate has unusual Δ17O signatures associated with it, indicating a formation mechanism involving O3, which suggests an atmospheric origin of the perchlorate and associated large isotopic anomalies. Identification of non-zero positive Δ17O signatures in the O2 released during EGA runs would allow definitive evidence for a similar process having occurred on Mars. Perchlorate is thought to be the most likely source of HCl in EGA runs due to the simultaneous onset of O2 release. If perchlorate is indeed the HCl source, atmospheric chemistry could be responsible for the observed isotopic anomalies, with variable extents of perchlorate production producing the isotopic variability. However, chloride salts have also been observed to release HCl upon heating; if the timing of O2 release is merely coincidental, observed HCl could be coming from chlorides. At thermodynamic equilibrium, the fractionation factor of perchlorate reduction is 0.93, meaning that differing amounts of post-deposition reduction of isotopically normal perchlorate to chloride could account for the highly variable Cl isotopes. Additionally, post-deposition reduction could account for the difference between the two Cl isotopic groups if perchlorate is the HCl source, as the residual perchlorate after reduction will be isotopically heavy. Therefore, conclusive determination of the origin of HCl released during EGA is vital to understanding the origin of this large δ37Cl anomaly.

Isotopic (d18O/d2H) integrity of water samples collected and stored by automatic samplers

USDA-ARS?s Scientific Manuscript database

Stable water isotopes are increasingly becoming part of routine monitoring programs that utilize automatic samplers. The objectives of this study were to quantify the uncertainty in isotope signatures due to the length of sample storage (1-24 d) inside autosamplers over a range of air temperatures (...

A Comparative Analysis of the Influence of Surface Mining on Hydrological and Geochemical Response of Selected Headwater Streams in the Elk Valley, British Columbia, Canada.

NASA Astrophysics Data System (ADS)

Carey, S. K.; Shatilla, N. J.; Szmudrowska, B.; Rastelli, J.; Wellen, C.

2014-12-01

Surface mining is a common method of accessing coal. Blasting of overburden rock allows access to mineable ore. In high-elevation environments, the removed overburden rock is deposited in adjacent valleys as waste rock spoils. As part of a multi-year R&D program examining the influence of surface mining on watershed hydrological and water quality responses in the Elk Valley, British Columbia, this study reports on how surface mining affects streamflow hydrological and geochemical response at four reference and four mine-influenced catchments. The hydrology of this environment is dominated by snowmelt and steep topographic gradients. Flows were attenuated in mine-influenced catchments, with spring freshet delayed and more muted responses to precipitation events observed. Dissolved ions were an order of magnitude greater in mine-influenced streams, with more dilution-based responses to flows compared with chemostatic behavior observed in reference streams. Stable isotope signatures in stream water suggested that in both mine-influenced and reference watersheds, stream water was derived from well mixed groundwater as annual variability of stream isotope signatures was dampened compared with precipitation signatures. However, deflection of stream isotopes in response to precipitation were more apparent in reference watersheds. As a group, mine influenced catchments had a heavier isotope signature than reference watersheds, suggesting an enhanced influence of rainfall on recharge. Transit time distributions indicate existing waste rock spoils increase the average time water takes to move through the catchment.

Fluid flow in deforming media: interpreting stable isotope signatures of marbles

NASA Astrophysics Data System (ADS)

Bond, C. E.

2016-12-01

Fluid flow in the crust is controlled by permeable networks. These networks can be created and destroyed dynamically during rock deformation. Rock deformation is therefore critical in controlling fluid pathways in the crust and hence the location of mineral and other resources. Here, evidence for deformation-enhanced fluid infiltration shows that a range of deformation mechanisms control fluid flow and chemical and isotopic equilibration. The results attest to localised fluid infiltration within a single metamorphic terrain (12km) over a range of metamorphic grades; ecologite- blueschist to greenschist. For fluid infiltrating marbles during ductile deformation, chemical and isotopic signatures are now homogenous; whilst fluid infiltration associated with brittle deformation results in chemical and isotopic heterogeneity at a microscale. The findings demonstrate how ductile deformation enhances equilibration of δ18O at a grain scale whilst brittle deformation does not. The control of deformation mechanisms in equilibrating isotopic and chemical heterogeneities have implications for the understanding of fluid-rock interaction in the crust. Interpretation of bulk stable isotope data, particularly in the use of isotope profiles to determine fluid fluxes into relatively impermeable units that have been deformed need to be used with care when trying to determine fluid fluxes and infiltration mechanisms.

Revisiting the Si Isotope Record of Precambrian Cherts and Banded Iron Formations Using New Experimental Results

NASA Astrophysics Data System (ADS)

Zheng, X. Y.; Satkoski, A.; Beard, B. L.; Reddy, T. R.; Beukes, N. J.; Johnson, C.

2017-12-01

Precambrian Banded iron formations (BIFs) and cherts provide a record of Fe and Si biogeochemical cycling in early Earth marine environments. Much of the focus on BIFs has been the origin and pathways for Fe, but Si is intimately tied to BIF genesis through its connection to Fe minerals, either through direct structural bonding or through sorption. In the Precambrian ocean, aqueous Si contents were high, and it is increasingly recognized that Fe(III)-Si gels were the most likely precursor to BIFs [1]. It is known that Fe-Si bonding affects stable Fe isotope fractionations [2], and our recent experimental work shows this to be true for stable Si isotope fractionations [3, 4]. Silicon isotope fractionations in the Fe-Si system vary from 0‰ to nearly 4‰ in 30Si/28Si ratios with the solid phase being isotopically light depending on Fe:Si ratio [3, 4, and this study], a range far larger than that of 56Fe/54Fe ratios, highlighting the fact that Si isotopes are a highly sensitive tracer of the Fe-Si cycle. This range in Si isotope fractionation factors for the Fe-Si system can explain the full range of δ30Si values measured in Precambrian BIFs, providing a new framework to interpret Precambrian δ30Si records. Our results provide strong support for a model where Fe(III)-Si gels are the precursor phase for BIFs, which in turn affects estimates for the aqueous Fe and Si contents of the Precambrian oceans through changes in Fe-Si gel solubility. Our experiments also showed that microbial dissimilatory iron reduction (DIR) of Fe(III)-Si gel can easily produce a solid with Fe(II)-Fe(III) stoichiometry equal to magnetite, in marked contrast to abiotic incorporation of Fe(II) into Fe(III)-Si gel that resulted in a solid with Fe(II)-Fe(III) stoichiometry much lower than magnetite. Moreover, this DIR process produces a unique, negative δ30Si signature that should be eventually preserved in quartz closely associated with magnetite upon phase transformation of Fe-Si gel, and serve as a bio-signature. This experimental finding well explains the tendency of magnetite-rich BIFs to have lower δ30Si values than hematite-rich BIFs. [1] Konhauser et al., Earth-Science Rev, 2017 [2] Wu et al., GCA, 2012 [3] Zheng et al., GCA, 2016 [4] Reddy et al., GCA, 2016

Chemical and U-Sr isotopic variations of stream and source waters at a small catchment scale (the Strengbach case; Vosges mountains; France)

NASA Astrophysics Data System (ADS)

Pierret, M. C.; Stille, P.; Prunier, J.; Viville, D.; Chabaux, F.

2014-03-01

This is the first comprehensive study dealing with major and trace element data as well as 87Sr/86Sr isotope and (234U/238U) activity ratios (AR) determined on the totality of springs and brooks of the Strengbach catchment. It shows that the small and more or less monolithic catchment drains different sources and streamlets with very different isotopic and geochemical signatures. Different parameters control the diversity of the source characteristics. Of importance is especially the hydrothermal overprint of the granitic bedrock, which was stronger for the granite from the northern than from the southern slope; also significant are the different meteoric alteration processes of the bedrock causing the formation of 0.5 to 9 m thick saprolite and above the formation of an up to 1 m thick soil system. These processes mainly account for springs and brooks from the northern slope having higher Ca/Na, Mg/Na, Sr/Na ratios but lower 87Sr/86Sr isotopic ratios than those from the southern slope. The chemical compositions of the source waters in the Strengbach catchment are only to a small extent the result of alteration of primary bedrock minerals and rather reflect dissolution/precipitation processes of secondary mineral phases like clay minerals. The (234U/238U) AR, however, are decoupled from the 87Sr/86Sr isotope system and reflect to some extent the level of altitude of the source and, thus, the degree of alteration of the bedrock. The sources emerging at high altitudes have circulated through already weathered materials (saprolite and fractured rock depleted in 234U) implying (234U/238U) AR < 1, which is uncommon for surface waters. Preferential flow paths along constant fractures in the bedrocks might explain the over time homogeneous U AR of the different spring waters. However, the geochemical and isotopic variations of stream waters at the outlet of the catchment are controlled by variable contributions of different springs depending on the hydrological conditions. It appears that the (234U/238U) AR is an appropriate very important tracer for studying and deciphering the contribution of the different source fluxes at the catchment scale because this unique geochemical parameter is different for each individual spring and at the same time remains unchanged for each of the springs with changing discharge and fluctuating hydrological conditions. This study further highlights the important impact of different and independent water pathways in fractured granite controlling the different geochemical and isotopic signatures of the waters.

Constraints on Nucleosynthesis from Xenon Isotopes in Presolar Material

NASA Astrophysics Data System (ADS)

Gilmour, J. D.; Turner, G.

2007-03-01

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

Calcium Isotope Systematics During Development of the Domestic Chicken (Gallus gallus)

NASA Astrophysics Data System (ADS)

Wheatley, P. V.

2003-12-01

Calcium isotope distributions have been recognized as showing systematic and predictable fractionation in nature. However, most of the observed calcium isotope fractionation to date is due to biological processes. The presence of abundant amounts of calcium in mineralized tissues makes the isotopic system of calcium particularly valuable in biological and paleobiological questions involving biomineralization. In order to apply calcium isotope systematics to paleobiological questions the changes in the calcium isotope signatures of mineralized tissue in modern animals should be studied. My study observed the domestic chicken (Gallus gallus) through embryologic ontogeny. This was accomplished by obtaining fertilized eggs staged in a growth series from day 12 to day 20. The eggs were dissected and shell, embryonic bone, albumen, and yolk were analyzed in order to characterize the calcium isotopic composition of the individual components over the course of the growth series. Several systematic changes in the isotopic signatures of various tissues were observed during the course of the development of the embryos. In general, mineralization in biological systems preferentially partitions the lighter isotopes of calcium into hard parts. As a result of this fractionation during mineralization, partitioning of light isotopes of calcium into the mineralized tissues may result in residual tissues being enriched in the heavier isotopes as ontogeny progresses. Better understanding of the behavior of calcium in modern biological systems will improve its application to fossils and expand the number of paleobiological and evolutionary questions that can be addressed using calcium isotopic data.

Mass-dependent and -independent fractionation of Fe isotopes in magnetotactic bacteria

NASA Astrophysics Data System (ADS)

Amor, M.; Busigny, V.; Louvat, P.; Gelabert, A.; Cartigny, P.; Durand-Dubief, M.; Ona-Nguema, G.; Alphandéry, E.; Chebbi, I.; Guyot, F. J.

2016-12-01

Magnetotactic bacteria (MTB) perform biomineralization of intracellular magnetite (Fe3O4) nanoparticles. Although they may be among the oldest microorganisms capable of biomineralization on Earth, identification of their activity in the geological record remains poorly resolved because of the lack of reliable signatures. Here, we determined Fe isotope fractionation by the magnetotactic bacterium Magnetospirillum magneticum strain AMB-1 to better understand Fe cycling in MTB and provide new signatures of the contribution of MTB to iron geochemistry. AMB-1 strain was cultivated with either Fe(III)-quinate or Fe(II)-ascorbate as Fe sources. Iron isotope composition of Fe sources, bacterial growth media after AMB-1 cultures, bacterial lysates (corresponding to AMB-1 cells devoid of magnetite) and magnetite samples were analyzed by MC-ICP-MS after column chromatography. In the two culture conditions, growth media after AMB-1 cultures were enriched in light Fe isotopes relative to Fe sources. Two distinct bacterial Fe reservoirs were characterized in AMB-1: (1) magnetite enriched in the light Fe isotopes by 1.5 to 2.5‰ in δ56Fe relative to Fe sources, and (2) lysate enriched in the heavy Fe isotopes by 0.3 to 0.8‰ relative to Fe sources. More importantly, mass-independent fractionations in odd (57Fe) but not in even isotopes (54Fe, 56Fe and 58Fe) were observed for the first time, highlighting a magnetic isotope effect. Magnetite samples were significantly enriched in 57Fe by 0.23‰ relative to 54Fe, 56Fe and 58Fe. Based on our results, we propose a model for Fe cycling and magnetite biomineralization in AMB-1, and propose to use this specific mass-independent signature of Fe isotopes to evaluate the contribution of MTB to the iron biogeochemistry of recent and ancient environmental samples.

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

PubMed

Fekiacova, Z; Cornu, S; Pichat, S

2015-06-01

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

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial magma ocean. Whether such endogenous isotopic heterogeneity would survive as an observable signature in the modern silicate Earth is an open question.

Unique proteomic signature for radiation sensitive patients; a comparative study between normo-sensitive and radiation sensitive breast cancer patients.

PubMed

Skiöld, Sara; Azimzadeh, Omid; Merl-Pham, Juliane; Naslund, Ingemar; Wersall, Peter; Lidbrink, Elisabet; Tapio, Soile; Harms-Ringdahl, Mats; Haghdoost, Siamak

2015-06-01

Radiation therapy is a cornerstone of modern cancer treatment. Understanding the mechanisms behind normal tissue sensitivity is essential in order to minimize adverse side effects and yet to prevent local cancer reoccurrence. The aim of this study was to identify biomarkers of radiation sensitivity to enable personalized cancer treatment. To investigate the mechanisms behind radiation sensitivity a pilot study was made where eight radiation-sensitive and nine normo-sensitive patients were selected from a cohort of 2914 breast cancer patients, based on acute tissue reactions after radiation therapy. Whole blood was sampled and irradiated in vitro with 0, 1, or 150 mGy followed by 3 h incubation at 37°C. The leukocytes of the two groups were isolated, pooled and protein expression profiles were investigated using isotope-coded protein labeling method (ICPL). First, leukocytes from the in vitro irradiated whole blood from normo-sensitive and extremely sensitive patients were compared to the non-irradiated controls. To validate this first study a second ICPL analysis comparing only the non-irradiated samples was conducted. Both approaches showed unique proteomic signatures separating the two groups at the basal level and after doses of 1 and 150 mGy. Pathway analyses of both proteomic approaches suggest that oxidative stress response, coagulation properties and acute phase response are hallmarks of radiation sensitivity supporting our previous study on oxidative stress response. This investigation provides unique characteristics of radiation sensitivity essential for individualized radiation therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Assessing Precipitation Isotope Variations during Atmospheric River Events to Reveal Dominant Atmospheric/Hydrologic Processes

NASA Astrophysics Data System (ADS)

McCabe-Glynn, S. E.; Johnson, K. R.; Yoshimura, K.; Buenning, N. H.; Welker, J. M.

2015-12-01

Extreme precipitation events across the Western US commonly associated with atmospheric rivers (ARs), whereby extensive fluxes of moisture are transported from the subtropics, can result in major damage and are projected by most climate models to increase in frequency and severity. However, they are difficult to project beyond ~ten days and the location of landfall and topographically induced precipitation is even more uncertain. Water isotopes, often used to reconstruct past rainfall variability, are useful natural tracers of atmospheric hydrologic processes. Because of the typical tropical and sub-tropical origins, ARs can carry unique water isotope (δ18O and δ2H, d-excess) signatures that can be utilized to provide source and process information that can lead to improving AR predictions. Recent analysis of the top 10 weekly precipitation total samples from Sequoia National Park, CA, of which 9 contained AR events, shows a high variability in the isotopic values. NOAA Hysplit back trajectory analyses reveals a variety of trajectories and varying latitudinal source regions contributed to moisture delivered to this site, which may explain part of the high variability (δ2H = -150.03 to -49.52 ‰, δ18O = -19.27 to -7.20 ‰, d-excess = 4.1 to 25.8). Here we examine the top precipitation totals occurring during AR events and the associated isotopic composition of precipitation samples from several sites across the Western US. We utilize IsoGSM, an isotope-enabled atmospheric general circulation model, to characterize the hydrologic processes and physical dynamics contributing to the observed isotopic variations. We investigate isotopic influences from moisture source location, AR speed, condensation height, and associated temperature. We explore the dominant controls on spatial and temporal variations of the isotopic composition of AR precipitation which highlights different physical processes for different AR events.

The peculiar geochemical signatures of São Miguel (Azores) lavas: Metasomatised or recycled mantle sources?

NASA Astrophysics Data System (ADS)

Beier, Christoph; Stracke, Andreas; Haase, Karsten M.

2007-07-01

The island of São Miguel, Azores consists of four large volcanic systems that exhibit a large systematic intra-island Sr-Nd-Pb-Hf isotope and trace element variability. The westernmost Sete Cidades volcano has moderately enriched Sr-Nd-Pb-Hf isotope ratios. In contrast, lavas from the easternmost Nordeste volcano have unusually high Sr and Pb and low Nd and Hf isotope ratios suggesting a long-term evolution with high Rb/Sr, U/Pb, Th/Pb, Th/U and low Sm/Nd and Lu/Hf parent-daughter ratios. They have trace element concentrations similar to those of the HIMU islands, with the exception of notably higher alkali element (Cs, Rb, K, Ba) and Th concentrations. The time-integrated parent-daughter element evolution of both the Sete Cidades and Nordeste source matches the incompatibility sequence commonly observed during mantle melting and consequently suggests that the mantle source enrichment is caused by a basaltic melt, either as a metasomatic agent or as recycled oceanic crust. Our calculations show that a metasomatic model involving a small degree basaltic melt is able to explain the isotopic enrichment but, invariably, produces far too enriched trace element signatures. We therefore favour a simple recycling model. The trace element and isotopic signatures of the Sete Cidades lavas are consistent with the presence of ancient recycled oceanic crust that has experienced some Pb loss during sub-arc alteration. The coherent correlation of the parent-daughter ratios (e.g. Rb/Sr, Th/U, U/Pb) and incompatible element ratios (e.g. Nb/Zr, Ba/Rb, La/Nb) with the isotope ratios in lavas from the entire island suggest that the Sete Cidades and Nordeste source share a similar genetic origin. The more enriched trace element and isotopic variations of Nordeste can be reproduced by recycled oceanic crust in the Nordeste source that contains small amounts of evolved lavas (˜ 1-2%), possibly from a subducted seamount. The rare occurrence of enriched source signatures comparable to Nordeste may be taken as circumstantial evidence that stirring processes in the Earth's mantle are not able to homogenise material within the size of seamounts over timescales of mantle recycling.

Improved estimation of sediment source contributions by concentration-dependent Bayesian isotopic mixing model

NASA Astrophysics Data System (ADS)

Ram Upadhayay, Hari; Bodé, Samuel; Griepentrog, Marco; Bajracharya, Roshan Man; Blake, Will; Cornelis, Wim; Boeckx, Pascal

2017-04-01

The implementation of compound-specific stable isotope (CSSI) analyses of biotracers (e.g. fatty acids, FAs) as constraints on sediment-source contributions has become increasingly relevant to understand the origin of sediments in catchments. The CSSI fingerprinting of sediment utilizes CSSI signature of biotracer as input in an isotopic mixing model (IMM) to apportion source soil contributions. So far source studies relied on the linear mixing assumptions of CSSI signature of sources to the sediment without accounting for potential effects of source biotracer concentration. Here we evaluated the effect of FAs concentration in sources on the accuracy of source contribution estimations in artificial soil mixture of three well-separated land use sources. Soil samples from land use sources were mixed to create three groups of artificial mixture with known source contributions. Sources and artificial mixture were analysed for δ13C of FAs using gas chromatography-combustion-isotope ratio mass spectrometry. The source contributions to the mixture were estimated using with and without concentration-dependent MixSIAR, a Bayesian isotopic mixing model. The concentration-dependent MixSIAR provided the closest estimates to the known artificial mixture source contributions (mean absolute error, MAE = 10.9%, and standard error, SE = 1.4%). In contrast, the concentration-independent MixSIAR with post mixing correction of tracer proportions based on aggregated concentration of FAs of sources biased the source contributions (MAE = 22.0%, SE = 3.4%). This study highlights the importance of accounting the potential effect of a source FA concentration for isotopic mixing in sediments that adds realisms to mixing model and allows more accurate estimates of contributions of sources to the mixture. The potential influence of FA concentration on CSSI signature of sediments is an important underlying factor that determines whether the isotopic signature of a given source is observable even after equilibrium. Therefore inclusion of FA concentrations of the sources in the IMM formulation is standard procedure for accurate estimation of source contributions. The post model correction approach that dominates the CSSI fingerprinting causes bias, especially if the FAs concentration of sources differs substantially.

A protocol to correct for intra- and interspecific variation in tail hair growth to align isotope signatures of segmentally cut tail hair to a common time line.

PubMed

Burnik Šturm, Martina; Pukazhenthi, Budhan; Reed, Dolores; Ganbaatar, Oyunsaikhan; Sušnik, Stane; Haymerle, Agnes; Voigt, Christian C; Kaczensky, Petra

2015-06-15

In recent years, segmental stable isotope analysis of hair has been a focus of research in animal dietary ecology and migration. To correctly assign tail hair segments to seasons or even Julian dates, information on tail hair growth rates is a key parameter, but is lacking for most species. We (a) reviewed the literature on tail hair growth rates in mammals; b) made own measurements of three captive equid species; (c) measured δ(2)H, δ(13)C and δ(15)N values in sequentially cut tail hairs of three sympatric, free-ranging equids from the Mongolian Gobi, using isotope ratio mass spectrometry (IRMS); and (d) collected environmental background data on seasonal variation by measuring δ(2)H values in precipitation by IRMS and by compiling pasture productivity measured by remote sensing via the normalized difference vegetation index (NDVI). Tail hair growth rates showed significant inter- and intra-specific variation making temporal alignment problematic. In the Mongolian Gobi, high seasonal variation of δ(2)H values in precipitation results in winter lows and summer highs of δ(2)H values of available water sources. In water-dependent equids, this seasonality is reflected in the isotope signatures of sequentially cut tails hairs. In regions which are subject to strong seasonal patterns we suggest identifying key isotopes which show strong seasonal variation in the environment and can be expected to be reflected in the animal tissue. The known interval between the maxima and minima of these isotope values can then be used to correctly temporally align the segmental stable isotope signature for each individual animal. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.

A protocol to correct for intra- and interspecific variation in tail hair growth to align isotope signatures of segmentally cut tail hair to a common time line

PubMed Central

Burnik Šturm, Martina; Pukazhenthi, Budhan; Reed, Dolores; Ganbaatar, Oyunsaikhan; Sušnik, Stane; Haymerle, Agnes; Voigt, Christian C; Kaczensky, Petra

2015-01-01

Rationale In recent years, segmental stable isotope analysis of hair has been a focus of research in animal dietary ecology and migration. To correctly assign tail hair segments to seasons or even Julian dates, information on tail hair growth rates is a key parameter, but is lacking for most species. Methods We (a) reviewed the literature on tail hair growth rates in mammals; b) made own measurements of three captive equid species; (c) measured δ2H, δ13C and δ15N values in sequentially cut tail hairs of three sympatric, free-ranging equids from the Mongolian Gobi, using isotope ratio mass spectrometry (IRMS); and (d) collected environmental background data on seasonal variation by measuring δ2H values in precipitation by IRMS and by compiling pasture productivity measured by remote sensing via the normalized difference vegetation index (NDVI). Results Tail hair growth rates showed significant inter- and intra-specific variation making temporal alignment problematic. In the Mongolian Gobi, high seasonal variation of δ2H values in precipitation results in winter lows and summer highs of δ2H values of available water sources. In water-dependent equids, this seasonality is reflected in the isotope signatures of sequentially cut tails hairs. Conclusions In regions which are subject to strong seasonal patterns we suggest identifying key isotopes which show strong seasonal variation in the environment and can be expected to be reflected in the animal tissue. The known interval between the maxima and minima of these isotope values can then be used to correctly temporally align the segmental stable isotope signature for each individual animal. © 2015 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26044272

An investigation of mercury sources in the Puyango-Tumbes River: Using stable Hg isotopes to characterize transboundary Hg pollution.

PubMed

Schudel, Gary; Miserendino, Rebecca Adler; Veiga, Marcello M; Velasquez-López, P Colon; Lees, Peter S J; Winland-Gaetz, Sean; Davée Guimarães, Jean Remy; Bergquist, Bridget A

2018-07-01

Mercury (Hg) concentrations and stable isotopes along with other trace metals were examined in environmental samples from Ecuador and Peru's shared Puyango-Tumbes River in order to determine the extent to which artisanal- and small-scale gold mining (ASGM) in Portovelo-Zaruma, Ecuador contributes to Hg pollution in the downstream aquatic ecosystem. Prior studies investigated the relationship between ASGM activities and downstream Hg pollution relying primarily on Hg concentration data. In this study, Hg isotopes revealed an isotopically heavy Hg signature with negligible mass independent fractionation (MIF) in downstream sediments, which was consistent with the signature observed in the ASGM source endmember. This signature was traced as far as ∼120 km downstream of Portovelo-Zaruma, demonstrating that Hg stable isotopes can be used as a tool to fingerprint and trace sources of Hg over vast distances in freshwater environments. The success of Hg isotopes as a source tracer in fresh waters is largely due to the particle-reactive nature of Hg. Furthermore, the magnitude and extent of downstream Hg, lead, copper and zinc contamination coupled with the Hg isotopes suggest that it is unlikely that the smaller artisanal-scale activities, which do not use cyanidation, are responsible for the pollution. More likely it is the scale of ores processed and the cyanide leaching, which can release other metals and enhance Hg transport, used during small-scale gold mining that is responsible. Thus, although artisanal- and small-scale gold mining occur in tandem in Portovelo-Zaruma, a distinction should be made between these two activities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Contribution of stable isotopes (C,N,S) in collagen of late Pleistocene large mammal trophic ecology and landscape use: a case study in Goyet and Scladina cave (30-40,000 years BP)

NASA Astrophysics Data System (ADS)

Bocherens, Hervé; Germonpré, Mietje

2010-05-01

Two Belgian caves yielded very rich large mammal associations dating around 30 to 40,000 years ago: Goyet and Scladina cave (layer 1A). These sites are only 5 km apart but the cave entrances open on different valleys, in a quite diverse landscape ranging between open, unprotected uplands, steep cliffs and sheltered sun-exposed gorges, with the larger Meuse valley nearby. This mosaic scenery permitted during the Last Glacial a rich diversity of fossil flora and fauna. The faunal association includes a large diversity of taxa including Aurochs Bos primigenius, steppe bison Bison priscus, reindeer Rangifer tarandus, giant deer Megaloceros giganteus, horse Equus ferus, woolly rhinoceros Coelodonta antiquitatis, woolly mammoth Mammuthus primigenius, cave bear Ursus spelaeus, brown bear Ursus arctos, wolf Canis lupus, cave lion Panthera leo spelaea, and cave hyaena Crocuta crocuta spelaea. All the 90 studied bones and teeth yielded collagen with excellent collagen preservation, allowing reliable investigations of carbon, nitrogen and sulfur isotopic biogeochemistry. The combination of three different isotopic tracers allows to deciphering the effects of food selection and landscape use by different herbivorous and carnivorous taxa. This is the first study to include sulfur isotopic signatures in the study of late Quaternary large mammal palaeobiology. This new tracer yields evidence on mobility and differences in pasture areas, as different geological bedrock may exhibit various sulfur isotopic signatures that will pass on the herbivores and further on their predators. Using this feature in addition to the trophic information provided by carbon and nitrogen isotopic signatures, it appears that for some species present in both sites, such as horse and woolly rhinoceros, the individuals found in each site probably did not use the same pasture areas. This seems to also the case for the overwhelmingly vegetarian cave bears. In addition, individuals from the same species found in one site sometimes exhibit clear isotopic differences in the three isotopic tracers that suggest different pasture grounds as well, and therefore the possibility of different herds in the vicinity of the cave site. In the case of cave hyeanas, the isotopic signatures of individuals from both caves are not significantly different and suggest that these predators obtained their prey from a large territory including the pasture grounds of herbivores from both caves. In addition, direct radiocarbon dating of some of the studied collagen allows to investigating possible chronological trends. This study shows how new isotopic tracers can provide invaluable information on late Quaternary large mammal palaeobiology.

U, Th, and Pb isotopes in hot springs on the Juan de Fuca Ridge

NASA Technical Reports Server (NTRS)

Chen, J. H.

1987-01-01

Concentrations and isotopic compositions of U, Th, and Pb in three hydrothermal fluids from the Juan de Fuca Ridge were determined from samples obtained by the Alvin submersible. The samples were enriched in Pb and Th relative to deep-sea water, and were deficient in U. No clear relationship with Mg was found, suggesting nonideal mixing between the hot hydrothermal fluids and the cold ambient seawater. Values for U-234/U-238 have a seawater signature, and show a U-234 enrichment relative to the equilibrium value. The Pb isotopic composition has a uniform midocean ridge basalt signature, and it is suggested that Pb in these fluids may represent the best average value of the local oceanic crust.

Copper isotope signatures in modern marine sediments

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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.

Multi-stage metasomatism revealed by trace element and Li isotope distributions in minerals of peridotite xenoliths from Allègre volcano (French Massif Central)

NASA Astrophysics Data System (ADS)

Gu, Xiaoyan; Deloule, Etienne; France, Lydéric; Ingrin, Jannick

2016-11-01

The modal, chemical, and isotopic compositions of mantle peridotite are largely modified by metasomatic processes, which may affect them repeatedly. Xenoliths are commonly used to characterize those metasomatic processes along with the structure, and chemical and isotopic compositions of mantle domains. Nevertheless, the original mantle signatures born by mantle xenoliths are potentially obscured by the interactions occurring between the host magma and the xenolith itself. Here we attempt to identify to which degree the original Li content and isotopic composition, as well as other trace element contents of mantle xenoliths, can be modified by interaction with the host magma. Peridotite xenoliths that have suffered extensive exchange with the entraining magma were sampled in the solidified lava lake of Allègre, Southern French Massif Central, in order to decipher the signature related to peridotite-melt interaction, and to further unravel the evolution of the sub-continental lithospheric mantle. In-situ trace element analyses of clinopyroxene (Cpx) were performed via LA-ICP-MS, and the Li content and isotopic composition of pyroxene and olivine (Ol) via SIMS. Negative HFSE anomalies (Ti/Eu ratios as low as 437) and markedly high LREE/HREE ratios ((La/Yb)N as high as 79) are characteristic of mantle metasomatism at depth. Lithium isotope systematics indicates that at least two different metasomatic events affected the peridotite. Exceptionally high Li contents in Cpx (up to 50 ppm) and slight Li enrichment of Ol rims are ascribed to diffusive Li influx with a positive δ7Li value (+ 3.2‰) from the host magma after entrainment. Conversely, Ol cores preserve extremely light Li isotopic compositions (δ7Li as low as - 25‰) with high Li contents (up to 4.4 ppm) compared to normal mantle, indicating a metasomatic event that occurred before xenolith entrainment. The negative δ7Li signature of this early metasomatism may be related to subduction-related fluids released during the Variscan orogeny. Trace element distributions in minerals reveal that the HFSE and REE composition of Cpx and the negative δ7Li signature in Ol cores were not acquired simultaneously. Therefore at least three successive metasomatic events affected the Allegre peridotites, as revealed through the use of detailed in-situ Li isotopic analyses to trace melt-rock interactions.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

Zinc stable isotopes measurements by MC-ICP-MS, validated by laboratory intercalibrations, were performed on wild oysters, suspended particles and filtered river/estuarine water samples to provide new constraints for the use of Zn isotopes as environmental tracers. The samples selected were representative of the long range (400 km) transport of metal (Zn, Cd, etc.) contamination from former Zn-refining activities at Decazeville (i.e. δ66Zn > 1‰) and its phasing out, recorded during 30 years in wild oysters from the Gironde Estuary mouth (RNO/ROCCH sample bank). The study also addresses additional anthropogenic sources (urban and viticulture) and focuses on geochemical reactivity of Zn in the turbidity gradient and the maximum turbidity zone (MTZ) of the fluvial Gironde Estuary. In this area, dissolved Zn showed a strong removal onto suspended particulate matter (SPM) and progressive enrichment in heavy isotopes with increasing SPM concentrations varying from δ66Zn = -0.02‰ at 2 mg/L to +0.90‰ at 1310 mg/L. These signatures were attributed to kinetically driven adsorption due to strongly increasing sorption sites in the turbidity gradient and MTZ of the estuary. Oysters from the estuary mouth, contaminated sediments from the Lot River and SPM entering the estuary showed parallel historical evolutions (1979-2010) for Zn/Cd ratios but not for δ66Zn values. Oysters had signatures varying from δ66Zn = 1.43‰ in 1983 to 1.18‰ in 2010 and were offset by δ66Zn = 0.6-0.7‰ compared to past (1988) and present SPM from the salinity gradient. Isotopic signatures in river-borne particles entering the Gironde Estuary under contrasting freshwater discharge regimes during 2003-2011 showed similar values (δ66Zn ≈ 0.35 ± 0.03‰; 1SD, n = 15), i.e. they were neither related to former metal refining activities at least for the past decade nor clearly affected by other anthropogenic sources. Therefore, the Zn isotopic signatures in Gironde oysters reflect the geochemical reactivity of Zn in the estuary rather than signatures of past metallurgical contaminations in the watershed as recorded in contaminated river sediments. The study also shows that the isotopic composition of Zn is strongly fractionated by its geochemical reactivity in the Gironde Estuary, representative of meso-macrotidal estuarine systems.

Evidence of the exploitation of marine resource by the terrestrial insect Scapteriscus didactylus through stable isotope analyzes of its cuticle.

PubMed

Maros, Alexandra; Louveaux, Alain; Lelarge, Caroline; Girondot, Marc

2006-05-08

About 4 x 10(5) eggs in more than 5000 marine turtle nests are deposited every year on a 3.6 km long beach in French Guiana (South America). The dry biomass of eggs is estimated to be 5 x 10(3) kg, yet only 25% of this organic matter will return to the ocean in the form of hatchlings. Such amounts of organic matter are supposed to drive the functioning of the beach ecosystem. Previous studies have shown that egg predators and detritivorous organisms dominate the trophic relationships and the dynamics of the system. The role of a terrestrial insect Scapteriscus didactylus (Latreille), which damages up to 40% of the eggs of the marine turtle (Dermochelys coriacea), was unexpected. However it was impossible from direct observations to prove that the mole cricket consumed a significant amount of these eggs. Therefore, the precise place of the mole cricket in the nitrogen and carbon cycles of the beach ecosystem could not be determined. In order to answer this question, we looked for a marine signature of carbon and nitrogen source metabolized by the mole cricket. This study estimated the individual variability of delta13C and delta15N in the cuticle of Scapteriscus didactylus. The isotopic signature was compared between individuals collected at two sites: a village where mole crickets fed on human food scraps and the nearby Awala-Yalimapo beach, where food availability depends seasonally on the nesting sea turtles. The mole crickets collected near the habitations garbage showed no significant variations in the stable isotopic signature, within-and between age groups. On the contrary, isotopic values shifted from a signature of a terrestrial herbivorous diet in the mole crickets during early developmental stages, to isotopic values in adults in accordance with the exploitation of marine animal resources. The heterogeneity of individual signatures during the year is due to a selective exploitation of the food sources, differing in space and time. Some individuals, from the beach sample consumed a sufficient quantity of turtle eggs to induce the increase of isotopic enrichment observed in the cuticle. Scapteriscus didactylus is an opportunist feeder and plays a role in the turn over of the beach organic matter.

Evidence of the exploitation of marine resource by the terrestrial insect Scapteriscus didactylus through stable isotope analyzes of its cuticle

PubMed Central

Maros, Alexandra; Louveaux, Alain; Lelarge, Caroline; Girondot, Marc

2006-01-01

Background About 4 × 105 eggs in more than 5000 marine turtle nests are deposited every year on a 3.6 km long beach in French Guiana (South America). The dry biomass of eggs is estimated to be 5 × 103 kg, yet only 25% of this organic matter will return to the ocean in the form of hatchlings. Such amounts of organic matter are supposed to drive the functioning of the beach ecosystem. Previous studies have shown that egg predators and detritivorous organisms dominate the trophic relationships and the dynamics of the system. The role of a terrestrial insect Scapteriscus didactylus (Latreille), which damages up to 40% of the eggs of the marine turtle (Dermochelys coriacea), was unexpected. However it was impossible from direct observations to prove that the mole cricket consumed a significant amount of these eggs. Therefore, the precise place of the mole cricket in the nitrogen and carbon cycles of the beach ecosystem could not be determined. In order to answer this question, we looked for a marine signature of carbon and nitrogen source metabolized by the mole cricket. Results This study estimated the individual variability of δ13C and δ15N in the cuticle of Scapteriscus didactylus. The isotopic signature was compared between individuals collected at two sites: a village where mole crickets fed on human food scraps and the nearby Awala-Yalimapo beach, where food availability depends seasonally on the nesting sea turtles. The mole crickets collected near the habitations garbage showed no significant variations in the stable isotopic signature, within-and between age groups. On the contrary, isotopic values shifted from a signature of a terrestrial herbivorous diet in the mole crickets during early developmental stages, to isotopic values in adults in accordance with the exploitation of marine animal resources. Conclusion The heterogeneity of individual signatures during the year is due to a selective exploitation of the food sources, differing in space and time. Some individuals, from the beach sample consumed a sufficient quantity of turtle eggs to induce the increase of isotopic enrichment observed in the cuticle. Scapteriscus didactylus is an opportunist feeder and plays a role in the turn over of the beach organic matter. PMID:16681850

Comparative genomics provides evidence for the 3-hydroxypropionate autotrophic pathway in filamentous anoxygenic phototrophic bacteria and in hot spring microbial mats.

PubMed

Klatt, Christian G; Bryant, Donald A; Ward, David M

2007-08-01

Stable carbon isotope signatures of diagnostic lipid biomarkers have suggested that Roseiflexus spp., the dominant filamentous anoxygenic phototrophic bacteria inhabiting microbial mats of alkaline siliceous hot springs, may be capable of fixing bicarbonate via the 3-hydroxypropionate pathway, which has been characterized in their distant relative, Chloroflexus aurantiacus. The genomes of three filamentous anoxygenic phototrophic Chloroflexi isolates (Roseiflexus sp. RS-1, Roseiflexus castenholzii and Chloroflexus aggregans), but not that of a non-photosynthetic Chloroflexi isolate (Herpetosiphon aurantiacus), were found to contain open reading frames that show a high degree of sequence similarity to genes encoding enzymes in the C. aurantiacus pathway. Metagenomic DNA sequences from the microbial mats of alkaline siliceous hot springs also contain homologues of these genes that are highly similar to genes in both Roseiflexus spp. and Chloroflexus spp. Thus, Roseiflexus spp. appear to have the genetic capacity for carbon dioxide reduction via the 3-hydroxypropionate pathway. This may contribute to heavier carbon isotopic signatures of the cell components of native Roseiflexus populations in mats compared with the signatures of cyanobacterial cell components, as a similar isotopic signature would be expected if Roseiflexus spp. were participating in photoheterotrophic uptake of cyanobacterial photosynthate produced by the reductive pentose phosphate cycle.

Lipid Biomarkers and Carbon Isotope Ratios of Lipids Isolated from Acid Mine Drainage Biofilms: Dual Biosignatures for Eukaryotic Evolution and Oxygenation of Primitive Earth

NASA Astrophysics Data System (ADS)

Dasgupta, S.; Fang, J.; Zhang, L.; Li, J.

2012-12-01

Lipid analysis and carbon isotope ratios (δ13C) of lipids in biofilms in an acid mine drainage site (AMD) site in western Indiana revealed unique biogeochemical signatures of microeukaryotes, never recorded before. Dominance of photosynthetic microeukaryote Euglena was indicated by the detection of abundant phytadiene, phytol, phytanol, polyunsaturated n-alkenes, polyunsaturated fatty acids, short-chain (C25-32) wax esters (WE), ergosterol, and tocopherols. The WE were probably synthesized in mitochondria under anoxic conditions by the reverse β-oxidation pathway, whereas the sterols (ergosterol and ergosta-7,22-dien-3β-ol) were likely synthesized in the cytosol in the presence of molecular oxygen. The dual aerobic and anaerobic biosynthetic pathways of Euglena may be a response to survive the recurring anoxic and oxic conditions in primitive Earth, whereby microeukaryotes retained this mechanism of conserved compartmentalization within their physiology to evolve and diversify in extreme conditions. Hydrocarbons, including n-alkenes, phytadienes, and wax esters showed heavy δ13C values than usual. The primary cause for the 13C-enrichment can be attributed to a CO2-limiting system that exists in the AMD, which is further regulated by the pH of the AMD. Floating biofilms BF2, 4, and 6 showed more depleted δ13C values for phytadienes and n-alkenes (average of -23.6‰) as compared to benthic biofilm BF5 (average of -20.8‰), indicating that physiology plays an important role in isotopic discrimination. 13C-enriched values of the esters could result from kinetic isotope effects at two branch points (pyruvate and/or acetyl CoA) in the biosynthetic pathway. Our understanding of biogeochemical conditions in this AMD environment would allow us to identify unique sets of biosignatures that can act as a proxy in deciphering the links between eukaryotic evolutions, oxygenation of the early atmosphere, formation of BIF, and possibly iron-rich extraterrestrial environments.

"Anticlumping" and Other Combinatorial Effects on Clumped Isotopes: Implications for Tracing Biogeochemical Cycling

NASA Astrophysics Data System (ADS)

Yeung, L.

2015-12-01

I present a mode of isotopic ordering that has purely combinatorial origins. It can be important when identical rare isotopes are paired by coincidence (e.g., they are neighbors on the same molecule), or when extrinsic factors govern the isotopic composition of the two atoms that share a chemical bond. By itself, combinatorial isotope pairing yields products with isotopes either randomly distributed or with a deficit relative to a random distribution of isotopes. These systematics arise because of an unconventional coupling between the formation of singly- and multiply-substituted isotopic moieties. In a random distribution, rare isotopes are symmetrically distributed: Single isotopic substitutions (e.g., H‒D and D‒H in H2) occur with equal probability, and double isotopic substitutions (e.g., D2) occur according to random chance. The absence of symmetry in a bond-making complex can yield unequal numbers of singly-substituted molecules (e.g., more H‒D than D‒H in H2), which is recorded in the product molecule as a deficit in doubly-substituted moieties and an "anticlumped" isotope distribution (i.e., Δn < 0). Enzymatic isotope pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect. Chemical-kinetic isotope effects, which are related to the bond-forming transition state, arise independently and express second-order combinatorial effects. In general, both combinatorial and chemical factors are important for calculating and interpreting clumped-isotope signatures of individual reactions. In many reactions relevant to geochemical oxygen, carbon, and nitrogen cycling, combinatorial isotope pairing likely plays a strong role in the clumped isotope distribution of the products. These isotopic signatures, manifest as either directly bound isotope clumps or as features of a molecule's isotopic anatomy, could be exploited as tracers of biogeochemistry that can relate molecular mechanisms to signals observable at environmentally relevant spatial scales.

ALPHA SPECTROMETRIC EVALUATION OF SRM-995 AS A POTENTIAL URANIUM/THORIUM DOUBLE TRACER SYSTEM FOR AGE-DATING URANIUM MATERIALS

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

Beals, D.

2011-12-06

Uranium-233 (t{sub 1/2} {approx} 1.59E5 years) is an artificial, fissile isotope of uranium that has significant importance in nuclear forensics. The isotope provides a unique signature in determining the origin and provenance of uranium-bearing materials and is valuable as a mass spectrometric tracer. Alpha spectrometry was employed in the critical evaluation of a {sup 233}U standard reference material (SRM-995) as a dual tracer system based on the in-growth of {sup 229}Th (t{sub 1/2} {approx} 7.34E3 years) for {approx}35 years following radiochemical purification. Preliminary investigations focused on the isotopic analysis of standards and unmodified fractions of SRM-995; all samples were separatedmore » and purified using a multi-column anion-exchange scheme. The {sup 229}Th/{sup 233}U atom ratio for SRM-995 was found to be 1.598E-4 ({+-} 4.50%) using recovery-corrected radiochemical methods. Using the Bateman equations and relevant half-lives, this ratio reflects a material that was purified {approx} 36.8 years prior to this analysis. The calculated age is discussed in contrast with both the date of certification and the recorded date of last purification.« less

Unraveling the nitrogen isotopic signature of symbiotic corals

NASA Astrophysics Data System (ADS)

Devlin, Q.; Swart, P. K.; Altabet, M. A.

2013-12-01

Coral reefs thrive in shallow, tropical, low nutrient waters. Nutrient inputs to a reef environment are often interpreted by measuring the nitrogen isotopic composition of reef organisms. The δ15N signature of scleractinian corals has been historically measured to assess the presence of anthropogenic influences such as sewage and fertilizer runoff. The majority of reef building corals form a symbiotic partnership with the dinoflagellate algae, Symbiodinium microadriaticum. The δ15N signature of symbiotic corals is complex as it is not only dependent on nitrogen acquisition by the coral, but also by the algal symbionts that reside within the gastrodermal tissue layer. The relationship between the δ15N of dissolved inorganic nitrogen (DIN) and the δ15N of coral tissue has not been established. The aim of this study is to identify considerations necessary when interpreting nitrogen sources based on δ15N of coral tissue. Incubations were carried out in order to measure isotopic fractionation associated with nitrate and ammonium incorporation by the Pacific branching coral, Pocillopora damicornis. We investigated the dependence of nitrogen isotope fractionation on species of DIN (nitrate or ammonium), concentration of DIN (range: 1-50 μM N), genetic diversity of algal symbionts (clade C or clade D) and light levels.

Multi-element compound specific stable isotope analysis of chlorinated aliphatic contaminants derived from chlorinated pitches.

PubMed

Filippini, Maria; Nijenhuis, Ivonne; Kümmel, Steffen; Chiarini, Veronica; Crosta, Giovanni; Richnow, Hans H; Gargini, Alessandro

2018-05-30

Tetrachloroethene and trichloroethene are typical by-products of the industrial production of chloromethanes. These by-products are known as "chlorinated pitches" and were often dumped in un-contained waste disposal sites causing groundwater contaminations. Previous research showed that a strongly depleted stable carbon isotope signature characterizes chlorinated compounds associated with chlorinated pitches whereas manufactured commercial compounds have more enriched carbon isotope ratios. The findings were restricted to a single case study and one element (i.e. carbon). This paper presents a multi-element Compound-Specific Stable Isotope Analysis (CSIA, including carbon, chlorine and hydrogen) of chlorinated aliphatic contaminants originated from chlorinated pitches at two sites with different hydrogeology and different producers of chloromethanes. The results show strongly depleted carbon signatures at both sites whereas the chlorine and the hydrogen signatures are comparable to those presented in the literature for manufactured commercial compounds. Multi-element CSIA allowed the identification of sources and site-specific processes affecting chloroethene transformation in groundwater as a result of emergency remediation measures. CSIA turned out to be an effective forensic tool to address the liability for the contamination, leading to a conviction for the crimes of unintentional aggravated public water supply poisoning and environmental disaster. Copyright © 2018 Elsevier B.V. All rights reserved.

Precision mass measurements of neutron-rich Co isotopes beyond N =40

NASA Astrophysics Data System (ADS)

Izzo, C.; Bollen, G.; Brodeur, M.; Eibach, M.; Gulyuz, K.; Holt, J. D.; Kelly, J. M.; Redshaw, M.; Ringle, R.; Sandler, R.; Schwarz, S.; Stroberg, S. R.; Sumithrarachchi, C. S.; Valverde, A. A.; Villari, A. C. C.

2018-01-01

The region near Z =28 and N =40 is a subject of great interest for nuclear structure studies due to spectroscopic signatures in 68Ni suggesting a subshell closure at N =40 . Trends in nuclear masses and their derivatives provide a complementary approach to shell structure investigations via separation energies. Penning trap mass spectrometry has provided precise measurements for a number of nuclei in this region; however, a complete picture of the mass surfaces has so far been limited by the large uncertainty remaining for nuclei with N >40 along the iron (Z =26 ) and cobalt (Z =27 ) chains because these species are not available from traditional isotope separator online rare isotope facilities. The Low-Energy Beam and Ion Trap Facility at the National Superconducting Cyclotron Laboratory is the first and only Penning trap mass spectrometer coupled to a fragmentation facility and therefore presents the unique opportunity to perform precise mass measurements of these elusive isotopes. Here we present the first Penning trap measurements of Co,6968, carried out at this facility. Some ambiguity remains as to whether the measured values are ground-state or isomeric-state masses. A detailed discussion is presented to evaluate this question and to motivate future work. In addition, we perform ab initio calculations of ground-state and two-neutron separation energies of cobalt isotopes with the valence-space in-medium similarity renormalization group approach based on a particular set of two- and three-nucleon forces that predict saturation in infinite matter. We discuss the importance of these measurements and calculations for understanding the evolution of nuclear structure near 68Ni.

A new approach to the solution of the linear mixing model for a single isotope: application to the case of an opportunistic predator.

PubMed

Hall-Aspland, S A; Hall, A P; Rogers, T L

2005-03-01

Mixing models are used to determine diets where the number of prey items are greater than one, however, the limitation of the linear mixing method is the lack of a unique solution when the number of potential sources is greater than the number (n) of isotopic signatures +1. Using the IsoSource program all possible combinations of each source contribution (0-100%) in preselected small increments can be examined and a range of values produced for each sample analysed. We propose the use of a Moore Penrose (M-P) pseudoinverse, which involves the inverse of a 2x2 matrix. This is easily generalized to the case of a single isotope with (p) prey sources and produces a specific solution. The Antarctic leopard seal (Hydrurga leptonyx) was used as a model species to test this method. This seal is an opportunistic predator, which preys on a wide range of species including seals, penguins, fish and krill. The M-P method was used to determine the contribution to diet from each of the four prey types based on blood and fur samples collected over three consecutive austral summers. The advantage of the M-P method was the production of a vector of fractions f for each predator isotopic value, allowing us to identify the relative variation in dietary proportions. Comparison of the calculated fractions from this method with 'means' from IsoSource allowed confidence in the new approach for the case of a single isotope, N.

Surface area dependence of calcium isotopic reequilibration in carbonates: Implications for isotopic signatures in the weathering zone

NASA Astrophysics Data System (ADS)

Fernandez, N. M.; Druhan, J. L.; Potrel, A.; Jacobson, A. D.

2016-12-01

The concept of dynamic equilibrium carries the implicit assumption of continued isotopic exchange between a mineral and the surrounding fluid. While this effect has received much attention in the marine paleoproxy literature, it has been relatively overlooked in application to the terrestrial environment. In weathering systems, a potential consequence is that rapid reequilibration may alter or erase isotopic signatures generated during secondary mineral formation. The extent and timescale over which isotopic signatures are reset in these hydrologic systems is unknown. Using reactive transport modeling, we show isotopic reequilibration under conditions reflecting terrestrial hydrologic settings to be significant and dependent on the reactive surface area of the solid. In particular, we suggest that the non-traditional stable isotopes commonly used in application to carbonates (e.g., Ca, Mg, Sr) are sensitive to these effects due to their rapid reaction rates. We aim to characterize the dependence of Ca isotopic reequilibration on surface area during calcite precipitation via batch experiments conducted at ambient temperature over 48-hour time periods. Calcite precipitation was performed in a closed batch reactor utilizing a controlled free-drift method. The batch reactors contained mixed supersaturated solutions of CaCl2 and NaHCO3 at an initial pH of 8.54. Precipitation was initiated by seed inoculation of calcite crystals with two distinct, pre-constrained surface areas. All experiments achieved the same final state of chemical equilibrium, but as expected, the fastest approach to equilibrium occurred for experiments employing calcite seeds with the highest surface area. This implies that differences in equilibrated Ca isotope ratios (δ44/40Ca) should reflect differences in surface area. This prediction is upheld by models of the experiments, indicating a measureable difference in δ44Ca during calcite precipitation where the higher surface area corresponds to lower δ44Ca values and a faster approach to isotopic equilibrium. The dependence of δ44Ca resetting on calcite surface areas has broad ramifications for tracing carbonate weathering in the Critical Zone.

Stable isotope signatures in bulk samples from two soils with contrasting characteristics. What do they tell about ongoing pedogenic processes?

NASA Astrophysics Data System (ADS)

Jiménez-Morillo, Nicasio T.; dos Anjos Leal, Otávio; Knicker, Heike; Pinheiro Dick, Deborah; González-Vila, Francisco J.; González-Pérez, José A.

2014-05-01

Isotopic ratio mass spectrometry (IRMS) has been proven as a promising tool for the monitoring of biogeochemical processes in soil. In this work, stable isotope signatures of light elements δ15N, δ13C, δ18O and δD were determined for two soils with contrasting characteristics in terms of climate, vegetation, land use and management. The studied soils were a Cambisol from a subtropical area (Paraná region, South Brazil) and an Arenosol from a Mediterranean climate (Andalusia, South Spain). A Flash 2000 HT (N, C, S, H and O) elemental analyzer (Thermo Scientific) coupled to a Delta V Advantage IRMS (Thermo Scientific) was used. Isotopic ratios are reported as parts per thousand (o ) deviations from appropriate standards recognized by the international atomic energy agency (IAEA). In a first approach we took advantage of the well-known different δ13C signature between plants using either the C4 or C3 carbon fixation pathway (O'Leary, 1981). The Arenosol (Spain) revealed a δ13C signature which is clearly in the range of C3 plants (-26 to -30 o ). Different plant canopies (tree, shrubs or ferns) caused only slight variations δ13C (STD= 0.98). In contrast, the Cambisol (Brazil) showed less depletion of the heavier carbon isotope corresponding to C4 predominant vegetation. In addition an increase from -19 o in the soil surface (0 - 5 cm) to -16 o in the subsoil (20 - 30 cm) was observed in line with a recent (2 years old) shift of the land use from the predominant C4 grassland to eucalypt (C3) cultivation. Crossplots of δ15N vs. δ18O may provide information about nitrate (NO3-) sources and N cycling (Kendall, 1998). In the Mediterranean Arenosol this signal (δ18O = 30o δ15N = 2o ) was found compatible with a predominant nitrate atmospheric deposition, whereas the signal in the Brazilian Cambisol pointed to the use of a mineral N fertilization with signs of denitrification processes (δ18O = 13o δ15N = 9o ). No conclusive results could be obtained from the δD isotopic signature probably due to overlapping of the δD signals from the organic and the mineral fractions. For a more detailed analysis steps allowing their separation are necessary (Ruppenthal et al. (2013) and references therein). Kendall, C. 1998. Tracing nitrogen sources and cycling in catchments. In Isotopes Tracers in Catchments Hydrology (C. Kendall and J. J. McDonnell, Eds). Elsevier Science B. V., Amsterdam, 519-576. O'Leary, M.H. 1981. Carbon isotope fraction in plants. Phytochemistry 20: 553-567. Ruppenthal, M., Oelmann, Y., Wilcke, W. 2013. Optimized demineralization technique for the measurement of stable isotope ratios of nonexchangeable H in soil organic matter. Environmental Science and Technology 47: 949-957.

SrNdPb isotopic and trace element evidence for crustal contamination of plume-derived flood basalts: Oligocene flood volcanism in western Yemen

NASA Astrophysics Data System (ADS)

Baker, J. A.; Thirlwall, M. F.; Menzies, M. A.

1996-07-01

Oligocene flood basalts from western Yemen have a relatively limited range in initial isotopic composition compared with other continental flood basalts: 87Sr/86Sr = 0.70365-0.70555 ; 143Nd/144Nd = 0.5129-0.51248 ( ɛNd = +6.0 to -2.4) ; 206pb/204Pb = 17.9-19.3 . Most compositions lie outside the isotopic ranges of temporally and spatially appropriate mantle source compositions observed in this area, i.e., Red Sea/Gulf of Aden MORB mantle, the Afar plume, and Pan-African lithospheric mantle Correlations between indices of fractionation, silica, and isotope ratios suggest that crustal contamination has substantially modified the primary isotopic and incompatible trace element characteristics of the flood basalts. However, significant scatter in these correlations was produced by: (a) the heterogeneous isotopic composition of Pan-African crust; (b) the difference in susceptibility of magmas to contamination as a result of variable incompatible trace element contents in primary melts produced by differing degrees of partial melting; (c) the presence or absence of plagioclase as a fractionating phase generating complex contamination trajectories for Sr; (d) sampling over a wide area not representing a single coherent magmatic system; and (e) variation in contamination mechanisms from assimilation associated with fractionation (AFC) to assimilation by hot mafic magmas with little concomitant fractionation. The presence of plagioclase as a fractionating phase in some suites that were undergoing AFC requires assimilation to have taken place within the crust and, coupled with the limited LREE-enrichment accompanying isotopic variations, excludes the possibility that an AFC-type process took place during magma transfer through the lithospheric mantle. Isotopic compositions of some of the inferred crustal assimilants are similar to those postulated by other workers for an enriched lithospheric mantle source of many flood basalts in southwestern Yemen, Ethiopia, and Djibouti. The western Yemen flood basalts contain 0-30% crust which largely swamps their primary lead isotopic signature, but the primary SrNd isotopic signature is close to that of the least contaminated and isotopically most depleted flood basalts. LREE/HFSE and LILE/HFSE ratios also correlate with isotopic data as a result of crustal contamination. However, Nb/La and K/Nb ratios of >1.1 and <150, respectively, in least contaminated samples require an OIB-like source. The pre-contamination isotopic signature is estimated to be: 87Sr/86Sr ˜ 0.7036; 143Nd/144Nd ˜ 0.51292 ; 206Pb/204Pb ˜ 18.4-19.0 . This, coupled with low LILE/HFSE ratios, suggest the source has characteristics akin to the Afar plume. A mantle source isotopically more depleted than Bulk Earth, but not as depleted as MORB, coupled with LILE depletion, also characterises other examples of plume-derived flood volcanism. This mantle reservoir is responsible for the second largest outbursts of volcanism on Earth and has radiogenic isotopic characteristics akin to PREMA mantle, but the incompatible trace element signature of HIMU mantle.

Chondritic Earth: comparisons, guidelines and status

NASA Astrophysics Data System (ADS)

McDonough, W. F.

2014-12-01

The chemical and isotopic composition of the Earth is rationally understood within the context of the chondritic reference frame, without recourse to hidden reservoirs, collision erosion, or strict interpretation of an enstatite chondrite model. Challenges to interpreting the array of recent and disparate chemical and isotopic observations from meteorites need to be understood as rich data harvests that inform us of the compositional heterogeneity in the early solar system. Our ability to resolve small, significant compositional differences between chondrite families provide critical insights into integrated compositional signatures at differing annuli distances from the Sun (i.e., 1-6 AU). Rigorous evaluation of chondritic models for planets requires treatment of both statistical and systematic uncertainties - to date these efforts are uncommonly practiced. Planetary olivine to pyroxene ratio reflects fO2 and temperature potentials in the nebular, given possible ISM compositional conditions; thus this ratio is a non-unique parameter of terrestrial bodies. Consequently the Mg/Si value of a planet (ie., olivine to pyroxene ratio) is a free variable; there is no singular chondritic Mg/Si value. For the Earth, there is an absence of physical and chemical evidence requiring a major element, chemical distinction between the upper and lower mantle, within uncertainties. Early Earth differentiation likely occurred, but there is an absence of chemical and isotopic evidence of its imprint. Chondrites, peridotites, komatiites, and basalts (ancient and modern) reveal a coherent picture of a chondritic compositional Earth, with compositionally affinities to enstatite chondrites. At present results from geoneutrino studies non-uniquely support these conclusions. Future experiments can provide true transformative insights into the Earth's thermal budget, define compositional BSE models, and will restrict discussions on Earth dynamics and its thermal evolution.

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

NASA Technical Reports Server (NTRS)

Boering, Kristie A.; Connell, Peter; Rotman, Douglas

2005-01-01

Until recently, the stable isotopic composition of chemically and datively important stratospheric species, such as ozone (O3), carbon dioxide (CO2), nitrous oxide (N2O), and methane (CH4), was largely unexplored, despite indications from the few measurements available and theoretical studies that global-scale isotopic variations will provide a unique tool for quantifying rates of global-scale mass transport into, within, and out of the stratosphere and for understanding the mechanisms of chemical reactions involved in ozone production. The number and geographical extent of observations are beginning to increase rapidly, however, as access to the stratosphere, both directly and by remote-sensing, has increased over the last 10 years and as new analytical techniques have been developed that make global-scale isotope measurements by whole-air sampling more feasible. The objective of this study, begun in April 1999, is to incorporate into the Livermore 2D model the likely photochemical fractionation processes that determine the isotopic compositions of stratospheric CO2, N2O, CH4, and O3, and to use the model results and new observations from NASA field campaigns in 1996 and 1997 to investigate stratospheric chemistry and mass transport. Additionally, since isotopic signatures from the stratosphere are transferred to the troposphere by downward transport at middle and high latitudes, the isotopic compositions may also serve as sensitive tracers of stratosphere-totroposphere transport. Comparisons of model results with stratospheric and upper tropospheric observations from these campaigns, as well as with ground-based observations from new NOAA and NSF-sponsored studies, will help determine whether the magnitudes of the stratospheric fractionation processes are large enough to use as global-scale tracers of transport into the troposphere and, if so, will be used to help constrain the degree of coupling between the troposphere and the stratosphere.

Evidence of hydraulic lift for pre-rainy season leaf out and dry-season stem water enrichment in Sclerocarya birrea, a tropical agroforestry tree

NASA Astrophysics Data System (ADS)

Ceperley, Natalie; Mande, Theophile; Rinaldo, Andrea; Parlange, Marc B.

2014-05-01

We use stable isotopes of water as tracers to follow water use by five Sclerocarya birrea trees in a catchment in South Eastern Burkina Faso interspersed with millet fields, gallery forest, Sudanian savanna, and fallow fields. Isotopic ratios were determined from water extracted from stems of the trees and sub-canopy soil of two of them, while nearby ground water, precipitation, and surface water was sampled weekly. A unique configuration of sensors connected with a wireless sensor network of meteorological stations measured sub-canopy shading, the temperature and humidity in the canopy, through-fall, and soil moisture under two of the trees. Both water extracted from sap and water extracted from soil is extremely enriched in the dry season, but drop to levels close to the ground water in February or March, which coincides with the growth of leaves. Dates of leaf out were confirmed by changes in δDH and δO18 concentrations of water, photographic documentation & pixel analysis, and analysis of sub-canopy radiation and proceeded the rise in humidity and flow that was later detected in the sub-canopy soil, the trunk of the tree (sap-flow), and atmosphere (canopy VPD). Examination of the isotopic signature suggests that size of tree plays an important role in duration and timing of this leaf-out as well as the degree of enrichment during the peak of the dry season. Further examination of the isotopic signatures of the roots suggested that the trees are performing hydraulic redistribution, or lifting the ground water and "sharing it" with the soil in the rooting zone in the dry season. The enriched level of xylem in this case is a product of water loss, and enrichment, along the travel path of the water from the roots to the tip of the stem, as evidenced by the variation according to size of tree. Vapor pressure deficit, soil water, and soil moisture interactions support this picture of interacting controls, separate from hydrologic triggers on the water movement in the tree.

Abrupt Late Holocene Shift in Atmospheric Circulation Recorded by Mineral Dust in the Siple Dome Ice Core, Antarctica

NASA Astrophysics Data System (ADS)

Koffman, B. G.; Goldstein, S. L.; Kaplan, M. R.; Winckler, G.; Bory, A. J. M.; Biscaye, P.

2015-12-01

Atmospheric dust directly influences Earth's climate by altering the radiative balance and by depositing micronutrients in the surface ocean, affecting global biogeochemical cycling. In addition, mineral dust particles provide observational evidence constraining past atmospheric circulation patterns. Because dust can originate from both local and distant terrestrial sources, knowledge of dust provenance can substantially inform our understanding of past climate history, atmospheric transport pathways, and differences in aerosol characteristics between glacial and interglacial climate states. Dust provenance information from Antarctic ice cores has until now been limited to sites in East Antarctica. Here we present some of the first provenance data from West Antarctica. We use Sr-Nd isotopes to characterize dust extracted from late Holocene ice (~1000-1800 C.E.) from the Siple Dome ice core. The data form a tight array in Sr-Nd isotope space, with 87Sr/86Sr ranging between ~0.7087 and 0.7102, and ɛNd ranging between ~ -7 and -16. This combination is unique for Antarctica, with low Nd and low Sr isotope ratios compared to high-elevation East Antarctic sites, requiring a dust source from ancient (Archean to early Proterozoic) and unweathered continental crust, which mixes with young volcanic material. Both components are likely sourced from Antarctica. We also observe significant, systematic variability in Sr and Nd isotopic signatures through time, reflecting changes in the mixing ratio of these sources, and hypothesize that these changes are driven by shifts in circulation patterns. A large change occurs over about 10 years at ca. 1125 C.E. (ΔɛNd = +3 and Δ87Sr/86Sr = -0.0014). This shift coincides with changes in climate proxies in Southern Hemisphere paleoclimate records reflecting variability in the Westerlies. We therefore interpret the shift in dust provenance at Siple Dome to be related to larger-scale circulation changes. In general, the observed shifts in the particle source signatures indicate that dust transport pathways to and around the West Antarctic Ice Sheet are highly responsive to perturbations in atmospheric circulation, and can record rapid shifts in provenance.

Evaluating methane inventories by isotopic analysis in the London region.

PubMed

Zazzeri, G; Lowry, D; Fisher, R E; France, J L; Lanoisellé, M; Grimmond, C S B; Nisbet, E G

2017-07-07

A thorough understanding of methane sources is necessary to accomplish methane reduction targets. Urban environments, where a large variety of methane sources coexist, are one of the most complex areas to investigate. Methane sources are characterised by specific δ 13 C-CH 4 signatures, so high precision stable isotope analysis of atmospheric methane can be used to give a better understanding of urban sources and their partition in a source mix. Diurnal measurements of methane and carbon dioxide mole fraction, and isotopic values at King's College London, enabled assessment of the isotopic signal of the source mix in central London. Surveys with a mobile measurement system in the London region were also carried out for detection of methane plumes at near ground level, in order to evaluate the spatial allocation of sources suggested by the inventories. The measured isotopic signal in central London (-45.7 ±0.5‰) was more than 2‰ higher than the isotopic value calculated using emission inventories and updated δ 13 C-CH 4 signatures. Besides, during the mobile surveys, many gas leaks were identified that are not included in the inventories. This suggests that a revision of the source distribution given by the emission inventories is needed.

Compound Specific Isotope Analysis of Fatty Acids in Southern African Aerosols

NASA Astrophysics Data System (ADS)

Billmark, K. A.; Macko, S. A.; Swap, R. J.

2003-12-01

This study, conducted as a part of the Southern African Regional Science Initiative (SAFARI 2000), applied compound specific isotope analysis to describe aerosols at source regions and rural locations. Stable carbon isotopic compositions of individual fatty acids were determined for aerosol samples collected at four sites throughout southern Africa. Mongu, Zambia and Skukuza, South Africa were chosen for their location within intense seasonal Miombo woodland savanna and bushveld savanna biomass burning source regions, respectively. Urban aerosols were collected at Johannesburg, South Africa and rural samples were collected at Sua Pan, Botswana. Fatty acid isotopic compositions varied temporally. Urban aerosols showed significant isotopic enrichment of selected short chain fatty acids (C < 20) compared to aerosols produced during biomass combustion. Sua Pan short chain fatty acid signatures were significantly different from the other non-urban sites, which suggests that sources other than biomass combustion products, such as organic eolian material, impact the Sua Pan aerosol profile. However, a high degree of correlation between Sua Pan and Skukuza long chain fatty acid δ 13C values confirm atmospheric linkages between the two areas and that isotopic signatures of combusted fatty acids are unaltered during atmospheric transport highlighting their potential for use as a conservative tracer.

Use of Lead Isotopes to Identify Sources of Metal and Metalloid Contaminants in Atmospheric Aerosol from Mining Operations

PubMed Central

Félix, Omar I.; Csavina, Janae; Field, Jason; Rine, Kyle P.; Sáez, A. Eduardo; Betterton, Eric A.

2014-01-01

Mining operations are a potential source of metal and metalloid contamination by atmospheric particulate generated from smelting activities, as well as from erosion of mine tailings. In this work, we show how lead isotopes can be used for source apportionment of metal and metalloid contaminants from the site of an active copper mine. Analysis of atmospheric aerosol shows two distinct isotopic signatures: one prevalent in fine particles (< 1 μm aerodynamic diameter) while the other corresponds to coarse particles as well as particles in all size ranges from a nearby urban environment. The lead isotopic ratios found in the fine particles are equal to those of the mine that provides the ore to the smelter. Topsoil samples at the mining site show concentrations of Pb and As decreasing with distance from the smelter. Isotopic ratios for the sample closest to the smelter (650 m) and from topsoil at all sample locations, extending to more than 1 km from the smelter, were similar to those found in fine particles in atmospheric dust. The results validate the use of lead isotope signatures for source apportionment of metal and metalloid contaminants transported by atmospheric particulate. PMID:25496740

Extreme Monsoon Rainfall Signatures Preserved in the Invasive Terrestrial Gastropod Lissachatina fulica

NASA Astrophysics Data System (ADS)

Ghosh, Prosenjit; Rangarajan, Ravi; Thirumalai, Kaustubh; Naggs, Fred

2017-11-01

Indian summer monsoon (ISM) rainfall lasts for a period of 4 months with large variations recorded in terms of rainfall intensity during its period between June and September. Proxy reconstructions of past ISM rainfall variability are required due to the paucity of long instrumental records. However, reconstructing subseasonal rainfall is extremely difficult using conventional hydroclimate proxies due to inadequate sample resolution. Here, we demonstrate the utility of the stable oxygen isotope composition of gastropod shells in reconstructing past rainfall on subseasonal timescales. We present a comparative isotopic study on present day rainwater and stable isotope ratios of precipitate found in the incremental growth bands of giant African land snail Lissachatina fulica (Bowdich) from modern day (2009) and in the historical past (1918). Isotopic signatures present in the growth bands allowed for the identification of ISM rainfall variability in terms of its active and dry spells in the modern as well as past gastropod record. Our results demonstrate the utility of gastropod growth band stable isotope ratios in semiquantitative reconstructions of seasonal rainfall patterns. High resolution climate records extracted from gastropod growth band stable isotopes (museum and archived specimens) can expand the scope for understanding past subseasonal-to-seasonal climate variability.

Examination of an Oligocene Lacustrine Ecosystem Using C and N Stable Isotopes

NASA Astrophysics Data System (ADS)

Schweizer, M. K.; Wooller, M. J.; Toporski, J.; Fogel, M.; Steele, A.

2003-12-01

Stable isotopes of C and N are used to reconstruct the fossil Oligocene (25.8Ma) ecosystem at Lake Enspel, Westerwald, Germany. Enspel was a steep-sided, deep maar lake with anoxic bottom waters. Upon dying, terrestrial and aquatic organisms sank into the sediment where they were colonized by bacteria. These bacteria quickly became fossilized, preserving morphological detail and large amounts of organic matter from the original macroorganism. Carbon and nitrogen are sufficiently preserved in these fossils to permit stable isotope analysis. Stable isotopic signatures identify several trophic levels, including primary producers (terrigenous and aquatic plants, diatoms), primary consumers (tadpoles, some insects), and secondary consumers (carnivores such as fish). Primary producers are associated with depleted d13C and d15N values, primary consumers such as flies are one trophic shift higher, and fish are another shift higher. Signatures for the fish species show heavy-isotope enrichment correlated with increasing length, indicating an increasingly carnivorous diet. This study marks the first attempt to reconstruct a complete fossil ecosystem using stable isotope analysis, and confirms that techniques used to study modern food webs can be applied to extinct webs as well.

Using carbon isotopes of methane from porewater to understand methane emissions across a permafrost thaw gradient

NASA Astrophysics Data System (ADS)

Varner, R. K.; McCalley, C. K.; Clarizia, P. E.; Verbeke, B. A.; Werner, S. L.; Burke, S. A.; Malhotra, A.; Rocci, K.

2016-12-01

Methane (CH4) emissions from high latitude ecosystems are controlled in part by the presence/absence of permafrost and concomitant modifications in vegetation composition. Rapid transitions in habitat impact CH4 emissions both by changing the moisture regime as well as the production and emission pathways. Measurement of the isotopic composition of CH4 in porewater in these thawed ecosystems can indicate shifts in production pathways of CH4. We measured CH4 and carbon dioxide (CO2) emission, belowground CH4 concentration and 13CH4 of porewater, vegetative type, and vascular greenness area (VGA) along a thaw gradient during summers 2012-2016 in Stordalen Mire, Sweden. Concentrations of CH4 belowground showed positive correlation with aboveground emissions. Carbon isotopic signatures of CH4 varied varied between sites with more hydrogenotrophic signatures in sites dominated by Sphagnum spp. and acetate fermentation signatures in sedge dominated sites (Carex and Eriophorum spp.). These data indicate that these ecosystems transition from thaw, their 13CH4 emissions will change and therefore need to be accounted for in global atmospheric budgets and models.

Tellurium stable isotope fractionation in chondritic meteorites and some terrestrial samples

NASA Astrophysics Data System (ADS)

Fehr, Manuela A.; Hammond, Samantha J.; Parkinson, Ian J.

2018-02-01

New methodologies employing a 125Te-128Te double-spike were developed and applied to obtain high precision mass-dependent tellurium stable isotope data for chondritic meteorites and some terrestrial samples by multiple-collector inductively coupled plasma mass spectrometry. Analyses of standard solutions produce Te stable isotope data with a long-term reproducibility (2SD) of 0.064‰ for δ130/125Te. Carbonaceous and enstatite chondrites display a range in δ130/125Te of 0.9‰ (0.2‰ amu-1) in their Te stable isotope signature, whereas ordinary chondrites present larger Te stable isotope fractionation, in particular for unequilibrated ordinary chondrites, with an overall variation of 6.3‰ for δ130/125Te (1.3‰ amu-1). Tellurium stable isotope variations in ordinary chondrites display no correlation with Te contents or metamorphic grade. The large Te stable isotope fractionation in ordinary chondrites is likely caused by evaporation and condensation processes during metamorphism in the meteorite parent bodies, as has been suggested for other moderately and highly volatile elements displaying similar isotope fractionation. Alternatively, they might represent a nebular signature or could have been produced during chondrule formation. Enstatite chondrites display slightly more negative δ130/125Te compared to carbonaceous chondrites and equilibrated ordinary chondrites. Small differences in the Te stable isotope composition are also present within carbonaceous chondrites and increase in the order CV-CO-CM-CI. These Te isotope variations within carbonaceous chondrites may be due to mixing of components that have distinct Te isotope signatures reflecting Te stable isotope fractionation in the early solar system or on the parent bodies and potentially small so-far unresolvable nucleosynthetic isotope anomalies of up to 0.27‰. The Te stable isotope data of carbonaceous and enstatite chondrites displays a general correlation with the oxidation state and hence might provide a record of the nebular formation environment. The Te stable isotope fractionation of the carbonaceous chondrites CI and CM (and CO potentially) overlap within uncertainty with data for terrestrial Te standard solutions, sediments and ore samples. Assuming the silicate Earth displays similar Te isotope fractionation as the studied terrestrial samples, the data indicate that the late veneer might have been delivered by material similar to CI or CM (or possibly) CO carbonaceous chondrites in terms of Te isotope composition. Nine terrestrial samples display resolvable Te stable isotope fractionation of 0.85 and 0.60‰ for δ130/125Te for sediment and USGS geochemical exploration reference samples, respectively. Tellurium isotopes therefore have the potential to become a new geochemical sedimentary proxy, as well as a proxy for ore-exploration.

Source Signature of Sr Isotopes in Fluids Emitting From Mud volcanoes in Taiwan

NASA Astrophysics Data System (ADS)

Chung, C.; You, C.; Chao, H.

2003-12-01

Located at the boundary between the Philippine Sea Plate and the Asia Continental Plate, abundance of mud volcanoes were erupted on land in Taiwan. According to their occurrences and associated tectonic settings, these mud volcanoes were classified into four groupies. The group (I) mud volcanoes are located in the western coastal plane, whereas group (II) and (III) are situated near the Kutinkung anticline axis and the Chishan fault respectively. The group (IV) mud volcanoes are discovered at the Coastal Range. Although there are numerous studies focused on morphology, possible fluid migration paths and sources are poorly understood. We have collected and analyzed major ions and Sr isotopic ratios in fluids separated from various mud volcanoes in Taiwan. Chemical contents of these fluids were measured by IC and the emitted gasses were analyzed by GC. The Sr concentrations in these fluids were determined using AA and the isotopic compositions were analyzed by TIMS. The dominated ions in fluids are Na and Cl which account for 98% of dissolved materials. All fluids show similar Na/Cl ratios(0.7-0.8), slightly higher than seawater but each group has unique Sr isotopic signature. Waters expelled from group I mud volcanoes featured with low salinity and high Sr isotopic ratios ranged from 0.71150 to 0.71175. Groups II and III were outcroped in the Kutinkung formation but show distinctive chemical compositions. Group II fluids have four times Cl concentrations(358-522mM) compared with those of group III(85-162mM). The latter fluids appear to be more radiogenic(0.71012- 0.71075) indicating possible influence due to water-rock interactions. Low 87Sr/86Sr(0.70692-0.70939) is typical characteristic of mud volcano fluids in group IV where large Mg and K depletion were discovered, suggesting effects due to sediment diagenetic processes. The chemical compositions of mud volcano associated gasses show similar distribution pattern. The major gas constituents in mud volcano zones II and III are methane(>80%), air(1-10%) and carbon dioxide(1-5%). Gases collected from zone IV display significantly higher air content(5-20%) with low carbon dioxide(<0.2%). These results are useful for gaining a better understanding of mud volcano fluid sources.

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.

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

PubMed Central

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

2018-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Composition of Hydrothermal Vent Microbial Communities as Revealed by Analyses of Signature Lipids, Stable Carbon Isotopes and Aquificales Cultures

NASA Technical Reports Server (NTRS)

Jahnke, L. L.; Eder, W.; Huber, Robert; Hinrichs, K-U.; Hayes, J. M.; DesMarais, D. J.; Cady, S. L.; Hope, J. M.; Summons, R. E.

2001-01-01

This paper describes a study of lipid biomarker composition and carbon isotopic fractionation in cultured Aquificales and natural analogues from Yellowstone National Park. Additional information is contained in the original extended abstract.

Helium isotope study of geothermal features in Chile with field and laboratory data

DOE Data Explorer

Dobson, Patrick

2013-02-11

Helium isotope and stable isotope data from the El Tatio, Tinginguirica, Chillan, and Tolhuaca geothermal systems, Chile. Data from this submission are discussed in: Dobson, P.F., Kennedy, B.M., Reich, M., Sanchez, P., and Morata, D. (2013) Effects of volcanism, crustal thickness, and large scale faulting on the He isotope signatures of geothermal systems in Chile. Proceedings, 38th Workshop on Geothermal Reservoir Engineering, Stanford University, Feb. 11-13, 2013

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

Pb-Sr-Nd-O isotopic characterization of Mesozoic rocks throughout the northern end of the Peninsular Ranges batholith: Isotopic evidence for the magmatic evolution of oceanic arc–continental margin accretion during the Late Cretaceous of southern California

USGS Publications Warehouse

Kistler, Ronald W.; Wooden, Joseph L.; Premo, Wayne R.; Morton, Douglas M.

2014-01-01

Within the duration of the U.S. Geological Survey (USGS)–based Southern California Areal Mapping Project (SCAMP), many samples from the northern Peninsular Ranges batholith were studied for their whole-rock radioisotopic systematics (rubidium-strontium [Rb-Sr], uranium-thorium-lead [U-Th-Pb], and samarium-neodymium [Sm-Nd]), as well as oxygen (O), a stable isotope. The results of three main studies are presented separately, but here we combine them (>400 analyses) to produce a very complete Pb-Sr-Nd-O isotopic profile of an arc-continent collisional zone—perhaps the most complete in the world. In addition, because many of these samples have U-Pb zircon as well as argon mineral age determinations, we have good control of the timing for Pb-Sr-Nd-O isotopic variations.The ages and isotopic variations help to delineate at least four zones across the batholith from west to east—an older western zone (126–108 Ma), a transitional zone (111–93 Ma), an eastern zone (94–91 Ma), and a much younger allochthonous thrust sheet (ca. 84 Ma), which is the upper plate of the Eastern Peninsular Ranges mylonite zone. Average initial 87Sr/86 Sr (Sri), initial 206Pb/204Pb (206 Pbi), initial 208Pb/204Pb (average 208Pbi), initial epsilon Nd (average εNdi), and δ18O signatures range from 0.704, 18.787, 38.445, +3.1, and 4.0‰–9.0‰, respectively, in the westernmost zone, to 0.7071, 19.199, 38.777, −5, and 9‰–12‰, respectively, in the easternmost zone. The older western zone is therefore the more chemically and isotopically juvenile, characterized mostly by values that are slightly displaced from a mantle array at ca. 115 Ma, and similar to some modern island-arc signatures. In contrast, the isotopic signatures in the eastern zones indicate significant amounts of crustal involvement in the magmatic plumbing of those plutons. These isotopic signatures confirm previously published results that interpreted the Peninsular Ranges batholith as a progressively contaminated magmatic arc. The Peninsular Ranges batholith magmatic arc was initially an oceanic arc built on Panthalassan lithosphere that eventually evolved into a continental margin magmatic arc collision zone, eventually overriding North American cratonic lithosphere. Our Pb-Sr-Nd data further suggest that the western arc rocks represent a nearshore or inboard oceanic arc, as they exhibit isotopic signatures that are more enriched than typical mid-ocean-ridge basalt (MORB). Isotopic signatures from the central zone are transitional and indicate that enriched crustal magma sources were becoming involved in the northern Peninsular Ranges batholith magmatic plumbing. As the oceanic arc–continental margin collision progressed, a mixture of oceanic mantle and continental magmatic sources transpired. Magmatic production in the northern Peninsular Ranges batholith moved eastward and continued to tap enriched crustal magmatic sources. Similar modeling has been previously proposed for two other western margin magmatic arcs, the Sierra Nevada batholith of central California and the Idaho batholith.Calculated initial Nd signatures at ca. 100 Ma for Permian–Jurassic and Proterozoic basement rocks from the nearby San Gabriel Mountains and possible source areas along the southwestern Laurentian margin of southern California, southwestern Arizona, and northern Sonora strongly suggest their involvement with deep crustal magma mixing beneath the eastern zones of the Peninsular Ranges batholith, as well as farther east in continental lithospheric zones.Last, several samples from the allochthonous, easternmost upper-plate zone, which are considerably younger (ca. 84 Ma) than any of the rocks from the northern Peninsular Ranges batholith proper, have even more enriched average Sri, 206Pbi, 208Pbi, and εNdisignatures of 0.7079, 19.344, 38.881, and −6.6, respectively, indicative of the most-evolved magma sources in the northern Peninsular Ranges batholith and similar to radioisotopic values for rocks from the nearby Transverse Ranges, suggesting a genetic connection between the two.

The nature of Archean terrane boundaries: an example from the northern Wyoming Province

USGS Publications Warehouse

Mogk, D.W.; Mueller, P.A.; Wooden, J.L.

1992-01-01

The Archean northern Wyoming Province can be subdivided into two geologically distinct terranes, the Beartooth-Bighorn magmatic terrane (BBMT) and the Montana metasedimentary terrane (MMT). The BBMT is characterized by voluminous Late Archean (2.90-2.74 Ga) magmatic rocks (primarily tonalite, trondhjemite, and granite); metasedimentary rocks are preserved only as small, rare enclaves in this magmatic terrane. The magmatic rocks typically have geochemical and isotopic signatures that suggest petrogenesis in a continental magmatic arc environment. The MMT, as exposed in the northern Gallatin and Madison Ranges, is dominated by Middle Archean trondhjemitic gneisses (3.2-3.0 Ga); metasedimentary rocks, however, are significantly more abundant than in the BBMT. Each terrane has experienced a separate and distinct geologic history since at least 3.6 Ga ago based on differences in metamorphic and structural styles, composition of magmatic and metasupracrustal rocks, and isotopic ages; consequently, these may be described as discrete terranes in the Cordilleran sense. Nonetheless, highly radiogenic and distinctive Pb-Pb isotopic signatures in rocks of all ages in both terranes indicate that the two terranes share a significant aspect of their history. This suggests that these two Early to Middle Archean crustal blocks, that initially evolved as part of a larger crustal province, experienced different geologic histories from at least 3.6 Ga until their juxtaposition in the Late Archean (between 2.75 to 2.55 Ga ago). Consequently, the boundary between the BBMT and MMT appears to separate terranes that are not likely to be exotic in the sense of their Phanerozoic counterparts. Other Archean provinces do appear to contain crustal blocks with different isotopic signatures (e.g. West Greenland, India, South Africa). The use of the term exotic, therefore, must be cautious in situations where geographic indicators such as paleontologic and/or paleomagnetic data are not available. In these cases, isotopic signatures are one of the most useful features for assessing overall genetic relations amongst geologically distinct terranes. ?? 1992.

Diffusion-driven D/H fractionation in silicates during hydration, dehydration and degassing

NASA Astrophysics Data System (ADS)

Roskosz, Mathieu; Laporte, Didier; Deloule, Etienne; Ingrin, Jannick; Remusat, Laurent; Depecker, Christophe; Leroux, Hugues

2017-04-01

Understanding how degassing occurs during accretion and differentiation is crucial to explain the water budget of planetary bodies. In this context, the hydrogen isotopic signature of water in mantle minerals and melts is particularly useful to trace reservoirs and their interactions. Nonetheless, little is known on the influence of mantle processes on the D/H signatures of silicates. In this study, we performed controlled hydration/dehydration experiments. We explore the possibility that diffusion-driven fractionation could affect the D/H signature of partially hydrated amorphous or molten silicates and nominally anhydrous minerals (NAMs). High purity synthetic fused silica samples were annealed at between 200 and 1000°C at 20 mbar water partial pressure for 1 to 30 days. Dehydration of initially hydrated silica was also performed at 1000°C for a few hours. A set of rhyolitic samples previously synthesized in order to study bubble nucleation during magma decompression was also analyzed. Finally a natural grossular monocrystal (Zillertaler Alps, Austria), partially dehydrated in air at 800°C for 10 hours was studied. Water content and speciation were measured both by Fourier-Transform Infra-Red and Raman spectroscopies. Isotopic analyses were performed with the IMS 1270 and 1280 ion microprobes. The silica samples, the rhyolitic glasses and the grossular monocrystal exhibit typical water concentration profiles. In all cases, water speciation does not change significantly along concentration profiles. Concerning D/H signatures, no isotopic variation is detectable across amorphous silica and rhyolitic glasses. The situation is however very different in the grossular monocrystal. A strong isotopic gradient appears correlated to the water concentration profile. Our data are interpreted in terms of diffusion mechanisms in both amorphous (and molten) silicates and NAMs. Hydration, dehydration and magma degassing are probably not able to promote large diffusion-driven fractionation of hydrogen in amorphous silicates. Conversely, the diffusion of water through the structure of NAMs affects the overall isotopic composition of dissolved water.

Iron and nickel isotope fractionation by diffusion, with applications to iron meteorites

NASA Astrophysics Data System (ADS)

Watson, Heather C.; Richter, Frank; Liu, Ankun; Huss, Gary R.

2016-10-01

Mass-dependent, kinetic fractionation of isotopes through processes such as diffusion can result in measurable isotopic signatures. When these signatures are retained in geologic materials, they can be used to help interpret their thermal histories. The mass dependence of the diffusion coefficient of isotopes 1 and 2 can be written as (D1 /D2) =(m2 /m1) β, where D1 and D2 are the diffusion coefficients of m1 and m2 respectively, and β is an empirical coefficient that relates the two ratios. Experiments have been performed to measure β in the Fe-Ni alloy system. Diffusion couple experiments between pure Fe and Ni metals were run in a piston cylinder at 1300-1400 °C and 1 GPa. Concentration and isotopic profiles were measured by electron microprobe and ion microprobe respectively. We find that a single β coefficient of β = 0.32 ± 0.04 can describe the isotopic effect in all experiments. This result is comparable to the isotope effect determined in many other similar alloy systems. The new β coefficient is used in a model of the isotopic profiles to be expected during the Widmanstätten pattern formation in iron meteorites. The results are consistent with previous estimates of the cooling rate of the iron meteorite Toluca. The application of isotopic constraints based on these results in addition to conventional cooling rate models could provide a more robust picture of the thermal history of these early planetary bodies.

Symbiodinium Clade Affects Coral Skeletal Isotopic Ratio

NASA Astrophysics Data System (ADS)

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

2011-12-01

The influence of different physiologies of Symbiodinium dinoflagellate symbiont clades on the skeletal chemistry of associated coral hosts has not previously been investigated. This is an important issue because coral skeletons are routinely used for tropical paleoclimatic reconstructions. We analyzed coral skeletal samples collected simultaneously from neighboring colonies off Belize and found that those harboring different clades of Symbiodinium displayed significantly different skeletal oxygen isotopic compositions. We also found evidence for mean shifts in skeletal oxygen isotopic composition after coral bleaching (the loss and potential exchange of symbionts) in two of four longer coral cores from the Mesoamerican Reef, though all experienced similar climatic conditions. Thus, we suggest that symbiont clade identity leaves a signature in the coral skeletal archive and that this influence must be considered for quantitative environmental reconstruction. In addition, we suggest that the skeletal isotopic signature may be used to identify changes in the dominant symbiont clade that have occurred in the past, to identify how common and widespread this phenomenon is--a potential adaptation to climate change.

Cenozoic intra-plate magmatism in the Darfur volcanic province: mantle source, phonolite-trachyte genesis and relation to other volcanic provinces in NE Africa

NASA Astrophysics Data System (ADS)

Lucassen, Friedrich; Pudlo, Dieter; Franz, Gerhard; Romer, Rolf L.; Dulski, Peter

2013-01-01

Chemical and Sr, Nd and Pb isotopic compositions of Late Cenozoic to Quaternary small-volume phonolite, trachyte and related mafic rocks from the Darfur volcanic province/NW-Sudan have been investigated. Isotope signatures indicate variable but minor crustal contributions. Some phonolitic and trachytic rocks show the same isotopic composition as their primitive mantle-derived parents, and no crustal contributions are visible in the trace element patterns of these samples. The magmatic evolution of the evolved rocks is dominated by crystal fractionation. The Si-undersaturated strongly alkaline phonolite and the Si-saturated mildly alkaline trachyte can be modelled by fractionation of basanite and basalt, respectively. The suite of basanite-basalt-phonolite-trachyte with characteristic isotope signatures from the Darfur volcanic province fits the compositional features of other Cenozoic intra-plate magmatism scattered in North and Central Africa (e.g., Tibesti, Maghreb, Cameroon line), which evolved on a lithosphere that was reworked or formed during the Neoproterozoic.

Plant protein-based feeds and commercial feed enable isotopic tracking of aquaculture emissions into marine macrozoobenthic bioindicator species.

PubMed

Kusche, Henrik; Hillgruber, Nicola; Rößner, Yvonne; Focken, Ulfert

2017-06-01

Brittle stars (Ophiura spp.) and other benthic macrofauna were collected in a prospective mariculture area in the North Sea to determine if these taxa could be used as indicator species to track nutrients released from future offshore aquaculture sites. We analysed natural carbon and nitrogen stable isotopic signatures in tissues from macrofauna and compared these to six feed ingredients and four experimental diets made thereof, as well as to a commercial feed with and without lipid and carbonate removal. Our data suggest practicability of using isotopic signatures of Ophiura spp. to track aquaculture-derived organic material if plant-based fish diet ingredients and commercial feed were used for fish farming in the German Exclusive Economic Zone. Diets with high fish meal content would not be detected in Ophiura spp. using isotopic measures due to the similarity with the marine background. Our data provide valuable baseline information for studies on the impact of offshore aquaculture on the marine environment.

Variable Flow Pathways and Geochemical History of Seepage Under Mississippi River Levees: 2011, 2015, and 2016 Floods

NASA Astrophysics Data System (ADS)

Voll, K.; Davidson, G. R.; Borrok, D. M.; Corcoran, M. K.; Kelley, J.; Ma, L.

2017-12-01

Seepage beneath levees during flood stage is a concern when piping occurs, creating channels under the levee and forming sand boils where transported sediments discharge. The flow depth beneath a levee varies with surface geology, following deeper paths where the levee sits on channel fill deposits and shallower paths where it sits on sandbar deposits. Piping along shallow pathways poses an increased risk of levee failure. The Lower Mississippi River Valley alluvial aquifer is geochemically stratified, with reducing waters at greater depth, resulting in unique geochemical signatures for water passing beneath the Mississippi River levee along variable flow paths. Sampling from sand boils and flowing relief wells north of Vicksburg, MS, during the 2011, 2015, and 2016 flood events demonstrates the utility of using the geochemistry of discharge water to identify different flow pathways, and to provide greater insight on the variable water-rock interactions as a function of depth. Relief wells discharge water mainly from deeper zones, reflected by low redox potential, high Fe and As, and low 87Sr/86Sr ratios. High variability in As concentrations may result from varying degrees of reductive dissolution of Fe and Mn and release of co-precipitated As. At shallower depths the aquifer is mostly oxic, lower in Fe, As, and bicarbonate, and higher in sulfate concentrations and 87Sr/86Sr ratios. The geochemical signatures of sand-boil discharge varied between boils that were short distances apart. Water samples plotted on a Piper Diagram fell along two distinct trends starting with river water and diverging along pathways reflecting unique water-rock interaction at different depths. Strontium isotope ratios indicate differences in geochemistry are not just from variable redox reactions, but also reflect dissolution of primary minerals of unique composition or provenance. Oxygen and hydrogen isotopes of all subsurface samples reflect an unexpected level of evaporation of river water prior to recharge to the aquifer, attributed to the presence of numerous water-filled depressions between the river channel and levee system. Tritium levels from wells and boils ranged from 2.3 to 7.4 TU, with some high values coming from deeper zones indicating localized variation in the residence time of water at equal depths beneath levees.

Opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes

NASA Astrophysics Data System (ADS)

Lough, A. J. M.; Klar, J. K.; Homoky, W. B.; Comer-Warner, S. A.; Milton, J. A.; Connelly, D. P.; James, R. H.; Mills, R. A.

2017-04-01

Iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean. The mechanisms and rates of Fe supply to the ocean interior are still poorly understood and quantified. Iron isotope ratios of different Fe pools can potentially be used to trace sources and sinks of the global Fe biogeochemical cycle if these boundary fluxes have distinct signatures. Seafloor hydrothermal vents emit metal rich fluids from mid-ocean ridges into the deep ocean. Iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of Fe isotopes during plume dispersal in the deep ocean are understood. In this study we assess the behaviour of Fe isotopes in a Southern Ocean hydrothermal plume using a sampling program of Total Dissolvable Fe (TDFe), and dissolved Fe (dFe). We demonstrate that δ56Fe values of dFe (δ56dFe) within the hydrothermal plume change dramatically during early plume dispersal, ranging from -2.39 ± 0.05‰ to -0.13 ± 0.06‰ (2 SD). The isotopic composition of TDFe (δ56TDFe) was consistently heavier than dFe values, ranging from -0.31 ± 0.03‰ to 0.78 ± 0.05‰, consistent with Fe oxyhydroxide precipitation as the plume samples age. The dFe present in the hydrothermal plume includes stabilised dFe species with potential to be transported to the deep ocean. We estimate that stable dFe exported from the plume will have a δ56Fe of -0.28 ± 0.17‰. Further, we show that the proportion of authigenic iron-sulfide and iron-oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved Fe passed into the neutrally buoyant plume. We show that such controls yield variable dissolved Fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere, and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records.

Quantifying the relative contribution of natural gas fugitive emissions to total methane emissions in Weld County Colorado using δ13CH4 analysis

NASA Astrophysics Data System (ADS)

Rella, C.; Jacobson, G. A.; Crosson, E.; Sweeney, C.; Karion, A.; Petron, G.

2012-12-01

Fugitive emissions of methane into the atmosphere are a major concern facing the natural gas production industry. Given that the global warming potential of methane is many times greater than that of carbon dioxide (Forster et al. 2007), the importance of quantifying methane emissions becomes clear. Companion presentations at this meeting describe efforts to quantify the overall methane emissions in two separate gas producing areas in Colorado and Utah during intensive field campaigns undertaken in 2012. A key step in the process of assessing the emissions arising from natural gas production activities is partitioning the observed methane emissions between natural gas fugitive emissions and other sources of methane, such as from landfills or agricultural activities. One method for assessing the contribution of these different sources is stable isotope analysis. In particular, the δ13CH4 signature of natural gas (-37 permil) is significantly different that the signature of other significant sources of methane, such as landfills or ruminants (-50 to -70 permil). In this paper we present measurements of δ13CH4 in Colorado in Weld County, a region of intense natural gas production, using a mobile δ13CH4¬ analyzer capable of high-precision measurements of the stable isotope ratio of methane at ambient levels. This analyzer was used to make stable isotope measurements at a fixed location near the center of the gas producing region, from which an overall isotope ratio for the regional emissions is determined. In addition, mobile measurements in the nocturnal boundary layer have been made, over a total distance of 150 km throughout Weld County, allowing spatially resolved measurements of this isotope signature. Finally, this analyzer was used to quantify the isotopic signature of those individual sources (natural gas fugitive emissions, concentrated animal feeding operations, and landfills) that constitute the majority of methane emissions in this region, by making measurements of the isotope ratio directly in the downwind plume from each source. These data are combined to establish the fraction of the observed methane emissions that can be attributed to natural gas activities in the region. The results are compared to inventories as well as other measurement techniques, and the uncertainty of the measurement is estimated.

Stable isotopic composition of anguilliform leptocephali and other food web components from west of the Mascarene Plateau

NASA Astrophysics Data System (ADS)

Feunteun, Eric; Miller, Michael J.; Carpentier, Alexandre; Aoyama, Jun; Dupuy, Christine; Kuroki, Mari; Pagano, Marc; Réveillac, Elodie; Sellos, Daniel; Watanabe, Shun; Tsukamoto, Katsumi; Otake, Tsuguo

2015-09-01

Leptocephali are the poorly-understood transparent larvae of elopomorph fishes that live in the ocean surface layer throughout the world's tropical and subtropical oceans. Their feeding ecology has been difficult to understand because they appear to primarily feed on particulate organic material (POM), which contains few identifiable objects, and there have been few studies on their diets or trophic positions. This study presents the first comparative results on the stable isotope ratios of 7 families of leptocephali in relation to the ratios of 30 taxa of other marine animals and POM samples. The carbon and nitrogen stable isotope ratios were analyzed using 50 specimens of leptocephali, 354 specimens of mesozooplankton, cephalopods, fishes, and POM collected west of the Mascarene Plateau in the western Indian Ocean. Nitrogen and carbon isotopic ratio analyses indicated that the 12 taxa of DNA barcoded leptocephali (⩾15 species) could be separated into 2 groups of species with either higher (Group 1: 9 taxa of 7 families, 25-91 mm) or lower (Group 2: 3 taxa of 2 families, 43-275 mm) δ15N ranges. Group 2 exclusively included species that reach much larger sizes of >150-200 mm (Nemichthys and Avocettina, 3 species of Ariosoma-type), whereas Group 1 included Anguilla bicolor bicolor, Serrivomeridae, Muraenidae, Congridae (3 species), Chlopsidae, Ophichthidae (2 species), and Thalassenchelys. Differences in feeding depths, the types of POM ingested by preference or because of different jaw morphology, or the transport of larvae from other regions with different isotopic signatures are possible reasons for the differences between the two groups. The isotopic signatures of 14 taxa of copepods had higher but slightly overlapping δ15N and δ13C signatures compared to leptocephali and most crustaceans and other mezozooplankton, cephalopods and mesopelagic fish taxa had even higher values. The δ15N and δ13C signatures and composition of POM were variable spatially and with depth and may have been influenced by particulates originating from the shallow banks of the Mascarene Plateau. The two apparent isotopic groups of leptocephali should be examined in relation to their consumption of POM, which can include various proportions of prokaryotes, phytoplankton, protozoans, discarded appendicularian houses and other materials, by conducting further studies in different regions and using a variety of techniques.

Landscape cultivation alters δ30Si signature in terrestrial ecosystems

PubMed Central

Vandevenne, Floor I.; Delvaux, Claire; Hughes, Harold J.; André, Luc; Ronchi, Benedicta; Clymans, Wim; Barão, Lúcia; Govers, Gerard; Meire, Patrick; Struyf, Eric

2015-01-01

Despite increasing recognition of the relevance of biological cycling for Si cycling in ecosystems and for Si export from soils to fluvial systems, effects of human cultivation on the Si cycle are still relatively understudied. Here we examined stable Si isotope (δ30Si) signatures in soil water samples across a temperate land use gradient. We show that – independent of geological and climatological variation – there is a depletion in light isotopes in soil water of intensive croplands and managed grasslands relative to native forests. Furthermore, our data suggest a divergence in δ30Si signatures along the land use change gradient, highlighting the imprint of vegetation cover, human cultivation and intensity of disturbance on δ30Si patterns, on top of more conventionally acknowledged drivers (i.e. mineralogy and climate). PMID:25583031

UTEX modeling of xenon signature sensitivity to geology and explosion cavity characteristics following an underground nuclear explosion

NASA Astrophysics Data System (ADS)

Lowrey, J. D.; Haas, D.

2013-12-01

Underground nuclear explosions (UNEs) produce anthropogenic isotopes that can potentially be used in the verification component of the Comprehensive Nuclear-Test-Ban Treaty. Several isotopes of radioactive xenon gas have been identified as radionuclides of interest within the International Monitoring System (IMS) and in an On-Site Inspection (OSI). Substantial research has been previously undertaken to characterize the geologic and atmospheric mechanisms that can drive the movement of radionuclide gas from a well-contained UNE, considering both sensitivities on gas arrival time and signature variability of xenon due to the nature of subsurface transport. This work further considers sensitivities of radioxenon gas arrival time and signatures to large variability in geologic stratification and generalized explosion cavity characteristics, as well as compares this influence to variability in the shallow surface.

Does Short-term Litter Input Manipulation Affect Soil Respiration and the Carbon-isotopic Signature of Soil Respired CO2

NASA Astrophysics Data System (ADS)

Cheng, X.; Wu, J.

2016-12-01

Global change greatly alters the quality and quantity of plant litter inputs to soils, and further impacts soil organic matter (SOM) dynamics and soil respiration. However, the process-based understanding of how soil respiration may change with future shift in litter input is not fully understood. The Detritus Input and Removal Treatment (DIRT) experiment was conducted in coniferous forest (Platycladus orientalis (Linn.) Franco) ecosystem of central China to investigate the impact of above- and belowground litter input on soil respiration and the carbon-isotopic signature of soil respired CO2. Short-term (1-2 years) litter input manipulation significantly affected soil respiration, based on annual flux values, soil respiration was 31.9%, 20.5% and 37.2% lower in no litter (NL), no root (NR) and no input (NRNL), respectively, compared to control (CK). Whereas double litter (DL) treatment increased soil respiration by 9.1% compared to CK. The recalcitrance index of carbon (RIC) and the relative abundance of fungi increased under litter removal or root exclusion treatment (NL, NR and NRNL) compared to CK. Basal soil respiration was positively related to liable C and microbial biomass and negatively related to RIC and fungi to bacteria (F: B) ratio. The carbon-isotopic signature of soil respired CO2 enriched under litter removal and no input treatment, and slightly depleted under litter addition treatment compared to CK. Our results suggest that short-term litter input manipulation can affect the soil respiration by altering substrate availability and microbial community structure, and also impact the carbon-isotopic signature of soil respired CO2 possibly duo to change in the component of soil respiration and soil microclimate.

Paleozoic tectonics of the Ouachita Orogen through Nd isotopes

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

Gleason, J.D.; Patchett, P.J.; Dickinson, W.R.

1992-01-01

A combined isotopic and trace-element study of the Late Paleozoic Ouachita Orogenic belt has the following goals: (1) define changing provenance of Ouachita sedimentary systems throughout the Paleozoic; (2) constrain sources feeding into the Ouachita flysch trough during the Late Paleozoic; (3) isolate the geochemical signature of proposed colliding terranes to the south; (4) build a data base to compare with possible Ouachita System equivalents in Mexico. The ultimate aim is to constrain the tectonic setting of the southern margin of North America during the Paleozoic, with particular emphasis on collisional events leading to the final suturing of Pangea. Ndmore » isotopic data identify 3 distinct groups: (1) Ordovician passive margin sequence; (2) Carboniferous proto-flysch (Stanley Fm.), main flysch (Jackfork and Atoka Fms.) and molasse (foreland Atoka Fm.); (3) Mississippian ash-flow tuffs. The authors interpret the Ordovician signature to be essentially all craton-derived, whereas the Carboniferous signature reflects mixed sources from the craton plus orogenic sources to the east and possibly the south, including the evolving Appalachian Orogen. The proposed southern source is revealed by the tuffs to be too old and evolved to be a juvenile island arc terrane. They interpret the tuffs to have been erupted in a continental margin arc-type setting. Surprisingly, the foreland molasse sequence is indistinguishable from the main trough flysch sequence, suggesting the Ouachita trough and the craton were both inundated with sediment of a single homogenized isotopic signature during the Late Carboniferous. The possibility that Carboniferous-type sedimentary dispersal patterns began as early as the Silurian has important implications for the tectonics and paleogeography of the evolving Appalachian-Ouachita Orogenic System.« less

Dual-Carbon sources fuel the OCS deep-reef Community, a stable isotope investigation

USGS Publications Warehouse

Sulak, Kenneth J.; Berg, J.; Randall, Michael T.; Dennis, George D.; Brooks, R.A.

2008-01-01

The hypothesis that phytoplankton is the sole carbon source for the OCS deep-reef community (>60 m) was tested. Trophic structure for NE Gulf of Mexico deep reefs was analyzed via carbon and nitrogen stable isotopes. Carbon signatures for 114 entities (carbon sources, sediment, fishes, and invertebrates) supported surface phytoplankton as the primary fuel for the deep reef. However, a second carbon source, the macroalga Sargassum, with its epiphytic macroalgal associate, Cladophora liniformis, was also identified. Macroalgal carbon signatures were detected among 23 consumer entities. Most notably, macroalgae contributed 45 % of total carbon to the 13C isotopic spectrum of the particulate-feeding reef-crest gorgonian Nicella. The discontinuous spatial distribution of some sessile deep-reef invertebrates utilizing pelagic macroalgal carbon may be trophically tied to the contagious distribution of Sargassum biomass along major ocean surface features.

Atmospheric mercury inputs in montane soils increase with elevation: evidence from mercury isotope signatures.

PubMed

Zhang, Hua; Yin, Run-sheng; Feng, Xin-bin; Sommar, Jonas; Anderson, Christopher W N; Sapkota, Atindra; Fu, Xue-wu; Larssen, Thorjørn

2013-11-25

The influence of topography on the biogeochemical cycle of mercury (Hg) has received relatively little attention. Here, we report the measurement of Hg species and their corresponding isotope composition in soil sampled along an elevational gradient transect on Mt. Leigong in subtropical southwestern China. The data are used to explain orography-related effects on the fate and behaviour of Hg species in montane environments. The total- and methyl-Hg concentrations in topsoil samples show a positive correlation with elevation. However, a negative elevation dependence was observed in the mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) signatures of Hg isotopes. Both a MIF (Δ(199)Hg) binary mixing approach and the traditional inert element method indicate that the content of Hg derived from the atmosphere distinctly increases with altitude.

Effects of preservatives on stable isotope analyses of four marine species

NASA Astrophysics Data System (ADS)

Carabel, Sirka; Verísimo, Patricia; Freire, Juan

2009-04-01

The aim of the present study is to quantify the effect of formalin-ethanol preservation on the carbon and nitrogen stable isotope signatures of four taxonomical groups of marine species ( Himanthalia elongata, Anemonia sulcata, Mytilus galloprovincialis and Patella vulgata). To examine temporal changes in the effects of preservation and to determine if preservation induced predictable shifts in δ13C and δ15N signatures, repeated analyses were carried out after 6, 12 and 24 months of preservation. Data from our study showed highly variable effects of the formalin-ethanol preservation on carbon and nitrogen isotope signatures between species. The use of a general correction factor was not possible, or else it should be species-specific. Differences in nitrogen isotopic values between preserved and unpreserved samples were minor compared to the assumed enrichment between trophic levels. The combined use of data from preserved and unpreserved samples could lead to biases in the estimation of the trophic level of organisms. Changes that preservatives caused in carbon values were variable between species and not always small enough to be ignored. So the use of data from preserved samples could change the interpretation of the mixing models used to determine the importance of multiple sources of carbon. In order to elucidate the effects that preservatives have in other species, further studies will be necessary.

Evaluating Snowmelt Runoff Processes Using Stable Isotopes in a Permafrost Hillslope

NASA Astrophysics Data System (ADS)

Carey, S. K.

2004-05-01

Conceptual understanding of runoff generation in permafrost regions have been derived primarily from hydrometric information, with isotope and hydrochemical data having only limited application in delineating sources and pathways of water. Furthermore, when stable isotope data are used to infer runoff processes, it often provides conflicting results from hydrometric measurements. In a small subarctic alpine catchment within the Wolf Creek Research Basin, Yukon, Canada, experiments were conducted during the melt period of 2002 and 2003 to trace the stable isotopic signature (d18O) of meltwater from a melting snowpack into permafrost soils and laterally to the stream to identify runoff processes and evaluate sources of error for traditional hydrograph separation studies in snowmelt-dominated permafrost basins. Isotopic variability in the snowpack was recorded at 0.1 m depth intervals during the melt period and compared with the meltwater isotopic signature at the snowpack base collected in lysimeters. Throughout the melt period in both years, there was an isotopic enrichment of meltwater as the season progressed. A downslope transect of wells and piezometers were used to evaluate the influence of infiltrating meltwater and thawing ground on the subsurface d18O signature. As melt began, meltwater infiltrated the frozen porous organic layer, leading to liquid water saturation in the unsaturated pore spaces. Water sampled during this initial melt stage show soil water d18O mirroring that of the meltwater signal. As the melt season progressed, frozen soil began to melt, mixing enriched pre-melt soil water with meltwater. This mixing increased the overall value of d18O obtained from the soil, which gradually increased as thaw progressed. At the end of snowmelt, soil water had a d18O value similar to values from the previous fall, suggesting that much of the initial snowmelt water had been flushed from the hillslope. Results from the hillslope scale are compared with two-component hydrograph separations and sources of error are discussed.

Chlorine isotopic compositions of apatite in Apollo 14 rocks: Evidence for widespread vapor-phase metasomatism on the lunar nearside ∼4 billion years ago

NASA Astrophysics Data System (ADS)

Potts, Nicola J.; Barnes, Jessica J.; Tartèse, Romain; Franchi, Ian A.; Anand, Mahesh

2018-06-01

Compared to most other planetary materials in the Solar System, some lunar rocks display high δ37Cl signatures. Loss of Cl in a H ≪ Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with δ37Cl values ranging from +14.6 ± 1.6‰ to +40.0 ± 2.9‰. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and δ37Cl values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of δ37Cl values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks ∼4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event.

Accessory Mineral Records of Early Earth Crust-Mantle Systematics: an Example From West Greenland

NASA Astrophysics Data System (ADS)

Storey, C. D.; Hawkesworth, C. J.

2008-12-01

Conditions for the formation and the nature of Earth's early crust are enigmatic due to poor preservation. Before c.4 Ga the only archives are detrital minerals eroded from earlier crust, such as the Jack Hills zircons in western Australia, or extinct isotope systematics. Zircons are particularly powerful since they retain precise records of their ages of crystallisation, and the Lu-Hf radiogenic isotope and O stable isotope systematics of the reservoir from which they crystallised. In principle, this allows insight into the nature of the crust, the mantle reservoir from which the melt was extracted and any reworked material incorporated into that melt. We have used in situ methods to measure U-Pb, O and Lu-Hf within single zircon crystals from tonalitic gneisses from West Greenland in the vicinity of the Isua Supracrustal Belt. They have little disturbed ages of c.3.8 Ga, mantle-like O isotope signatures and Lu-Hf isotope signatures that lie on the CHUR evolution line at 3.8 Ga. These samples have previously been subjected to Pb isotope feldspar and 142Nd whole rock analysis and have helped constrain models in which early differentiation of a proto-crust must have occurred. The CHUR-like Lu-Hf signature, along with mantle-like O signature from these zircons suggests juvenile melt production at 3.8 Ga from undifferentiated mantle, yet the other isotope systems preclude this possibility. Alternatively, this is further strong evidence for a heterogeneous mantle in the early Earth. Whilst zircons afford insight into the nature of the early crust and mantle, it is through the Sm-Nd system that the mantle has traditionally been viewed. Titanite often contains several thousand ppm Nd, making it amenable to precise analysis, and is a common accessory phase. It has a reasonably high closure temperature for Pb and O, and it can retain cores with older ages and distinct REE chemistry. It is often the main accessory phase alongside zircon, and it is the main carrier of Nd within the whole rock such that Nd isotope analysis of titanite may be able to see-through later alteration that may have partially reset the whole rock system. We present new in-situ U-Pb, O and Sm-Nd and high-precision U-Pb ID-TIMS and Sm-Nd MC- ICPMS data from individual or fragmented titanite grains. We discuss how these data complement the zircon data and may help to resolve long-standing debates in ancient gneiss terranes, with utility to the nature and formation of crust on the early Earth.

Modeling calcification periods of Cytheridella ilosvayi from Florida based on isotopic signatures and hydrological data

NASA Astrophysics Data System (ADS)

Meyer, Juliane; Wrozyna, Claudia; Leis, Albrecht; Piller, Werner E.

2017-11-01

The isotopic signatures of ostracod shells are the result of the temperature and composition of their host water and the phenology and ecology of the target species. Investigations addressing the influence of site-specific environmental variations on the isotopic ranges of ostracod shells are still rare but can provide important information on habitat-dependent variations and may signify a seasonally restricted timing of calcification periods. Here we present isotopic signatures (δ18Oostr, δ13Costr) of living Cytheridella ilosvayi (Ostracoda) and physical, chemical, and isotopic (δD, δ18Owater, δ13CDIC) compositions of 14 freshwater habitats (rivers, lakes, canals, marshes, sinkholes) in South Florida from winter 2013 and summer 2014. We also present instrumental data of river temperatures and δ18O of precipitation (δ18Oprec) from this region. The physicochemical and isotopic compositions of the selected sites characterize the different habitats and show the influence of the source water, biological activity, and duration of exposure to the surface. Mean δ18Oostr and δ13Costr signatures of C. ilosvayi shells correlate well with the isotopic composition of their host waters. Within-sample variabilities in repeated isotopic measurements of single ostracod shells reflect habitat-dependent ranges. The similarly high range of ostracod δ18O in rivers and one marsh sample indicates that both temperature and δ18Oprec are responsible for their variation in the whole study area. Rivers and canals, which are predominantly influenced by the input and mixing of inorganic carbon from the catchment, show smaller δ13Costr ranges than the marsh dominated by local fluctuations in biological activities. Based on these observations, background data of water temperatures and δ18Oprec were used to calculate monthly δ18O variations in a theoretical calcite formed in rivers in Florida assuming a direct reaction on precipitation changes. The calculated values showed a high variation coupled with low mean values during the summer wet season, while during the winter dry season the variation remains small and mean values increased. Inferred configurations were used to approximate possible calcification periods of C. ilosvayi. For a plausible calcification period, mean values and ranges of δ18Oostr had to be equal to the theoretical calcite with a slight positive offset (vital effect). The applied model suggests a seasonal calcification period of C. ilosvayi in early spring that is probably coupled to the hydrologic cycle of Florida.

Spatial and temporal variance in fatty acid and stable isotope signatures across trophic levels in large river systems

USGS Publications Warehouse

Fritts, Andrea; Knights, Brent C.; Lafrancois, Toben D.; Bartsch, Lynn; Vallazza, Jon; Bartsch, Michelle; Richardson, William B.; Karns, Byron N.; Bailey, Sean; Kreiling, Rebecca

2018-01-01

Fatty acid and stable isotope signatures allow researchers to better understand food webs, food sources, and trophic relationships. Research in marine and lentic systems has indicated that the variance of these biomarkers can exhibit substantial differences across spatial and temporal scales, but this type of analysis has not been completed for large river systems. Our objectives were to evaluate variance structures for fatty acids and stable isotopes (i.e. δ13C and δ15N) of seston, threeridge mussels, hydropsychid caddisflies, gizzard shad, and bluegill across spatial scales (10s-100s km) in large rivers of the Upper Mississippi River Basin, USA that were sampled annually for two years, and to evaluate the implications of this variance on the design and interpretation of trophic studies. The highest variance for both isotopes was present at the largest spatial scale for all taxa (except seston δ15N) indicating that these isotopic signatures are responding to factors at a larger geographic level rather than being influenced by local-scale alterations. Conversely, the highest variance for fatty acids was present at the smallest spatial scale (i.e. among individuals) for all taxa except caddisflies, indicating that the physiological and metabolic processes that influence fatty acid profiles can differ substantially between individuals at a given site. Our results highlight the need to consider the spatial partitioning of variance during sample design and analysis, as some taxa may not be suitable to assess ecological questions at larger spatial scales.

Internal loading of phosphate in Lake Erie Central Basin.

PubMed

Paytan, Adina; Roberts, Kathryn; Watson, Sue; Peek, Sara; Chuang, Pei-Chuan; Defforey, Delphine; Kendall, Carol

2017-02-01

After significant reductions in external phosphorus (P) loads, and subsequent water quality improvements in the early 1980s, the water quality of Lake Erie has declined considerably over the past decade. The frequency and magnitude of harmful algal blooms (primarily in the western basin) and the extent of hypoxic bottom waters in the central basin have increased. The decline in ecosystem health, despite meeting goals for external P loads, has sparked a renewed effort to understand P cycling in the lake. We use pore-water P concentration profiles and sediment cores incubation experiments to quantify the P flux from Lake Erie central basin sediments. In addition, the oxygen isotopes of phosphate were investigated to assess the isotopic signature of sedimentary phosphate inputs relative to the isotopic signature of phosphate in lake water. Extrapolating the total P sediment flux based on the pore-water profiles to the whole area of the central basin ranged from 300 to 1250metric tons per year and using the flux based on core incubation experiments an annual flux of roughly 2400metric tons of P is calculated. These estimates amount to 8-20% of the total external input of P to Lake Erie. The isotopic signature of phosphate in the extractable fraction of the sediments (~18‰) can explain the non-equilibrium isotope values of dissolved phosphate in the deep water of the central basin of Lake Erie, and this is consistent with sediments as an important internal source of P in the Lake. Copyright © 2016 Elsevier B.V. All rights reserved.

Stable isotope signatures and element stoichiometry of Fucus vesiculosus as indicators for environmental conditions in the Kiel Bight, Baltic Sea

NASA Astrophysics Data System (ADS)

Winde, Vera; Mahler, Annika; Voss, Maren; Böttcher, Michael E.

2014-05-01

In the frame of the BMBF project BIOACID II we aim for an understanding of the natural distribution and variation of isotopic composition and C-N-S stoichiometry in Fucus vesiculosus growing around the coast line of the Kiel fjord (part of the Kiel bight). Environmental conditions (aquatic chemistry, temperature, salinity) were monitored, too. Some changes in aquatic chemistry are related to stress factors like human activity (e.g., waste input) and further factors leading to specific changes in the composition of Fucus vesiculosus. Sampling was carried out at different stations at the west and east coast of the Kiel Fjord. For each sampling station the aquatic chemistry (TA, pH, salinity, d13C(DIC), main and trace elements and nutrients) as well as the composition of the Fucus organic tissues (stoichiometry and stable isotope composition of carbon, nitrogen) are analysed. The Fucus tissue was sampled in three size classes (small, medium, large). It is shown, that Fucus vesiculosus indicates clear differences in the N contents and stable isotopes between the west and the east site of the Kiel Fjord. Stable nitrogen isotope signatures in Fucus vesiculosus, are useful proxies to identify the influence factors in the Fucus habitat. From the data it is obtained that the influence of human activity (wastewater treatment plant, harbour), small stream and drainage channels, which flow from the near coastal area into the bight, leads to different Fucus vesiculosus compositions. In future work, it is intended to extend the investigation to trace element signatures to further estimate environmental impacts.

Biodiversity on the Rocks: Macrofauna Inhabiting Authigenic Carbonate at Costa Rica Methane Seeps

PubMed Central

Levin, Lisa A.; Mendoza, Guillermo F.; Grupe, Benjamin M.; Gonzalez, Jennifer P.; Jellison, Brittany; Rouse, Greg; Thurber, Andrew R.; Waren, Anders

2015-01-01

Carbonate communities: The activity of anaerobic methane oxidizing microbes facilitates precipitation of vast quantities of authigenic carbonate at methane seeps. Here we demonstrate the significant role of carbonate rocks in promoting diversity by providing unique habitat and food resources for macrofaunal assemblages at seeps on the Costa Rica margin (400–1850 m). The attendant fauna is surprisingly similar to that in rocky intertidal shores, with numerous grazing gastropods (limpets and snails) as dominant taxa. However, the community feeds upon seep-associated microbes. Macrofaunal density, composition, and diversity on carbonates vary as a function of seepage activity, biogenic habitat and location. The macrofaunal community of carbonates at non-seeping (inactive) sites is strongly related to the hydrography (depth, temperature, O2) of overlying water, whereas the fauna at sites of active seepage is not. Densities are highest on active rocks from tubeworm bushes and mussel beds, particularly at the Mound 12 location (1000 m). Species diversity is higher on rocks exposed to active seepage, with multiple species of gastropods and polychaetes dominant, while crustaceans, cnidarians, and ophiuroids were better represented on rocks at inactive sites. Macro-infauna (larger than 0.3 mm) from tube cores taken in nearby seep sediments at comparable depths exhibited densities similar to those on carbonate rocks, but had lower diversity and different taxonomic composition. Seep sediments had higher densities of ampharetid, dorvilleid, hesionid, cirratulid and lacydoniid polychaetes, whereas carbonates had more gastropods, as well as syllid, chrysopetalid and polynoid polychaetes. Stable isotope signatures and metrics: The stable isotope signatures of carbonates were heterogeneous, as were the food sources and nutrition used by the animals. Carbonate δ13Cinorg values (mean = -26.98‰) ranged from -53.3‰ to +10.0‰, and were significantly heavier than carbonate δ13Corg (mean = -33.83‰), which ranged from -74.4‰ to -20.6‰. Invertebrates on carbonates had average δ13C (per rock) = -31.0‰ (range -18.5‰ to -46.5‰) and δ15N = 5.7‰ (range -4.5‰ to +13.4‰). Average δ13C values did not differ between active and inactive sites; carbonate fauna from both settings depend on chemosynthesis-based nutrition. Community metrics reflecting trophic diversity (SEAc, total Hull Area, ranges of δ13C and δ15N) and species packing (mean distance to centroid, nearest neighbor distance) also did not vary as a function of seepage activity or site. However, distinct isotopic signatures were observed among related, co-occurring species of gastropods and polychaetes, reflecting intense microbial resource partitioning. Overall, the substrate and nutritional heterogeneity introduced by authigenic seep carbonates act to promote diverse, uniquely adapted assemblages, even after seepage ceases. The macrofauna in these ecosystems remain largely overlooked in most surveys, but are major contributors to biodiversity of chemosynthetic ecosystems and the deep sea in general. PMID:26158723

Returning from the deep: Archean atmospheric fingerprints in modern hotspot lavas (Invited)

NASA Astrophysics Data System (ADS)

Jackson, M. G.; Cabral, R. A.; Rose-Koga, E. F.; Koga, K. T.; Whitehouse, M. J.; Antonelli, M. A.; Farquhar, J.; Day, J. M.; Hauri, E. H.

2013-12-01

Ocean plates transport surface materials, including oceanic crust and sediment, into the mantle at subduction zones. However, the fate of the subducted package--oceanic crust and sediment--in the mantle is poorly understood. A long-standing hypothesis maintains that subducted materials reside in the mantle for an extended, but unknown, period of time and are then recycled back to the Earth's surface in regions of buoyantly upwelling mantle and melted beneath hotspots. Sulfur isotopes provide an important new tool to evaluate the presence of ancient recycled materials in hotspot lavas. Widespread terrestrial mass independently fractionated sulfur (MIF-S) isotope signatures were generated exclusively through atmospheric photochemical reactions until ~2.45 Ga. In fact, the only significant reservoirs of MIF-S containing rocks documented so far are sediments and hydrothermal rocks older than ~2.45 Ga. Armed with this insight, we examined sulfur isotopes in olivine phenocrysts and olivine-hosted sulfides in lavas from the island of Mangaia, Cook Islands. Lavas from this location host unusually radiogenic Pb-isotopic compositions--referred to as a HIMU (high U/Pb) component--and this has been attributed to ancient recycled oceanic crust in the mantle source. In Cabral et al. (2013), we report MIF-S in olivine phenocrysts and olivine-hosted sulfides. The discovery of MIF-S isotopic signatures in young hotspot lavas appears to provide a "timestamp" and "signature" for preservation of subducted Archean surface materials in the mantle sourcing Mangaia lavas. We report new sulfur isotope data on olivine-hosted sulfides from the Mangaia lavas that reinforce our discovery of MIF-S anomalies reported in Cabral et al. (2013). We also report new sulfur isotopic data on Mangaia whole rock powders, and we find no evidence of MIF-S signatures. It is not yet clear why the individual Mangaia sulfides and the olivine separates have more extreme MIF-S than the whole rocks. We consider it likely that the MIF-S anomaly measured in the olivine separates was diminished relative to the olivine-hosted sulfides by incorporation of modern sulfur into the olivine separates by low-temperature processes operating on the rocks during the 20 Ma since eruption: The absence of a MIF-S anomaly in the whole rock that has olivine-hosted sulfides with MIF-S anomalies may be a result of near-complete replacement of the magmatic sulfur (with a MIF-S anomaly) with modern sulfur (with no MIF-S anomaly) during surficial weathering over 20 Ma. The sulfur in the olivine-hosted sulfides with the largest MIF-S anomalies represents a very small proportion of the sulfur in a bulk basaltic rock and therefore do not impart a clear MIF-S anomaly on the bulk rock analysis. Very few data are available to evaluate this hypothesis. Therefore, pairing sulfur isotope measurements with whole rocks, mineral separates and olivine-hosted sulfides with careful petrographic and electron probe analyses of the samples will be critical for evaluating the origin of the sulfides--primary magmatic or secondary--and the origin and distribution of the sulfur-isotopic signatures in OIB.

Update on NRF Measurements on ^237Np for National Security and Safeguards Applications

NASA Astrophysics Data System (ADS)

Angell, C. T.; Joshi, T.; Yee, R.; Swanberg, E.; Norman, E. B.; Kulp, W. D.; Warren, G.; Hicks, C. L., Jr.; Korbly, S.; Klimenko, A.; Wilson, C.; Bray, T. H.; Copping, R.; Shuh, D. K.

2010-11-01

Nuclear resonance fluorescence (NRF) uses γ rays to excite nuclear levels and measure their properties. This provides a unique isotopic signature, and can be used to identify and assay material. This is particularly important for applications that detect the smuggling of nuclear material or the diversion of fissile material for covert weapon programs, both of which present grave risks to world security. ^237Np presents significant safeguard challenges; it is fissile yet currently has fewer safeguard restrictions potentially making it an attractive material for covert weapon programs. This talk will present the final results of two measurements of NRF on ^237Np using a bremsstrahlung photon source. 15 NRF states have been identified between 1.5 and 2.5 MeV excitation energy.

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.

Characterizing the impact of diffusive and advective soil gas transport on the measurement and interpretation of the isotopic signal of soil respiration

Treesearch

Zachary E. Kayler; Elizabeth W. Sulzman; William D. Rugh; Alan C. Mix; Barbara J. Bond

2010-01-01

By measuring the isotopic signature of soil respiration, we seek to learn the isotopic composition of the carbon respired in the soil (δ13CR-S) so that we may draw inferences about ecosystem processes. Requisite to this goal is the need to understand how (δ13CR-S) is affected by...

Ages and Nd, Sr isotopic systematics in the Sierran foothills ophiolite belt, CA: the Smartville and Feather River complexes

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

Shaw, H.F.; Niemeyer, S.

1985-01-01

Sm-Nd dating has shown the Kings-Kaweah ophiolite to be approx. 480 My old. Its Nd, Sr, and Pb isotopic compositions require an unusually old depleted mantle source. Samples from the Smartville and Feather River complexes have been analyzed in a search for similar highly depleted, early Paleozoic ophiolites in the northern foothills ophiolite belt. Six whole rocks from Smartville, encompassing representative lithologies, plus plagioclase and pyroxene mineral separates define a 183 +/- 22 My Sm-Nd isochron. This age, interpreted as the igneous age, is older than, but within error of, approx. 160 My U-Pb ages previously obtained from plagiogranite zirconmore » analyses. One diabase with unusually high Rb/Sr yields a depleted mantle Sr model age of 200 +/- 25 My, consistent with the Sm-ND age. These compositions are clearly oceanic in character but do not discriminate among possible tectonic settings for the formation of the Smartville complex. Sm-Nd data for flaser gabbros and related rocks from Feather River scatter about an approx. 230 My errorchron with element of/sub Nd/(T) = +6.3 to +8.7. Initial /sup 87/Sr//sup 86/Sr ranges from 0.7028 to 0.7031. These results indicate a complex history with initial isotopic heterogeneities and/or disturbances of the isotopic systems. If primary, the element of/sub Nd/ (T) values are somewhat low, suggesting a possible arc origin for these rocks. Neither the Smartville nor Feather R. complexes appear to be related to the Kings-Kaweah ophiolite which, so far, is unique among foothill ophiolites in having an early Paleozoic age and a clear MORB, as opposed to arc or marginal basin, isotopic signature.« less

High-resolution (SIMS) versus bulk sulfur isotope patterns of pyrite in Proterozoic microbialites with diverse mat textures

NASA Astrophysics Data System (ADS)

Gomes, M. L.; Fike, D. A.; Bergmann, K.; Knoll, A. H.

2015-12-01

Sulfur (S) isotope signatures of sedimentary pyrite preserved in marine rocks provide a rich suite of information about changes in biogeochemical cycling associated with the evolution of microbial metabolisms and oxygenation of Earth surface environments. Conventionally, these S isotope records are based on bulk rock measurements. Yet, in modern microbial mat environments, S isotope compositions of sulfide can vary by up to 40‰ over a spatial range of ~ 1 mm. Similar ranges of S isotope variability have been found in Archean pyrite grains using both Secondary Ion Mass Spectrometry and other micro-analytical techniques. These micron-scale patterns have been linked to changes in rates of microbial sulfate reduction and/or sulfide oxidation, isotopic distillation of the sulfate reservoir due to microbial sulfate reduction, and post-depositional alteration. Fine-scale mapping of S isotope compositions of pyrite can thus be used to differentiate primary environmental signals from post-depositional overprinting - improving our understanding of both. Here, we examine micron-scale S isotope patterns of pyrite in microbialites from the Mesoproterozoic-Neoproterozoic Sukhaya Tunguska Formation and Neoproterozoic Draken Formation in order to explore S isotope variability associated with different mat textures and pyrite grain morphologies. A primary goal is to link modern observations of how sulfide spatial isotope distributions reflect active microbial communities present at given depths in the mats to ancient processes driving fine-sale pyrite variability in microbialites. We find large (up to 60‰) S isotope variability within a spatial range of less than 2.5cm. The micron-scale S isotope measurements converge around the S isotope composition of pyrite extracted from bulk samples of the same microbialites. These micron-scale pyrite S isotope patterns have the potential to reveal important information about ancient biogeochemical cycling in Proterozoic mat environments with implications for interpreting S isotope signatures from the geological record.

Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite

NASA Astrophysics Data System (ADS)

Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang

2014-05-01

Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

The two water worlds hypothesis: Addressing multiple working hypotheses and proposing a way forward

USDA-ARS?s Scientific Manuscript database

Recent studies using water isotopes have shown that trees and streams appear to return distinct water pools to the hydrosphere. Cryogenically extracted plant and soil water isotopic signatures diverge from the Meteoric Water Lines (MWL), suggesting that plants would preferentially use bound soil wat...

RIBBED MUSSEL NITROGEN ISOTOPE SIGNATURES REFLECT NITROGEN SOURCES IN COASTAL MARSHES

EPA Science Inventory

The stable nitrogen isotope ratio in tissue of the ribbed mussel (Geukensia demissa) was investigated as an indicator of the source of nitrogen inputs to coastal salt marshes. Initially, mussels were fed a diet of 15N-enriched algae in the laboratory to determine how the tissue n...

Comparing isotope signatures of prey fish: does gut removal affect δ13C or δ15N?

USGS Publications Warehouse

Chipps, Steven R.; Fincel, Mark J.; VanDeHey, Justin A.; Wuestewald, Andrew

2011-01-01

Stable isotope analysis is a quick and inexpensive method to monitor the effects of food web changes on aquatic communities. Traditionally, whole specimens have been used when determining isotope composition of prey fish or age-0 recreational fishes. However, gut contents of prey fish could potentially alter isotope composition of the specimen, especially when recent foraging has taken place or when the gut contains non-assimilated material that would normally pass through fishes undigested. To assess the impacts of gut content on prey fish isotope signatures, we examined the differences in isotopic variation of five prey fish species using whole fish, whole fish with the gut contents removed, and dorsal muscle only. We found significant differences in both δ15N and δ13C between the three tissue treatments. In most cases, muscle tissue was enriched compared to whole specimens or gut-removed specimens. Moreover, differences in mean δ15N within a species were up to 2‰ among treatments. This would result in a change of over half a trophic position (TP) based on a 3.4‰ increase per trophic level. However, there were no apparent relationships between tissue isotope values in fish with increased gut fullness (more prey tissue present). We suggest that muscle tissue should be used as the standard tissue for determining isotope composition of prey fish or age-0 recreational fishes, especially when determining enrichment for mixing models, calculating TP, or constructing aquatic food webs.

Isotopic analysis of individual refractory metal nuggets using atom probe tomography

NASA Astrophysics Data System (ADS)

Daly, L.; Bland, P.; Schaefer, B. F.; Saxey, D. W.; Reddy, S.; Fougerouse, D.; William, R. D. A.; Forman, L. V.; Trimby, P.; La Fontaine, A.; Yang, L.; Cairney, J.; Ringer, S.

2016-12-01

Sub-micrometre metallic alloys of the highly siderophile elements, known as refractory metal nuggets (RMNs), can be found in primitive carbonaceous chondrites. There has been some suggestion that these grains may have a pre-solar origin, however their <1 µm size has meant that isotopic analysis of individual grains has not previously been possible. Atom probe microscopy has sufficient spatial resolution to quantify the isotopic compositions, across the entire mass range, of small sample volumes (<0.02 µm3) with high sensitivity and precision. We present analyses of four individual RMNs from the same refractory inclusion within the ALH 77307 meteorite. The results indicate that these RMNs have significant isotopic deviations from solar relative isotope abundances and therefore preserve a pre-solar isotopic signature. All RMNs exhibit large p-process enrichments in 98Ru and depletions in s-process 186Os. Two RMNs have a similar isotopic signature, suggesting formation in the same stellar environment. This similarity between two RMNs indicates that there may be a significant contribution of material to our solar system from a single source. The other two RMNs are isotopically dissimilar. Finally, three of the RMNs plot on a 187Re -187Os isochron from which we can derive a galactic age of 12.5 Ga ±1.8. To the best of our knowledge this is the first direct determination of the age of the Milky Way through physical analysis of non-solar material.

Highly Sensitive Tunable Diode Laser Spectrometers for In Situ Planetary Exploration

NASA Technical Reports Server (NTRS)

Vasudev, Ram; Mansour, Kamjou; Webster, Christopher R.

2013-01-01

This paper describes highly sensitive tunable diode laser spectrometers suitable for in situ planetary exploration. The technology developed at JPL is based on wavelength modulated cavity enhanced absorption spectroscopy. It is capable of sensitively detecting chemical signatures of life through the abundance of biogenic molecules and their isotopic composition, and chemicals such as water necessary for habitats of life. The technology would be suitable for searching for biomarkers, extinct life, potential habitats of extant life, and signatures of ancient climates on Mars; and for detecting biomarkers, prebiotic chemicals and habitats of life in the outer Solar System. It would be useful for prospecting for water on the Moon and asteroids, and characterizing its isotopic composition. Deployment on the Moon could provide ground truth to the recent remote measurements and help to uncover precious records of the early bombardment history of the inner Solar System buried at the shadowed poles, and elucidate the mechanism for the generation of near-surface water in the illuminated regions. The technology would also be useful for detecting other volatile molecules in planetary atmospheres and subsurface reservoirs, isotopic characterization of planetary materials, and searching for signatures of extinct life preserved in solid matrices.

The origin of groundwater in Zhangye Basin, northwestern China, using isotopic signature

NASA Astrophysics Data System (ADS)

Chen, Jiansheng; Liu, Xiaoyan; Sun, Xiaoxu; Su, Zhiguo; Yong, Bin

2014-03-01

Zhangye Basin, in arid northwestern China, has recently been repeatedly flooded by rising groundwater. Isotope signatures of sampled waters gained insight into the recharge source of the groundwater. The summer Heihe River water and most of the spring water in Zhangye and Yongchang basins plotted above the global meteoric water line (GMWL) on the δ18O-δD plot. The spring water had R/Ra ratio >1, low TDS and high tritium, which indicates origin from Qilian Mountain glacier meltwater. The groundwater of Qilian Mountains was transported to the Hexi Corridor (in which Zhangye Basin is located) through underground fault zones. Additionally, some of the groundwater in the alluvial plain, and all spring water surrounding Zhangye Basin, plotted below the GMWL on the δ18O-δD plot along an evaporation line, and had R/Ra ratio < 1 and high TDS. It is proposed that the Tibetan rivers or lakes source the Hexi Corridor groundwater through either the NE-trending or NW-trending buried fault zones. The isotopic signatures presented as part of this study rule out the conventional viewpoint that groundwater of the Zhangye Basin was recharged by local precipitation and infiltration of Heihe River water on the alluvial plain.

Combinatorial effects on clumped isotopes and their significance in biogeochemistry

NASA Astrophysics Data System (ADS)

Yeung, Laurence Y.

2016-01-01

The arrangement of isotopes within a collection of molecules records their physical and chemical histories. Clumped-isotope analysis interrogates these arrangements, i.e., how often rare isotopes are bound together, which in many cases can be explained by equilibrium and/or kinetic isotope fractionation. However, purely combinatorial effects, rooted in the statistics of pairing atoms in a closed system, are also relevant, and not well understood. Here, I show that combinatorial isotope effects are most important when two identical atoms are neighbors on the same molecule (e.g., O2, N2, and D-D clumping in CH4). When the two halves of an atom pair are either assembled with different isotopic preferences or drawn from different reservoirs, combinatorial effects cause depletions in clumped-isotope abundance that are most likely between zero and -1‰, although they could potentially be -10‰ or larger for D-D pairs. These depletions are of similar magnitude, but of opposite sign, to low-temperature equilibrium clumped-isotope effects for many small molecules. Enzymatic isotope-pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect, although it is not limited to biological reactions. Chemical-kinetic isotope effects, which are related to a bond-forming transition state, arise independently and express second-order combinatorial effects related to the abundance of the rare isotope. Heteronuclear moeties (e.g., Csbnd O and Csbnd H), are insensitive to direct combinatorial influences, but secondary combinatorial influences are evident. In general, both combinatorial and chemical-kinetic factors are important for calculating and interpreting clumped-isotope signatures of kinetically controlled reactions. I apply this analytical framework to isotope-pairing reactions relevant to geochemical oxygen, carbon, and nitrogen cycling that may be influenced by combinatorial clumped-isotope effects. These isotopic signatures, manifest as either directly bound isotope ;clumps; or as features of a molecule's isotopic anatomy, are linked to molecular mechanisms and may eventually provide additional information about biogeochemical cycling on environmentally relevant spatial scales.

Kinetic control on Zn isotope signatures recorded in marine diatoms

NASA Astrophysics Data System (ADS)

Köbberich, Michael; Vance, Derek

2017-08-01

Marine diatoms dominate the oceanic cycle of the essential micronutrient zinc (Zn). The stable isotopes of zinc and other metals are increasingly used to understand trace metal micronutrient cycling in the oceans. One clear feature of the early isotope data is the heavy Zn isotope signature of the average oceanic dissolved pool relative to the inputs, potentially driven by uptake of light isotopes into phytoplankton cells and export to sediments. However, despite the fact that diatoms strip Zn from surface waters across the Antarctic polar front in the Southern Ocean, the local upper ocean is not isotopically heavy. Here we use culturing experiments to quantify the extent of Zn isotope fractionation by diatoms and to elucidate the mechanisms driving it. We have cultured two different open-ocean diatom species (T. oceanica and Chaetoceros sp.) in a series of experiments at constant medium Zn concentration but at bioavailable medium Fe ranging from limiting to replete. We find that T. oceanica can maintain high growth rates and Zn uptake rates over the full range of bioavailable iron (Fe) investigated, and that the Zn taken up has a δ66Zn that is unfractionated relative to that of the bioavailable free Zn in the medium. The studied representative of the genus Chaetoceros, on the other hand, shows more significantly reduced Zn uptake rates at low Fe and records more variable biomass δ66Zn signatures, of up to 0.85‰ heavier than the medium. We interpret the preferential uptake of heavy isotopes at extremely low Zn uptake rates as potentially due to either of the following two mechanisms. First, the release of extracellular polymeric substances (EPS), at low Fe levels, may preferentially scavenge heavy Zn isotopes. Second, the Zn uptake rate may be slow enough to establish pseudo-equilibrium conditions at the transporter site, with heavy Zn isotopes forming more stable surface complexes. Thus we find that, in our experiments, Fe-limitation exerts a key control that not only limits diatom growth, but also affects the Zn uptake physiology of diatoms. Uptake of heavy isotopes occurs under Fe-limiting conditions that drive extremely low Zn uptake rates. On the other hand, more rapid Zn uptake rates result in biomass that is indistinguishable from the external bioavailable free Zn pool. These experimental results can, in principle, explain the range of Zn isotopic compositions found in the real surface ocean, given the geographically variable interplay between Fe-limitation, Zn uptake rates, and the degree of organic complexation of oceanic Zn.

Signatures of Extended Storage of Used Nuclear Fuel in Casks

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

Rauch, Eric Benton

2016-09-28

As the amount of used nuclear fuel continues to grow, more and more used nuclear fuel will be transferred to storage casks. A consolidated storage facility is currently in the planning stages for storing these casks, where at least 10,000 MTHM of fuel will be stored. This site will have potentially thousands of casks once it is operational. A facility this large presents new safeguards and nuclear material accounting concerns. A new signature based on the distribution of neutron sources and multiplication within casks was part of the Department of Energy Office of Nuclear Energy’s Material Protection, Account and Controlmore » Technologies (MPACT) campaign. Under this project we looked at fingerprinting each cask's neutron signature. Each cask has a unique set of fuel, with a unique spread of initial enrichment, burnup, cooling time, and power history. The unique set of fuel creates a unique signature of neutron intensity based on the arrangement of the assemblies. The unique arrangement of neutron sources and multiplication produces a reliable and unique identification of the cask that has been shown to be relatively constant over long time periods. The work presented here could be used to restore from a loss of continuity of knowledge at the storage site. This presentation will show the steps used to simulate and form this signature from the start of the effort through its conclusion in September 2016.« less

Astrochronology of the Late Turonian: implications for the behavior of the carbon cycle at the demise of peak greenhouse

NASA Astrophysics Data System (ADS)

Laurin, Jiří; Čech, Stanislav; Uličný, David; Štaffen, Zdeněk; Svobodová, Marcela

2014-05-01

A series of prominent carbon-cycle perturbations, indicated by carbon-isotope excursions of up to 2‰, marked climatic and oceanographic changes that followed the peak mid-Cretaceous greenhouse. The nature and forcing mechanisms of these changes remain poorly understood, partly due to the lack of a detailed temporal control in this interval. Here we present an orbitally calibrated time scale, which is based on hemipelagic rhythmites in the Bohemian Cretaceous Basin, and which can be linked to the established chronostratigraphic framework using inoceramid biostratigraphy and carbon-isotope signature. In the new age model, the Late Turonian, defined by the first occurrence of I. perplexus below and the first occurrence of C. deformis erectus above, spans 1.56(±0.07) Myr. When anchored to the newly refined age of the Turonian-Coniacian boundary (Sageman et al., in press), the onset of the Late Turonian is 91.31(±0.45) Ma. Inoceramid zones I. perplexus and M. scupini span 0.76(±0.05) Myr and 0.80(±0.05) Myr, respectively. A time-domain record of carbon-isotope variations was obtained by pinning published δ13Ccarb data to the orbital time scale using 9 biostratigraphic and carbon-isotope markers. The timing of major carbon-isotope excursions suggests a link to 405-kyr eccentricity changes and, in the early Late Turonian, to ˜100 kyr eccentricity variations. However, over 80% of the variance in the Late Turonian δ13C occurs at longer (million-year) scales. The key features of the δ13Ccarb signature, including the amplified long-term variance, can be reproduced with simple models of orbitally driven isotopic mass balance. At a constant carbon-isotope fractionation, the best fit to the δ13Ccarb signature is obtained with enhanced organic burial at high eccentricity (in accordance with monsoonal forcing of organic accumulation in the low-latitude Atlantic and/or buildup of low-latitude, terrestrial carbon reservoirs). Alternative solutions should consider changing carbon-isotope fractionation due to pCO2 and/or nutrient-flux changes.

Multiple sources supply eolian mineral dust to the Atlantic sector of coastal Antarctica: Evidence from recent snow layers at the top of Berkner Island ice sheet

NASA Astrophysics Data System (ADS)

Bory, Aloys; Wolff, Eric; Mulvaney, Robert; Jagoutz, Emil; Wegner, Anna; Ruth, Urs; Elderfield, Harry

2010-03-01

The Sr and Nd isotopic composition of dust extracted from recent snow layers at the top of Berkner Island ice sheet (located within the Filchner-Ronne Ice Shelf at the southern end of the Weddell Sea) enables us, for the first time, to document dust provenance in Antarctica outside the East Antarctic Plateau (EAP) where all previous studies based on isotopic fingerprinting were carried out. Berkner dust displays an overall crust-like isotopic signature, characterized by more radiogenic 87Sr/ 86Sr and much less radiogenic 143Nd/ 144Nd compared to dust deposited on the EAP during glacial periods. Differences with EAP interglacial dust are not as marked but still significant, indicating that present-day Berkner dust provenance is distinct, at least to some extent, from that of the dust reaching the EAP. The fourteen snow-pit sub-seasonal samples that were obtained span a two-year period (2002-2003) and their dust Sr and Nd isotopic composition reveals that multiple sources are at play over a yearly time period. Southern South America, Patagonia in particular, likely accounts for part of the observed spring/summer dust deposition maxima, when isotopic composition is shifted towards "younger" isotopic signatures. In the spring, possible additional inputs from Australian sources would also be supported by the data. Most of the year, however, the measured isotopic signatures would be best explained by a sustained background supply from putative local sources in East Antarctica, which carry old-crust-like isotopic fingerprints. Whether the restricted East Antarctic ice-free areas produce sufficient eolian material has yet to be substantiated however. The fact that large (> 5 μm) particles represent a significant fraction of the samples throughout the entire time-series supports scenarios that involve contributions from proximal sources, either in Patagonia and/or Antarctica (possibly including snow-free areas in the Antarctic Peninsula and other areas as well). This also indicates that additional dust transport, which does not reach the EAP, must occur at low-tropospheric levels to this coastal sector of Antarctica.

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.

Stable isotopes of Hawaiian spiders reflect substrate properties along a chronosequence

PubMed Central

Dawson, Todd E.; Gillespie, Rosemary G.

2018-01-01

The Hawaiian Islands offer a unique opportunity to test how changes in the properties of an isolated ecosystem are propagated through the organisms that occur within that ecosystem. The age-structured arrangement of volcanic-derived substrates follows a regular progression over space and, by inference, time. We test how well documented successional changes in soil chemistry and associated vegetation are reflected in organisms at higher trophic levels—specifically, predatory arthropods (spiders)—across a range of functional groups. We focus on three separate spider lineages: one that builds capture webs, one that hunts actively, and one that specializes on eating other spiders. We analyze spiders from three sites across the Hawaiian chronosequence with substrate ages ranging from 200 to 20,000 years. To measure the extent to which chemical signatures of terrestrial substrates are propagated through higher trophic levels, we use standard stable isotope analyses of nitrogen and carbon, with plant leaves included as a baseline. The target taxa show the expected shift in isotope ratios of δ15N with trophic level, from plants to cursorial spiders to web-builders to spider eaters. Remarkably, organisms at all trophic levels also precisely reflect the successional changes in the soil stoichiometry of the island chronosequence, demonstrating how the biogeochemistry of the entire food web is determined by ecosystem succession of the substrates on which the organisms have evolved. PMID:29576984

Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

USGS Publications Warehouse

Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.

2013-01-01

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

Chemical and Physical Signatures for Microbial Forensics

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

Cliff, John B.; Kreuzer, Helen W.; Ehrhardt, Christopher J.

Chemical and physical signatures for microbial forensics John Cliff and Helen Kreuzer-Martin, eds. Humana Press Chapter 1. Introduction: Review of history and statement of need. Randy Murch, Virginia Tech Chapter 2. The Microbe: Structure, morphology, and physiology of the microbe as they relate to potential signatures of growth conditions. Joany Jackman, Johns Hopkins University Chapter 3. Science for Forensics: Special considerations for the forensic arena - quality control, sample integrity, etc. Mark Wilson (retired FBI): Western Carolina University Chapter 4. Physical signatures: Light and electron microscopy, atomic force microscopy, gravimetry etc. Joseph Michael, Sandia National Laboratory Chapter 5. Lipids: FAME,more » PLFA, steroids, LPS, etc. James Robertson, Federal Bureau of Investigation Chapter 6. Carbohydrates: Cell wall components, cytoplasm components, methods Alvin Fox, University of South Carolina School of Medicine David Wunschel, Pacific Northwest National Laboratory Chapter 7. Peptides: Peptides, proteins, lipoproteins David Wunschel, Pacific Northwest National Laboratory Chapter 8. Elemental content: CNOHPS (treated in passing), metals, prospective cell types John Cliff, International Atomic Energy Agency Chapter 9. Isotopic signatures: Stable isotopes C,N,H,O,S, 14C dating, potential for heavy elements. Helen Kreuzer-Martin, Pacific Northwest National Laboratory Michaele Kashgarian, Lawrence Livermore National Laboratory Chapter 10. Extracellular signatures: Cellular debris, heme, agar, headspace, spent media, etc Karen Wahl, Pacific Northwest National Laboratory Chapter 11. Data Reduction and Integrated Microbial Forensics: Statistical concepts, parametric and multivariate statistics, integrating signatures Kristin Jarman, Pacific Northwest National Laboratory« less

Investigation of triaxiality in 54122-128Xe isotopes in the framework of sdg-IBM

NASA Astrophysics Data System (ADS)

Jafarizadeh, M. A.; Ranjbar, Z.; Fouladi, N.; Ghapanvari, M.

In this paper, a transitional interacting boson model (IBM) Hamiltonian in both sd-(IBM) and sdg-IBM versions based on affine SU(1, 1) Lie algebra is employed to describe deviations from the gamma-unstable nature of Hamiltonian along the chain of Xe isotopes. sdg-IBM Hamiltonian proposed a better interpretation of this deviation which cannot be explained in the sd-boson models. The nuclei studied have well-known γ bands close to the γ-unstable limit. The energy levels, B(E2) transition rates and signature splitting of the γ -vibrational band are calculated via the affine SU(1,1) Lie algebra. An acceptable degree of agreement was achieved based on this procedure. It is shown that in these isotopes the signature splitting is better reproduced by the inclusion of sdg-IBM. In none of them, any evidence for a stable, triaxial ground state shape is found.

Active Microbial Methane Production and Organic Matter Degradation in a Devonian Black Shale

NASA Astrophysics Data System (ADS)

Martini, A. M.; Petsch, S. T.; Nuesslein, K.; McIntosh, J. C.

2003-12-01

Microorganisms employ many novel strategies to derive energy and obtain nutrients, and in doing so alter the chemistry of their environments in ways that are significant for formation and transformation of geologic materials. One such strategy is natural gas generation in sedimentary basins. Previous research has shown that stable isotopic signatures of CH4, CO2 and H2O in formation waters of gas-producing black shales indicate a microbial origin for several economically viable natural gas reserves. However, these signatures leave several intriguing issues unaddressed, including the identity of the organisms and their metabolic roles and impacts on mineral, isotopic and biomarker signatures. We hypothesize that the extreme reducing conditions required for sedimentary basin methanogenesis are simply the end product of a cascade of microbial processes, initiated by anaerobic respiration of shale organic matter through NO3, SO4 and/or Fe(III) reduction, secondary processing of anaerobe biomass by fermentative organisms yielding volatile fatty acids and H2, and ultimately CO2 reduction and/or acetate fermentation to produce CH4. This research holds importance for the several aspects of the geochemical carbon cycle. It describes anaerobic hydrocarbon degradation leading to methanogenesis in a sedimentary basin; in many instances this activity has generated economically viable reserves of natural gas. It also provides a benchmark detailing how post-depositional microbial activity in rocks may confound and overprint ancient biosignatures. Interpretation of past environmental conditions depends on molecular and isotopic signatures contained in ancient sedimentary rocks, separated from signatures of metabolically similar modern microbiota living in sedimentary basins. In addition, this research sheds light on an unrecognized and thus unconstrained source of reduced gases to Earth's atmosphere, important for understanding the rates and controls on carbon cycling through geologic time.

Global Inventory of Gas Geochemistry Data from Fossil Fuel, Microbial and Burning Sources, version 2017

NASA Astrophysics Data System (ADS)

Sherwood, Owen A.; Schwietzke, Stefan; Arling, Victoria A.; Etiope, Giuseppe

2017-08-01

The concentration of atmospheric methane (CH4) has more than doubled over the industrial era. To help constrain global and regional CH4 budgets, inverse (top-down) models incorporate data on the concentration and stable carbon (δ13C) and hydrogen (δ2H) isotopic ratios of atmospheric CH4. These models depend on accurate δ13C and δ2H end-member source signatures for each of the main emissions categories. Compared with meticulous measurement and calibration of isotopic CH4 in the atmosphere, there has been relatively less effort to characterize globally representative isotopic source signatures, particularly for fossil fuel sources. Most global CH4 budget models have so far relied on outdated source signature values derived from globally nonrepresentative data. To correct this deficiency, we present a comprehensive, globally representative end-member database of the δ13C and δ2H of CH4 from fossil fuel (conventional natural gas, shale gas, and coal), modern microbial (wetlands, rice paddies, ruminants, termites, and landfills and/or waste) and biomass burning sources. Gas molecular compositional data for fossil fuel categories are also included with the database. The database comprises 10 706 samples (8734 fossil fuel, 1972 non-fossil) from 190 published references. Mean (unweighted) δ13C signatures for fossil fuel CH4 are significantly lighter than values commonly used in CH4 budget models, thus highlighting potential underestimation of fossil fuel CH4 emissions in previous CH4 budget models. This living database will be updated every 2-3 years to provide the atmospheric modeling community with the most complete CH4 source signature data possible. Database digital object identifier (DOI): https://doi.org/10.15138/G3201T.

Visualization of Radioisotope Detectability Over Time.

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

Huynh, Brady

A radioactive isotope is an atom that has an unstable nucleus. The isotope can undergo radioactive decay, the process in which excessive nuclear energy is emitted from the nucleus in many different forms, such as gamma radiation, alpha particles, or beta particles. The important thing to note is that these emissions act as a signature for the isotope. Each radioisotope has a particular emission spectrum, emitting radiation at different energies and at different rates.

21 CFR 11.100 - General requirements.

Code of Federal Regulations, 2010 CFR

2010-04-01

... RECORDS; ELECTRONIC SIGNATURES Electronic Signatures § 11.100 General requirements. (a) Each electronic signature shall be unique to one individual and shall not be reused by, or reassigned to, anyone else. (b... signature, or any element of such electronic signature, the organization shall verify the identity of the...

Major Sources of Organic Matter in a Complex Coral Reef Lagoon: Identification from Isotopic Signatures (δ13C and δ15N)

PubMed Central

Briand, Marine J.; Bonnet, Xavier; Goiran, Claire; Guillou, Gaël; Letourneur, Yves

2015-01-01

A wide investigation was conducted into the main organic matter (OM) sources supporting coral reef trophic networks in the lagoon of New Caledonia. Sampling included different reef locations (fringing, intermediate and barrier reef), different associated ecosystems (mangroves and seagrass beds) and rivers. In total, 30 taxa of macrophytes, plus pools of particulate and sedimentary OM (POM and SOM) were sampled. Isotopic signatures (C and N) of each OM sources was characterized and the composition of OM pools assessed. In addition, spatial and seasonal variations of reef OM sources were examined. Mangroves isotopic signatures were the most C-depleted (-30.17 ± 0.41 ‰) and seagrass signatures were the most C-enriched (-4.36 ± 0.72 ‰). Trichodesmium spp. had the most N-depleted signatures (-0.14 ± 0.03 ‰) whereas mangroves had the most N-enriched signatures (6.47 ± 0.41 ‰). The composition of POM and SOM varied along a coast-to-barrier reef gradient. River POM and marine POM contributed equally to coastal POM, whereas marine POM represented 90% of the POM on barrier reefs, compared to 10% river POM. The relative importance of river POM, marine POM and mangroves to the SOM pool decreased from fringing to barrier reefs. Conversely, the relative importance of seagrass, Trichodesmium spp. and macroalgae increased along this gradient. Overall, spatial fluctuations in POM and SOM were much greater than in primary producers. Seasonal fluctuations were low for all OM sources. Our results demonstrated that a large variety of OM sources sustain coral reefs, varying in their origin, composition and role and suggest that δ13C was a more useful fingerprint than δ15N in this endeavour. This study also suggested substantial OM exchanges and trophic connections between coral reefs and surrounding ecosystems. Finally, the importance of accounting for environmental characteristics at small temporal and spatial scales before drawing general patterns is highlighted. PMID:26134985

Isotope evolution and contribution to geochemical investigations in aquifer storage and recovery: a case study using reclaimed water at Bolivar, South Australia

NASA Astrophysics Data System (ADS)

Le Gal La Salle, C.; Vanderzalm, J.; Hutson, J.; Dillon, P.; Pavelic, P.; Martin, R.

2005-11-01

Aquifer storage and recovery (ASR) is an important resource management tool whereby water from an available source is stored in a suitable aquifer for later use in periods of higher demand. Important issues in ASR include maintaining the injection rate and recovering water of suitable quality. Both of these depend on subsurface biogeochemical processes. This paper investigates the use of deuterium, 18O, 13C, 14C and 34S in understanding the reactions induced by reclaimed water injection in a carbonate aquifer at Bolivar, South Australia. Additionally, the injection scheme provides a natural laboratory to observe the process of carbon isotope exchange. The injectant deuterium (-6.4 +/- 2.9 versus Vienna standard mean ocean water (V-SMOW)) and 18O (-0.9 +/- 0.5 V-SMOW) signature is more enriched and variable than the native groundwater signature of -26 +/- 1 and -4.4 +/- 0.1 respectively. The variability of the injectant signature is maintained with injectant migration and is useful in constraining the portion of the injected end-member reaching observation wells. Effluent treatment results in total dissolved inorganic carbon (TDIC) enriched in 13C (-3.3 +/- 2.5 versus Pee Dee belemnite) and modern carbon (100 +/- 7 per cent modern carbon (pmC)), which is distinct from the native groundwater comparatively depleted in 13C (-11 +/- 1) and 14C (5.6 +/- 2.1 pmC). The carbon isotopic signature in groundwater 4 m from the ASR well is dominated by the injectant signature modified by some organic matter oxidation and calcite dissolution. However, with further migration to the 50 m radius, both 13C and ¹⁴C signatures are dominated by isotopic exchange with the matrix surface (initially in equilibrium with the ambient groundwater) and little overall dissolution. During storage, biogeochemical processes, including sulphate reduction and methanogenesis, are dominant near the ASR well. These are indicated by a sulphate decline of up to 1.5 mmol l^-1 with around 12 enrichment in the residual sulphate (versus Canyon Diablo troilite) and the addition of TDIC enriched in ¹³C, while maintaining a modern ¹⁴C activity. Copyright

Time for cotton to uptake water of a known isotopic signature as measured in leaf petioles

USDA-ARS?s Scientific Manuscript database

While stable isotopes of water have been used to study nutrient cycling, nitrogen fixation and other environmental studies they generally have not been used to examine shorter, more transient events, such as disposition of rainfall into soil water evaporation (E) and transpiration (T). With the deve...

Analysis of anaerobic BTX biodegradation in a subarctic aquifer using isotopes and benzylsuccinates.

PubMed

McKelvie, Jennifer R; Lindstrom, Jon E; Beller, Harry R; Richmond, Sharon A; Sherwood Lollar, Barbara

2005-12-01

In situ biodegradation of benzene, toluene, and xylenes in a petroleum hydrocarbon contaminated aquifer near Fairbanks, Alaska was assessed using carbon and hydrogen compound specific isotope analysis (CSIA) of benzene and toluene and analysis of signature metabolites for toluene (benzylsuccinate) and xylenes (methylbenzylsuccinates). Carbon and hydrogen isotope ratios of benzene were between -25.9 per thousand and -26.8 per thousand for delta13C and -119 per thousand and -136 per thousand for delta2H, suggesting that biodegradation of benzene is unlikely at this site. However, biodegradation of both xylenes and toluene were documented in this subarctic aquifer. Biodegradation of xylenes was indicated by the presence of methylbenzylsuccinates with concentrations of 17-50 microg/L in three wells. Anaerobic toluene biodegradation was also indicated by benzylsuccinate concentrations of 10-49 microg/L in the three wells with the highest toluene concentrations (1500-5000 microg/L toluene). Since benzylsuccinate typically accounts for a very small fraction of the toluene present in groundwater (generally <1 mol%), the signature metabolite approach works best at higher toluene concentrations when it is not constrained by detection limits. In wells with lower toluene concentrations (410-640 microg/L), carbon and hydrogen isotopic values were enriched by up to approximately 2 per thousand for delta13C and approximately 70 per thousand for delta2H. This evidence of isotopic fractionation verifies the effects of biodegradation in these low concentration wells where metabolites may already be below detection limits. The combined use of signature metabolite and CSIA data is particularly valuable given the challenge of verifying biodegradation in subarctic environments where degradation rates are typically much slower than in temperate environments.

Oceans Apart: Using Stable Isotopes to Assess the Role of Fog in Two Semi-Arid Island Ecosystems

NASA Astrophysics Data System (ADS)

Schmitt, S.; Riveros-Iregui, D.; Hu, J.

2017-12-01

Fog is a significant hydrologic input in many tropical island systems, and is a water source particularly susceptible to the effects of global climate change. To better understand the role of fog as a hydrological input in two oceanic islands, we address two principal questions: 1) Do seasonal or extreme precipitation events lead to distinguishable differences in stable isotopic signatures of water inputs within and between sites and islands? 2) Does microclimatic zonation lead to distinguishable differences in isotopic signatures of meteoric inputs between different sites on a given island? To perform this analysis, meteoric water samples (fog, rain and throughfall) were collected over three sites (one windward and two leeward) and three field seasons in San Cristobal, Galapagos to ascertain the isotopic signature of each water balance input during different times of year. An additional field season of data in Ascension Island, UK, was also used to perform a comparative analysis between islands. A stable isotope mixing model was used to determine the relative proportion of surface water and groundwater that is composed of fog, and to demonstrate spatiotemporal patterns of recharge dynamics in each island system. Local meteoric water lines were generated for each site and over each field season to determine the source of hydrologic inputs (trade wind-generated orographic precipitation versus storm precipitation) and the role of locally recycled water in the overall water balance of each site. Our results will approximate potential changes in water inputs to San Cristobal and Ascension, respectively, that could be impacted by an increase in cloud base height or a change in weather patterns brought about by climate change.

Compound-specific nitrogen and carbon isotope analysis of nitroaromatic compounds in aqueous samples using solid-phase microextraction coupled to GC/IRMS.

PubMed

Berg, Michael; Bolotin, Jakov; Hofstetter, Thomas B

2007-03-15

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry was used to determine the delta15N and delta13C signatures of selected nitroaromatic contaminants such as the explosive 2,4,6-trinitrotoluene (TNT) for derivation of isotopic enrichment factors of contaminant transformation. Parameters for efficient extraction of nitroaromatic compounds (NACs) and substituted anilines from water samples were evaluated by SPME-GC/MS. delta13C signatures determined by SPME-GC/IRMS and elemental analyzer IRMS (EA-IRMS) were in good agreement, generally within +/-0.7 per thousand, except for 2,4-dinitrotoluene (2,4-DNT) and TNT, which showed slight deviations (<1.3 per thousand). Limits of detection (LODs) for delta13C analysis by SPME-GC/IRMS were between 73 and 780 microg L-1 and correlated with the extraction efficiencies of the compounds determined by SPME-GC/MS. Nitrogen isotope measurements by SPME-GC/IRMS were of similar precision (standard deviations <0.8 per thousand) for all NACs except for TNT. delta15N signatures matched the reference values obtained by EA-IRMS within +/-1.3 per thousand (+2.5 per thousand for TNT), but no systematic trend was found for the deviations. LODs of delta15N measurements ranged from 1.6 to 9.6 mg L-1 for nitrotoluenes, chlorinated NACs and DNTs (22 mg L-1 for TNT). The SPME-GC/IRMS method is well suited for the determination of isotopic enrichment factors of various NAC transformation processes and provides so far unexplored possibilities to elucidate behavior and degradation mechanisms of nitroaromatic contaminants in soils and groundwaters.

Cellulose and Lignin Carbon Isotope Signatures in Sphagnum Moss Reveal Complementary Environmental Properties

NASA Astrophysics Data System (ADS)

Loisel, J.; Nichols, J. E.; Kaiser, K.; Beilman, D. W.; Yu, Z.

2016-12-01

The carbon isotope signature (δ13C) of Sphagnum moss is increasingly used as a proxy for past surface wetness in peatlands. However, conflicting interpretations of these carbon isotope records have recently been published. While the water film hypothesis suggests that the presence of a thick (thin) water film around hollow (hummock) mosses leads to less (more) negative δ13C values, the carbon source hypothesis poses that a significant (insignificant) amount of CH4 assimilation by hollow (hummock) mosses leads to more (less) negative δ13C values. To evaluate these competing mechanisms and their impact on moss δ13C, we gathered 30 moss samples from 6 peatlands in southern Patagonia. Samples were collected along a strong hydrological gradient, from very dry hummocks (80 cm above water table depth) to submerged hollows (5 cm below water surface). These peat bogs have the advantage of being colonized by a single cosmopolitan moss species, Sphagnum magellanicum, limiting potential biases introduced by species-specific carbon discrimination. We measured δ13C from stem cellulose and leaf waxes on the same samples to quantify compound-specific carbon signatures. We found that stem cellulose and leaf-wax lipids were both strongly negatively correlated with moss water content, suggesting a primary role of water film thickness on carbon assimilation. In addition, isotopic fractionation during wax synthesis was greater than for cellulose. This offset decreases as conditions get drier, due to (i) a more effective carbon assimilation, or (ii) CH4 uptake through symbiosis with methanotrophic bacteria within the leaves of wet mosses. Biochemical analysis (carbohydrates, amino acids, hydrophenols, cutin acids) of surface moss are currently being conducted to characterize moss carbon allocation under different hydrological conditions. Overall, this modern calibration work should be of use for interpreting carbon isotope records from peatlands.

Holocene provenance shift of suspended particulate matter in the Amazon River basin

NASA Astrophysics Data System (ADS)

Höppner, Natalie; Lucassen, Friedrich; Chiessi, Cristiano M.; Sawakuchi, André O.; Kasemann, Simone A.

2018-06-01

The strontium (Sr), neodymium (Nd) and lead (Pb) isotope signatures of suspended particulate matter (SPM) in rivers reflect the radiogenic isotope signatures of the rivers' drainage basin. These signatures are not significantly affected by weathering, transport or depositional cycles, but document the sedimentary contributions of the respective sources. We report new Sr, Nd and Pb isotope ratios and element concentrations of modern SPM from the Brazilian Amazon River basin and document the past evolution of the basin by analyzing radiogenic isotopes of a marine sediment core from the slope off French Guiana archiving the last 40 kyr of Amazon River SPM, and the Holocene section of sediment cores raised between the Amazon River mouth and the slope off French Guiana. The composition of modern SPM confirms two main source areas, the Andes and the cratonic Shield. In the marine sediment core notable changes occurred during the second phase of Heinrich Stadial 1 (i.e. increased proportion of Shield rivers SPM) and during the last deglaciation (i.e. increased proportion of Madeira River SPM) together with elsewhere constant source contributions. Furthermore, we report a prominent offset in Sr and Nd isotopic composition between the average core value (εNd: -11.7 ± 0.9 (2SD), 87Sr/86Sr: 0.7229 ± 0.0016 (2SD)) and the average modern Amazon River SPM signal (εNd: -10.5 ± 0.5 (2SD), 87Sr/86Sr: 0.7213 ± 0.0036 (2SD)). We suggest that a permanent change in the Amazon River basin sediment supply during the late Holocene to a more Andean dominated SPM was responsible for the offset.

Fractionation of metal stable isotopes by higher plants

USGS Publications Warehouse

Von Blanckenburg, F.; Von Wiren, N.; Guelke, M.; Weiss, D.J.; Bullen, T.D.

2009-01-01

Higher plants induce chemical reactions in the rhizosphere, facilitating metal uptake by roots. Fractionation of the isotopes in nutrients such as calcium, iron, magnesium, and zinc produces a stable isotope composition in the plants that generally differs from that of the growth medium. Isotope fractionation also occurs during transport of the metals within most plants, but its extent depends on plant species and on the metal, in particular, on the metal's redox state and what ligand it is bound to. The metal stable isotope variations observed in plants create an isotope signature of life at the Earth's surface, contributing substantially to our understanding of metal cycling processes in the environment and in individual organisms.

Uranium isotopes fingerprint biotic reduction.

PubMed

Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; Monga, Nikhil; Romaniello, Stephen J; Weyer, Stefan; Bernier-Latmani, Rizlan

2015-05-05

Knowledge of paleo-redox conditions in the Earth's history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth's crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium.

Principles and limitations of stable isotopes in differentiating organic and conventional foodstuffs: 1. Plant products.

PubMed

Inácio, Caio Teves; Chalk, Phillip Michael; Magalhães, Alberto M T

2015-01-01

Among the lighter elements having two or more stable isotopes (H, C, N, O, S), δ(15)N appears to be the most promising isotopic marker to differentiate plant products from conventional and organic farms. Organic plant products vary within a range of δ(15)N values of +0.3 to +14.6%, while conventional plant products range from negative to positive values, i.e. -4.0 to +8.7%. The main factors affecting δ(15)N signatures of plants are N fertilizers, biological N2 fixation, plant organs and plant age. Correlations between mode of production and δ(13)C (except greenhouse tomatoes warmed with natural gas) or δ(34)S signatures have not been established, and δ(2)H and δ(18)O are unsuitable markers due to the overriding effect of climate on the isotopic composition of plant-available water. Because there is potential overlap between the δ(15)N signatures of organic and conventionally produced plant products, δ(15)N has seldom been used successfully as the sole criterion for differentiation, but when combined with complementary analytical techniques and appropriate statistical tools, the probability of a correct identification increases. The use of organic fertilizers by conventional farmers or the marketing of organic produce as conventional due to market pressures are additional factors confounding correct identification. The robustness of using δ(15)N to differentiate mode of production will depend on the establishment of databases that have been verified for individual plant products.

Ubiquitous tar balls with a California-source signature on the shorelines of Prince William Sound, Alaska

USGS Publications Warehouse

Kvenvolden, K.A.; Hostettler, F.D.; Carlson, P.R.; Rapp, J.B.; Threlkeld, C.N.; Warden, A.

1995-01-01

Although the shorelines of Prince William Sound still bear traces of the 1989 Exxon Valdez oil spill, most of the flattened tar balls that can be found today on these shorelines are not residues of Exxon Valdez oil. Instead, the carbon-isotopic and hydrocarbon-biomarker signatures of 61 tar ball samples, collected from shorelines throughout the northern and western parts of the sound, are all remarkably similar and have characteristics consistent with those of oil products that originated from the Monterey Formation source rocks of California. The carbon-isotopic compositions of the tar balls are all closely grouped (??13CPDB = -23.7 ?? 0.2???), within the range found in crude oils from those rocks, but are distinct from isotopic compositions of 28 samples of residues from the Exxon Valdez oil spill (??13CPDB = -29.4 ?? 0.1???). Likewise, values for selected biomarker ratios in the tar balls are all similar but distinct from values of residues from the 1989 oil spill. Carbon-isotopic and biomarker signatures generally relate the tar balls to oil products used in Alaska before ???1970 for construction and pavements. How these tar balls with such similar geochemical characteristics became so widely dispersed throughout the northern and western parts of the sound is not known with certainty, but the great 1964 Alaska earthquake was undoubtedly an important trigger, causing spills from ruptured storage facilities of California-sourced asphalt and fuel oil into Prince William Sound.

Isotopic links between atmospheric chemistry and the deep sulphur cycle on Mars.

PubMed

Franz, Heather B; Kim, Sang-Tae; Farquhar, James; Day, James M D; Economos, Rita C; McKeegan, Kevin D; Schmitt, Axel K; Irving, Anthony J; Hoek, Joost; Dottin, James

2014-04-17

The geochemistry of Martian meteorites provides a wealth of information about the solid planet and the surface and atmospheric processes that occurred on Mars. The degree to which Martian magmas may have assimilated crustal material, thus altering the geochemical signatures acquired from their mantle sources, is unclear. This issue features prominently in efforts to understand whether the source of light rare-earth elements in enriched shergottites lies in crustal material incorporated into melts or in mixing between enriched and depleted mantle reservoirs. Sulphur isotope systematics offer insight into some aspects of crustal assimilation. The presence of igneous sulphides in Martian meteorites with sulphur isotope signatures indicative of mass-independent fractionation suggests the assimilation of sulphur both during passage of magmas through the crust of Mars and at sites of emplacement. Here we report isotopic analyses of 40 Martian meteorites that represent more than half of the distinct known Martian meteorites, including 30 shergottites (28 plus 2 pairs, where pairs are separate fragments of a single meteorite), 8 nakhlites (5 plus 3 pairs), Allan Hills 84001 and Chassigny. Our data provide strong evidence that assimilation of sulphur into Martian magmas was a common occurrence throughout much of the planet's history. The signature of mass-independent fractionation observed also indicates that the atmospheric imprint of photochemical processing preserved in Martian meteoritic sulphide and sulphate is distinct from that observed in terrestrial analogues, suggesting fundamental differences between the dominant sulphur chemistry in the atmosphere of Mars and that in the atmosphere of Earth.

Evaluation of 4 years of continuous δ13C(CO2) data using a moving Keeling plot method

NASA Astrophysics Data System (ADS)

Vardag, Sanam Noreen; Hammer, Samuel; Levin, Ingeborg

2016-07-01

Different carbon dioxide (CO2) emitters can be distinguished by their carbon isotope ratios. Therefore measurements of atmospheric δ13C(CO2) and CO2 concentration contain information on the CO2 source mix in the catchment area of an atmospheric measurement site. This information may be illustratively presented as the mean isotopic source signature. Recently an increasing number of continuous measurements of δ13C(CO2) and CO2 have become available, opening the door to the quantification of CO2 shares from different sources at high temporal resolution. Here, we present a method to compute the CO2 source signature (δS) continuously and evaluate our result using model data from the Stochastic Time-Inverted Lagrangian Transport model. Only when we restrict the analysis to situations which fulfill the basic assumptions of the Keeling plot method does our approach provide correct results with minimal biases in δS. On average, this bias is 0.2 ‰ with an interquartile range of about 1.2 ‰ for hourly model data. As a consequence of applying the required strict filter criteria, 85 % of the data points - mainly daytime values - need to be discarded. Applying the method to a 4-year dataset of CO2 and δ13C(CO2) measured in Heidelberg, Germany, yields a distinct seasonal cycle of δS. Disentangling this seasonal source signature into shares of source components is, however, only possible if the isotopic end members of these sources - i.e., the biosphere, δbio, and the fuel mix, δF - are known. From the mean source signature record in 2012, δbio could be reliably estimated only for summer to (-25.0 ± 1.0) ‰ and δF only for winter to (-32.5 ± 2.5) ‰. As the isotopic end members δbio and δF were shown to change over the season, no year-round estimation of the fossil fuel or biosphere share is possible from the measured mean source signature record without additional information from emission inventories or other tracer measurements.

Landscape cultivation alters δ30Si signature in terrestrial ecosystems.

NASA Astrophysics Data System (ADS)

Vandevenne, F. I.; Delvaux, C.; Huyghes, H.; Ronchi, B.; Govers, G.; Barão, A. L.; Clymans, W.; Meire, P.; André, L.; Struyf, E.

2014-12-01

Despite increasing recognition of the importance of biological Si cycling in controlling dissolved Si (DSi) in soil and stream water, effects of human cultivation on the Si cycle remain poorly understood. Sensitive tracer techniques to identify and quantify Si in the soil-plant-water system could be highly relevant in addressing these uncertainties. Stable Si isotopes are promising tools to define Si sources and sinks along the ecosystem flow path, as intense fractionation occurs during chemical weathering and uptake of dissolved Si in plants. Yet they remain underexploited in the end product of the soil-plant system: the soil water. Here, stable Si isotope ratios (δ30Si) of dissolved Si in soil water were measured along a land use gradient (continuous forest, continuous pasture, young cropland and continuous cropland) with similar parent material (loess) and homogenous bulk mineralogical and climatological properties (Belgium). Soil water δ30Si signatures are clearly separated along the gradient, with highest average signatures in continuous cropland (+1.61‰), intermediate in pasture (+1.05‰) and young cropland (+0.89 ‰) and lowest in forest soil water (+0.62‰). Our data do not allow distinguishing biological from pedogenic/lithogenic processes, but point to a strong interaction of both. We expect that increasing export of light isotopes in disturbed land uses (i.e. through agricultural harvest), and higher recycling of 28Si and elevated weathering intensity (including clay dissolution) in forest systems will largely determine soil water δ30Si signatures of our systems. Our results imply that soil water δ30Si signature is biased through land management before it reaches rivers and coastal zones, where other fractionation processes take over (e.g. diatom uptake and reverse weathering in floodplains). In particular, a direct role of agriculture systems in lowering export Si fluxes towards rivers and coastal systems has been shown. Stable Si isotopes have a large potential to track human disturbance on the Si cycle, including subtle changes in clay evolution and biogenic sink/source functions as induced by land use conversions.

Landscape cultivation alters δ30Si signature in terrestrial ecosystems

NASA Astrophysics Data System (ADS)

Vandevenne, Floor; Delvaux, Claire; Hughes, Harold; Ronchi, Benedicta; Clymans, Wim; Barao, Ana Lucia; Govers, Gerard; Cornelis, Jean Thomas; André, Luc; Struyf, Eric

2015-04-01

Despite increasing recognition of the importance of biological Si cycling in controlling dissolved Si (DSi) in soil and stream water, effects of human cultivation on the Si cycle remain poorly understood. Sensitive tracer techniques to identify and quantify Si in the soil-plant-water system could be highly relevant in addressing these uncertainties. Stable Si isotopes are promising tools to define Si sources and sinks along the ecosystem flow path, as intense fractionation occurs during chemical weathering and uptake of dissolved Si in plants. Yet they remain underexploited in the end product of the soil-plant system: the soil water. Here, stable Si isotope ratios (δ30Si) of dissolved Si in soil water were measured along a land use gradient (continuous forest, continuous pasture, young cropland and continuous cropland) with similar parent material (loess) and homogenous bulk mineralogical and climatological (Belgium). Soil water δ30Si signatures are clearly separated along the gradient, with highest average signatures in continuous cropland (+1.61%), intermediate in pasture (+1.05%) and young cropland (+0.89%) and lowest in forest soil water (+0.62%). Our data do not allow distinguishing biological from pedogenic/lithogenic processes, but point to a strong interaction of both. We expect that increasing export of light isotopes in disturbed land uses (i.e. through agricultural harvest), and higher recycling of 28Si and elevated weathering intensity (including clay dissolution) in forest systems will largely determine soil water δ30Si signatures of our systems. Our results imply that soil water δ30Si signature is biased through land management before it reaches rivers and coastal zones, where other fractionation processes take over (e.g. diatom uptake and reverse weathering in floodplains). In particular, a direct role of agriculture systems in lowering export Si fluxes towards rivers and coastal systems has been shown. Stable Si isotopes have a large potential to track human disturbance on the Si cycle, including subtle changes in clay evolution and biogenic sink/source functions as induced by land use conversions.

Sources and fate of mercury pollution in Almadén mining district (Spain): Evidences from mercury isotopic compositions in sediments and lichens.

PubMed

Jiménez-Moreno, María; Barre, Julien P G; Perrot, Vincent; Bérail, Sylvain; Rodríguez Martín-Doimeadios, Rosa C; Amouroux, David

2016-03-01

Variations in mercury (Hg) isotopic compositions have been scarcely investigated until now in the Almadén mining district (Spain), which is one of the most impacted Hg areas worldwide. In this work, we explore and compare Hg isotopic signatures in sediments and lichens from Almadén mining district and its surroundings in order to identify and trace Hg aquatic and atmospheric contamination sources. No statistically significant mass independent fractionation was observed in sediments, while negative Δ(201)Hg values from -0.12 to -0.21‰ (2SD = 0.06‰) were found in lichens. A large range of δ(202)Hg values were reported in sediments, from -1.86 ± 0.21‰ in La Serena Reservoir sites far away from the pollution sources to δ(202)Hg values close to zero in sediments directly influenced by Almadén mining district, whereas lichens presented δ(202)Hg values from -1.95 to -0.40‰ (2SD = 0.15‰). A dilution or mixing trend in Hg isotope signatures versus the distance to the mine was found in sediments along the Valdeazogues River-La Serena Reservoir system and in lichens. This suggests that Hg isotope fingerprints in these samples are providing a direct assessment of Hg inputs and exposure from the mining district, and potential information on diffuse atmospheric contamination and/or geochemical alteration processes in less contaminated sites over the entire hydrosystem. This study confirms the applicability of Hg isotope signatures in lichens and sediments as an effective and complementary tool for tracing aquatic and atmospheric Hg contamination sources and a better constraint of the spatial and temporal fate of Hg released by recent or ancient mining activities. Copyright © 2015 Elsevier Ltd. All rights reserved.

First measurements of water and D/H on Mars with ExoMars / NOMAD

NASA Astrophysics Data System (ADS)

Villanueva, Geronimo Luis; Liuzzi, Giuliano; Mumma, Michael J.; Carine Vandaele, Ann; Thomas, Ian; Smith, Michael D.; Daerden, Frank; Ristic, Bojan; Patel, Manish; Bellucci, Giancarlo; Lopez-Moreno, Jose; NOMAD Team

2017-10-01

We present preliminary data collected by the high-resolution NOMAD (Nadir and Occultation for MArs Discovery) instrument onboard the ExoMars / Trace Gas Orbiter (TGO) targeting several lines of water (H2O), deuterated water (HDO) and carbon dioxide (CO2). TGO is the first spacecraft on Mars specifically tailored to search for trace constituents, with the NOMAD instrument providing high spectral resolution (λ/dλ~ 20,000) over the 2-5 um spectral region. Such capabilities allow us to probe with unprecedented accuracy and sensitivity a multitude of organic species (e.g., CH4, CH3OH, H2CO, C2H6) and to map isotopic signatures (e.g., D/H, 13C/12C) across the whole planet.In particular, isotopic ratios are among the most valuable indicators for the loss of volatiles from an atmosphere. Because the escape rates for each isotope are slightly different (larger for the lighter forms), over long times the atmosphere becomes enriched in the heavy isotopic forms. By probing the current isotopic ratios, one can then infer the amount of matter lost to space over the planet’s evolution. Deuterium fractionation also reveals information about the cycle of water on the planet and informs us of its stability on short- and long-term scales, including its release from active regions on Mars having a characteristic D/H signature.Upon its successful launch in March/2016, we acquired critical calibration data in Apr/2016 and in June/2016, while during the Mars-Orbit-Capture phase, we also acquired Mars nadir data in Nov/2016 and in Feb-Mar/2017. Full science operations are expected to start upon final orbit insertion in early 2018. In this paper, we report initial retrievals of water and D/H derived during the Mars-Orbit-Capture phase and discuss the prospects for mapping of isotopic signatures during the nominal science phase.

First real-time measurements of N2O isotopic signatures above intensively managed grassland: analytical performance, validation and illustrative examples

NASA Astrophysics Data System (ADS)

Wolf, Benjamin; Tuzson, Béla; Merbold, Lutz; Decock, Charlotte; Emmenegger, Lukas; Mohn, Joachim

2014-05-01

Measurement of the four main N2O isotopic species (14N15N16O / 15N14N16O / 14N14N18O / 14N14N16O) has been suggested as a powerful tool to trace the biogeochemical cycle of N2O and to allocate its emission sources. Studies carried out with microbial pure cultures and mixed population systems (Wunderlin et al. 2012) allowed the determination of characteristic isotopic signatures for the most important production processes. These characteristic signatures have been applied to identify relevant sources at different scales (Park et al. 2012). However, current studies suffer from limited spatial and temporal resolution due to the combination of discrete flask sampling in conjunction with laboratory-based mass spectrometric analysis. We recently demonstrated that a quantum cascade laser (QCL) based absorption spectrometer is capable of simultaneously measuring the three main N2O isotopomers at trace levels (Waechter et al. 2008). Furthermore, its potential for in-situ measurements in conjunction with a liquid nitrogen-free preconcentration unit has been proven (Mohn et al. 2012). Here we present results from the first long-term field measurement campaign conducted on intensively managed grassland in central Switzerland during three months. A modified state-of-the-art laser spectrometer (Aerodyne Research, Inc.) employing a mid-infrared cw-QCL (4.54 μm) and a novel astigmatic multipass cell with 204 m optical path-length was connected to a N2O preconcentration unit. High analytical performance in combination with the applied calibration strategy resulted in excellent long-term precision of 0.20, 0.12 and 0.11o for δ15Nα, δ15Nβ and δ18O which was determined from repeated preconcentration and measurement of target gas from a compressed air tank. This instrumental setup allowed investigating responses of isotopic composition in soil-emitted N2O to management events and weather influences. The accompanying measurements of soil temperature, soil water content, ammonia, and nitrate concentrations made the identification of controls on N2O isotopic composition possible. Furthermore, simultaneous eddy-covariance N2O flux measurements (Merbold et al. 2014) were used to derive a flux-averaged isotopic signature of soil-emitted N2O of intensively managed grassland. In this context, the potential of the derived N2O isotopic signatures for partitioning of microbial source processes will be discussed in relation to available literature data. Merbold, L, W Eugster, J Stieger, M Zahniser, D Nelson and N Buchmann. 2014. 'Greenhouse gas budget (CO2, CH4 and N2O) of intensively managed grassland following restoration' Global Change Biology doi:10.1111/gcb.12518 Mohn, J, B Tuzson, A Manninen, N Yoshida, S Toyoda, W A Brand, and L Emmenegger. 2012. 'Site selective real-time measurements of atmospheric N2O isotopomers by laser spectroscopy.' Atmospheric Measurement Techniques 5(7): 1601-1609 Park, S, P Croteau, K A Boering, D M Etheridge, D Ferretti, P J Fraser, K-R Kim, P B Krummel, R L Langenfelds, T D van Ommen, L P Steele, and C M Trudinger. 2012. 'Trends and seasonal cycles in the isotopic composition of nitrous oxide since 1940.' Nature Geoscience 5(4): 261-265. Waechter, H, J Mohn, B Tuzson, L Emmenegger, and M W Sigrist. 2008. 'Determination of N2O isotopomers with quantum cascade laser based absorption spectroscopy.' Optics Express 16(12): 9239-44. Wunderlin, P, M Lehmann, H Siegrist, B Tuzson, A Joss, L Emmenegger, and J Mohn. 2013. 'Isotope signatures of N2O in a mixed microbial population system: Constraints on N2O producing pathways in wastewater treatment.' Environmental Science and Technology 47: 1339-48.

Multiple sulfur isotope characteristics of 3.46-2.7 Ga sedimentary rocks from drill cores of the Archean Biosphere Drilling Project (Invited)

NASA Astrophysics Data System (ADS)

Watanabe, Y.; Ohmoto, H.

2010-12-01

As part of the Archean Biosphere Drilling Project (ABDP), we have determined the multiple sulfur isotope ratios and examined the mineralogical and geochemical characteristics of the sulfur-bearing minerals (e.g., pyrite, sphalerite, barite) and the host rocks (e.g., major and trace element chemistry; Corg, Ccarb and S contents; δ13Corg and δ13Ccarb) of >100 samples of sedimentary rocks from five ABDP drill cores in the Pilbara Craton, Western Australia. The total ranges of Δ33S and δ34S values of the studied samples are -0.9 to +1.2‰ and -4 to +8‰, respectively. We have found that the Δ33S and δ34S relationships show unique values depending on their depositional environment: (1) Pyrites in the 3.46 Ga Marble Bar Chert Member (ABDP #1), which were formed by submarine hydrothermal fluids, show no AIF-S (anomalously fractionated sulfur isotope) signatures: Δ33S = -0.08 to +0.08‰ and δ34S = -3.3 to +0.6‰ (n = 5). This indicates that the H2S presented in the submarine hydrothermal fluid, which was partly generated through seawater sulfate reduction by Fe2+, did not possess AIF-S signatures. (2) Pyrites in organic C-poor lacustrine shales of the 2.76 Ga Hardey Formation (ABDP #3) also show no or very little AIF-S signatures: Δ33S = -0.38 to +0.25‰ and δ34S = -2.7 to +1.9‰ (n = 18). (3) Pyrites in organic C-poor marine shales of the 2.92 Ga Mosquito Creek Formation (ABDP#5) show no or small negative AIF-S signatures: Δ33S = -0.59 to 0.19 ‰ and all positive δ34S = +1.4 to +7.7‰ (n = 24). (4) Pyrites in organic C-rich (> 1 wt%) and hydrothermally altered marine shales in the 3.46 Ga Panorama Formation (ABDP #2) show constant and small positive AIF-S signatures (+0.44 to +0.61‰) and the smallest variation in δ34S (-1.1 to +1.6‰) (n = 35). In contrast, pyrites in organic C-rich shales in the 2.72 Ga Mt. Roe Basalt show negative Δ33S = -0.50 to -0.10‰ and δ34S = -3.7 to 1.8‰ (n = 10). (5) Pyrites in stromatolitic carbonates of the 2.7 Ga Tumbiana Formation (ABDP #10), which deposited in shallow evaporating marine basins, possess the largest variation in AIF-S signatures among five ABDP cores: Δ33S = -0.86 to 1.19‰ and δ34S = -3.2 to +1.5‰ (n = 10). (6) Compared to the negative Δ33S values (-1.28 to -0.47‰) of barites in the 3.2 Ga Dresser Formation (e.g., Ueno et al., 2009), Δ33S values of barites in the 3.46 Ga Panorama Formation (ABDP #2) are all positive (+0.55 to +0.61‰) and identical to those of reduced sulfur species (sphalerite and pyrite) in the same sample. The observed relationships between AIF-S signatures and depositional environments, and the abundance of samples with no AIF-S signatures, are difficult to explain by the current popular model that links AIF-S to atmospheric UV reactions. However, the data can be best explained by our model that links AIF-S to thermochemical sulfate reduction (TSR) by various solid phases and S-bearing aqueous/gaseous species (e.g., TSR by organic matter; replacement of iron oxides by pyrite) under hydrothermal conditions in a local and/or regional (basin wide) scale. Therefore, the AIF-S record of sedimentary rocks may be linked to the Earth’s thermal and biological evolution, rather than to the atmospheric evolution.

Preliminary use of compound-specific stable isotope (CSSI) technique to identify and apportion sediment origin in a small Austrian catchment

NASA Astrophysics Data System (ADS)

Mabit, Lionel; Gibbs, Max; Chen, Xu; Meusburger, Katrin; Toloza, Arsenio; Resch, Christian; Klik, Andreas; Eder, Alexander; Strauss, Peter; Alewell, Christine

2015-04-01

The overall impacts of climate change on agriculture are expected to be negative, threatening global food security. In the agricultural areas of the European Union, water erosion risk is expected to increase by about 80% by the year 2050. Reducing soil erosion and sedimentation-related environmental problems represent a key requirement for mitigating the impact of climate change. A new forensic stable isotope technique, using the compound specific stable isotope (CSSI) signatures of inherent soil organic biomarkers, can discriminate and apportion the source soil contribution from different land uses. Plant communities label the soil where they grow by exuding organic biomarkers. Although all plants produce the same biomarkers, the stable isotopic signature of those biomarkers is different for each plant species. For agri-environmental investigation, the CSSI technique is based on the measurement of carbon-13 (13-C) natural abundance signatures of specific organic compounds such as natural fatty acids (FAs) in the soil. By linking fingerprints of land use to the sediment in deposition zones, this approach has been shown to be a useful technique for determining the source of eroded soil and thereby identifying areas prone to soil degradation. The authors have tested this innovative stable isotopic approach in a small Austrian agricultural catchment located 60 km north of Vienna. A previous fallout radionuclide (i.e. 137-Cs) based investigation established a sedimentation rate of 4 mm/yr in the lowest part of the study site. To gain knowledge about the origin of these sediments, the CSSI technique was then tested using representative samples from the different land-uses of the catchment as source material. Values of 13-C signatures of specific FAs (i.e. C22:0 = Behenic Acid ; C24:0 = Lignoceric Acid) and the bulk 13-C of the sediment mixture and potential landscape sources were analyzed with the mixing models IsoSource and CSSIAR v1.00. Using both mixing models, preliminary results highlighted that about 50-55% of the sediment located in the deposition area originated from the main grassed waterway of the catchment.

Investigation of Benthic Foraminiferal Non-Traditional Stable Isotopes to Reconstruct Methane Fluxes in Sedimentary Environments

NASA Technical Reports Server (NTRS)

Borrelli, C.; Gabitov, R. I.; Messenger, S. R.; Nguyen, A. N.; Torres, M. E.; Kessler, J. D.

2015-01-01

Methane (CH4) is an important greenhouse gas, with a global warming potential much higher than carbon dioxide (CO2) on a short time scale. Even if the residence time of CH4 in the atmosphere is relatively short (tens of years), one of the products of CH4 oxidation is CO2, a greenhouse gas with a much longer residence time in the atmosphere (tens to hundreds of years). CH4 has been proposed as one of the trigger mechanisms for rapid global climate change today and in the geological past. With regards to the geological past, numerous studies proposed the benthic foraminiferal carbon isotope ratio (Delta13C) as a tool to reconstruct the impact of marine CH4 on rapid climate changes; however, the investigation of modern benthic foraminiferal Delta13C have produced inconclusive results. CH4 has a distinctive hydrogen isotope (Delta(D)) and Delta13C signature compared to seawater, and sulfate reduction, often coupled to CH4 anaerobic oxidation in sediments, changes the sulfur isotope signature (Delta34S) of the remaining sulfate in porewater. Therefore, we hypothesize that the Delta(D) and Delta34S signature of infaunal benthic foraminiferal species can provide a complementary approach to Delta13C to study CH4 dynamics in sedimentary environments. Here, we present the preliminary results obtained analyzing Uvigerina peregrina Delta(D) and Delta34S from three different locations at Hydrate Ridge, offshore Oregon. Unfortunately, the lack of chemical data related to the moment of foraminiferal calcification makes difficult to build a robust relationship among the U. peregrina stable isotopes and the CH4 fluxes at the sampling sites. However, our results look very promising, as each site is characterized by a different Delta(D) and Delta34S signature. We emphasize that this study represents the first step in the development of new proxies (Delta(D)) and Delta34S), which may complement the more traditional benthic foraminiferal Delta13C values, to reconstruct marine CH4 fluxes in the geological past.

Methane Emissions from Landfill: Isotopic Evidence for Low Percentage of Oxidation from Gas Wells, Active and Closed Cells

NASA Astrophysics Data System (ADS)

Lowry, David; Fisher, Rebecca; Zazzeri, Giulia; al-Shalaan, Aalia; France, James; Lanoisellé, Mathias; Nisbet, Euan

2017-04-01

Large landfill sites remain a significant source of methane emissions in developed and developing countries, with a global estimated flux of 29 Tg / yr in the EDGAR 2008 database. This is significantly lower than 20 years ago due to the introduction of gas extraction systems, but active cells still emit significant amounts of methane before the gas is ready for extraction. Historically the methane was either passively oxidized through topsoil layers or flared. Oxidation is still the primary method of methane removal in many countries, and covered, remediated cells across the world continue to emit small quantities of methane. The isotopic signatures of methane from landfill gas wells, and that emitted from active and closed cells have been characterized for more than 20 UK landfills since 2011, with more recent work in Kuwait and Hong Kong. Since 2013 the emission plumes have been identified by a mobile measurement system (Zazzeri et al., 2015). Emissions in all 3 countries have a characteristic δ13C signature of -58 ± 3 ‰ dominated by emissions from the active cells, despite the hot, dry conditions of Kuwait and the hot, humid conditions of Hong Kong. Gas well samples define a similar range. Surface emissions from closed cells and closed landfills are mostly in the range -56 to -52 ‰Ṫhese are much more depleted values than those observed in the 1990s (up to -35 ) when soil oxidation was the dominant mechanism of methane removal. Calculations using isotopic signatures of the amount of methane oxidised in these closed areas before emission to atmosphere range from 5 to 15%, but average less than 10%, and are too small to calculate from the high-emitting active cells. Compared to other major methane sources, landfills have the most consistent isotopic signature globally, and are distinct from the more 13C-enriched natural gas, combustion and biomass burning sources. Zazzeri, G. et al. (2015) Plume mapping and isotopic characterization of anthropogenic methane sources, Atmospheric Environment, 110, 151-162, doi.org/10.1016/j.atmosenv.2015.03.029.

Lead isotope determinations from sulfide mineral occurrences--Russian Far East

USGS Publications Warehouse

Church, Stan E.; Goryachev, Nikolai A.; Shpikerman, Vladimir I.

2013-01-01

The lead isotope database for sulfide deposits and occurrences in the Russian Far East was funded by the Mineral Resources Program, U.S. Geological Survey (USGS) in conjunction with the collaborative studies of mineral resources by the Russian Academy of Sciences and the U. S. Geological Survey (Nokleberg and others, 1996). Comparisons of these data with similar lead isotope data from Alaska published in Church, Delevaux, and others (1987) and Gaccetta and Church (1989) provide a basis for the following three-fold project objectives: 1. To utilize lead isotope signatures, in conjunction with regional mapping, to assess the relative ages and to categorize the types of mineral deposits studied, 2. To relate the lead isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and 3. To use the lead isotope data to correlate lithotectonic terranes within the northern Cordillera (Alaska, Yukon Territories and British Columbia in Canada, and the western Cordillera of the United States). The report by Church, Gray, and others (1987) shows how this fingerprinting methodology can be applied to trace the offset of lithotectonic (or lithostratigraphic as labeled by some authors) terranes.The lead isotope data presented in table 1 represent the work completed on sulfide mineral deposits located in the Russian Far East from 1993 to 1995, when this study was terminated due to lack of funding. The lead isotope data are reported here for use by investigators who may find them of value in mineral exploration. No attempt is made to summarize the voluminous literature on these mineral deposits.

DISSOLUTION AND ANALYSIS OF YELLOWCAKE COMPONENTS FOR FINGERPRINTING UOC SOURCES

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

Hexel, Cole R; Bostick, Debra A; Kennedy, Angel K

2012-01-01

There are a number of chemical and physical parameters that might be used to help elucidate the ore body from which uranium ore concentrate (UOC) was derived. It is the variation in the concentration and isotopic composition of these components that can provide information as to the identity of the ore body from which the UOC was mined and the type of subsequent processing that has been undertaken. Oak Ridge National Laboratory (ORNL) in collaboration with Lawrence Livermore and Los Alamos National Laboratories is surveying ore characteristics of yellowcake samples from known geologic origin. The data sets are being incorporatedmore » into a national database to help in sourcing interdicted material, as well as aid in safeguards and nonproliferation activities. Geologic age and attributes from chemical processing are site-specific. Isotopic abundances of lead, neodymium, and strontium provide insight into the provenance of geologic location of ore material. Variations in lead isotopes are due to the radioactive decay of uranium in the ore. Likewise, neodymium isotopic abundances are skewed due to the radiogenic decay of samarium. Rubidium decay similarly alters the isotopic signature of strontium isotopic composition in ores. This paper will discuss the chemical processing of yellowcake performed at ORNL. Variations in lead, neodymium, and strontium isotopic abundances are being analyzed in UOC from two geologic sources. Chemical separation and instrumental protocols will be summarized. The data will be correlated with chemical signatures (such as elemental composition, uranium, carbon, and nitrogen isotopic content) to demonstrate the utility of principal component and cluster analyses to aid in the determination of UOC provenance.« less

Getting the Lead Out of Bermuda; The Legacy of a Forty Year Record in the North Atlantic Using a Transient Experiment in the Atmosphere and Water

NASA Astrophysics Data System (ADS)

Church, T. M.; Alleman, L. Y.; Veron, A. J. J.; Boyle, E. A.; Zurbrick, C.; Patterson, C. C.; Flegal, A. R., Jr.

2015-12-01

Some forty years ago, Schaule and Patterson established the first accurate profile of lead in waters off Bermuda. In evidence was a massive environmental insult from lead emissions being carried seaward by the atmosphere over the Sargasso Sea. Further documentation was possible using contiguous time series in the atmosphere on Bermuda, surface sea water nearby and recorded in local corals. Lead had then an overwhelming source from the combustion of gasoline, primarily in the USA and secondarily in Europe. These were carried to Bermuda on seasonally alternating temperate and trade winds from the west and east, respectively. The anthropogenic sources were well distinguished based on the unique radiogenic nature of stable lead isotopes in the gasoline being used by these countries. Subsequently, decreasing use in the west (USA) followed by that in the east (Europe) was isotopically evident. As such, the two signatures were subjected to transient mixing in the atmosphere and subsequently with depth in ocean. A transient experiment uses data during 1996-1998, a period of transition in leaded gasoline use in the USA and Europe. Here are complimentary records of lead concentration and stable isotopes in atmospheric deposition and surface waters. The results allow an isotopic mass balance, indicating much of the lead in Bermuda surface water at that time may not have been deposited locally. As such, it may be presumed to reflect easterly advection of some lead at the surface under limited scavenging via the prevailing subtropical gyre circulation. These annual circulation periods are consistent with both physical data and another lead isotopic mass balance in the east. Going forward, Bermuda time series of trace elements and isotopes such as lead could continue to record climatological (e.g. NAO) transients in atmospheric scavenging, potential impact on surface ecosystems, and changes in mixing into deeper waters of the Sargasso Sea and points further afield.

Modern rather than Mesoarchaean oxidative weathering responsible for the heavy stable Cr isotopic signatures of the 2.95 Ga old Ijzermijn iron formation (South Africa)

NASA Astrophysics Data System (ADS)

Albut, Gülüm; Babechuk, Michael G.; Kleinhanns, Ilka C.; Benger, Manuela; Beukes, Nicolas J.; Steinhilber, Bernd; Smith, Albertus J. B.; Kruger, Stephanus J.; Schoenberg, Ronny

2018-05-01

Previously reported stable Cr isotopic fractionation in Archaean paleosols and iron formations (IFs) have been interpreted as a signature of oxidative weathering of Cr(III) to Cr(VI) in soils, and delivery of isotopically heavy Cr(VI) into the oceans. One of the oldest reported fingerprints of this process is isotopically heavy Cr preserved in the 2.95 Ga old Ijzermijn IF, Sinqeni Formation of the Mozaan Group (Pongola Supergroup), South Africa and could suggest that atmospheric free oxygen was present ca. 600 million years earlier than the Great Oxidation Event (GOE). However, fractionated stable Cr isotopic signatures have only been found to date in surface outcrop samples of the White Mfolozi Inlier exposed along the White Mfolozi River Gorge. In this study, the latter outcrop was resampled along with two drill cores of the Ijzermijn IF and a drill core of the Scotts Hill IF to represent multiple exposures of Mozaan Group IFs with different states of preservation. A detailed geochemical comparison on bulk samples of different units was undertaken using stable Cr isotopes coupled with trace and major elements. Outcrop iron-rich mudstones (Fe - lutites) show very low LOI [wt] %, and very low Fe(II)/Fetot ratios, and lower Ca and Mg relative to equivalent facies in drill cores, indicating the effects that oxidative recent surface weathering had on Fe/Mn-rich carbonate minerals of the IF. Overall rare earth element and yttrium (REE + Y) mixing models agree well with previous studies, confirming that they were minimally disturbed by weathering and are consistent with a high magnitude of continental solutes delivered in a near-shore depositional environment, with a minor contribution of hydrothermally derived fluids that upwelled into shallower depositional setting. Importantly, all drill core samples of this study revealed δ53/52Cr values within the igneous inventory, despite variable amounts of detrital Cr input that includes nearly detritus-free, chert/jasper-rich units. By contrast, a specific group of Fe-lutite samples near the base of White Mfolozi River outcrop bear fractionated Cr isotopic signatures with δ53/52Cr values up to 0.418‰. These outcrop samples also display unusually high U/Th ratios (max. 12.6) as well as enrichments of other elements (W, Tl, As, MREE) that far exceed that observed in correlative drill core units. These observations together with the lack of Cr isotopic fractionation in drill core samples lead us to propose that the heavy δ53/52Cr values of Fe-lutites from outcrop Ijzermijn IF samples reported here and in a previous study are the product of modern oxidative weathering rather than an indicator for Mesoarchaean oxidative weathering at ca. 2.95 Ga.

Stable C and N isotope analysis of hair suggest undernourishment as a factor in the death of a mummified girl from late 19th century San Francisco, CA.

PubMed

Eerkens, Jelmer W; Hull, Bryna; Goodman, Jena; Evoy, Angela; Kapp, Joshua D; Hussain, Sidra; Green, Richard E

2017-01-01

The chance discovery of a 1.5-3.5 years old mummified girl presents a unique opportunity to further our understanding of health and disease among children in 19th Century San Francisco. This study focuses on carbon and nitrogen stable isotope signatures in serial samples of hair that cover the last 14 months of her life. Results suggest an initial omnivorous diet with little input from marine resources or C4 plants. Around six months before death δ15N starts a steady increase, with a noticeable acceleration just two months before she died. The magnitude of δ15N change, +1.5‰ in total, is consistent with severe undernourishment or starvation. Cemetery records from this time period in San Francisco indicate high rates of infant and child mortality, mainly due to bacterial-borne infectious diseases, about two orders of magnitude higher than today. Taken together, we hypothesize that the girl died after a prolonged battle with such an illness. Results highlight the tremendous impacts that modern sanitation and medicine have had since the 1800s on human health and lifespan in the United States.

Archean recycled oceanic crust sampled in Azores lavas

NASA Astrophysics Data System (ADS)

Beguelin, P.; Bizimis, M.; Beier, C.; Turner, S.

2016-12-01

Azores lava compositions extend below the mantle array in ɛNd-ɛHf space and define the steepest slope of all plume provinces [1], but this pattern is largely controlled by low ɛHf lavas from Eastern São Miguel island (SM). Here we present new Hf isotope data on well-characterized on-land and submarine Azores lavas from several islands, the Terceira Rift and João do Castro seamount (JdC), in order to further constrain this trend. While Azores lavas fall along the mantle array with relatively steep slopes (e.g. São Jorge slope = 2.1), both SM and JdC fall below the mantle array as two distinct steep arrays with slopes of 2.0 and 2.6 respectively, extending to ɛHf = 0 at ɛNd = 2 (SM) and 4 (JdC). This is a unique feature in OIBs. The new Hf-Nd data overlaps the HIMU-type Mangaia and St Helena compositions. However, SM and JdC have distinctly less radiogenic and more variable Pb isotopes (e.g. 206Pb/204Pb = 18.8 to 20.2) than HIMU. Hf-Nd isotope decoupling below the mantle array is therefore not an exclusive HIMU signature. The coupled Hf-Nd-Pb-Sr isotope compositions of the enriched SM and JdC end-members can be modeled by recycled 2.5-3.0 Ga N-MORB, with some E-MORB affinity for SM. Unlike HIMU however, no Pb-loss during subduction is required for recycled MORB to explain their Pb isotopes. The relatively high κ (232Th/238U 4.3) required by the Azores data is also consistent with a high Th/U Archean mantle [2]. Aged, metasomatised mantle lithosphere based on a global peridotite and pyroxenite compilation is too variable and only fortuitously could explain the Azores compositions. Both enriched JdC and SM endmembers can therefore be explained by a recycled Archean oceanic crust that is locally heterogeneous, as presently observed in some MOR segments where N-and E-MORB exist closely [3, 4]. The lack of mixing between SM and JdC end-members some 100 km apart further implies that this recycled crust has retained its distinct signature through mantle convection and stirring for 2.5-3.0 Ga. [1] Salters et al. (2011) G3 12(8): Q08001. [2] Elliott et al. (1999) EPSL 169(1), 129-145. [3] Donnelly et al. (2004) EPSL 226(3), 347-366. [4] Gale et al. (2013) EPSL 365, 209-220.

Megafauna and frozen soil: the drivers of atmospheric CH4 dynamics

NASA Astrophysics Data System (ADS)

Zimov, N.; Zimov, S. A.

2010-12-01

During the last deglaciation (LD) a strong increase in atmospheric methane (CH4) concentrations occurred simultaneously with a rise in Greenland temperatures indicating that in the north, during this time period, strong CH4 sources “awakened”, as additionally documented by the appearance of a strong gradient between northern (Greenland) and southern (Antarctica) hemisphere atmospheric CH4 concentrations. This rise could not be caused by wetland expansion. A reconstruction of peatland formation dynamics has indicated that wetlands on Earth were few in LD and only actively expanded 10,000 yr BP, after atmospheric CH4 concentrations began to decline. Destabilization of methane clathrates also could not be the source for atmospheric CH4 increase. Geological CH4 (including methane clathrates) has the highest deuterium content (δD) among all of the known sources of CH4 while atmospheric CH4 δD values determined for the LD were record low. To explain recorded atmospheric CH4 and its isotopic dynamics required a strong northern source, which was active only during the LD and that provided very low δD CH4 values. Such a source is permafrost thawing under anaerobic conditions (or better stated soils of mammoth steppe-tundra ecosystems). Permafrost thawing is the strongest, among known, wetland sources (usually over 100g CH4/m2yr) and has a unique isotopic signature (δD = -400 per mil (-338 to -479 per mil), δ13C = -73 per mil (-58 to -99 per mil)). The main sources of atmospheric CH4 have different isotopic signatures (δ13C, δD). The isotopic content of atmospheric CH4 is a simple function of the weight average for all of the sources. Inclusion of permafrost source into a budget model of the atmospheric methane and its isotopes allowed us to reconstruct the dynamics of methane’s main sources. Model indicated geological source to be negligible as in LGM so and in LD and Holocene. During the glaciation, the largest methane source was megafauna, whose 1.4-1.7 billion ton biomass was larger than the modern biomass of human and domestic animals combined. During the LD, the largest methane source was the thawing of steppe-tundra soils. During the Holocene the largest CH4 source was wetlands. All these estimates correspond with the scales of permafrost degradation in the LD, megafaunal extinction and increase in fire intensity derived from charcoal within stratigraphic columns.

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.

Installation of a Rudist Biostrome after the Late Aptian - Early Albian OAE1B (mural Formation, Southeastern Arizona)

NASA Astrophysics Data System (ADS)

Godet, A.; Helfrich-Dennis, M. M.; Suarez, M. B.

2015-12-01

Mesozoic climate change has been extensively studied in the Tethys, while their expression in the proto Gulf of Mexico can still be precised, especially for the time period straddling the Aptian-Albian boundary. During this time period, significant climatic events may correlate between the proto-Atlantic and the Tethys, amongst which the Oceanic Anoxic Event 1b that corresponds to a period of marine anoxia across this stage boundary. We hypothesized that this event may have impacted the shallow-marine carbonate factory that is now preserved near the town of Bisbee (Mule Mountains, southern Arizona). This sedimentary succession has been chosen because it documents a switch from a siliclastic- to carbonate-dominated sedimentation during the targeted time interval. Using carbon isotope chemostratigraphy, we were able to refine the stratigraphic framework of the Mural Formation, which was previously based on benthic organisms such as rudist bivalves and orbitolinids, such as Mesorbitolina texana. The OAE1b has been identified based on its peculiar δ13C signature supported by biostratigraphic data. Concurrently, microfacies analysis helped in reconstructing variations in sea levels. In southern Arizona, the OAE1b equivalent belongs to a third-order transgressive systems tract, and extends into the following highstand systems track. The maximum flooding surface is defined within a thick rudist biostrome with chondrodonts. It thus seems that the OAE1b did not strongly affected the carbonate factory in this region of the proto Gulf of Mexico. As a conclusion, limestone rocks now preserved in southeastern Arizona were deposited during the Late Aptian to Early Albian time period, during which the OAE1b developed. This paleoceanographic perturbation is expressed in the sedimentary record by its unique carbon isotope signature, with no significant impact on benthic ecosystems.

Recent summer precipitation trends in the Greater Horn of Africa and the emerging role of Indian Ocean sea surface temperature

NASA Astrophysics Data System (ADS)

Williams, A. Park; Funk, Chris; Michaelsen, Joel; Rauscher, Sara A.; Robertson, Iain; Wils, Tommy H. G.; Koprowski, Marcin; Eshetu, Zewdu; Loader, Neil J.

2012-11-01

We utilize a variety of climate datasets to examine impacts of two mechanisms on precipitation in the Greater Horn of Africa (GHA) during northern-hemisphere summer. First, surface-pressure gradients draw moist air toward the GHA from the tropical Atlantic Ocean and Congo Basin. Variability of the strength of these gradients strongly influences GHA precipitation totals and accounts for important phenomena such as the 1960s-1980s rainfall decline and devastating 1984 drought. Following the 1980s, precipitation variability became increasingly influenced by the southern tropical Indian Ocean (STIO) region. Within this region, increases in sea-surface temperature, evaporation, and precipitation are linked with increased exports of dry mid-tropospheric air from the STIO region toward the GHA. Convergence of dry air above the GHA reduces local convection and precipitation. It also produces a clockwise circulation response near the ground that reduces moisture transports from the Congo Basin. Because precipitation originating in the Congo Basin has a unique isotopic signature, records of moisture transports from the Congo Basin may be preserved in the isotopic composition of annual tree rings in the Ethiopian Highlands. A negative trend in tree-ring oxygen-18 during the past half century suggests a decline in the proportion of precipitation originating from the Congo Basin. This trend may not be part of a natural cycle that will soon rebound because climate models characterize Indian Ocean warming as a principal signature of greenhouse-gas induced climate change. We therefore expect surface warming in the STIO region to continue to negatively impact GHA precipitation during northern-hemisphere summer.

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.

The Laccaria and Tuber Genomes Reveal Unique Signatures of Mycorrhizal Symbiosis Evolution (2010 JGI User Meeting)

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

Martin, Francis

Francis Martin from the French National Institute for Agricultural Research (INRA) talks on how "The Laccaria and Tuber genomes reveal unique signatures of mycorrhizal symbiosis evolution" on March 24, 2010 at the 5th Annual DOE JGI User Meeting

High-resolution stable isotope signature of a land-falling atmospheric river in Southern Norway

NASA Astrophysics Data System (ADS)

Weng, Yongbiao; Sodemann, Harald

2017-04-01

Gathering observational evidence of the long-range moisture versus local source contributions remains a scientific challenge, but is critical for understanding how hydrological extremes develop. Moisture transport to the west coast of Norway is often connected to elongated meridional structures of high water vapour flux known as Atmospheric Rivers. It is still an open question how well moisture sources estimated by different numerical models for such events of long-range transport correspond with reality. In this study, we present high resolution stable isotope information collected during a land-falling Atmospheric River in Southern Norway during winter 2016, and analyse the data with the aim to differentiate between moisture source signatures and below-cloud processes affecting the stable isotope composition. The precipitation characterised by a pronounced warm front was sampled manually on a rooftop platform at a 10-20 minute interval during the 24h of the event and later measured by a laser spectrometer (Picarro L2140-i) in the lab for δ18O, δD, and d-excess. Simultaneously, the stable isotope composition of water vapor was continuously measured at high resolution. To that end, ambient air was continuously pumped from a nearby inlet at 25 m above the ground and measured by another laser spectrometer (Picarro L2130-i). Stable water isotope measurements were supplemented by detailed precipitation parameters from a laser disdrometer (OTT Parsivel2), Micro Rain Radar (MRR-2), Total Precipitation Sensor (TPS-3100), and a nearby weather station. Measurements show a signature of two depletion periods in the main stable isotope parameters that are not apparent in precipitation amount and atmospheric temperature measurements. The deuterium excess in rainfall responds differently, with first and increase and then a decrease during these depletion periods. We interpret this as a combined consequence of airmass change, cloud microphysics, and below-cloud effects. Moisture sources identified during the atmospheric river event show a clear transition that points to the need to constrain this kind of analysis by additional stable water isotope observations en route and upstream.

A petrologic comparison of Triassic plutonism in the San Gabriel and Mule Mountains, southern California

NASA Astrophysics Data System (ADS)

Barth, Andrew P.; Tosdal, R. M.; Wooden, J. L.

1990-11-01

Triassic magmatism in the southwest U.S. Cordillera forms a semicontinuous magmatic arc extending from northwestern Nevada to southeastern California. Quartz monzodioritic and quartz monzonitic rocks and associated diorites and granites are widespread in southeastern California, and we suggest that these rocks represent exposure of a structurally deeper part of the Triassic arc, where it was emplaced into comparatively thick Proterozoic crust. Elemental and isotopic data suggest that Triassic quartz monzodiorites and quartz monzonites in the Mule and San Gabriel Mountains were derived from a relatively undepleted, nonradiogenic mafic lithospheric source, with virtually no upper crustal interaction. Very limited data for associated Triassic(?) diorites indicate a wide range in composition and a surprisingly radiogenic isotopic signature. Younger Triassic(?) granites record a strong geochemical signature of interaction with continental crust, including inherited zircon and high initial Sr ratios but comparatively less radiogenic Pb isotopic compositions. The major and trace element geochemistry of Late Triassic plutonic rocks in southeastern California is similar in many respects to alkalic components of the Triassic arc in the Mojave Desert. However, contemporaneous rocks farther north have a calc-alkalic signature, perhaps reflecting the variation in age and composition of lithosphere across which the Triassic arc was constructed.

A petrologic comparison of Triassic plutonism in the San Gabriel and Mule Mountains, southern California

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

Barth, A.P.; Tosdal, R.M.; Wooden, J.L.

1990-11-10

Triassic magmatism in the southwest US Cordillera forms a semicontinuous magmatic arc extending from northwestern Nevada to southeastern California. Quartz monzodioritic and quartz monzonitic rocks and associated diorites and granites are widespread in southeastern California, and the authors suggest that these rocks represent exposure of a structurally deeper part of the Triassic arc, where it was emplaced into comparatively thick Proterozoic crust. Elemental and isotopic data suggest that Triassic quartz monzodiorites and quartz monzonites in the Mule and San Gabriel Mountains were derived from a relatively undepleted, nonradiogenic mafic lithospheric source, with virtually no upper crustal interaction. Very limited datamore » for associated Triassic ( ) diorites indicate a wide range in composition and a surprisingly radiogenic isotopic signature. Younger Triassic( ) granites record a strong geochemical signature of interaction with continental crust, including inherited zircon and high initial Sr ratios but comparatively less radiogenic Pb isotopic compositions. The major and trace element geochemistry of Late Triassic plutonic rocks in southeastern California is similar in many respects to akalic components of the Triassic arc in the Mojave Desert. However, contemporaneous rocks farther north have a calc-alkalic signature, perhaps reflecting the variation in age and composition of lithosphere across which the Triassic arc was constructed.« less

Relationships between tree height and carbon isotope discrimination

Treesearch

Nate G. McDowell; Barbara J. Bond; Lee T. Dickman; Michael G. Ryan; David Whitehead

2011-01-01

Understanding how tree size impacts leaf- and crown-level gas exchange is essential to predicting forest yields and carbon and water budgets. The stable carbon isotope ratio of organic matter has been used to examine the relationship of gas exchange to tree size for a host of species because it carries a temporally integrated signature of foliar photosynthesis and...

Proterozoic crustal evolution of the Eucla basement, Australia: Implications for destruction of oceanic crust during emergence of Nuna

NASA Astrophysics Data System (ADS)

Kirkland, C. L.; Smithies, R. H.; Spaggiari, C. V.; Wingate, M. T. D.; Quentin de Gromard, R.; Clark, C.; Gardiner, N. J.; Belousova, E. A.

2017-05-01

The crystalline basement beneath the Cretaceous to Cenozoic Bight and Eucla Basins, in Western Australia has received comparatively little attention even though it lies on the eastern margin of one of the most mineral resource endowed regions on the planet. This basement is characterized by a complex geological evolution spanning c. 2 billion years, but paucity of outcrop and younger basin cover present a daunting challenge to understand the basement geology. In this work the composition of the unexposed Proterozoic crystalline basement to the Bight and Eucla Basins is investigated through zircon Hf isotopes and whole rock geochemistry from new drillcore samples. This region includes two geophysically defined basement entities: The Madura Province, containing: 1) c. 1478 Ma Sleeper Camp Formation, which has variable isotopic signatures including evolved values interpreted to reflect reworking of rare slivers of hyperextended Archean crust, 2) 1415-1389 Ma Haig Cave Supersuite, with mantle-like isotope values interpreted as melting of subduction-modified N-MORB source, and 3) 1181-1125 Ma Moodini Supersuite, with juvenile isotopic signatures interpreted to reflect mixed mafic lower-crustal and asthenospheric melts produced at the base of thinned crust. The Coompana Province, to the east of the Madura Province, has three major magmatic components: 1) c. 1610 Ma Toolgana Supersuite, with chemical and isotopic characteristics of primitive arc rock, 2) c. 1490 Ma Undawidgi Supersuite, with juvenile isotope values consistent with extensional processes involving asthenospheric input and 3) 1192-1140 Ma Moodini Supersuite, with strong isotopic similarity to Moodini Supersuite rocks in the Madura Province. This new isotopic and geochemical data shows that the Madura and Coompana regions together represent a huge tract of predominantly juvenile material. Magma sources recognised, include; 1) depleted mantle, producing MORB-like crust at c. 1950 Ma, but also contributing to younger magmatism; 2) recycled c. 1950 Ma crust reworked in primitive arcs and in intra-plate settings and; 3) minor evolved material representing fragments of hyperextended continent. The observed isotopic evolution pattern is comparable to that of other central Australian Proterozoic provinces, including the Musgrave Province, the northern margin of the Gawler Craton, and components within the Rudall Province. Linking these isotopic signatures defines the Mirning Ocean, and its subducted and underplated equivalents. In a global context we suggest c. 1950 Ma crust production reflects the onset of ordered oceanic spreading centres, which swept juvenile crustal fragments into Nuna.

Mass-Dependent and -Independent Fractionation of Mercury Isotopes in Aquatic Systems

NASA Astrophysics Data System (ADS)

Bergquist, B. A.; Joel, B. D.; Jude, D. J.

2008-12-01

Mercury is a globally distributed and highly toxic pollutant. Although Hg is a proven health risk, much of the natural cycle of Hg is not well understood and new approaches are needed to track Hg and the chemical transformations it undergoes in the environment. Recently, we demonstrated that Hg isotopes exhibit two types of isotope fractionation: (1) mass dependent fractionation (MDF) and (2) mass independent fractionation (MIF) of only the odd isotopes (Bergquist and Blum, 2007). The observation of large MIF of Hg isotopes (up to 5 permil) is exciting because only a few other isotopic systems have been documented to display large MIF, the most notable of which are oxygen and sulfur. In both cases, the application of MIF has proven very useful in a variety of fields including cosmochemistry, paleoclimatology, physical chemistry, atmospheric chemistry, and biogeochemistry. Both MDF and MIF isotopic signatures are observed in natural samples, and together they open the door to a new method for tracing Hg pollution and for investigating Hg behavior in the environment. For example, fish record MDF that appears to be related to size and age. Additionally, fish display MIF signatures that are consistent with the photo-reduction of methylmercury (Bergquist and Blum, 2007). If the MDF and MIF in ecosystems can be understood, the signatures in fish could inform us about the sources and processes transforming Hg and why there are differences in the bioaccumulation of Hg in differing ecosystems and populations of fish. This requires sampling of a variety of ecosystems, the sampling of many components of the ecosystems, and the use of other tracers such as carbon and nitrogen isotopes. We have expanded our studies of aquatic ecosystems to include several lakes in North America. Similar to other isotopic systems used to study food web dynamics and structure (i.e., C and N), the MDF of Hg in fish appears to be related to size and age. The MDF recorded in fish likely reflects both the sources of Hg to the fish and the excretion of Hg by the fish. Thus, MDF alone provides new insights into sources and bioaccumulation of Hg in food web. Fish populations from different lakes display distinct MIF and relationships between MDF and MIF. The degree of MIF is likely related to the amount of photo-reduction in a lake and dissolved organic carbon. We also sampled food sources and livers of fish to understand processes of isotopic fractionation in the food web.

The Upper Mantle Flow Field around South-Africa as Reflected by Isotopic Provinciality

NASA Astrophysics Data System (ADS)

Meyzen, C.; Blichert-Toft, J.; Ludden, J.; Humler, E.; Mevel, C.; Albarede, F.

2006-12-01

Isotopic studies of MORB have established the existence of broad isotopic provinces within the underlying asthenosphere, such as in the Indian Ocean (DUPAL). How these features relate to mantle circulation is, however, still unknown. The steepness of the transition between such isotopic provinces will define the geometry of the velocity field in the upper mantle. In this respect, the transition between the Indian and South Atlantic provinces, two domains that are isotopically contrasted, should be readily identifiable over this long ridge segment. Here, we present Hf isotope data for 60 samples dredged along the SWIR between 35° and 69°E. The new Hf isotope data show that the Indian asthenosphere does not spill directly into the South Atlantic upper mantle: the general decreasing southward gradient observed for ^{176}Hf/^{177}Hf down the mid- Atlantic Ridge, and also for Sr isotopes and model Th/U ratios (derived from Pb isotopes), is overprinted by material with radiogenic Sr, unradiogenic Hf and high Th/U. The Indian domain grades into the South Atlantic around Bouvet, while the South Atlantic collides with the Atlantic province around Tristan. We interpret these features to represent fronts between three adjacent isotopic provinces similar to what has been suggested for the Australian-Antarctic Discordance. The common DUPAL signature of MORB and OIB from the Indian province and the geochemistry of Gulf of Aden MORB and the Afar plume suggest that the source of this distinctive mantle component is deep and lies to the north of the province. This is also what the three-dimensional flow field computed by Behn et al. (2004) from shear-wave splitting shows with a major lower mantle upwelling radiating at the base of the asthenosphere under the Afar plume. Lower mantle gushing out from this source flows southward unimpeded along the Indian ridges, whereas it only reaches the South Atlantic ridge after first having been deflected under the deep roots of the South African Archean cratons. Erosion of these roots by the asthenospheric drift confers a distinct continental signature on the source of South Atlantic MORB. This pattern is also consistent with the observation that the lowest He isotope values occur, on average, along the South Atlantic ridge. To some extent, the dynamics of the North Atlantic upper mantle mirrors the Indian situation: the flow field of Behn et al. (2004) shows that the North Atlantic asthenosphere also fills up through deep mantle upwellings, which is consistent with the Dupal-like isotopic signature of the Arctic ridges. M.D. Behn, C.P. Conrad and P.G. Silver (2004), Detection of upper mantle flow associated with the African Superplume, Earth. Planet. Sci. Lett., 224, 259-274.

Geochronological and geochemical assessment of Cenozoic volcanism from the Terror Rift region of the West Antarctic Rift System

NASA Astrophysics Data System (ADS)

Rilling, Sarah E.

The work presented in this dissertation explains results from three different methods to determine the relation between tectonism and rift-related volcanism in the Terror Rift region of the West Antarctic Rift System (WARS). Alkaline lavas from seven submarine features, Beaufort Island and Franklin Islands, and several locations near Mt Melbourne were dated by 40Ar/39Ar geochronology and analyzed for elemental and isotopic chemical signatures. Each chapter addresses a different aspect of the hypothesis that the presence of volatiles, primarily H2O or CO2, in the magma source has led to anomalously high volumes of magmatism after rift-related decompressional melting rather than requiring an active mantle plume source. Chapter 2 provides the temporal framework, illustrating that the sampled features range in age from 6.7 Ma to 89 ka, post-dating the main Miocene age phase of Terror Rift extension. Chapter 3 illustrates the traditional enriched elemental and isotopic chemical signatures to support the overall homogeneity of these lavas and previously analyzed areas of the WARS. This chapter also provides a new model for the generation of the Pb isotopic signatures consistent with a history of metasomatism in the magma source. Chapter 4 provides an entirely new chemical dataset for the WARS. The first platinum group element (PGE) abundances and extremely unradiogenic Os isotopic signatures of Cenozoic lavas from Antarctica provide the strongest evidence of melting contributions from a lithospheric mantle source. The combined results from these three studies consistently support the original hypothesis of this dissertation. New evidence suggests that WARS related lavas are not related to a mantle plume(s) as previously proposed. Instead, they are generated by passive, decompressional melting of a source, likely a combination of the asthenospheric and lithospheric mantle, which has undergone previous melting events and metasomatism.

Signature inversion / chiral-twin bands in odd-odd Pr nuclei?

NASA Astrophysics Data System (ADS)

Fetea, Mirela; Thompson, Sarah

2001-10-01

Over the past few years, sufficient data have been accumulated to enable a meaningful study of the systematic trends of the signature inversion (inversion point shift in spin with increasing proton and neutron numbers in a chain of isotones / isotopes as well as the magnitude of odd-even staggering). Our aim is to understand these systematic features within the framework of particle rotor model including both a residual pn interaction and a γ deformation. Signature inversion is present in the bands of odd-odd nuclei , ^120-130Cs, ^124-132La, ^126-134Pr and ^132-136Pm and having an yrast structure built on π h_11/2ν h_11/2 orbitals. Pr isotopes seem to indicate an inversion decreasing for smaller neutron numbers, trend that is opposite for the Cs nuclei(J.F. Smith et al., Phys. Lett B 406, 7 (1997)). Why? A question that remains to be answered is if there is any relation of signature inversion to chiral twin bands (two ''look alike positive parity'' bands proposed for as in ). The lower band has signature inversion all the way up. Could these effects be related to triaxiality? Can one trust an apparent conclusion suggested by L.L. Riedinger( L.L. Riedinger, talk presented at High) Spin Physics 2001, Warsaw, Poland, February, 2001, to be published in Acta Phys. Pol.: ''signature inversion in an odd-odd band of two quasiparticles pointed along different axes is always associated with the formation of chiral twin bands''?

Re-cycling mercury: the role of stocking non-native fish in high-altitude lakes

NASA Astrophysics Data System (ADS)

Hansson, S. V.; Le Roux, G.; Sonke, J.

2016-12-01

Mercury (Hg) is a globally distributed pollutant that can be carried long distances and be deposited remote from its original source. It is also one of the few natural abundant trace metals that serves no biological purpose, i.e. is highly toxic to humans and other biota. Studies have also shown that Hg-deposition increases with increasing altitude, leading to a higher load of contamination to these already sensitive environments. Any additional sources of Hg to high-altitude aquatic systems are therefore of high concern. Today introduced non-indigenous fish can be found in aquatic systems on all contents, with the exception of Antarctica. However, the social and economic benefits gained by these introductions often weighs against the ecological impacts. E.g. studies have shown that introduction of carnivore fish can lead to alternation of the aquatic food web and introduce pathogens causing population declines or even extinction. Few studies however have looked at the introduction of non-native fish to high altitude aquatic systems in the scope of heavy-metal contamination. By using a combined geochemical and isotopic approach, we therefore study the introduction of brown trout as a potential source of Hg-contamination in three high altitude lakes in the French Pyrenees. We combine analysis of δ13C and δ15N, with tot-Hg and Hg-isotopes in samples of biofilm, invertebrates, common minnow and brow trout and compare these with data from trout bred at a local fish farm, providing the fish used when stocking lakes in the nearby region. Our results show that levels of tot-Hg in trout from our sites surpasses literature values by 5 times or more and that MIF and MDF Hg-isotope signatures shows clear relationship with fish size and with δ15N. However, there is a clear difference in the Hg-isotopic signatures of the wild trout compared to the farmed. Whereas δ202Hg and Δ199Hg-signatures of the wild trout aligns with the onsite food chain (biofilm, plankton, common minnow), the farmed trout show isotopic signatures identical to marine biota, e.g. tuna and dolphin. This is also reflected in the δ15N-signatures where the farmed trout corresponds to trophic levels two steps above those of the wild trout. Drawing on these data we therefore ask; are we recycling mercury and shortcutting the natural Hg-cycle by stocking lakes with farmed fish?

Chemical and U-Sr isotopic variations in stream and source waters of the Strengbach watershed (Vosges mountains, France)

NASA Astrophysics Data System (ADS)

Pierret, M. C.; Stille, P.; Prunier, J.; Viville, D.; Chabaux, F.

2014-10-01

This is the first comprehensive study dealing with major and trace element data as well as 87Sr/86Sr isotope and (234U/238U) activity ratios (AR) determined on the totality of springs and brooks of the Strengbach catchment. It shows that the small and more or less monolithic catchment drains different sources and streamlets with very different isotopic and geochemical signatures. Different parameters control the diversity of the source characteristics. Of importance is especially the hydrothermal overprint of the granitic bedrock, which was stronger for the granite from the northern slope; also significant are the different meteoric alteration processes of the bedrock causing the formation of 0.5 to 9 m thick saprolite and above the formation of an up to 1m thick soil system. These processes mainly account for springs and brooks from the northern slope having higher Ca / Na, Mg / Na, and Sr / Na ratios, but lower 87Sr/86Sr isotopic ratios than those from the southern slope. The chemical compositions of the source waters in the Strengbach catchment are only to a small extent the result of alteration of primary bedrock minerals, and rather reflect dissolution/precipitation processes of secondary mineral phases like clay minerals. The (234U/238U) AR, however, are decoupled from the 87Sr/86Sr isotope system, and reflect to some extent the level of altitude of the source and, thus, the degree of alteration of the bedrock. The sources emerging at high altitudes have circulated through already weathered materials (saprolite and fractured bedrock depleted in 234U), implying (234U/238U) AR below 1, which is uncommon for surface waters. Preferential flow paths along constant fractures in the bedrocks might explain the - over time - homogeneous U AR of the different spring waters. However, the geochemical and isotopic variations of stream waters at the outlet of the catchment are controlled by variable contributions of different springs, depending on the hydrological conditions. It appears that the (234U/238U) AR are a very appropriate, important tracer for studying and deciphering the contribution of the different source fluxes at the catchment scale, because this unique geochemical parameter is different for each individual spring and at the same time remains unchanged for each of the springs with changing discharge and fluctuating hydrological conditions. This study further highlights the important impact of different and independent water pathways on fractured granite controlling the different geochemical and isotopic signatures of the waters. Despite the fact that soils and vegetation cover have a great influence on the water cycle balance (evapotranspiration, drainage, runoff), the chemical compositions of waters are strongly modified by processes occurring in deep saprolite and bedrock rather than in soils along the specific water pathways.

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.

Global and Latitudinal Estimates of del 13C from Fossil-Fuel Consumption and Cement Manufacture (DB1013)

DOE Data Explorer

Andres, R. J. [University of Alaska, Fairbanks, Alaska (USA); Marland, Greg [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (USA); Bischof, Steve [Connecticut College, New London, Connecticut

1996-01-01

This database contains estimates of the annual mean value of 13C of CO2 emissions from fossil-fuel consumption and cement manufacture for 1860-1992. It also contains estimates of the value of 13C for 1° latitude bands for the years 1950, 1960, 1970, 1980, 1990, 1991, and 1992. These estimates of the carbon isotopic signature account for the changing mix of coal, petroleum, and natural gas being consumed and for the changing mix of petroleum from various producing areas with characteristic isotopic signatures. This time series of fossil-fuel 13C signature provides an additional constraint for balancing the sources and sinks of the global carbon cycle and complements the atmospheric 13C measurements that are used to partition the uptake of fossil carbon emissions among the ocean, atmosphere, and terrestrial biosphere reservoirs. The data are in two files ranging in size from 2.8 to 12.9 kB.

Constraining N2O emissions since 1940 by firn air isotope measurements in both hemispheres

NASA Astrophysics Data System (ADS)

Prokopiou, Markella; Martinerie, Patricia; Sapart, Celia; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Kaiser, Jan; Levin, Ingeborg; Sowers, Todd; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik; Röckmann, Thomas

2017-04-01

N2O is currently the 3rd most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290±1) nmol mol-1 in 1940 to (322±1) nmol mol-1 in 2008 the isotopic δ values of atmospheric N2O decreased by (- 2.2±0.2) ‰ for δ15Nav, (- 1.0±0.3) ‰ for δ18O, (- 1.3±0.6) ‰ for δ15Nα, and (- 2.8±0.6) ‰ for δ15Nβover the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to be 123 a. Adopting this lifetime results in total average source isotopic signatures of (- 7.6±0.8) ‰ (vs. Air-N2) for δ15Nav, (32.2±0.2) ‰ (vs. VSMOW) for δ18O, (- 3.0±1.9) ‰ (vs. Air-N2) for δ15Nα, and (- 11.7±2.3) ‰ (vs. Air-N2) for δ15Nβ over the investigated period. δ15Navand δ15Nβ show some temporal variability while the other source isotopic signatures remain unchanged. The 15N site-preference (= δ15Nα - δ15Nβ) can be used to reveal further information on the source emission origins. Based on the changes in the isotopes we conclude that the main contribution to N2O changes in the atmosphere since 1940 is from soils, with agricultural soils being the principal anthropogenic component, which is in line with previous studies.

Hydrogen and carbon isotope systematics in hydrogenotrophic methanogenesis under H2-limited and H2-enriched conditions: implications for the origin of methane and its isotopic diagnosis

NASA Astrophysics Data System (ADS)

Okumura, Tomoyo; Kawagucci, Shinsuke; Saito, Yayoi; Matsui, Yohei; Takai, Ken; Imachi, Hiroyuki

2016-12-01

Hydrogen and carbon isotope systematics of H2O-H2-CO2-CH4 in hydrogenotrophic methanogenesis and their relation to H2 availability were investigated. Two H2-syntrophic cocultures of fermentatively hydrogenogenic bacteria and hydrogenotrophic methanogens under conditions of <102 Pa-H2 and two pure cultures of hydrogenotrophic methanogens under conditions of 105 Pa-H2 were tested. Carbon isotope fractionation between CH4 and CO2 during hydrogenotrophic methanogenesis was correlated with pH2, as indicated in previous studies. The hydrogen isotope ratio of CH4 produced during rapid growth of the thermophilic methanogen Methanothermococcus okinawensis under high pH2 conditions ( 105 Pa) was affected by the isotopic composition of H2, as concluded in a previous study of Methanothermobacter thermautotrophicus. This " {δ D}_{{H}_2} effect" is a possible cause of the diversity of previously reported values for hydrogen isotope fractionation between CH4 and H2O examined in H2-enriched culture experiments. Hydrogen isotope fractionation between CH4 and H2O, defined by (1000 + {δ D}_{{CH}_4} )/(1000 + {δ D}_{{H}_2O} ), during hydrogenotrophic methanogenesis of the H2-syntrophic cocultures was in the range 0.67-0.69. The hydrogen isotope fractionation of our H2-syntrophic dataset overlaps with those obtained not only from low- pH2 experiments reported so far but also from natural samples of "young" methane reservoirs (0.66-0.74). Conversely, such hydrogen isotope fractionation is not consistent with that of "aged" methane in geological samples (≥0.79), which has been regarded as methane produced via hydrogenotrophic methanogenesis from the carbon isotope fractionation. As a possible process inducing the inconsistency in hydrogen isotope signatures between experiments and geological samples, we hypothesize that the hydrogen isotope signature of CH4 imprinted at the time of methanogenesis, as in the experiments and natural young methane, may be altered by diagenetic hydrogen isotope exchange between extracellular CH4 and H2O through reversible reactions of the microbial methanogenic pathway in methanogenic region and/or geological methane reservoirs.

Mantle End-Members: The Trace Element Perspective

NASA Astrophysics Data System (ADS)

Willbold, M.; Stracke, A.; Hofmann, A. W.

2004-12-01

On the basis of their isotopic composition, ocean island basalts (OIB) have been classified into three to four end-members; HIMU with the most radiogenic Pb isotope ratios of OIB and Enriched Mantle 1 and 2 (EM1, EM2) with less radiogenic but variable Pb isotope and highly radiogenic Sr isotope signatures. It has also been argued that each of these isotopic families has common trace element characteristics that distinguish them from one another and so substantiated this classification. Here, we present new high-precision trace element data for samples from St. Helena, Tristan da Cunha and Gough in the Atlantic Ocean. The overall data-set is augmented by OIB data from the GEOROC database and includes data from all major isotopic families (HIMU: St. Helena, Mangaia, Tubuai, and Rururtu; EM1: Tristan da Cunha, Gough, Pitcairn; and EM2: Samoa, Marquesas, and Society). For each locality we use only islands defining the most extreme isotopic compositions. The entire data-set has been screened to exclude altered and highly differentiated samples. HIMU basalts have a very uniform trace element composition. Compared to HIMU-type basalts, EM-type basalts are enriched in Rb, Ba, and K, and depleted in U, Nb, and Ta, relative to La. Different EM-type OIBs from the same isotopic family (EM1 or EM2), have distinct trace element characteristics that can ultimately only be caused by different source compositions. For example, Ba/Th ratios in samples from both Tristan da Cunha (EM1) and Samoa (EM2) are similarly high (ca. 110) whereas Ba/Th ratios in samples from Pitcairn (EM1) and Society (EM2) samples are consistently lower (ca. 70). Thus on the basis of their trace element composition, EM-type OIB cannot be classified into EM1 and EM2 type basalts, nor can any other grouping be identified. The remarkably uniform isotopic and trace element composition of HIMU-type basalts suggests derivation from a single common source reservoir, most likely subduction-modified oceanic crust. Although there are some trace element characteristics common to all EM-type basalts, which distinguish them from HIMU-type basalts (e.g. uniformly high Th/U ratios of 4.7 ± 0.3, and enrichment in Cs-U), each suite of EM-type basalts has unique trace element signatures that distinguish them from any other suite of EM-type basalts. This is especially obvious when comparing the trace element composition of EM basalts from one isotopic family, for example EM1-type basalts from Tristan, Gough and Pitcairn. Consequently, the trace element systematics of EM-type basalts suggest that there are many different EM-type sources, whereas the isotopic composition of EM-type basalts suggest derivation from two broadly similar sources, i.e. EM1 and EM2. The large variability in subducting sediments with respect to both parent-daughter (e.g. Rb/Sr, Sm/Nd, U/Pb, Th/Pb,...) and other trace element ratios makes it unlikely that there are reproducible mixtures of sediments leading to two different isotopic evolution paths (EM1 and EM2) while preserving a range of incompatible element contents for each isotopic family, as would be required to reconcile the isotopic and trace element characteristics of EM-type basalts. Although this does not a priori argue against sediments as possible source components for OIB, it does argue against two distinct groups of sediments as EM1 and EM2 sources. Further characterization of sources with the same general origin (e.g. a certain type of crust or lithosphere) or identification of processes leading to reservoirs with similar parent-daughter ratio characteristics but different incompatible trace element contents could resolve the apparent conundrum.

Plume-stagnant slab-lithosphere interactions: Origin of the late Cenozoic intra-plate basalts on the East Eurasia margin

NASA Astrophysics Data System (ADS)

Kimura, Jun-Ichi; Sakuyama, Tetsuya; Miyazaki, Takashi; Vaglarov, Bogdan S.; Fukao, Yoshio; Stern, Robert J.

2018-02-01

Intra-plate basalts of 35-0 Ma in East Eurasia formed in a broad backarc region above the stagnant Pacific Plate slab in the mantle transition zone. These basalts show regional-scale variations in Nd-Hf isotopes. The basalts with the most radiogenic Nd-Hf center on the Shandong Peninsula with intermediate Nd-Hf at Hainan and Datong. The least radiogenic basalts occur in the perimeters underlain by the thick continental lithosphere. Shandong basalts possess isotopic signatures of the young igneous oceanic crust of the subducted Pacific Plate. Hainan and Datong basalts have isotopic signatures of recycled subduction materials with billions of years of storage in the mantle. The perimeter basalts have isotopic signatures similar to pyroxenite xenoliths from the subcontinental lithospheric mantle beneath East Eurasia. Hainan basalts exhibit the highest mantle potential temperature (Tp), while the Shandong basalts have the lowest Tp. We infer that a deep high-Tp plume interacted with the subducted Pacific Plate slab in the mantle transition zone to form a local low-Tp plume by entraining colder igneous oceanic lithosphere. We infer that the subducted Izanagi Plate slab, once a part of the Pacific Plate mosaic, broke off from the Pacific Plate slab at 35 Ma to sink into the lower mantle. The sinking Izanagi slab triggered the plume that interacted with the stagnant Pacific slab and caused subcontinental lithospheric melting. This coincided with formation of the western Pacific backarc marginal basins due to Pacific Plate slab rollback and stagnation.

Stable Isotope Signatures Suggest Different Feeding Strategies for Atlantic and Gulf Menhaden

NASA Astrophysics Data System (ADS)

Perez-Perez, N.; Smith, S. L.; Gonsalves, L. C.; Lamb, M.

2016-02-01

Atlantic menhaden (Brevoortia tyrannus) is a keystone forage species that ranges on the Atlantic Coast from Nova Scotia to Florida. A related species, the Gulf menhaden (Brevoortia patronus) is found in the northern Gulf of Mexico from Florida to Texas. They each serve as prey for important recreational and commercial fish, such as blue fish, tuna and striped bass. Menhaden are filter feeders whose diets consist mostly of phytoplankton and zooplankton, and menhaden act as direct links between primary producers and larger valuable predators. In this study, we investigated and compared the isotopic signatures of water column nitrate (δ15N), bulk plankton and juvenile menhaden (δ 15N and δ 13C) collected from 5 sites in both the Choptank River, MD, and Apalachicola Bay, FL. We determined that menhaden inhabiting the temperate zone versus the sub-tropical region exhibited statistically different isotopic signatures, suggesting different feeding strategies. Choptank River menhaden were enriched 4‰ in δ 15N over Apalachicola Bay menhaden. Choptank River menhaden are mostly likely obtaining their diet from a higher trophic level (copepods, primary consumers) than Apalachicola Bay fish, who may consume more phytoplankton. The Choptank River menhaden also may be consuming more allochthonous material, and those from the Gulf area eat a more authochthonous diet. In addition, Atlantic menhaden collected from fresh water creeks versus those collected closer to the bay differed in their δ 13C compositions, depending on site collection, with creek fish being more depleted in the heavier carbon isotope. The δ 15N values of water column nitrate were similar at Choptank and Apalachicola sites.

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

USGS Publications Warehouse

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

2011-01-01

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

Uranium isotopes fingerprint biotic reduction

DOE PAGES

Stylo, Malgorzata; Neubert, Nadja; Wang, Yuheng; ...

2015-04-20

Knowledge of paleo-redox conditions in the Earth’s history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U),more » i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth’s crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. In addition, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium.« less

Formation of Tellurium Nanocrystals during Anaerobic Growth of Bacteria That Use Te Oxyanions as Respiratory Electron Acceptors▿

PubMed Central

Baesman, Shaun M.; Bullen, Thomas D.; Dewald, James; Zhang, Donghui; Curran, Seamus; Islam, Farhana S.; Beveridge, Terry J.; Oremland, Ronald S.

2007-01-01

Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [ɛ] = −0.4 to −1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods (∼10-nm diameter by 200-nm length), which cluster together, forming larger (∼1,000-nm) rosettes composed of numerous individual shards (∼100-nm width by 1,000-nm length). In contrast, Sulfurospirillum barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods. PMID:17277198

Formation of tellurium nanocrystals during anaerobic growth of bacteria that use Te oxyanions as respiratory electron acceptors

USGS Publications Warehouse

Baesman, S.M.; Bullen, T.D.; Dewald, J.; Zhang, Dongxiao; Curran, S.; Islam, F.S.; Beveridge, T.J.; Oremland, R.S.

2007-01-01

Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [??] = -0.4 to -1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods (???10-nm diameter by 200-nm length), which cluster together, forming larger (???1,000-nm) rosettes composed of numerous individual shards (???100-nm width by 1,000-nm length). In contrast, Sulfurospirillium barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods. Copyright ?? 2007, American Society for Microbiology. All Rights Reserved.

Stable and radiocarbon isotopic composition of dissolved organic matter in the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Walker, B. D.; Druffel, E. R. M.; Kolasinski, J.; Roberts, B. J.; Xu, X.; Rosenheim, B. E.

2017-08-01

Dissolved organic carbon (DOC) is of primary importance to marine ecosystems and the global carbon cycle. Stable carbon (δ13C) and radiocarbon (Δ14C) isotopic measurements are powerful tools for evaluating DOC sources and cycling. However, the isotopic signature of DOC in the Gulf of Mexico (GOM) remains almost completely unknown. Here we present the first DOC Δ14C and δ13C depth profiles from the GOM. Our results suggest the Mississippi River exports large amounts of DOC with an anthropogenic "bomb" Δ14C signature. Riverine DOC is removed and recycled offshore, and some marine production of DOC is observed in the river plume. Offshore profiles show that DOC has higher Δ14C than its Caribbean feed waters, indicative of a modern deep DOC source in the GOM basin. Finally, high DOC with negative δ13C and Δ14C values were observed near the Macondo Wellhead, suggesting a transformation of Deepwater Horizon hydrocarbons into a persistent population of DOC.

Geogenic lead isotope signatures from meat products in Great Britain: Potential for use in food authentication and supply chain traceability.

PubMed

Evans, Jane A; Pashley, Vanessa; Richards, Gemma J; Brereton, Nicola; Knowles, Toby G

2015-12-15

This paper presents lead (Pb) isotope data from samples of farm livestock raised in three areas of Britain that have elevated natural Pb levels: Central Wales, the Mendips and the Derbyshire Peak District. This study highlights three important observations; that the Pb found in modern British meat from these three areas is geogenic and shows no clear evidence of modern tetraethyl anthropogenic Pb contribution; that the generally excellent match between the biological samples and the ore field data, particularly for the Mendip and Welsh data, suggests that this technique might be used to provenance biological products to specific ore sites, under favourable conditions; and that modern systems reflect the same process of biosphere averaging that is analogous to cultural focusing in human archaeological studies that is the process of biological averaging leading to an homogenised isotope signature with increasing Pb concentration. Copyright © 2015. Published by Elsevier B.V.

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

PubMed

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

2013-03-01

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

Robustness of fossil fish teeth for seawater neodymium isotope reconstructions under variable redox conditions in an ancient shallow marine setting

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

Searching for signatures of life on Mars: an Fe-isotope perspective.

PubMed

Anand, M; Russell, S S; Blackhurst, R L; Grady, M M

2006-10-29

Recent spacecraft and lander missions to Mars have reinforced previous interpretations that Mars was a wet and warm planet in the geological past. The role of liquid water in shaping many of the surface features on Mars has long been recognized. Since the presence of liquid water is essential for survival of life, conditions on early Mars might have been more favourable for the emergence and evolution of life. Until a sample return mission to Mars, one of the ways of studying the past environmental conditions on Mars is through chemical and isotopic studies of Martian meteorites. Over 35 individual meteorite samples, believed to have originated on Mars, are now available for lab-based studies. Fe is a key element that is present in both primary and secondary minerals in the Martian meteorites. Fe-isotope ratios can be fractionated by low-temperature processes which includes biological activity. Experimental investigations of Fe reduction and oxidation by bacteria have produced large fractionation in Fe-isotope ratios. Hence, it is considered likely that if there is/were any form of life present on Mars then it might be possible to detect its signature by Fe-isotope studies of Martian meteorites. In the present study, we have analysed a number of Martian meteorites for their bulk-Fe-isotope composition. In addition, a set of terrestrial analogue material has also been analysed to compare the results and draw inferences. So far, our studies have not found any measurable Fe-isotopic fractionation in bulk Martian meteorites that can be ascribed to any low-temperature process operative on Mars.

Searching for signatures of life on Mars: an Fe-isotope perspective

PubMed Central

Anand, M; Russell, S.S; Blackhurst, R.L; Grady, M.M

2006-01-01

Recent spacecraft and lander missions to Mars have reinforced previous interpretations that Mars was a wet and warm planet in the geological past. The role of liquid water in shaping many of the surface features on Mars has long been recognized. Since the presence of liquid water is essential for survival of life, conditions on early Mars might have been more favourable for the emergence and evolution of life. Until a sample return mission to Mars, one of the ways of studying the past environmental conditions on Mars is through chemical and isotopic studies of Martian meteorites. Over 35 individual meteorite samples, believed to have originated on Mars, are now available for lab-based studies. Fe is a key element that is present in both primary and secondary minerals in the Martian meteorites. Fe-isotope ratios can be fractionated by low-temperature processes which includes biological activity. Experimental investigations of Fe reduction and oxidation by bacteria have produced large fractionation in Fe-isotope ratios. Hence, it is considered likely that if there is/were any form of life present on Mars then it might be possible to detect its signature by Fe-isotope studies of Martian meteorites. In the present study, we have analysed a number of Martian meteorites for their bulk-Fe-isotope composition. In addition, a set of terrestrial analogue material has also been analysed to compare the results and draw inferences. So far, our studies have not found any measurable Fe-isotopic fractionation in bulk Martian meteorites that can be ascribed to any low-temperature process operative on Mars. PMID:17008212

Stable Carbon Isotope Ratios of Lipid Biomarkers and Biomass for Sulfate-reducing Bacteria Grown with Different Substrates

NASA Technical Reports Server (NTRS)

Londry, K. L.; Jahnke, L. L.; Des Marais, D. J.

2001-01-01

We have determined isotope ratios of biomass and Fatty Acids Methyl Esters (FAME) for four Sulfate-Reducing Bacteria (SRB) grown lithotrophically and heterotrophically, and are investigating whether these biomarker signatures can reveal the ecological role and distribution of SRB within microbial mats. Additional information is contained in the original extended abstract.

Precise dating of Dansgaard-Oeschger climate oscillations in western Europe from stalagmite data.

PubMed

Genty, D; Blamart, D; Ouahdi, R; Gilmour, M; Baker, A; Jouzel, J; Van-Exter, Sandra

2003-02-20

The signature of Dansgaard-Oeschger events--millennial-scale abrupt climate oscillations during the last glacial period--is well established in ice cores and marine records. But the effects of such events in continental settings are not as clear, and their absolute chronology is uncertain beyond the limit of (14)C dating and annual layer counting for marine records and ice cores, respectively. Here we present carbon and oxygen isotope records from a stalagmite collected in southwest France which have been precisely dated using 234U/230Th ratios. We find rapid climate oscillations coincident with the established Dansgaard-Oeschger events between 83,000 and 32,000 years ago in both isotope records. The oxygen isotope signature is similar to a record from Soreq cave, Israel, and deep-sea records, indicating the large spatial scale of the climate oscillations. The signal in the carbon isotopes gives evidence of drastic and rapid vegetation changes in western Europe, an important site in human cultural evolution. We also find evidence for a long phase of extremely cold climate in southwest France between 61.2 +/- 0.6 and 67.4 +/- 0.9 kyr ago.

Origin of the Indian Ocean-type isotopic signature in basalts from Philippine Sea plate spreading centers: An assessment of local versus large-scale processes

NASA Astrophysics Data System (ADS)

Hickey-Vargas, Rosemary

1998-09-01

Basalts erupted from spreading centers on the Philippine Sea plate between 50 Ma and the present have the distinctive isotopic characteristics of Indian Ocean mid-ocean ridge basalt (MORB), such as high 208Pb/204Pb and low 143Nd/144Nd for a given 206Pb/204Pb compared with Pacific and Atlantic Ocean MORB. This feature may indicate that the upper mantle of the Philippine Sea plate originated as part of the existing Indian Ocean upper mantle domain, or, alternatively, that local processes duplicated these isotopic characteristics within the sub-Philippine Sea plate upper mantle. Synthesis of new and published isotopic data for Philippine Sea plate basin basalts and island arc volcanic rocks, radiometric ages, and tectonic reconstructions of the plate indicates that local processes, such as contamination of the upper mantle by subducted materials or by western Pacific mantle plumes, did not produce the Indian Ocean-type signature in Philippine Sea plate MORB. It is more likely that the plate originated over a rapidly growing Indian Ocean upper mantle domain that had spread into the area between Australia/New Guinea and southeast Asia before 50 Ma.

Isotope signatures of N2O emitted from vegetable soil: Ammonia oxidation drives N2O production in NH4(+)-fertilized soil of North China.

PubMed

Zhang, Wei; Li, Yuzhong; Xu, Chunying; Li, Qiaozhen; Lin, Wei

2016-07-08

Nitrous oxide (N2O) is a potent greenhouse gas. In North China, vegetable fields are amended with high levels of N fertilizer and irrigation water, which causes massive N2O flux. The aim of this study was to determine the contribution of microbial processes to N2O production and characterize isotopic signature effects on N2O source partitioning. We conducted a microcosm study that combined naturally abundant isotopologues and gas inhibitor techniques to analyze N2O flux and its isotopomer signatures [δ(15)N(bulk), δ(18)O, and SP (intramolecular (15)N site preference)] that emitted from vegetable soil after the addition of NH4(+) fertilizers. The results show that ammonia oxidation is the predominant process under high water content (70% water-filled pore space), and nitrifier denitrification contribution increases with increasing N content. δ(15)N(bulk) and δ(18)O of N2O may not provide information about microbial processes due to great shifts in precursor signatures and atom exchange, especially for soil treated with NH4(+) fertilizer. SP and associated two end-member mixing model are useful to distinguish N2O source and contribution. Further work is needed to explore isotopomer signature stability to improve N2O microbial process identification.

Isotope signatures of N2O emitted from vegetable soil: Ammonia oxidation drives N2O production in NH4+-fertilized soil of North China

NASA Astrophysics Data System (ADS)

Zhang, Wei; Li, Yuzhong; Xu, Chunying; Li, Qiaozhen; Lin, Wei

2016-07-01

Nitrous oxide (N2O) is a potent greenhouse gas. In North China, vegetable fields are amended with high levels of N fertilizer and irrigation water, which causes massive N2O flux. The aim of this study was to determine the contribution of microbial processes to N2O production and characterize isotopic signature effects on N2O source partitioning. We conducted a microcosm study that combined naturally abundant isotopologues and gas inhibitor techniques to analyze N2O flux and its isotopomer signatures [δ15Nbulk, δ18O, and SP (intramolecular 15N site preference)] that emitted from vegetable soil after the addition of NH4+ fertilizers. The results show that ammonia oxidation is the predominant process under high water content (70% water-filled pore space), and nitrifier denitrification contribution increases with increasing N content. δ15Nbulk and δ18O of N2O may not provide information about microbial processes due to great shifts in precursor signatures and atom exchange, especially for soil treated with NH4+ fertilizer. SP and associated two end-member mixing model are useful to distinguish N2O source and contribution. Further work is needed to explore isotopomer signature stability to improve N2O microbial process identification.

Isotopic evolution of Mauna Loa Volcano: A view from the submarine southwest rift zone

NASA Astrophysics Data System (ADS)

Kurz, Mark D.; Kenna, T. C.; Kammer, D. P.; Rhodes, J. Michael; Garcia, Michael O.

New isotopic and trace element measurements on lavas from the submarine southwest rift zone (SWR) of Mauna Loa continue the temporal trends of subaerial Mauna Loa flows, extending the known compositional range for this volcano, and suggesting that many of the SWR lavas are older than any exposed on land. He and Nd isotopic compositions are similar to those in the oldest subaerial Mauna Loa lavas (Kahuku and Ninole Basalts), while 87Sr/86Sr ratios are slightly lower (as low as .7036) and Pb isotopes are higher (206Pb'204Pb up to 18.30). The coherence of all the isotopes suggests that helium behaves as an incompatible element, and that helium isotopic variations in the Hawaiian lavas are produced by melting and mantle processes, rather than magma chamber or metasomatic processes unique to the gaseous elements. The variations of He, Sr, and Nd are most pronounced in lavas of approximately 10 ka age range [Kurz and Kammer, 1991], but the largest Pb isotopic variation occurs earlier. These variations are interpreted as resulting from the diminishing contribution from the upwelling mantle plume material as the shield building ends at Mauna Loa. The order of reduction in the plume isotopic signature is inferred to be Pb (at >100 ka), He (at ˜14 ka), Sr (at ˜9 ka), and Nd (at ˜8 ka); the different timing may relate to silicate/melt partition coefficients, with most incompatible elements removed first, and also to concentration variations within the plume. Zr/Nb, Sr/Nb, and fractionation-corrected Nb concentrations, correlate with the isotopes and are significantly higher in some of the submarine SWR lavas, suggesting temporal variability on time scales similar to the Pb isotopes (i.e. ˜ 100 ka). Historical lavas define trace element and isotopic trends that are distinct from the longer term (10 to 100 ka) variations, suggesting that different processes cause the short term variability. The temporal evolution of Mauna Loa, and particularly the new data from the submarine SWR, suggest that the isotopic composition of the upwelling plume mantle is best represented by data from Loihi seamount tholeiites. The temporal evolution suggests that the mantle source of the latest stage of Mauna Loa, which is characterized by radiogenic 87Sr/86Sr (up to .70395), unradiogenic 206Pb/204Pb (˜18.0), 3He/4He ratios similar to MORB, and low Nb concentrations, is a small-volume contribution related to non-plume components (such as normal asthenosphere, or entrained mantle).

Are high 3He/4He ratios in oceanic basalts an indicator of deep-mantle plume components?

USGS Publications Warehouse

Meibom, A.; Anderson, D.L.; Sleep, Norman H.; Frei, R.; Chamberlain, C.P.; Hren, M.T.; Wooden, J.L.

2003-01-01

The existence of a primordial, undegassed lower mantle reservoir characterized by high concentration of 3He and high 3He/4He ratios is a cornerstone assumption in modern geochemistry. It has become standard practice to interpret high 3He/4He ratios in oceanic basalts as a signature of deep-rooted plumes. The unfiltered He isotope data set for oceanic spreading centers displays a wide, nearly Gaussian, distribution qualitatively similar to the Os isotope (187Os/188 Os) distribution of mantle-derived Os-rich alloys. We propose that both distributions are produced by shallow mantle processes involving mixing between different proportions of recycled, variably aged radiogenic and unradiogenic domains under varying degrees of partial melting. In the case of the Re-Os isotopic system, radiogenic mid-ocean ridge basalt (MORB)-rich and unradiogenic (depleted mantle residue) endmembers are constantly produced during partial melting events. In the case of the (U+Th)-He isotope system, effective capture of He-rich bubbles during growth of phenocryst olivine in crystallizing magma chambers provides one mechanism for 'freezing in' unradiogenic (i.e. high 3He/4He) He isotope ratios, while the higher than chondritic (U+Th)/He elemental ratio in the evolving and partially degassed MORB melt provides the radiogenic (i.e. low 3He/4He) endmember. If this scenario is correct, the use of He isotopic signatures as a fingerprint of plume components in oceanic basalts is not justified. Published by Elsevier Science B.V.

The influence of microclimates and fog on stable isotope signatures used in interpretation of regional hydrology: East Maui, Hawaii

USGS Publications Warehouse

Scholl, M.A.; Gingerich, S.B.; Tribble, G.W.

2002-01-01

Stable isotopes of precipitation, ground water and surface water measured on the windward side of East Maui from 0 to 3055 m altitude were used to determine recharge sources for stream flow and ground water. Correct interpretation of the hydrology using rainfall ??18O gradients with altitude required consideration of the influence of fog, as fog samples had isotopic signatures enriched by as much as 3??? in ??18O and 21??? in ??D compared to volume-weighted average precipitation at the same altitude. The isotopic analyses suggested that fog drip was a major component of stream flow and shallow ground water at higher altitudes in the watershed. 18O/altitude gradients in rainfall were comparable for similar microclimates on Maui (this study) and Hawaii Island (1990-1995 study), however, East Maui ??18O values for rain in trade-wind and high-altitude microclimates were enriched compared to those from Hawaii Island. Isotopes were used to interpret regional hydrology in this volcanic island aquifer system. In part of the study area, stable isotopes indicate discharge of ground water recharged at least 1000 m above the sample site. This deep-flowpath ground water was found in springs from sea level up to 240 m altitude, indicating saturation to altitudes much higher than a typical freshwater lens. These findings help in predicting the effects of ground water development on stream flow in the area. Published by Elsevier Science B.V.

Using stable isotopes to associate migratory shorebirds with their wintering locations in Argentina

USGS Publications Warehouse

Farmer, A.H.; Abril, M.; Fernandez, M.; Torres, J.; Kester, C.; Bern, C.

2004-01-01

We are evaluating the use of stable isotopes to identify the wintering areas of Neotropical migratory shorebirds in Argentina. Our goal is to associate individual birds, captured on the breeding grounds or in migration with specific winter sites, thereby helping to identify distinct areas used by different subpopulations. In January and February 2002 and 2003, we collected flight feathers from shorebirds at 23 wintering sites distributed across seven province s in Argentina (n = 170). Feathers samples were pre- pared and analyzed for δ13C, δ15N, δ34S, δ18O and δD by continuous flow methods. A discriminant function based on deuterium alone was not an accurate predictor of a shorebird’s province of origin, ranging from 8% correct (Santiago del Estero) to 80% correct (San ta Cruz). When other isotopes were included, the prediction accuracy increased substantially (from 56% in Buenos Aires to 100% in Tucumán). The improvement in accuracy was due to C/N, which separated D-depleted sites in the Andes from those in the south, and the inclusion of S separated sites with respect to their distance from the Atlantic. We also were able to correctly discriminate shorebirds from among two closely spaced sites within the province of Tierra del Fuego. These results suggest the feasibility of identifying the origin of a shorebird at a provincial level of accuracy, as well as uniquely identifying birds from some closely spaced sites. There is a high degree of intra- and inter-bird variability, especially in the Pampas region, where there is wide variety of wetland/water conditions. In that important shorebird region, the variability itself may in fact be the “signature.” Future addition of trace elements to the analyses may improve predictions based solely on stable isotopes.

Sequencing Needs for Viral Diagnostics

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

Gardner, S N; Lam, M; Mulakken, N J

2004-01-26

We built a system to guide decisions regarding the amount of genomic sequencing required to develop diagnostic DNA signatures, which are short sequences that are sufficient to uniquely identify a viral species. We used our existing DNA diagnostic signature prediction pipeline, which selects regions of a target species genome that are conserved among strains of the target (for reliability, to prevent false negatives) and unique relative to other species (for specificity, to avoid false positives). We performed simulations, based on existing sequence data, to assess the number of genome sequences of a target species and of close phylogenetic relatives (''nearmore » neighbors'') that are required to predict diagnostic signature regions that are conserved among strains of the target species and unique relative to other bacterial and viral species. For DNA viruses such as variola (smallpox), three target genomes provide sufficient guidance for selecting species-wide signatures. Three near neighbor genomes are critical for species specificity. In contrast, most RNA viruses require four target genomes and no near neighbor genomes, since lack of conservation among strains is more limiting than uniqueness. SARS and Ebola Zaire are exceptional, as additional target genomes currently do not improve predictions, but near neighbor sequences are urgently needed. Our results also indicate that double stranded DNA viruses are more conserved among strains than are RNA viruses, since in most cases there was at least one conserved signature candidate for the DNA viruses and zero conserved signature candidates for the RNA viruses.« less

Understanding the role of fog in forest hydrology: Stable isotopes as tools for determining input and partitioning of cloud water in montane forests

USGS Publications Warehouse

Scholl, M.; Eugster, W.; Burkard, R.

2011-01-01

Understanding the hydrology of tropical montane cloud forests (TMCF) has become essential as deforestation of mountain areas proceeds at an increased rate worldwide. Passive and active cloud-water collectors, throughfall and stemflow collectors, visibility or droplet size measurements, and micrometeorological sensors are typically used to measure the fog water inputs to ecosystems. In addition, stable isotopes may be used as a natural tracer for fog and rain. Previous studies have shown that the isotopic signature of fog tends to be more enriched in the heavier isotopes 2H and 18O than that of rain, due to differences in condensation temperature and history. Differences between fog and rain isotopes are largest when rain is from synoptic-scale storms, and fog or orographic cloud water is generated locally. Smaller isotopic differences have been observed between rain and fog on mountains with orographic clouds, but only a few studies have been conducted. Quantifying fog deposition using isotope methods is more difficult in forests receiving mixed precipitation, because of limitations in the ability of sampling equipment to separate fog from rain, and because fog and rain may, under some conditions, have similar isotopic composition. This article describes the various types of fog most relevant to montane cloud forests and the importance of fog water deposition in the hydrologic budget. A brief overview of isotope hydrology provides the background needed to understand isotope applications in cloud forests. A summary of previous work explains isotopic differences between rain and fog in different environments, and how monitoring the isotopic signature of surface water, soil water and tree xylem water can yield estimates of the contribution of fog water to streamflow, groundwater recharge and transpiration. Next, instrumentation to measure fog and rain, and methods to determine isotopic concentrations in plant and soil water are discussed. The article concludes with the identification of some of the more pressing research questions in this field and offers various suggestions for future research. ?? 2010 This article is a US Government work and is in the public domain in the USA.

Quantifying the relative contribution of natural gas fugitive emissions to total methane emissions in Colorado and Utah using mobile stable isotope (13CH4) analysis

NASA Astrophysics Data System (ADS)

Rella, Chris; Jacobson, Gloria; Crosson, Eric; Karion, Anna; Petron, Gabrielle; Sweeney, Colm

2013-04-01

Fugitive emissions of methane into the atmosphere are a major concern facing the natural gas production industry. Because methane is more energy-rich than coal per kg of CO2 emitted into the atmosphere, it represents an attractive alternative to coal for electricity generation. However, given that the global warming potential of methane is many times greater than that of carbon dioxide (Solomon et al. 2007), the importance of quantifying the fugitive emissions of methane throughout the natural gas production and distribution process becomes clear (Howarth et al. 2011). A key step in the process of assessing the emissions arising from natural gas production activities is partitioning the observed methane emissions between natural gas fugitive emissions and other sources of methane, such as from landfills or agricultural activities. One effective method for assessing the contribution of these different sources is stable isotope analysis. In particular, the 13CH4 signature of natural gas (-35 to -40 permil) is significantly different that the signature of other significant sources of methane, such as landfills or ruminants (-45 to -70 permil). In this paper we present measurements of mobile field 13CH4 using a spectroscopic stable isotope analyzer based on cavity ringdown spectroscopy, in two intense natural gas producing regions of the United States: the Denver-Julesburg basin in Colorado, and the Uintah basin in Utah. Mobile isotope measurements in the nocturnal boundary layer have been made, over a total path of 100s of km throughout the regions, allowing spatially resolved measurements of the regional isotope signature. Secondly, this analyzer was used to quantify the isotopic signature of those individual sources (natural gas fugitive emissions, concentrated animal feeding operations, and landfills) that constitute the majority of methane emissions in these regions, by making measurements of the isotope ratio directly in the downwind plume from each source. These data are combined to establish the fraction of the observed methane emissions that can be attributed to natural gas activities in the regions. The fraction of total methane emissions in the Denver-Julesburg basin that can be attributed to natural gas fugitive emissions has been determined to be 71 +/- 9%. References: 1. S. Solomon, D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M.Tignor and H.L. Miller (eds.). IPCC, 2007: Climate Change 2007: The Physical Science Basis of the Fourth Assessment Report. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA. 2. R.W. Howarth, R. Santoro, and A. Ingraffea. "Methane and the greenhouse-gas footprint of natural gas from shale formations." Climate Change, 106, 679 (2011).

Isotopic Characterisation of Methane Emissions: use of Keeling-plot Methods to Identify Source Signatures in Boreal Wetlands and Other Settings

NASA Astrophysics Data System (ADS)

Fisher, R. E.; Lowry, D.; France, J.; Lanoiselle, M.; Zazzeri, G.; Nisbet, E. G.

2012-12-01

Different methane sources have different δ13CCH4 and δDCH4 signatures, which potentially provides a powerful constraint on models of methane emission budgets. However source signatures remain poorly known and need to be studied in more detail if isotopic measurements of ambient air are to be used to constrain regional and global emissions. The Keeling plot method (plotting δ13CCH4 or δDCH4 against 1/CH4 concentration in samples of ambient air in the close vicinity of known sources) directly assesses the source signature of the methane that is actually emitted to the air. This contrasts with chamber studies, measuring air within a chamber, where local micro-meteorological and microbiological processes are occurring. Keeling plot methods have been applied to a wide variety of settings in this study. The selection of appropriate background measurements for Keeling plot analysis is also considered. The method has been used on a local scale to identify the source signature of summer emissions from subarctic wetlands in Fennoscandia. Samples are collected from low height (0.3-3m) over the wetlands during 24-hour periods, to collect daily emissions maxima (warm late afternoons), inversion maxima (at the coldest time of the 24hr daylight: usually earliest morning), and ambient minima when mixing occurs (often mid afternoon). Some results are comparable to parallel chamber studies, but in other cases there are small but significant shifts between CH4 in chamber air and CH4 that is dispersing in the above-ground air. On a regional to continental scale the isotopic signature of bulk sources of emissions can be identified using Keeling plots. The methodology is very applicable for use in urban and urban-rural settings. For example, the winter SE monsoon sweeps from inland central Asia over China to Hong Kong. Application of back trajectory analysis and Keeling plot methods implied coal emissions may be a significant Chinese source of methane in January, although in other months biological sources dominate. Similarly, in London the method has been used to test the London methane emission inventory.

Stable isotope evidence of terrestrial organic matter incorporation into coastal marine food webs: impact of Rhone River inputs on five NW Mediterranean marine flatfish species.

NASA Astrophysics Data System (ADS)

Darnaude, A. M.; Salen-Picard, C.; Harmelin-Vivien, M.

2003-04-01

The positive influence of land-based run-off on coastal fishery production is thought to be of particular importance for oligotrophic seas such as the Mediterranean. In order to estimate the impact of the Rhone River inputs of particulate organic matter (POM) on exploited demersal fish populations, stable isotope signature in nitrogen (δ15N) and carbon (δ13C) were determined for both juveniles and adults of the five main flatfish species living off the Rhone delta (Arnoglossus laterna, Buglossidium luteum, Citharus linguatula, Solea impar and Solea solea) and the main components of their food webs. The five flatfish species showed inter and intra-specific differences in isotopic signatures. The δ15N significantly increased from the smallest species to the largest ones and, in all species, from juveniles to adults (P<0.05), which indicated a global increase in trophic level with fish body size. Concerning the carbon signature, the δ13C obtained indicated an incorporation of organic material from terrestrial origin in the flesh of all the species. This incorporation was minimum for C. linguatula and reduced for all the species with the exception of S. solea for which a significantly (P<0.001) lower δ13C indicated an important use of organic matter from terrestrial origin. Mean δ13C values also differed significantly between juveniles and adults of B. luteum and S. impar (P<0.05), suggesting changes in terrestrial organic matter use with growth in these two species. To explain inter and intra-specific differences in δ13C, stable isotope data were compared with gut content analyses (prey % total contents mass, W%) performed on the same fishes. The δ13C signature of fishes was inversely related to the W% of polychaetes in their diet, and not to other prey categories. The common sole S. solea, that fed mainly on polychaetes (W% > 50% at all benthic stages of life), exhibited the most negative mean δ13C for both juveniles and adults among all the fish species studied. The isotopic analyses of the Rhone River water, the marine phytoplankton, the sediment and the main fish prey, confirmed that polychaetes represented the major pathway of terrestrial POM transfer up to fishes into coastal trophic webs. The effect of terrestrial inputs in enhancing the population dynamics of the five flatfish species studied differed thus according to their diet. Keywords : river run-off, food webs, stable isotopes, gut contents, flatfishes, fisheries, NW Mediterranean.

Are dual isotope and isotopomer ratios of N2O useful indicators for N2O turnover during denitrification in nitrate-contaminated aquifers?

NASA Astrophysics Data System (ADS)

Well, Reinhard; Eschenbach, Wolfram; Flessa, Heinz; von der Heide, Carolin; Weymann, Daniel

2012-08-01

Denitrifying aquifers are sources of the greenhouse gas N2O. Isotopic signatures reflect processes of production and reduction of N2O, but it is not clear to which extent these can be used to quantify those processes. We investigated the spatial distribution of isotopologue values of N2O (δ18O, average δ15N, and 15N site preference, SP) in two denitrifying sandy aquifers to study N2O production and reduction and associated isotope effects in groundwater. For the first time, we combined this approach with direct estimation of N2O reduction from excess-N2 analysis. Groundwater samples were collected from 15 monitoring wells and four multilevel sampling wells and analysed for NO3-, dissolved N2O, dissolved O2, excess N2 from denitrification and isotopic signatures of NO3- and N2O. Both aquifers exhibited high NO3- concentrations with average concentrations of 22 and 15 mg N L-1, respectively. Evidence of intense denitrification with associated N2O formation was obtained from mean excess-N2 of 3.5 and 4.3 mg N L-1, respectively. Isotopic signatures of N2O were highly variable with ranges of 17.6-113.2‰ (δ18O), -55.4 to 89.4‰ (δ15Nbulk) and 1.8-97.9‰ (SP). δ15N and δ18O of NO3- ranged from -2.1‰ to 65.5‰ and from -5‰ to 33.5‰, respectively. The relationships between δ15N of NO3-, δ15Nbulk and SP were not in good agreement with the distribution predicted by a Rayleigh-model of isotope fractionation. The large ranges of δ18O and SP of N2O as well as the close correlation between these values could be explained by the fact that N2O reduction to N2 was strongly progressed but variable. We confirm and explain that a large range in SP and δ18O is typical for N2O from denitrifying aquifers, showing that this source signature can be distinguished from the isotopic fingerprint of N2O emitted from soils without water-logging. We conclude that isotopologue values of N2O in our sites were not suitable to quantify production or reduction of N2O or the contribution of different processes to the total N2O flux, apparently because these values were not only governed by individual pathways but eventually also by the spatial distribution of substrates and activity within the aquifers. These observations could be explained by the dynamics of N2O production, reduction and transport in water-saturated systems with heterogenic distribution of microbial activity and by a combination of diffusive and enzymatic isotope effects.

Lesson 5: Defining Valid Electronic Signatures

EPA Pesticide Factsheets

A valid electronic signature on an electronic document is one that is created with an electronic signature device that is uniquely entitled to a signatory, not compromised, and used by a signatory who is authorized to sign the electronic document.

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

DOE PAGES

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

2016-11-17

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

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

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

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

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

Stable C and N isotopic composition of cold-water corals from the Newfoundland and Labrador continental slope: Examination of trophic, depth and spatial effects

NASA Astrophysics Data System (ADS)

Sherwood, Owen A.; Jamieson, Robyn E.; Edinger, Evan N.; Wareham, Vonda E.

2008-10-01

With the aim of understanding of the trophic ecology of cold-water corals, this paper explores the tissue δ13C and δ15N values of 11 'coral' species (8 alcyonacean, 1 antipatharian, 1 pennatulacean, 1 scleractinian) collected along the Newfoundland and Labrador continental slope. Isotopic results delimit species along continua of trophic level and food lability. With an isotopic signature similar to macrozooplankton, Paragorgia arborea occupies the lowest trophic level and most likely feeds on fresh phytodetritus. Primnoa resedaeformis occupies a slightly higher trophic level, likely supplementing its diet with microzooplankton. Bathypathes arctica, Pennatulacea and other alcyonaceans ( Acanella arbuscula, Acanthogorgia armata, Anthomastus grandiflorus, Duva florida, Keratoisis ornata, Paramuricea sp.) had higher δ13C and δ15N values, suggesting these species feed at higher trophic levels and on a greater proportion of more degraded POM. Flabellum alabastrum had an isotopic signature similar to that of snow crab, indicating a primarily carnivorous diet. Isotopic composition did not vary significantly over a depth gradient of 50-1400 m. Coral δ13C increased slightly (<1‰) from the Hudson Strait to the southern Grand Banks, but δ15N did not. By modulating the availability and quality of suspended foods, substrate likely exerts a primary influence on the feeding habits of cold-water corals.

Assigning king eiders to wintering regions in the Bering Sea using stable isotopes of feathers and claws

USGS Publications Warehouse

Oppel, S.; Powell, A.N.

2008-01-01

Identification of wintering regions for birds sampled during the breeding season is crucial to understanding how events outside the breeding season may affect populations. We assigned king eiders captured on breeding grounds in northern Alaska to 3 broad geographic wintering regions in the Bering Sea using stable carbon and nitrogen isotopes obtained from head feathers. Using a discriminant function analysis of feathers obtained from birds tracked with satellite transmitters, we estimated that 88 % of feathers were assigned to the region in which they were grown. We then assigned 84 birds of unknown origin to wintering regions based on their head feather isotope ratios, and tested the utility of claws for geographic assignment. Based on the feather results, we estimated that similar proportions of birds in our study area use each of the 3 wintering regions in the Bering Sea. These results are in close agreement with estimates from satellite telemetry and show the usefulness of stable isotope signatures of feathers in assigning marine birds to geographic regions. The use of claws is currently limited by incomplete understanding of claw growth rates. Data presented here will allow managers of eiders, other marine birds, and marine mammals to assign animals to regions in the Bering Sea based on stable isotope signatures of body tissues. ?? Inter-Research 2008.

Stream and tree water sources in a coast redwood forest

NASA Astrophysics Data System (ADS)

Dymond, S.; Bladon, K. D.; McDonnell, J.; McNamara, J. P.

2017-12-01

Recent investigations in forested watersheds have shown the prevalence of "two water worlds" whereby plants access tightly bound soil waters and streamflow is sustained via mobile soil water and groundwater sources. We tested this hypothesis in a coast redwood forest at the Caspar Creek Experimental Watersheds (CCEW), California, USA. We collected water samples from different water pools (streams, groundwater, precipitation, soil, and trees) from 20 sites over 2 years for dual isotope analysis (δ18O and δD). Our results show that plants accessed deep, but tightly-bound soil waters throughout the growing season. This was true regardless of topographic position (riparian, toeslope, sideslope, shoulder, summit) of the sampled vegetation. Sap flux measurements of tree evapotranspiration (ET) also revealed no topographic variation in monthly ET rates. As the upper soil horizons dried through the growing season, the isotopic signature of the soils became increasingly depleted. Alternatively, piezometer and isotope data showed relatively stable groundwater conditions throughout the summer months; groundwater isotope data routinely plotted along the local meteoric water line. Moreover, the isotopic signature of streamflow data suggested that summer streamflow is sustained via groundwater and not interflow. Overall, our results appear to support the two water worlds hypothesis in a coast redwood forest. Our next steps are to subject the system to different levels of forest harvesting to investigate the role of disturbance on plant water use, storage selection and rainfall-runoff mechanisms.

Assessment of diel chemical and isotopic techniques to investigate biogeochemical cycles in the upper Klamath River, Oregon, USA

USGS Publications Warehouse

Poulson, S.R.; Sullivan, A.B.

2009-01-01

The upper Klamath River experiences a cyanobacterial algal bloom and poor water quality during the summer. Diel chemical and isotopic techniques have been employed in order to investigate the rates of biogeochemical processes. Four diel measurements of field parameters (temperature, pH, dissolved oxygen concentrations, and alkalinity) and stable isotope compositions (dissolved oxygen-??18O and dissolved inorganic carbon-??13C) have been performed between June 2007 and August 2008. Significant diel variations of pH, dissolved oxygen (DO) concentration, and DO-??18O were observed, due to varying rates of primary productivity vs. respiration vs. gas exchange with air. Diel cycles are generally similar to those previously observed in river systems, although there are also differences compared to previous studies. In large part, these different diel signatures are the result of the low turbulence of the upper Klamath River. Observed changes in the diel signatures vs. sampling date reflect the evolution of the status of the algal bloom over the course of the summer. Results indicate the potential utility of applying diel chemical and stable isotope techniques to investigate the rates of biogeochemical cycles in slow-moving rivers, lakes, and reservoirs, but also illustrate the increased complexity of stable isotope dynamics in these low-turbulence systems compared to well-mixed aquatic systems. ?? 2009 Elsevier B.V.

Golan Heights Groundwater Systems: Separation By REE+Y And Stable Isotopes

NASA Astrophysics Data System (ADS)

Siebert, C.; Geyer, S.; Knoeller, K.; Roediger, T.; Weise, S.; Dulski, P.; Moeller, P.; Guttman, J.

2008-12-01

In a semi-arid to arid country like Israel, all freshwater resources are under (over-) utilization. Particularly, the Golan Heights rank as one of the most important extraction areas of groundwater of good quality and quantity. Additionally the mountain range feed to a high degree the most important freshwater reservoir of Israel, the Sea of Galilee. Hence, knowing the sources and characters of the Golan Heights groundwater systems is an instantaneous demand regarding sustainable management and protection. Within the "German-Israeli-Jordanian-Palestinian Joint Research Program for the Sustainable Utilisation of Aquifer Systems", hundreds of water samples were taken from all over the Jordan-Dead Sea rift-system to understand groundwater flow-systems and salinisation. For that purpose, each sample was analysed for major and minor ions, rare earth elements including yttrium (REY) and stable isotopes of water (d18O, d2H). The REY distribution in groundwater is established during infiltration by the first water-rock interaction and consequently reflects the leachable components of sediments and rocks of the recharge area. In well- developed flow-systems, REY are adsorbed onto pore surfaces are in equilibrium with the percolating groundwater, even if the lithology changes (e.g. inter-aquifer flow). Thus, groundwater sampled from wells and springs still show the REY distribution pattern established in the recharge area. Since high temperatures do not occur in Golan Heights, d2H and d18O are less controlled by water-rock interaction than by climatic and geomorphological factors at the time of replenishment. Applying the REY signature as a grouping criterion of groundwaters, d18O vs. d2H plots yield a new dimension in interpreting isotope data. The combined use of hydrochemical and isotopic methods enabled us to contain the areas of replenishment and the flow-paths of all investigated groundwater in the Golan Heights. Despite location, salinity or temperature of spring or well waters, stable isotopes showed, that the main area of recharge is the elevated Hermon-Massif, with high annually precipitation amounts. The major element composition of fresh water well Alonei HaBashan 3, situated in the basaltic Upper Golan Heights, is defined by a pre-Neogenic limy aquifer and the contact to basalts. However, REY pattern refer to a calcareous infiltration area. Stable isotope signatures are lighter than in the recharge of comparable elevated Upper Galilee. Further to the south, in the Yarmouk gorge hot Mezar springs occur, which show stable isotope signatures even lighter than in water of Alonei Habshan 3. Both, REY pattern and hydrochemistry show infiltration into and contact to the Sr-rich limestone aquifer of the Mt. Scopus group. That adds up to an infiltration area some 50 km to the north, the nearest elevated area where carbonates crop out. Nearby Mezar, hot Hammat Gader springs occur, which show comparable isotopic signatures and hydrochemical composition. However, the REY-patterns indicate infiltration in basalts. By means of those three examples we could show, that the use of a combined hydrochemical and isotopic approach reveals complex and large-scale groundwater infiltration- and flow-systems much better than a focused view on a specific band of elements.

High intraspecific variability in the diet of a deep-sea nematode: Stable isotope and fatty acid analyses of Deontostoma tridentum on Chatham Rise, Southwest Pacific

NASA Astrophysics Data System (ADS)

Leduc, Daniel; Brown, Julie C. S.; Bury, Sarah J.; Lörz, Anne-Nina

2015-03-01

Small deep-sea organisms may exhibit a high degree of intraspecific variability in diet due to their ability to exploit a wide range of food sources and patchiness in food availability. Trophic interactions of small deep-sea benthic organisms, however, remain poorly understood. Here we describe spatial variation in diet/trophic level of the common deep-sea nematode Deontostoma tridentum on Chatham Rise, Southwest Pacific, using carbon and nitrogen stable isotope and fatty acid analyses. We also analysed sediment organic matter (SOM) and compared the isotopic composition of D. tridentum to other benthic and suprabenthic macrofaunal taxa with a variety of feeding modes. Variability in D. tridentum δ13C and δ15N signatures was high both among sites and within a single site on the southern flank of Chatham Rise. Among-site variation in SOM δ13C signatures was not sufficient to explain variation in nematode isotopic signatures. The presence of a positive correlation between δ13C and δ15N signatures of D. tridentum (both among and within sites) could suggest that differences in trophic level is the cause behind this variation. Nitrogen isotope data suggest the presence of 1-3 trophic levels in this species, which may reflect differences in prey availability, nematode body size, or habitat (benthic versus epizoic). Nematode δ15N values exceeded those of all other taxa we investigated, including other predators, but reasons for this enrichment remain unclear. The fatty acid composition of D. tridentum did not vary substantially between sites and was characterised by relatively high levels of 18:1n9 (15-20%) and polyunsaturated fatty acids (PUFAs; 22%). Although limited inferences can be made based on fatty acid composition due to the potential impacts of non-dietary factors, high levels of PUFAs indicate that D. tridentum represents a good source of these essential nutrients to higher trophic levels. In conclusion, our results show that (1) some deep-sea organisms exhibit a high degree of intraspecific variability in diet, and (2) nematodes may be an important source of PUFAs for larger animals in deep-sea environments, where the quality of SOM is low.

Static, Mixed-Array Total Evaporation for Improved Quantitation of Plutonium Minor Isotopes in Small Samples

NASA Astrophysics Data System (ADS)

Stanley, F. E.; Byerly, Benjamin L.; Thomas, Mariam R.; Spencer, Khalil J.

2016-06-01

Actinide isotope measurements are a critical signature capability in the modern nuclear forensics "toolbox", especially when interrogating anthropogenic constituents in real-world scenarios. Unfortunately, established methodologies, such as traditional total evaporation via thermal ionization mass spectrometry, struggle to confidently measure low abundance isotope ratios (<10-6) within already limited quantities of sample. Herein, we investigate the application of static, mixed array total evaporation techniques as a straightforward means of improving plutonium minor isotope measurements, which have been resistant to enhancement in recent years because of elevated radiologic concerns. Results are presented for small sample (~20 ng) applications involving a well-known plutonium isotope reference material, CRM-126a, and compared with traditional total evaporation methods.

Static, Mixed-Array Total Evaporation for Improved Quantitation of Plutonium Minor Isotopes in Small Samples.

PubMed

Stanley, F E; Byerly, Benjamin L; Thomas, Mariam R; Spencer, Khalil J

2016-06-01

Actinide isotope measurements are a critical signature capability in the modern nuclear forensics "toolbox", especially when interrogating anthropogenic constituents in real-world scenarios. Unfortunately, established methodologies, such as traditional total evaporation via thermal ionization mass spectrometry, struggle to confidently measure low abundance isotope ratios (<10(-6)) within already limited quantities of sample. Herein, we investigate the application of static, mixed array total evaporation techniques as a straightforward means of improving plutonium minor isotope measurements, which have been resistant to enhancement in recent years because of elevated radiologic concerns. Results are presented for small sample (~20 ng) applications involving a well-known plutonium isotope reference material, CRM-126a, and compared with traditional total evaporation methods. Graphical Abstract ᅟ.

Evidence for Tautomerisation of Glutamine in BLUF Blue Light Receptors by Vibrational Spectroscopy and Computational Chemistry

NASA Astrophysics Data System (ADS)

Domratcheva, Tatiana; Hartmann, Elisabeth; Schlichting, Ilme; Kottke, Tilman

2016-03-01

BLUF (blue light sensor using flavin) domains regulate the activity of various enzymatic effector domains in bacteria and euglenids. BLUF features a unique photoactivation through restructuring of the hydrogen-bonding network as opposed to a redox reaction or an isomerization of the chromophore. A conserved glutamine residue close to the flavin chromophore plays a central role in the light response, but the underlying modification is still unclear. We labelled this glutamine with 15N in two representative BLUF domains and performed time-resolved infrared double difference spectroscopy. The assignment of the signals was conducted by extensive quantum chemical calculations on large models with 187 atoms reproducing the UV-vis and infrared signatures of BLUF photoactivation. In the dark state, the comparatively low frequency of 1,667 cm-1 is assigned to the glutamine C=O accepting a hydrogen bond from tyrosine. In the light state, the signature of a tautomerised glutamine was extracted with the C=N stretch at ~1,691 cm-1 exhibiting the characteristic strong downshift by 15N labelling. Moreover, an indirect isotope effect on the flavin C4=O stretch was found. We conclude that photoactivation of the BLUF receptor does not only involve a rearrangement of hydrogen bonds but includes a change in covalent bonds of the protein.

Pb isotope signatures in the North Atlantic: initial results from the U.S. GEOTRACES North Atlantic Transect

NASA Astrophysics Data System (ADS)

Noble, A.; Echegoyen-Sanz, Y.; Boyle, E. A.

2012-12-01

This study presents Pb isotope data from the US GEOTRACES North Atlantic Transect (US-GT-NAT) sampled during two cruises that took place during Fall 2010 and 2011. Almost all of the Pb in the modern ocean is derived from anthropogenic sources, and the North Atlantic has received major Pb inputs from the United States and Europe due to emissions from leaded gasoline and high temperature industrial processes. During the past three decades, Pb fluxes to the North Atlantic have decreased following the phasing out of leaded gasoline in the United States and Europe. Following the concentrations and isotope ratios of Pb in this basin over time reveals the temporal evolution of Pb in this highly-affected basin. The Pb isotope signatures reflect the relative importance of changing inputs from the United States and Europe as leaded gasoline was phased out faster in the United States relative to Europe. In the western North Atlantic, a shallow (~100-200m) low Pb-206/Pb-207 ratio feature was observed near the Subtropical Underwater salinity peak at many stations across the transect, coincident with shallow subsurface maxima in Pb concentration. This water mass originates from high-salinity surface water near 25°N (Defant), which is in the belt of European-Pb-gas-contaminated African aerosols, which we confirmed by Pb-206/Pb-207 ~ 1.17 from upper ocean samples from US-GT-NAT station 18 (23.24degN,38.04degW). At the Mid-Atlantic Ridge station, Pb scavenging onto iron oxides and sulfide was observed by a decrease in Pb concentrations within the TAG hydrothermal plume, although the isotopic signature within the plume was slightly (~3 permil) lower than the surrounding waters possibly indicating a small contribution of hydrothermal Pb or preferential uptake of the lighter isotope. In the Mediteranean Outflow plume near Lisbon, Pb-206/Pb-207 (~1.178) is also strongly influenced by European Pb. Further results from the section will be presented as more data will be available by the conference.

Mobile measurement of methane: plumes, isotopes and inventory verification

NASA Astrophysics Data System (ADS)

Lowry, D.; Zazzeri, G.; Fisher, R. E.; France, J.; Al-Shalaan, A.; Lanoisellé, M.; Nisbet, E. G.

2015-12-01

Since 2013 the RHUL group has been identifying methane plumes from major UK sources using a Picarro 2301 coupled to the A0941 mobile module. Once identified the plumes have been sampled by filling Tedlar or Flexfoil bags for later carbon isotopic analysis by high-precision IRMS. This method has ben successfully deployed to isotopically characterize the main anthropogenic methane emitters in the UK (natural gas, coal, landfill, wastewater treatment, cattle; Zazzeri et al., 2015) and during overseas campaigns in eastern Australia (coal, cattle, legacy gas wells) and Kuwait (landfill, wastewater treatment, oil refineries, cattle, camels). This has identified strong similarities of isotopic signature for some sources (landfill, cattle), but large variations for others (natural gas, coal), which must be isotopically resolved at regional scale. Both landfill and natural gas emissions in SE England have tightly-constrained δ13C signatures, averaging -58 ± 3‰ and -36 ± 2‰, respectively, the latter being characteristic of homogenised North Sea gas supply. In contrast, signatures for coal mines in England and Wales fall in a range of 51.2 ± 0.3‰ to 30.9 ± 1.4‰, but can be tightly constrained by region. On a local scale in west London, repeat surveys in the boroughs of Hounslow and Runnymede have been made for comparison with the latest 1x1 km grid UK inventories for 2009 and 2012, which are subdivided by UNECE categories. An excess methane map can be derived for comparison with inventory emissions maps by identifying daily background and binning the excess values from mobile measurements by grid-square. This shows that the spatial distribution of emissions in the UK 2012 inventory is a big improvement on that of 2009. It also suggests that there is an overestimation of emissions from old landfills (closed before 2000 and reliant on a topsoil cap for oxidation), and an underestimation on emissions from currently active landfill cells. Zazzeri, G. et al. (2015) Plume mapping and isotopic characterization of anthropogenic methane sources, Atmospheric Environment, 110, 151-162.

N-C isotopic investigation of a zeolite-amended agricultural field

NASA Astrophysics Data System (ADS)

Ferretti, Giacomo; Natali, Claudio; Faccini, Barbara; Di Giuseppe, Dario; Bianchini, Gianluca; Coltorti, Massimo

2016-04-01

In this study, a C and N isotopic investigation in the soil-plant system of the ZeoLIFE project experimental field have been carried out. Since many years, natural and NH4-enriched zeolites have been used as soil amendant in agricultural context in order to reduce N losses, increase NUE (Nitrogen Use Efficiency) and crop yield. Nevertheless up to now there are no studies that, using the stable isotopes approach, highlighted the interaction between zeolites and plants in agricultural systems. The main aims of this study is to verify if natural zeolites amendment can enhance chemical fertilization efficiency and if N transfer from NH4-enriched zeolites to plants really occurs. Plants grown following traditional cultivation methods (with no zeolite addition) and plants grown on soils amended with natural and NH4-enriched zeolites (the latter obtained after mixing with pig-slurry with a very high 15N) were compared for two cultivation cycles (maize and wheat). As widely known, plants grown under conventional farming systems (use of chemical fertilizers as urea) and plants grown under organic farming can be discriminated by the isotopic signatures of plant tissues. For both years the main results of the study reveals that plants grown on plots amended with natural zeolites generally have their nitrogen isotopic signature more similar to that of the chemical fertilizers employed during the cultivation with respect to the plants cultivated in the non-amended plot. This suggests an enhanced N uptake by the plant from this specific N source with respect to the non-amended plot. On the other hand, plants grown on NH4-enriched zeolites registered a higher 15N, approaching the pig-slurry isotopic signature, confirming that this material can constitute an N pool for plants at least for two cultivation cycles. The distinct agricultural practices seem to be reflected in the plant physiology as recorded by the carbon discrimination factor (13C) which generally increases in plots amended with natural zeolites indicating better water/nutrient conditions. At similar N availability it seems that plant prefer to use natural N from pig slurry instead of using that coming from chemical fertilizers.

Quantifying the relative contribution of natural gas fugitive emissions to total methane emissions in Colorado, Utah, and Texas using mobile δ13CH4 analysis

NASA Astrophysics Data System (ADS)

Rella, C.; Crosson, E.; Petron, G.; Sweeney, C.; Karion, A.

2013-12-01

Fugitive emissions of methane into the atmosphere are a major concern facing the natural gas production industry. Because methane is more energy-rich than coal per kg of CO2 emitted into the atmosphere, it represents an attractive alternative to coal for electricity generation, provided that the fugitive emissions of methane are kept under control. A key step in assessing these emissions in a given region is partitioning the observed methane emissions between natural gas fugitive emissions and other sources of methane, such as from landfills or agricultural activities. One effective method for assessing the contribution of these different sources is stable isotope analysis, using the δ13CH4 signature to distinguish between natural gas and landfills or ruminants. We present measurements of mobile field δ13CH4 using a spectroscopic stable isotope analyzer based on cavity ringdown spectroscopy, in three intense natural gas producing regions of the United States: the Denver-Julesburg basin in Colorado, the Uintah basin in Utah, and the Barnett Shale in Texas. Mobile isotope measurements of individual sources and in the nocturnal boundary layer have been combined to establish the fraction of the observed methane emissions that can be attributed to natural gas activities. The fraction of total methane emissions in the Denver-Julesburg basin attributed to natural gas emissions is 78 +/- 13%. In the Uinta basin, which has no other significant sources of methane, the fraction is 96% +/- 15%. In addition, results from the Barnett shale are presented, which includes a major urban center (Dallas / Ft. Worth). Methane emissions in this region are spatially highly heterogeneous. Spatially-resolved isotope and concentration measurements are interpreted using a simple emissions model to arrive at an overall isotope ratio for the region. (left panel) Distribution of oil and gas well pads (yellow) and landfills (blue) in the Dallas / Ft. Worth area. Mobile nocturnal measurements of methane are shown in red, indicating a strong degree of source heterogeneity. (right panel) Histogram of individual isotopic source signatures, showing distinct signatures for landfills (red) and oil and gas sources (green).

Oxygen and strontium isotope tracing of human migration at the Bell Beaker site Le Tumulus des Sables, France.

NASA Astrophysics Data System (ADS)

Willmes, Malte; James, Hannah; Boel, Ceridwen; Courtaud, Patrice; Chancerel, Antoine; McMorrow, Linda; Armstrong, Richard; Kinsley, Les; Aubert, Maxime; Eggins, Stephen; Moffat, Ian; Grün, Rainer

2014-05-01

Oxygen (δ18O) and strontium (87Sr/86Sr) isotopes were used as tools to investigate human migration at the early Bell Beaker site (2500-2000 BC) Le Tumulus des Sables, Saint-Laurent-Médoc, south-west France. The O and Sr isotope ratios measured in tooth enamel record the average dietary isotope signature ingested by that individual during their childhood. When this data is compared to the isotope signature of the burial site it can be used to indicate if the individual migrated into this area during their lifetime. The O isotopic composition of meteoric water changes depending on climate, temperature and quantity of precipitation. O isotope ratios in skeletal and dental remains are related to body water, which in turn is influenced by diet, physiology and climate. Most of the water consumed by large mammals comes from drinking water, typically sourced locally. Sr isotope ratios on the other hand vary between different geologic regions, depending on their age and composition. Sr is released through weathering and transported into the soil, ground and surface water, where it becomes available for uptake by plants, enters the food cycle and eventually ends up in skeletal and dental tissue where it substitutes for calcium. We analysed the teeth of 18 adult and 8 juvenile disarticulated skeletons from Le Tumulus des Sables. O isotopes were analysed in-situ by Sensitive High Resolution Ion Micro Probe (SHRIMP).The Sr isotope analysis involved drilling a 0.2-0.5 mg sample of enamel from the tooth. The Sr was then chemically separated and analysed by Thermal Ionization Mass Spectrometry (TIMS). These results were then compared to the O isoscape of Europe and bioavailable Sr isotope data (fauna, plants, soils) from the IRHUM database. We found that most of the individuals at Le Tumulus des Sables show O and Sr isotope ratios corresponding to the local environmental signal and we interpret these as part of the local population. 3 adults however show slightly higher 87Sr/86Sr ratios, which correspond to a clay and limestone unit in close proximity (

Assessing the Origins of Aliphatic Amines in the Murchison Meteorite from their Compound-Specific Carbon Isotopic Ratios and Enantiomeric Composition

NASA Technical Reports Server (NTRS)

Aponte, Jose; Dworkin, Jason; Elsila, Jamie E.

2014-01-01

The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for alpha-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are chemically related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with delta C-13 values ranging from +21% to +129%, showing a decrease in C-13 with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential linkage to meteoritic amino acids.

Geodynamic implications for zonal and meridional isotopic patterns across the northern Lau and North Fiji Basins

NASA Astrophysics Data System (ADS)

Price, Allison A.; Jackson, Matthew G.; Blichert-Toft, Janne; Kurz, Mark D.; Gill, Jim; Blusztajn, Jerzy; Jenner, Frances; Brens, Raul; Arculus, Richard

2017-03-01

We present new Sr-Nd-Pb-Hf-He isotopic data for 65 volcanic samples from the northern Lau and North Fiji Basins. This includes 47 lavas obtained from 40 dredge sites spanning an east-west transect across the Lau and North Fiji basins, 10 ocean island basalt (OIB)-type lavas collected from seven Fijian islands, and eight OIB lavas sampled on Rotuma. For the first time, we are able to map clear north-south and east-west geochemical gradients in 87Sr/86Sr across the northern Lau and North Fiji Basins: lavas with the most geochemically enriched radiogenic isotopic signatures are located in the northeast Lau Basin, while signatures of geochemical enrichment are diminished to the south and west away from the Samoan hot spot. Based on these geochemical patterns and plate reconstructions of the region, these observations are best explained by the addition of Samoa, Rurutu, and Rarotonga hot spot material over the past 4 Ma. We suggest that underplated Samoan material has been advected into the Lau Basin over the past ˜4 Ma. As the slab migrated west (and toward the Samoan plume) via rollback over time, younger and hotter (and therefore less viscous) underplated Samoan plume material was entrained. Thus, entrainment efficiency of underplated plume material was enhanced, and Samoan plume signatures in the Lau Basin became stronger as the trench approached the Samoan hot spot. The addition of subducted volcanoes from the Cook-Austral Volcanic Lineament first from the Rarotonga hot spot, then followed by the Rurutu hot spot, contributes to the extreme geochemical signatures observed in the northeast Lau Basin.

Feeding habitats of the Gulf sturgeon, Acipenser oxyrinchus desotoi, in the Suwannee and Yellow rivers, Florida, as identified by multiple stable isotope analyses

USGS Publications Warehouse

Sulak, Kenneth J.; Berg, James J.; Randall, Michael T.

2012-01-01

Stable 13C, 15N, and 34S isotopes were analyzed to define the feeding habitats of Acipenser oxyrinchus desotoi in the Suwannee and Yellow River populations. For the majority (93.9%) of Suwannee subadults and adults, 13C and 34S signatures indicate use of nearshore marine waters as primary winter feeding habitat, probably due to the limiting size of the Suwannee Sound estuary. In the Yellow River population, 13C isotope signatures indicate that adults remain primarily within Pensacola Bay estuary to feed in winter, rather than emigrating to the open Gulf of Mexico. A minor Suwannee River subset (6% of samples), comprised of juveniles and subadults, displayed 13C signatures indicating continued feeding in freshwater during the spring immigration and fall emigration periods. This cannot be interpreted as incidental feeding since it resulted in a 20.5% turnover in tissue δ13C signatures over a 1–3 month period. Cessation of feeding in the general population does not coincide with high river water temperatures. The hypothesis of reduced feeding in freshwater due to localized prey depletion as a result of spatial activity restriction is not supported by the present study. Instead, Suwannee River A. o. desotoi appear to follow two trophic alternatives; 1) complete cessation of feeding immediately upon immigration in spring, continuing through emigration 8–9 months later (the predominant alternative); 2) continued intensive feeding for 1–3 months following immigration, switching to freshwater prey, selected primarily from high trophic levels (i.e., large prey). Stable –34S data verifies that recently immigrated, fully-anadromous A. o. desotoi adults had fed in nearshore marine waters, not offshore waters.

Lithium and carbon isotopes in river catchment: combined tracers to constrain chemical weathering processes

NASA Astrophysics Data System (ADS)

Rad, S.; Rive, K.; Assayag, N.; Dictor, M.; Garcin, M.

2012-12-01

Water-rock interactions produced in river catchment are accompanied by fractionation or changes in stable isotopes such as H, Li, C and O during chemical weathering processes. Li is a fluid-mobile element that tends to preferentially partition into the fluid phase during water-rock interaction. The relative mass difference between the two isotopes is considerable, generating large mass dependent fractionation during chemical weathering processes. The CO2 dissolves into the water providing the main acid that attack the rock during chemical weathering. Carbon stable isotopes and concentration of Dissolved Inorganic Carbon (DIC) in the river catchment can be used to determine the origin and consumption rates of CO2. In the present work, stable isotopes were analyzed in Allier River, one of the major river basins of France. The lithology is dominated by granite rocks within current upstream, while it is mainly basaltic and Oligocene sediments in the downstream with hydrothermal manifestations. We propose a new isotopic approach by combining δ7Li and δ13CDIC analyses in river catchment waters. A first method has been applied to volcanic tropical environments with Li concentrations correlated to δ13CDIC (Rad et al., 2011). Here, we have completed this approach by lithium isotopes. Water samples were collected during several field trips. Our results show a large variation in Li isotopes and C isotopes within the catchment from 3.3 ‰ to 30.3 ‰ and from -17.9‰ to -3.5‰, respectively. Chemical weathering rates linearly increase from upstream to downstream over 400km distance, whereas Li isotope signatures decrease and global C signature increases. This is due to low water-rock interaction dominated in upstream, whereas the downstream is punctually impacted by hydrothermalism. From Li and C isotopes, our results show 4 groups reflecting different chemical weathering processes: the first group with high fractionation of Li and C, for Li, the heavy lithium partitioned into surface waters, leaving lighter lithium behind in the weathered products, the signature of C is mainly due to organic matter or partially due to biochemical interaction with assimilation of CO2 by microorganism. The second group involves atmospheric equilibrium with CO2 degassing with organic origin or "cold" CO2 degassing with important fraction of Li. The third group present high fractionation of C, reflecting presence of superficial C with organic origin, with low fractionation of Li underling the hydrothermalism impact. Finally a fourth group with low fractionation mainly due to high temperature water-rock interaction. Therefore, the combination of the two tracers, Li and C isotopes, offers a powerful tool to discriminate chemical weathering processes from sources of alteration during water-rock interactions under multi-lithology terrains. Reference: Rad, S., Rivé, K., Allègre, C.J., 2011. Weathering regime associated with subsurface circulation on volcanic islands. Aquat. Geochem. 17, 3, 221-241.

Methane sources in Hong Kong - identification by mobile measurement and isotopic analysis

NASA Astrophysics Data System (ADS)

Fisher, Rebecca; Brownlow, Rebecca; Lowry, David; Lanoisellé, Mathias; Nisbet, Euan

2017-04-01

Hong Kong (22.4°N, 114.1°E) has a wide variety of natural and anthropogenic sources of methane within a small densely populated area (1106 km2, population ˜7.3 million). These include emissions from important source categories that have previously been poorly studied in tropical regions such as agriculture and wetlands. According to inventories (EDGAR v.4.2) anthropogenic methane emissions are mainly from solid waste disposal, wastewater disposal and fugitive leaks from oil and gas. Methane mole fraction was mapped out across Hong Kong during a mobile measurement campaign in July 2016. This technique allows rapid detection of the locations of large methane emissions which may focus targets for efforts to reduce emissions. Methane is mostly emitted from large point sources, with highest concentrations measured close to active landfill sites, sewage works and a gas processing plant. Air samples were collected close to sources (landfills, sewage works, gas processing plant, wetland, rice, traffic, cows and water buffalo) and analysed by mass spectrometry to determine the δ13C isotopic signatures to extend the database of δ13C isotopic signatures of methane from tropical regions. Isotopic signatures of methane sources in Hong Kong range from -70 ‰ (cows) to -37 ‰ (gas processing). Regular sampling of air for methane mole fraction and δ13C has recently begun at the Swire Institute of Marine Science, situated at Cape d'Aguilar in the southeast of Hong Kong Island. This station receives air from important source regions: southerly marine air from the South China Sea in summer and northerly continental air in winter and measurements will allow an integrated assessment of emissions from the wider region.

Measuring N2 Pressure Using Cyanobacteria Discipline: Geomicrobiology

NASA Technical Reports Server (NTRS)

Silverman, Shaelyn N.; Kopf, Sebastian; Gordon, Richard; Bebout, Brad M.; Som, Sanjoy

2017-01-01

The evolution of Earth's atmosphere has been governed by biological evolution. Dinitrogen (N2) has been a major constituent of Earth's atmosphere throughout the planet's history, yet only a few constraints exist for the partial pressure of N2 (pN2). In this study we evaluate two new potential proxies for pN2: the physical spacing between heterocysts and the isotopic signature of nitrogen fixation in filamentous cyanobacteria. Heterocyst-forming filamentous cyanobacteria are some of the oldest photosynthetic microorganisms on Earth, and debated fossilized specimens have been found in sedimentary rocks as old as 2 Ga. These organisms overcome nitrogen limitation in their aqueous environment through cellular differentiation along their filaments. The specialized cells that develop, known as heterocysts, fix the nitrogen and laterally distribute it to neighboring cells along the filaments. Because the concentration of the dissolved N2 available to the filaments correlates directly with pN2, any preservable physiological response of the organism to the changed N2 availability constitutes a potential proxy for pN2. In the laboratory, we have examined how pN2 is reflected in the heterocyst spacing pattern and in the isotopic signature of nitrogen fixation by subjecting the representative species Anabaena cylindrica and Anabaena variabilis to different N2 partial pressures during growth at constant temperature and lighting (in media free of combined nitrogen). We show experimentally that the distance between heterocysts and the nitrogen isotope fractionation measured in bulk biomass reflect the pN2 experienced by Anabaena cylindrica. Current work is investigating these responses in Anabaena variabilis. When heterocystous cyanobacteria fossilize, these morphological and isotopic signatures should preserve information about pN2 at that time. Application of this relationship to the rock record may provide a paleoproxy to complement the two existing geobarometers.

Tracing geogenic and anthropogenic sources in urban dusts: Insights from lead isotopes

NASA Astrophysics Data System (ADS)

Del Rio-Salas, R.; Ruiz, J.; De la O-Villanueva, M.; Valencia-Moreno, M.; Moreno-Rodríguez, V.; Gómez-Alvarez, A.; Grijalva, T.; Mendivil, H.; Paz-Moreno, F.; Meza-Figueroa, D.

2012-12-01

Tracing the source of metals in the environment is critical to understanding their pollution level and fate. Geologic materials are an important source of airborne particulate matter, but the contribution of contaminated soil to concentrations of Pb in airborne dust is not yet widely documented. To examine the potential significance of this mechanism, surface soil samples were collected, as well as wind-transported dust trapped at 1 and 2 m height at seven different locations including residential, industrial, high-traffic and rural sites. Samples of dust deposited on roofs from 24 schools were also obtained and analyzed for Pb isotope ratios. Spatial distribution of Pb of airborne and sedimented dust suggests a process dominated by re-suspension/sedimentation, which was controlled by erosion, traffic and topography of the urban area. Anthropogenic lead input in the city grades outward the urban zone toward geogenic values. Our results shows that Pb-isotopic signatures of leaded gasoline are imprinted in dust sedimented on roofs. Considering that leaded-gasoline has not been in use in Mexico since two decades ago, this signature shows not only a Pb-legacy in soil, but also a re-suspension process affecting air column below 3 m in height. The combination of the 207Pb/206Pb data of the surrounding rocks and urban dust, reveal three well-defined zones with remarkable anthropogenic influence, which correspond to the oldest urban sectors. This work highlights the importance of spatial characterization of metals in particles suspended below a height of 3 m of the airborne column, a fact that should be considered to identify exposure paths to humans and the potential risks. Lead isotope signatures allowed the identification of geogenic and anthropogenic emission sources for dust, a matter that deserves consideration in the efforts to control airborne metal emissions.

Oxygen isotopes in tree rings record variation in precipitation δ18O and amount effects in the south of Mexico

NASA Astrophysics Data System (ADS)

Brienen, Roel J. W.; Hietz, Peter; Wanek, Wolfgang; Gloor, Manuel

2013-12-01

Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings (δ18Otr). Interannual variation in δ18Otr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ13C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ18Otr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18O-depleted rain in the region and seem to have affected the δ18Otr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ18Otr of M. acantholoba can be used as a proxy for source water δ18O and that interannual variation in δ18Oprec is caused by a regional amount effect. This contrasts with δ18O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in disentangling the processes influencing precipitation δ18O.

Oxygen isotopes in tree rings record variation in precipitation δ18O and amount effects in the south of Mexico

PubMed Central

Brienen, Roel J W; Hietz, Peter; Wanek, Wolfgang; Gloor, Manuel

2013-01-01

[1] Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings (δ18Otr). Interannual variation in δ18Otr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ13C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ18Otr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18O-depleted rain in the region and seem to have affected the δ18Otr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ18Otr of M. acantholoba can be used as a proxy for source water δ18O and that interannual variation in δ18Oprec is caused by a regional amount effect. This contrasts with δ18O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in disentangling the processes influencing precipitation δ18O. PMID:26213660

Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotopes in phosphate

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

Jaisi, Deb P.; Kukkadapu, Ravi K.; Stout, Lisa M.

2011-07-06

A key question to address in the development of oxygen isotope ratios in phosphate (18Op) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here we present experimental results aimed at understanding the biotic and abiotic pathway of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of specific sedimentary phosphate phases by Escherichia coli, Vibrio fischeri and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction ofmore » phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 hrs) due to efficient O-isotope exchange between phosphate and water (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate promoted the exchange of intact phosphate radicals (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli and V. fischeri ‘extracted’ loosely sorbed phosphate first while M. aquaeolei preferred iron-oxide bound phosphate. Each bacterium imprinted a biotic isotopic signature on each P phase that it took up and cycled. For example, the 18Op value of the sorbed phosphate phase shifted gradually towards equilibrium isotopic composition and the value of Fe oxide-bound phosphate showed slight changes at first, but when new iron oxides were formed, co-precipitated/occluded phosphate retained 18O values of aqueous phosphate at that time. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of 18Op as a tracer of phosphorus cycling in sediments, soils and aquatic environments and as an indicator of paleo- environmental conditions.« less

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.

Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

NASA Technical Reports Server (NTRS)

Yeung, Laurence Y.; Murray, Lee T.; Ash, Jeanine L.; Young, Edward D.; Boering, Kristie A.; Atlas, Elliot L.; Schauffler, Sue M.; Lueb, Richard A.; Langenfelds, Ray L.; Krummel, Paul B.;

Mercury stable isotope signatures of world coal deposits and historical coal combustion emissions.

PubMed

Sun, Ruoyu; Sonke, Jeroen E; Heimbürger, Lars-Eric; Belkin, Harvey E; Liu, Guijian; Shome, Debasish; Cukrowska, Ewa; Liousse, Catherine; Pokrovsky, Oleg S; Streets, David G

2014-07-01

Mercury (Hg) emissions from coal combustion contribute approximately half of anthropogenic Hg emissions to the atmosphere. With the implementation of the first legally binding UNEP treaty aimed at reducing anthropogenic Hg emissions, the identification and traceability of Hg emissions from different countries/regions are critically important. Here, we present a comprehensive world coal Hg stable isotope database including 108 new coal samples from major coal-producing deposits in South Africa, China, Europe, India, Indonesia, Mongolia, former USSR, and the U.S. A 4.7‰ range in δ(202)Hg (-3.9 to 0.8‰) and a 1‰ range in Δ(199)Hg (-0.6 to 0.4‰) are observed. Fourteen (p < 0.05) to 17 (p < 0.1) of the 28 pairwise comparisons between eight global regions are statistically distinguishable on the basis of δ(202)Hg, Δ(199)Hg or both, highlighting the potential application of Hg isotope signatures to coal Hg emissions tracing. A revised coal combustion Hg isotope fractionation model is presented, and suggests that gaseous elemental coal Hg emissions are enriched in the heavier Hg isotopes relative to oxidized forms of emitted Hg. The model explains to first order the published δ(202)Hg observations on near-field Hg deposition from a power plant and global scale atmospheric gaseous Hg. Yet, model uncertainties appear too large at present to permit straightforward Hg isotope source identification of atmospheric forms of Hg. Finally, global historical (1850-2008) coal Hg isotope emission curves were modeled and indicate modern-day mean δ(202)Hg and Δ(199)Hg values for bulk coal emissions of -1.2 ± 0.5‰ (1SD) and 0.05 ± 0.06‰ (1SD).

Stable isotopic composition of deep sea gorgonian corals (Primnoa spp.): a new archive of surface processes.

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

Sherwood, O A; Heikoop, J M; Scott, D B

2005-02-03

The deep-sea gorgonian coral Primnoa spp. lives in the Atlantic and Pacific Oceans at depths of 65-3200 m. This coral has an arborescent growth form with a skeletal axis composed of annual rings made from calcite and gorgonin. It has a lifespan of at least several hundred years. It has been suggested that isotopic profiles from the gorgonin fraction of the skeleton could be used to reconstruct long-term, annual-scale variations in surface productivity. We tested assumptions about the trophic level, intra-colony isotopic reproducibility, and preservation of isotopic signatures in a suite of modern and fossil specimens. Measurements of gorgonin {Delta}{supmore » 14}C and {delta}{sup 15}N indicate that Primnoa spp. feed mainly on zooplankton and/or sinking particulate organic matter (POM{sub SINK}), and not on suspended POM (POM{sub SUSP}) or dissolved organic carbon (DOC). Gorgonin {delta}{sup 13}C and {delta}{sup 15}N in specimens from NE Pacific shelf waters, NW Atlantic slope waters, the Sea of Japan, and a South Pacific (Southern Ocean sector) seamount were strongly correlated with Levitus 1994 surface apparent oxygen utilization (AOU; the best available measure of surface productivity), demonstrating coupling between skeletal isotopic ratios and biophysical processes in surface water. Time-series isotopic profiles from different sections along the same colony were identical for {delta}{sup 13}C, while {delta}{sup 15}N profiles became more dissimilar with increasing separation along the colony axis. Similarity in C:N, {delta}{sup 13}C and {delta}{sup 15}N between modern and fossil specimens suggest that isotopic signatures are preserved over millennial timescales. Finally, the utility of this new archive was demonstrated by reconstruction of 20th century bomb radiocarbon.« less

Zinc stable isotope fractionation upon accelerated oxidative weathering of sulfidic mine waste.

PubMed

Matthies, R; Krahé, L; Blowes, D W

2014-07-15

Accelerated oxidative weathering in a reaction cell (ASTM D 5744 standard protocol) was performed over a 33 week period on well characterized, sulfidic mine waste from the Kidd Creek Cu-Zn volcanogenic massive sulfide deposit, Canada. The cell leachate was monitored for physicochemical parameters, ion concentrations and stable isotope ratios of zinc. Filtered zinc concentrations (<0.45 μm) in the leachate ranged between 4.5 mg L(-1) and 1.9 g L(-1)-potentially controlled by pH, mineral solubility kinetics and (de)sorption processes. The zinc stable isotope ratios varied mass-dependently within +0.1 and +0.52‰ relative to IRMM 3702, and were strongly dependent on the pH (rpH-d66Zn=0.65, p<0.005, n=31). At a pH below 5, zinc mobilization was governed by sphalerite oxidation and hydroxide dissolution-pointing to the isotope signature of sphalerite (+0.1 to +0.16‰). Desorption processes resulted in enrichment of (66)Zn in the leachate reaching a maximum offset of +0.32‰ compared to the proposed sphalerite isotope signature. Over a period characterized by pH=6.1 ± 0.6, isotope ratios were significantly more enriched in (66)Zn with an offset of ≈ 0.23‰ compared to sphalerite, suggesting that zinc release may have been derived from a second zinc source, such as carbonate minerals, which compose 8 wt.% of the tailings. This preliminary study confirms the benefit of applying zinc isotopes alongside standard monitoring parameters to track principal zinc sources and weathering processes in complex multi-phase matrices. Copyright © 2014 Elsevier B.V. All rights reserved.

New Isotopic Tracers for Shale Gas and Hydraulic Fracturing Fluids

EPA Pesticide Factsheets

The combined application of geochemistry, stable isotopes (δ18O, δ2H), strontium isotopes (87Sr/86Sr), boron isotopes (δ11B), and radium isotopes (228Ra/226Ra) provides a unique methodology for tracing and monitoring shale gas and fracking fluids in the environment.

Genome-wide methylomic and transcriptomic analyses identify subtype-specific epigenetic signatures commonly dysregulated in glioma stem cells and glioblastoma.

PubMed

Pangeni, Rajendra P; Zhang, Zhou; Alvarez, Angel A; Wan, Xuechao; Sastry, Namratha; Lu, Songjian; Shi, Taiping; Huang, Tianzhi; Lei, Charles X; James, C David; Kessler, John A; Brennan, Cameron W; Nakano, Ichiro; Lu, Xinghua; Hu, Bo; Zhang, Wei; Cheng, Shi-Yuan

2018-06-21

Glioma stem cells (GSCs), a subpopulation of tumor cells, contribute to tumor heterogeneity and therapy resistance. Gene expression profiling classified glioblastoma (GBM) and GSCs into four transcriptomically-defined subtypes. Here, we determined the DNA methylation signatures in transcriptomically pre-classified GSC and GBM bulk tumors subtypes. We hypothesized that these DNA methylation signatures correlate with gene expression and are uniquely associated either with only GSCs or only GBM bulk tumors. Additional methylation signatures may be commonly associated with both GSCs and GBM bulk tumors, i.e., common to non-stem-like and stem-like tumor cell populations and correlating with the clinical prognosis of glioma patients. We analyzed Illumina 450K methylation array and expression data from a panel of 23 patient-derived GSCs. We referenced these results with The Cancer Genome Atlas (TCGA) GBM datasets to generate methylomic and transcriptomic signatures for GSCs and GBM bulk tumors of each transcriptomically pre-defined tumor subtype. Survival analyses were carried out for these signature genes using publicly available datasets, including from TCGA. We report that DNA methylation signatures in proneural and mesenchymal tumor subtypes are either unique to GSCs, unique to GBM bulk tumors, or common to both. Further, dysregulated DNA methylation correlates with gene expression and clinical prognoses. Additionally, many previously identified transcriptionally-regulated markers are also dysregulated due to DNA methylation. The subtype-specific DNA methylation signatures described in this study could be useful for refining GBM sub-classification, improving prognostic accuracy, and making therapeutic decisions.

Using stable isotopes to investigate individual diet specialization in California sea otters (Enhydra lutris nereis)

USGS Publications Warehouse

Newsome, S.D.; Tinker, M.T.; Monson, Daniel H.; Oftedal, O.T.; Ralls, K.; Staedler, M.M.; Fogel, M.L.; Estes, J.A.

2009-01-01

Differences in diet composition among conspecifics (dietary specialization) have been documented across a broad range of taxonomic groups and habitats, and such variation at the individual level is increasingly recognized as an important component of diversity in trophic interactions. Accurate identification of individual dietary specialization, however, requires longitudinal dietary records that are labor-intensive and cost-prohibitive to obtain for many species. Here we explore the use of stable isotopes (δ13C and δ15N) as a promising technique for detecting and quantifying patterns of individual dietary specialization. Southern sea otters (Enhydra lutris nereis) offer a unique opportunity for testing this approach because (1) they consume a wide variety of prey that span multiple trophic levels, habitats, and ecologically defined functional groups; and (2) individual diet specialization can be validated with existing observational data. We analyzed the isotopic composition of sea otter vibrissae (n = 31) in order to characterize inter- and intra-individual variation in sea otter diets at Monterey Bay, California, USA. At the population level, sea otters showed substantial variation in both δ13C and δ15N values, occupying nearly all of the “isotopic space” created by the diversity of isotopic signatures of potential prey taxa. Most of the variation in sea otter vibrissae was accounted for by differences between individuals, with much less contributed by within-individual variation. A majority of sea otters (∼80%) showed relatively little temporal variability in isotopic composition, suggesting that the proportional composition of most individuals' diets is relatively constant over time; a few individuals (∼20%) exhibited a high degree of intra-vibrissa isotopic variability, suggesting seasonal shifts in diet composition. These results and our interpretation of them were supported by long-term observational data on the diets of radio-tagged sea otters from the same population (n = 23). Our results demonstrate that stable isotopes can provide an efficient tool for measuring individual- and population-level dietary breadth and may be useful for studying populations where longitudinal data on individuals would otherwise be impossible to acquire. This will be critical for examining the causes and consequences of dietary variation within and among consumer populations, thereby improving our understanding of these important ecological and evolutionary processes at the community level.

RADIOLOGICAL SEALED SOURCE LIBRARY: A NUCLEAR FORENSICS TOOL

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

Canaday, Jodi; Chamberlain, David; Finck, Martha

If a terrorist were to obtain and possibly detonate a device that contained radiological material, radiological forensic analysis of the material and source capsule could provide law enforcement with valuable clues about the origin of the radiological material; this information could then provide further leads on where the material and sealed source was obtained, and the loss of control point. This information could potentially be utilized for attribution and prosecution. Analyses of nuclear forensic signatures for radiological materials are generally understood to include isotopic ratios, trace element concentrations, the time since irradiation or purification, and morphology. Radiological forensic signatures formore » sealed sources provide additional information that leverages information on the physical design and chemical composition of the source capsule and containers, physical markings indicative of an owner or manufacturer. Argonne National Laboratory (Argonne), in collaboration with Idaho National Laboratory (INL), has been working since 2003 to understand signatures that could be used to identify specific source manufacturers. These signatures include the materials from which the capsule is constructed, dimensions, weld details, elemental composition, and isotopic abundances of the radioactive material. These signatures have been compiled in a library known as the Argonne/INL Radiological Sealed Source Library. Data collected for the library has included open-source information from vendor catalogs and web pages; discussions with source manufacturers and touring of production facilities (both protected through non-disclosure agreements); technical publications; and government registries such as the U.S. Nuclear Regulatory Commission’s Sealed Source and Device Registry.« less

Plio-Pleistocene evolution of water mass exchange and erosional input at the Atlantic-Arctic gateway

NASA Astrophysics Data System (ADS)

Teschner, Claudia; Frank, Martin; Haley, Brian A.; Knies, Jochen

2016-05-01

Water mass exchange between the Arctic Ocean and the Norwegian-Greenland Seas has played an important role for the Atlantic thermohaline circulation and Northern Hemisphere climate. We reconstruct past water mass mixing and erosional inputs from the radiogenic isotope compositions of neodymium (Nd), lead (Pb), and strontium (Sr) at Ocean Drilling Program site 911 (leg 151) from 906 m water depth on Yermak Plateau in the Fram Strait over the past 5.2 Myr. The isotopic compositions of past bottom waters were extracted from authigenic oxyhydroxide coatings of the bulk sediments. Neodymium isotope signatures obtained from surface sediments agree well with present-day deepwater ɛNd signature of -11.0 ± 0.2. Prior to 2.7 Ma the Nd and Pb isotope compositions of the bottom waters only show small variations indicative of a consistent influence of Atlantic waters. Since the major intensification of the Northern Hemisphere Glaciation at 2.7 Ma the seawater Nd isotope composition has varied more pronouncedly due to changes in weathering inputs related to the waxing and waning of the ice sheets on Svalbard, the Barents Sea, and the Eurasian shelf, due to changes in water mass exchange and due to the increasing supply of ice-rafted debris (IRD) originating from the Arctic Ocean. The seawater Pb isotope record also exhibits a higher short-term variability after 2.7 Ma, but there is also a trend toward more radiogenic values, which reflects a combination of changes in input sources and enhanced incongruent weathering inputs of Pb released from freshly eroded old continental rocks.

The zinc stable isotope signature of waste rock drainage in Arctic Canada

NASA Astrophysics Data System (ADS)

Matthies, Romy; Blowes, David

2014-05-01

Leachate emerging from a pilot-scale waste rock pile of the Diavik diamond mine, Northwest Territories, was monitored. The well-characterized waste rock consists of granite, pegmatitic granite and biotite schist with an average total sulfur and carbonate carbon concentration of 0.053 and 0.027 wt. %, respectively. During the field seasons of 2011 and 2012, the Zn stable isotope footprint was characterized alongside standard monitoring parameters. pH ranged between 4.3 and 6.8 and carbonate alkalinity was low or undetectable. Al and Fe concentrations averaged 6.78 mg L-1 and 175 µg L-1, respectively. The pH and metal mobility were governed by sulfide oxidation and sorption and co-precipitation onto iron and aluminium hydroxides. The main processes controlling zinc mobility in the range of 0.4 and 4.7 mg L-1 was the oxidative dissolution of sphalerite (ZnS) in the biotite schist and the attenuation of zinc onto secondary iron and aluminium hydroxides and desorption upon the pH declining below the pHpzc. The isotope ratios between -0.16 and +0.19 ‰ (δ66Zn, avg = +0.05 ‰, n = 43) are consistent with values reported from other sphalerite containing deposits. Zn isotope ratios and concentrations were largely uncorrelated suggesting that the processes affecting Zn mobility had little or no impact on the Zn isotope signature. Data indicate, that the Zn isotope ratios of the waste rock leachate may be used as a fingerprint to track anthropogenic, mine-derived Zn sources under varying environmental conditions.

Impacts of a high-discharge submarine sewage outfall on water quality in the coastal zone of Salvador (Bahia, Brazil).

PubMed

Roth, F; Lessa, G C; Wild, C; Kikuchi, R K P; Naumann, M S

2016-05-15

Carbon and nitrogen stable isotopic signatures of suspended particulate organic matter and seawater biological oxygen demand (BOD) were measured along a coastal transect during summer 2015 to investigate pollution impacts of a high-discharge submarine sewage outfall close to Salvador, Brazil. Impacts of untreated sewage discharge were evident at the outfall site by depleted δ(13)Corg and δ(15)N signatures and 4-fold increased BOD rates. Pollution effects of a sewage plume were detectable for more than 6km downstream from the outfall site, as seasonal wind- and tide-driven shelf hydrodynamics facilitated its advective transport into near-shore waters. There, sewage pollution was detectable at recreational beaches by depleted stable isotope signatures and elevated BOD rates at high tides, suggesting high bacterial activity and increased infection risk by human pathogens. These findings indicate the urgent necessity for appropriate wastewater treatment in Salvador to achieve acceptable standards for released effluents and coastal zone water quality. Copyright © 2016 Elsevier Ltd. All rights reserved.

Integration of Stable Isotope and other Mass Spectral Data for Microbial Forensics

NASA Astrophysics Data System (ADS)

Kreuzer-Martin, H. W.; Jarman, K. H.

2008-12-01

The nascent field of microbial forensics requires the development of diverse signatures as indicators of various aspects of the production environment of microorganisms. We have characterized isotopic relationships between Bacillus subtilis ATCC 6051 spores and their growth environment, using as a database the carbon, nitrogen, oxygen and hydrogen stable isotope ratios of a total of 247 separate cultures of spores produced on a total of 32 different culture media. We have analyzed variation within individual samples, between cultures produced in tandem, and between cultures produced in the same medium but at different times in the context of using stable isotope ratios as a signature for sample matching. We have correlated the stable isotope ratios of carbon, nitrogen, oxygen, and hydrogen of growth medium nutrients or water and spores and show examples of how these relationships can be used to exclude nutrient or water samples as possible growth substrates for specific cultures. The power of stable isotope ratio data can be greatly enhanced by combining it with orthogonal datasets that speak to different aspects of an organism's production environment. We developed a Bayesian network that follows the causal relationship from culture medium recipe to spore elemental content as measured by secondary ion mass spectrometry (SIMS), carbon and nitrogen stable isotope ratios, and to the presence of residual agar by electrospray ionization MS (ESI-MS). The network was developed and tested on data from three replicate cultures of B. subtilis ATCC 49760 in broth and agar-containing versions of four different nutrient media. To test the network, data from SIMS analyses of B. subtilis 49760 produced in a different medium, from approximately 200 ESI MS analyses of B. thuringensis ATCC 58890 and B. anthracis Sterne grown in five additional media, and the stable isotope data from the 247 cultures of B. subtilis 6051 spores were used. This network was able to characterize Bacillus spores grown under multiple culture conditions with an error rate of less than 0.07 in characterizing carbon and nitrogen source, addition of metals, and presence of agar, and an error rate of 0.19 in characterizing the culture medium recipe. The integration of multiple analytical techniques allowed us to maximize the amount of information obtained from unknown source microorganisms. The Bayesian network approach allowed us to combine scientific understanding with well established statistical methodologies to characterize a microbe's growth environment without the need for reference signatures. Similar approaches could be applied to data from other scientific disciplines, as well as to other problems of attribution.

Characterizing Variation of Isotopic Markers in Northern Alaskan Caribou Forages

NASA Astrophysics Data System (ADS)

VanSomeren, L.; Barboza, P. S.; Gustine, D. D.; Parrett, L. S.; Stricker, C. A.

2013-12-01

Isotopic markers in feces and tissues are a potential tool for monitoring the importance of feeding areas for migratory herbivores such as caribou (Rangifer tarandus). Many of these techniques are currently limited by gaps in our knowledge of how these isotopic signatures vary over the landscape. We collected seven species of preferred caribou forages along a latitudinal gradient in the summer ranges of the Central Arctic (9 sites) and Teshekpuk Lake (4 sites) caribou herds during 2011 and 2012. We analyzed forages at peak protein content and at the end of the season to characterize temporal, species-specific, and spatial variation in isotopic markers. The availability of C and N was measured by digestion in vitro. Isotopic signatures of digested samples were used to calculate fractionation that would bias the isotopic signature of feces. The range of values for isotopes (all values ‰) of nitrogen (δ15N -9.5 - +4.3), and sulfur (δ34S -3.6 - +15.5) were greater than those for carbon (δ13C -30.5 - -24.9). Small declines in forage δ13C with latitude (Carex aquatilis, Eriophorum vaginatum, Salix pulchra, and S. richardsonii [all P < 0.01]), season (all species except C. bigelowii [all P ≤ 0.01]), and season x year (S. richardsonii; P = 0.01) were probably associated with changes in water availability. Fractionation of δ13C in early season forages was 0.1 × 1.0 and positively related to C availability (58% × 15%; P < 0.01) with the greatest fractionation for the highly digestible forb Pedicularis langsdorfii (1.43 × 0.44; P < 0.01). Sedges (Carex and Eriophorum) were significantly higher in δ15N than Salix spp. and other dicots (2.0 × 1.1 vs. -2.9 × 2.2; P < 0.01). For Salix spp., δ15N was consistent over the season and between years. Fractionation of δ15N in early season forages was 0.2 × 1.8 and not related to N availability (60% × 17%). For S. pulchra, δ34S may indicate usage of coastal habitats over foothills because δ34S was higher on the coastal plain than in the foothills (11.1 × 3.3 and 3.1 × 2.6; P < 0.01). Isotopic ratios in N and S show the greatest promise for tracking diet and location of migratory caribou whereas the narrow range in δ13C is affected by species, season and location.

A bench-scale constructed wetland as a model to characterize benzene biodegradation processes in freshwater wetlands.

PubMed

Rakoczy, Jana; Remy, Benjamin; Vogt, Carsten; Richnow, Hans H

2011-12-01

In wetlands, a variety of biotic and abiotic processes can contribute to the removal of organic substances. Here, we used compound-specific isotope analysis (CSIA), hydrogeochemical parameters and detection of functional genes to characterize in situ biodegradation of benzene in a model constructed wetland over a period of 370 days. Despite low dissolved oxygen concentrations (<30 μM), the oxidation of ammonium to nitrate and the complete oxidation of ferrous iron pointed to a dominance of aerobic processes, suggesting efficient oxygen transfer into the sediment zone by plants. As benzene removal became highly efficient after day 231 (>98% removal), we applied CSIA to study in situ benzene degradation by indigenous microbes. Combining carbon and hydrogen isotope signatures by two-dimensional stable isotope analysis revealed that benzene was degraded aerobically, mainly via the monohydroxylation pathway. This was additionally supported by the detection of the BTEX monooxygenase gene tmoA in sediment and root samples. Calculating the extent of biodegradation from the isotope signatures demonstrated that at least 85% of benzene was degraded by this pathway and thus, only a small fraction was removed abiotically. This study shows that model wetlands can contribute to an understanding of biodegradation processes in floodplains or natural wetland systems.

Chemical and isotopic fingerprinting of small ungauged watershed: How far the hydrological functioning can be understood?

NASA Astrophysics Data System (ADS)

Petelet-Giraud, Emmanuelle; Luck, Jean-Marc; Ben Othman, Dalila; Joseph, Christian; Négrel, Philippe

2016-05-01

This study presents the ability of major/trace elements together with strontium isotopes to trace water origins at small scale at the outlet of a small watershed (Peyne, Hérault, France). Two small sub-basins draining distinct lithologies in their headwater (Plio-Villafranchian conglomerate versus Triassic gypsum-rich marls and dolomites) and the Miocene formations downstream are investigated. The Ca/Na vs. Mg/Na ratios and Ca/Sr vs. 87Sr/86Sr ratios allow the different facies that imprint the water signature to be identified, according to the hydrological conditions (low/high flows). Moreover, Sr isotopes evidence the two distinct Miocene facies, the sandy marls and the marine carbonates. The variation of the signature at the outlet of the basin allows identifying the main contributing compartments according to the hydrological conditions. This approach, based on a limited number of samples, highlights the potential of geochemical and isotopic tracers to define the contributing compartments to the runoff at the outlet of a basin. It thus could be considered as a potential alternative way to classical hydrological monitoring to delineate the main contributing areas during floods, especially in small ungauged river basins, where most of the devastating flash floods are recorded.

Impact of diazotrophy on N stable isotope signatures of nitrate and particulate organic nitrogen: case studies in the north-eastern tropical Atlantic Ocean.

PubMed

Wannicke, Nicola; Liskow, Iris; Voss, Maren

2010-09-01

During two independent cruises in the north-eastern tropical Atlantic Ocean, we applied two different approaches to investigate the impact of diazotrophy on nitrogen stable isotope signatures in nitrate and particulate organic nitrogen (PON) of the food-web constituents. The first approach, used during the Poseidon cruise 348 in the Mauritanian upwelling, investigated the long-term influence of diazotrophy on the natural abundance of δ(15)N-NO(-)(3) and PON. The second approach, adopted during the Cape Verde field cruise, applied stable isotope tracer addition experiments. These served to determine the instantaneous transfer of diazotrophic N to the higher trophic level. Both approaches showed that N(2) fixation was compatible with the pattern and the magnitude of the isotopic depletion of dissolved NO(-)(3) during the Mauritanian upwelling cruise, as well as PON in zooplankton and phytoplankton during the Cape Verde cruises. An N-budget using (15)N incorporation rates and diazotrophic N(2) fixation rates showed that 6 % of the daily N(2) fixation was potentially taken up by the mesozooplankton community. Direct grazing accounted for 56 % of gross mesozooplanktonic N incorporation, while 46 % occurred due to channelling through the microbial loop.

New method for the measurement of osmium isotopes applied to a New Zealand Cretaceous/Tertiary boundary shale

USGS Publications Warehouse

Lichte, F.E.; Wilson, S.M.; Brooks, R.R.; Reeves, R.D.; Holzbecher, J.; Ryan, D.E.

1986-01-01

The determination of osmium content and isotopic abundances in geological materials has received increasing attention in recent years following the proposal of Alvarez et al.1 that mass extinctions at the end of the Cretaceous period were caused by the impact of a large (???10km) meteorite which left anomalously high iridium levels as a geochemical signature in the boundary shales. Here we report a new and simple method for measuring osmium in geological materials, involving fusion of the sample with sodium peroxide, distillation of the osmium as the tetroxide using perchloric acid, extraction into chloroform, and absorption of the chloroform extract onto graphite powder before instrumental neutron activation analysis. In a variant of this technique, the chloroform extract is back-extracted into an aqueous phase and the osmium isotopes are determined by plasma-source mass spectrometry (ICPMS). We have used this method on the Woodside Creek (New Zealand) Cretaceous/Tertiary boundary clay and have obtained the first osmium content (6g ng g-1) for this material. The 187Os/186Os ratio is 1.12??0.16, showing a typical non-crustal signature. This combined distillation-extraction- ICPMS method will prove to be useful for measuring osmium isotopes in other geological materials. ?? 1986 Nature Publishing Group.

Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs.

PubMed

Sherwood Lollar, B; Westgate, T D; Ward, J A; Slater, G F; Lacrampe-Couloume, G

2002-04-04

Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.

Spatial and temporal variation in winter condition of juvenile Pacific herring (Clupea pallasii) in Prince William Sound, Alaska: Oceanographic exchange with the Gulf of Alaska

NASA Astrophysics Data System (ADS)

Gorman, Kristen B.; Kline, Thomas C.; Roberts, Megan E.; Sewall, Fletcher F.; Heintz, Ron A.; Pegau, W. Scott

2018-01-01

Spatial variability in early and late winter measures of whole body energy density of juvenile (age-0) Pacific herring (Clupea pallasii) of Prince William Sound (PWS), Alaska was examined over nine years of study. Pacific herring in this region remain considered as an injured resource over the 25 years following the Exxon Valdez oil spill, however factors responsible for the lack of recovery by herring in PWS are a source of ongoing debate. Given the species' key ecological role in energy transfer to higher predators, and its economic role in a historical commercial fishery within the region, significant research effort has focused on understanding environmental factors that shape nutritional processes and the quality of these young forage fish. During November (early winter), factors such as juvenile herring body size, hydrological region of PWS, year, and the interaction between carbon (δ13C‧) or nitrogen (δ15N) stable isotope signature and hydrological region were all important predictors of juvenile herring energy density. In particular, analyses indicated that in the northern and western regions of PWS, juvenile herring with more depleted δ13C‧ values (which reflect a Gulf of Alaska carbon source) were more energy dense. Results suggest that intrusion of water derived from the Gulf of Alaska enhances the condition of age-0 herring possibly through alterations in zooplankton community structure and abundance, particularly in the northern and western regions of PWS in the fall, which is consistent with regional circulation. During March (late winter), factors such as juvenile herring body size, year, and the interaction between δ13C‧ or δ15N isotope signature and year were all important predictors of juvenile herring energy density. Results differed for early and late winter regarding the interaction between stable isotope signatures and region or year, suggesting important seasonal aspects of circulation contribute to variation in PWS juvenile herring energy density. In addition, winter-feeding may enrich herring without considerable energy gain, removing any relationship between energy density and δ13C‧ isotope signature in late winter.

An archaeal genomic signature

NASA Technical Reports Server (NTRS)

Graham, D. E.; Overbeek, R.; Olsen, G. J.; Woese, C. R.

2000-01-01

Comparisons of complete genome sequences allow the most objective and comprehensive descriptions possible of a lineage's evolution. This communication uses the completed genomes from four major euryarchaeal taxa to define a genomic signature for the Euryarchaeota and, by extension, the Archaea as a whole. The signature is defined in terms of the set of protein-encoding genes found in at least two diverse members of the euryarchaeal taxa that function uniquely within the Archaea; most signature proteins have no recognizable bacterial or eukaryal homologs. By this definition, 351 clusters of signature proteins have been identified. Functions of most proteins in this signature set are currently unknown. At least 70% of the clusters that contain proteins from all the euryarchaeal genomes also have crenarchaeal homologs. This conservative set, which appears refractory to horizontal gene transfer to the Bacteria or the Eukarya, would seem to reflect the significant innovations that were unique and fundamental to the archaeal "design fabric." Genomic protein signature analysis methods may be extended to characterize the evolution of any phylogenetically defined lineage. The complete set of protein clusters for the archaeal genomic signature is presented as supplementary material (see the PNAS web site, www.pnas.org).

Understanding N2O sources and sinks with laser based isotopic analysis

NASA Astrophysics Data System (ADS)

Mohn, Joachim; Harris, Eliza; Tuzson, Béla; Emmenegger, Lukas

2015-04-01

Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance. The main emissions of N2O are linked to different microbial processes, therefore the sources are disperse and highly variable, complicating the development of effective mitigation strategies. Isotopic measurements have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of N2O. Recent developments in quantum cascade laser spectroscopy (QCLAS) [1] allow both the intermolecular distribution of 15N substitutions ('site preference'; 15N14N16O versus 14N15N16O) and the oxygen isotopic composition (d18O) of N2O to be measured in real-time and at high precision of <0.2 ‰ [2]. Additionally, N2O isotopic analysis by QCLAS has demonstrated excellent compatibility to the standard technique isotope-ratio mass-spectrometry [3]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. Recently, high precision isotopic analysis at ambient N2O is also feasible by combining laser spectroscopy with automated preconcentration [5]. The field deployment was demonstrated by real-time monitoring isotopic composition of N2O emissions from an intensively managed grassland in central Switzerland for three months. The responses of the N2O isotopic signatures were analysed with respect to management events and weather influences [2]. In a follow-up project we intend to combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model of surface fluxes of N2O isotopomers. The working hypothesis is that this approach will allow us to quantify regional N2O sources, identify emission hot spots, and constrain source processes, which will be of upmost importance for developing targeted mitigation options. References: [1] H. Wächter, J. Mohn, B. Tuzson, L. Emmenegger, M. W. Sigrist, Opt. Express (2008), 16, 9239-9244. [2] B. Wolf, L. Merbold, C. Decock, B. Tuzson, E. Harris, J. Six, L. Emmenegger, J. Mohn, Biogeosci. Discuss. (2015), accepted. [3] J. Mohn et al., Rapid Commun. Mass Spectrom. (2014) 28, 1995-2007. [4] P. Wunderlin, M. F. Lehmann, H. Siegrist, B. Tuzson, A. Joss, L. Emmenegger, J. Mohn, Environ. Sci. Technol. (2013), 47, 1339-1348. [5] J. Mohn, B. Tuzson, A. Manninen, N. Yoshida, S. Toyoda, W. A. Brand, L. Emmenegger, Atmos. Meas. Tech. (2012), 5, 1601-1609.

Isotopic reconstruction of ancient human migrations: A comprehensive Sr isotope reference database for France and the first case study at Tumulus de Sables, south-western France

NASA Astrophysics Data System (ADS)

Willmes, M.; Boel, C.; Grün, R.; Armstrong, R.; Chancerel, A.; Maureille, B.; Courtaud, P.

2012-04-01

Strontium isotope ratios (87Sr/86Sr) can be used for the reconstruction of human and animal migrations across geologically different terrains. Sr isotope ratios in rocks are a product of age and composition and thus vary between geologic units. From the eroding environment Sr is transported into the soils, plants and rivers of a region. Humans and animals incorporate Sr from their diet into their bones and teeth, where it substitutes for calcium. Tooth enamel contains Sr isotope signatures acquired during childhood and is most resistant to weathering and overprinting, while the dentine is often diagenetically altered towards the local Sr signature. For the reconstruction of human and animal migrations the tooth enamel 87Sr/86Sr ratio is compared to the Sr isotope signature in the vicinity of the burial site and the surrounding area. This study focuses on the establishment of a comprehensive reference map of bioavailable 87Sr/86Sr ratios for France. In a next step we will compare human and animal teeth from key archaeological sites to this reference map to investigate mobility. So far, we have analysed plant and soil samples from ~200 locations across France including the Aquitaine basin, the western and northern parts of the Paris basin, as well as three transects through the Pyrenees Mountains. The isotope data, geologic background information (BRGM 1:1M), field images, and detailed method descriptions are available through our online database iRhum (http://rses.anu.edu.au/research/ee). This database can also be used in forensic studies and food sciences. As an archaeological case study teeth from 16 adult and 8 juvenile individuals were investigated from an early Bell Beaker (2500-2000 BC) site at Le Tumulus des Sables, south-west France (Gironde). The teeth were analysed for Sr isotope ratios using laser ablation ICP-MS. Four teeth were also analysed using solution ICP-MS, which showed a significant offset to the laser ablation results. This requires further detailed investigation. Nevertheless, the teeth showed clear differences between enamel and diagenetically overprinted dentine, which suggests mobility. Unfortunately, the sandy sediment units in the close vicinity of Le Tumulus des Sables show large variations in their 87Sr/86Sr ratios so it is currently not possible to distinguish between migration from outside of the Médoc region from mobility within the region based solely on Sr isotope ratios. The case study illustrates the importance of detailed reference maps, which are required for any isotope studies used for the reconstruction of migrations. Other isotope data, such as O and Pb, will complement the investigation at Tumulus de Sables and may enable us to tie down the range of mobility of the humans that were buried at Le Tumulus des Sables.

Nuclear and non-nuclear techniques for area-wide assessment of water use efficiency and ecohydrology outcomes among mixed land uses

NASA Astrophysics Data System (ADS)

Burgess, S. S. O.; Nguyen, M. L.

2009-04-01

Managing water use efficiency and ecohydrology is important for providing food, water and essential ecosystem services. Many agricultural, ecological, atmospheric and hydrological processes cannot be meaningfully managed without an area-wide or catchment-level perspective. However a vast number of factors, including mixed land uses are incorporated at such scales. There is a need for integrative, mobile and adaptable techniques to make water related measurements over large areas and mixed land uses. Nuclear techniques and analogous non-nuclear techniques may be deployed in a number of spheres within the soil-plant-atmosphere continuum (e.g. rhizosphere and above-canopy microclimate) with nuclear techniques having a distinct contribution owing to their unique ability to trace biogeochemical processes including the movement and transformation of water, nutrients and agrochemicals. 1) Soils. Isotopes can be used to trace water sources to understand groundwater dependence, rooting depth, etc. but not at all sites: early success in central USA studies has not always been repeatable in climates which produce more uniform isotopic signatures in various water sources. Soil water resources available to crops can also be studied using neutron moisture meters, but training, transport and safety issues argue for stringent management and inclusion of electrical capacitance probes for routine or automated applications. Results from capacitance probes can benefit from benchmarking against neutron probe measurements, which remain more powerful for sampling larger volumes in cases of heterogenous soils or where salinity levels are problematic. Because interpretation of soil water content in terms of plant available water also requires knowledge of soil organic matter characteristics, 13C and compound specific stable isotopes can help to identify changes in soil organic matter composition and hence water and plant nutrient availability. 2) Plants. Analysis of carbon isotope discrimination can be used to monitor water use efficiency and seasonal water stress. This includes analysis of carbon in structural leaf material and soluble sugars for different temporal scales. Some progress is also being made using 18O signatures to estimate transpiration. Furthermore xylem sap can be measured for isotopic composition can be used and absolute flow rates in the plant can be measured with thermometric tracers. Information on transpiration can help differentiate between wasteful evaporative processes versus efficient plant gas exchange. 3) Atmosphere (above & within canopy). Whilst traditional vapour related techniques such as Bowen ratio and eddy flux can measure total ET, modern cavity ring-down laser spectrometers can sample isotopes in water vapour. These devices hold much promise to identify water sources and evaporative processes using dual isotope mixing models and Keeling plots analysis: the result is improved partitioning of transpiration and evaporation. This above suite of measurements can provide knowledge to choose correct plant species, manage irrigation and microclimate, compare land uses and predict impacts on the environment, including nutrient and agrochemical movement in the landscape. We discuss current progress in IAEA and related projects which are aimed at bringing an integrated, multi-disciplinary framework for area-wide water management that can promote food security, water resources and essential ecosystem services.

Measurement of the Isotopic Signatures of Water on Mars: Implications for Studying Methane

NASA Technical Reports Server (NTRS)

Novak, R. E.; Mumma, M. J.; Villanueva, G. L.

2010-01-01

The recent discovery of methane on Mars has led to much discussion concerning its origin. On Earth, the isotopic signatures of methane vary with the nature of its production. Specifically, the ratios among 12CH4, 13CH4, and 12CH3D differ for biotic and abiotic origins. On Mars, measuring these ratios would provide insights into the origins of methane and measurements of water isotopologues co-released with methane would assist in testing their chemical relationship. Since 1997, we have been measuring HDO and H2O in Mars atmosphere and comparing their ratio to that in Earth s oceans. We recently incorporated a line-by-line radiative transfer model (LBLRTM) into our analysis. Here, we present a map for [HDO]/[H2O] along the central meridian (1541W) for Ls 501. From these results, we constructed models to determine the observational conditions needed to quantify the isotopic ratios of methane in Mars atmosphere. Current ground-based instruments lack the spectral resolution and sensitivity needed to make these measurements. Measurements of the isotopologues of methane will likely require in situ sampling.

Static, mixed-array total evaporation for improved quantitation of plutonium minor isotopes in small samples

DOE PAGES

Stanley, F. E.; Byerly, Benjamin L.; Thomas, Mariam R.; ...

2016-03-31

Actinide isotope measurements are a critical signature capability in the modern nuclear forensics “toolbox”, especially when interrogating anthropogenic constituents in real-world scenarios. Unfortunately, established methodologies, such as traditional total evaporation via thermal ionization mass spectrometry, struggle to confidently measure low abundance isotope ratios (<10 -6) within already limited quantities of sample. Herein, we investigate the application of static, mixed array total evaporation techniques as a straightforward means of improving plutonium minor isotope measurements, which have been resistant to enhancement in recent years because of elevated radiologic concerns. Furthermore, results are presented for small sample (~20 ng) applications involving a well-knownmore » plutonium isotope reference material, CRM-126a, and compared with traditional total evaporation methods.« less

Charge radii of neutron-deficient Ca isotopes

NASA Astrophysics Data System (ADS)

Miller, A. J.; Minamisono, K.; Klose, A.; Everett, N.; Kalman, C.; Powel, R. C.; Watkins, J.; Garand, D.; Sumithrarachchi, C.; Krämer, J.; Maa, B.; Nörtershäuser, W.; Rossi, D. M.; Kujawa, C.; Pineda, S.; Lantis, J.; Liu, Y.; Mantica, P. F.; Pearson, M. R.

2017-09-01

Nucleon shell closures are generally associated with a local minimum in mean-square charge radii, 〈r2 〉 , along an isotopic chain. The 〈r2 〉 of 18Ar and 19K isotopes, however, do not show this signature at the N = 20 neutron shell closure. To gain a microscopic understanding of this abnormal behavior, measurements of 〈r2 〉 of neutron-deficient Ca isotopes below N = 20 have been proposed at the BEam COoling and LAser spectroscopy (BECOLA) facility at NSCL/MSU. Preliminary results will be presented and the deduced charge radii will be compared to theoretical calculations and the trends in the nearby isotopic chains. Work supported in part by NSF Grant PHY-15-65546, U.S. DOE Grant DE-NA0002924 and by the Deutsche Forschungsgemeinschaft through Grant SFB 1245.

Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study

USGS Publications Warehouse

Warwick, Peter D.; Ruppert, Leslie F.

2016-01-01

The concentration of carbon dioxide (CO2) in the atmosphere has dramatically increased from the start of the industrial revolution in the mid-1700s to present levels exceeding 400 ppm. Carbon dioxide derived from fossil fuel combustion is a greenhouse gas and a major contributor to on-going climate change. Carbon and oxygen stable isotope geochemistry is a useful tool to help model and predict the contributions of anthropogenic sources of CO2 in the global carbon cycle. Surprisingly few studies have addressed the carbon and oxygen isotopic composition of CO2 derived from coal combustion. The goal of this study is to document the relationships between the carbon and oxygen isotope signatures of coal and signatures of the CO2 produced from laboratory coal combustion in atmospheric conditions.Six coal samples were selected that represent various geologic ages (Carboniferous to Tertiary) and coal ranks (lignite to bituminous). Duplicate splits of the six coal samples were ignited and partially combusted in the laboratory at atmospheric conditions. The resulting coal-combustion gases were collected and the molecular composition of the collected gases and isotopic analyses of δ13C of CO2, δ13C of CH4, and δ18O of CO2 were analysed by a commercial laboratory. Splits (~ 1 g) of the un-combusted dried ground coal samples were analyzed for δ13C and δ18O by the U.S. Geological Survey Reston Stable Isotope Laboratory.The major findings of this preliminary work indicate that the isotopic signatures of δ13C (relative to the Vienna Pee Dee Belemnite scale, VPDB) of CO2 resulting from coal combustion are similar to the δ13CVPDB signature of the bulk coal (− 28.46 to − 23.86 ‰) and are not similar to atmospheric δ13CVPDB of CO2 (~ − 8 ‰, see http://www.esrl.noaa.gov/gmd/outreach/isotopes/c13tellsus.html). The δ18O values of bulk coal are strongly correlated to the coal dry ash yields and appear to have little or no influence on the δ18O values of CO2 resulting from coal combustion in open atmospheric conditions. There is a wide range of δ13C values of coal reported in the literature and the δ13C values from this study generally follow reported ranges for higher plants over geologic time. The values of δ18O (relative to Vienna Standard Mean Ocean Water) of CO2 derived from atmospheric combustion of coal and other high-carbon fuels (peat and coal) range from + 19.03 to + 27.03‰ and are similar to atmospheric oxygen δ18OVSMOW values which average + 23.8‰. Further work is needed on a broader set of samples to better define the relationships between coal composition and combustion-derived gases.

Carbon-Isotopic Dynamics of Streams, Taylor Valley, Antarctica: Biological Effects

NASA Technical Reports Server (NTRS)

Neumann, K.; DesMarais, D. J.

1998-01-01

We have investigated the role of biological processes in the C-isotopic dynamics of the aquatic ecosystems in Taylor Valley, Antarctica. This cold desert ecosystem is characterized by the complete lack of vascular plants, and the presence of algal mats in ephemeral streams and perennially ice covered lakes. Streams having abundant algal mats and mosses have very low sigma CO2 concentrations, as well as the most depleted delta C-13 values (-4%). Previous work has shown that algal mats in these streams have delta C-13 values averaging -7.01%. These values are similar to those observed in the algal mats in shallow areas of the lakes in Taylor Valley, where CO2 is thought to be colimiting to growth. These low Sigma CO2 concentrations, and delta C(13) signatures heavier than the algal mats, suggest that CO2 may be colimiting in the streams, as well. Streams with little algal growth, especially the longer ones in Fryxell Basin, have higher Sigma CO2 concentrations and much more enriched isotopic signatures (as high as +8%). In these streams, the dissolution of isotopically enriched, cryogenic CaCO3 is probably the major source of dissolved carbonate. The delta C(13) geochemistry of Antarctic streams is radically different from the geochemistry of more temperate streams, as it is not affected by terrestrially produced, isotopically depleted Sigma CO2. These results have important implications for the understanding of "biogenic" carbonate that might have been produced from aquatic ecosystems in the past on Mars.

Stable Isotopes of N2O in a Large Canadian River Impacted by Agricultural and Urban Land Use

NASA Astrophysics Data System (ADS)

Thuss, S. J.; Rosamond, M. S.; Schiff, S.; Venkiteswaran, J. J.; Elgood, R. J.

2009-05-01

N2O is a potent greenhouse gas. Although denitrification is an important process in the global N cycle, N2O flux measurements from rivers worldwide are scarce. The two main processes producing N2O in rivers -- nitrification and denitrification -- result in N2O that is widely separated in isotopic signature. However, studies on the stable isotopes of N2O in rivers are almost non-existent. Here, we report the N2O fluxes and isotopic signatures in the Grand River, a large, heavily impacted river in southern Ontario. Land use in the basin is predominately agricultural and the river receives effluent from 26 wastewater treatment plants (WWTPs). River samples were collected over a 28 hour period to capture diel variation, along the entire length of the river to capture changing land use and throughout the year to capture the seasonal variability. A dynamic model was used to correct the measured N2O values for the effects of atmospheric exchange. Isotopic analysis of both the NH4+ and the NO3- end members in the WWTP effluent and in the river allowed the determination of N2O production pathways. N2O is produced along the entire length of the river but N2O from denitrification increases dramatically in the river below WWTPs at night when dissolved oxygen is low and nitrification of NH4+ decreases.

Molybdenum and zinc stable isotope variation in mining waste rock drainage and waste rock at the Antamina mine, Peru.

PubMed

Skierszkan, E K; Mayer, K U; Weis, D; Beckie, R D

2016-04-15

The stable isotope composition of molybdenum (Mo) and zinc (Zn) in mine wastes at the Antamina Copper-Zn-Mo mine, Peru, was characterized to investigate whether isotopic variation of these elements indicated metal attenuation processes in mine drainage. Waste rock and ore minerals were analyzed to identify the isotopic composition of Mo and Zn sources, namely molybdenites (MoS2) and sphalerites (ZnS). Molybdenum and Zn stable isotope ratios are reported relative to the NIST-SRM-3134 and PCIGR-1 Zn standards, respectively. δ(98)Mo among molybdenites ranged from -0.6 to +0.6‰ (n=9) while sphalerites showed no δ(66)Zn variations (0.11±0.01‰, 2 SD, n=5). Mine drainage samples from field waste rock weathering experiments were also analyzed to examine the extent of isotopic variability in the dissolved phase. Variations spanned 2.2‰ in δ(98)Mo (-0.1 to +2.1‰) and 0.7‰ in δ(66)Zn (-0.4 to +0.3‰) in mine drainage over a wide pH range (pH2.2-8.6). Lighter δ(66)Zn signatures were observed in alkaline pH conditions, which was consistent with Zn adsorption and/or hydrozincite (Zn5(OH)6(CO3)2) formation. However, in acidic mine drainage Zn isotopic compositions reflected the value of sphalerites. In addition, molybdenum isotope compositions in mine drainage were shifted towards heavier values (0.89±1.25‰, 2 SD, n=16), with some overlap, in comparison to molybdenites and waste rock (0.13±0.82‰, 2 SD, n=9). The cause of heavy Mo isotopic signatures in mine drainage was more difficult to resolve due to isotopic heterogeneity among ore minerals and a variety of possible overlapping processes including dissolution, adsorption and secondary mineral precipitation. This study shows that variation in metal isotope ratios are promising indicators of metal attenuation. Future characterization of isotopic fractionation associated to key environmental reactions will improve the power of Mo and Zn isotope ratios to track the fate of these elements in mine drainage. Copyright © 2015 Elsevier B.V. All rights reserved.

Rb-Sr Isotopic Systematics of Alkali-Rich Fragments in the Yamato-74442 LL-Chondritic Breccia

NASA Technical Reports Server (NTRS)

Yokoyama, T.; Misawa, K.; Okano, O.; Shih, C.-Y.; Nyquist, L. E.; Simo, J. I.; Tappa, M. J.; Yoneda, S.

2012-01-01

Alkali-rich igneous fragments were identified in the brecciated LL-chondrites, Kr henberg (LL5)], Bhola (LL3-6) and Yamato (Y)-74442 (LL4), and show characteristic fractionation patterns of alkaline elements. The K-Rb-Cs-rich fragments in Kr henberg, Bhola, and Y-74442 are very similar in mineralogy and petrography (olivine + pyroxene + glass), suggesting that they could have come from related precursor materials. We have undertaken Rb-Sr isotopic studies on alkali-rich fragments in Y-74442 to precisely determine their crystallization ages and the isotopic signatures of their precursor material(s).

Real-time Stack Monitoring at the BaTek Medical Isotope Production Facility

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

McIntyre, Justin I.; Agusbudiman, A.; Cameron, Ian M.

2016-04-01

Radioxenon emissions from radiopharmaceutical production are a major source of background concentrations affecting the radioxenon detection systems of the International Monitoring System (IMS). Collection of real-time emissions data from production facilities makes it possible to screen out some medical isotope signatures from the IMS radioxenon data sets. This paper describes an effort to obtain and analyze real-time stack emissions data with the design, construction and installation of a small stack monitoring system developed by a joint CTBTO-IDC, BATAN, and PNNL team at the BaTek medical isotope production facility near Jakarta, Indonesia.

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

NASA Astrophysics Data System (ADS)

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

2013-07-01

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

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.

New isotopic evidence for the origin of groundwater from the Nubian Sandstone Aquifer in the Negev, Israel

USGS Publications Warehouse

Vengosh, A.; Hening, S.; Ganor, J.; Mayer, B.; Weyhenmeyer, C.E.; Bullen, T.D.; Paytan, A.

2007-01-01

The geochemistry and isotopic composition (H, O, S, Osulfate, C, Sr) of groundwater from the Nubian Sandstone (Kurnub Group) aquifer in the Negev, Israel, were investigated in an attempt to reconstruct the origin of the water and solutes, evaluate modes of water-rock interactions, and determine mean residence times of the water. The results indicate multiple recharge events into the Nubian sandstone aquifer characterized by distinctive isotope signatures and deuterium excess values. In the northeastern Negev, groundwater was identified with deuterium excess values of ???16???, which suggests local recharge via unconfined areas of the aquifer in the Negev anticline systems. The ??18OH2O and ??2H values (-6.5??? and -35.4???) of this groundwater are higher than those of groundwater in the Sinai Peninsula and southern Arava valley (-7.5??? and -48.3???) that likewise have lower deuterium excess values of ???10???. Based on the geochemical differences between groundwater in the unconfined and confined zones of the aquifer, a conceptual geochemical model for the evolution of the groundwater in the Nubian sandstone aquifer has been reconstructed. The isotopic composition of shallow groundwater from the unconfined zone indicates that during recharge oxidation of pyrite to SO4 (??34SSO4 ???-13???; ??18OSO4 ???+7.7???) and dissolution of CaCO3 (87Sr/86Sr ???0.70787; ??13CDIC = -3.7???) occur. In the confined zone of the aquifer, bacterial SO4 reduction removes a significant part of dissolved SO42 -, thereby modifying its isotopic composition (??34SSO4 ???-2???; ??18OSO4 ???+8.5???) and liberating dissolved inorganic C that contains little or no radiocarbon (14C-free) with low ??13CDIC values (<-12???). In addition to local recharge, the Sr and S isotopic data revealed contribution of external groundwater sources to the Nubian Sandstone aquifer, resulting in further modifications of the groundwater chemical and isotopic signatures. In the northeastern Negev, it is shown that SO4-rich groundwater from the underlying Jurassic aquifer contributes significantly to the salt budget of the Nubian Sandstone aquifer. The unique chemical and isotopic composition of the Jurassic groundwater (??34SSO4 ??? +14???; ??18OSO4 ??? 14???; 87Sr/86Sr ???0.70764) is interpreted as reflecting dissolution of Late Triassic marine gypsum deposits. In the southern Arava Valley the authors postulate that SO4-rich groundwater with distinctively high Br/Cl (3 ?? 10-3) low 87Sr/86Sr (0.70734), and high ??34SSO4 values (+15???) is derived from mixing with underlying brines from the Paleozoic units. The radiocarbon measurements reveal low 14C activities (0.2-5.8 pmc) in both the northeastern Negev and southern Arava Valley. Taking into account dissolution of carbonate rocks and bacterial SO4 reduction in the unconfined area, estimated mean residence times of groundwater in the confined zone in the northeastern Negev are on the order of 21-38 ka, which suggests recharge predominantly during the last glacial period. The 14C signal in groundwater from the southern Arava Valley is equally low but due to evidence for mixing with external water sources the residence time estimates are questionable. ?? 2007 Elsevier Ltd. All rights reserved.

Xe-126 Excesses: Monoisotopic Anomalies in Regolith Samples?

NASA Technical Reports Server (NTRS)

Mathew, K. J.; Marti, K.; Levskii, L. K.

2003-01-01

We present new Xe isotopic signatures of Pesyanoe regolith samples which document excesses of 126Xe and we explore the possibility that it formed by low-energy reactions on transient Te-rich coatings.

Peridotite xenoliths from the Polynesian Austral and Samoa hotspots: Implications for the destruction of ancient 187Os and 142Nd isotopic domains and the preservation of Hadean 129Xe in the modern convecting mantle

NASA Astrophysics Data System (ADS)

Jackson, M. G.; Shirey, S. B.; Hauri, E. H.; Kurz, M. D.; Rizo, H.

2016-07-01

The Re-Os systematics in 13 peridotite xenoliths hosted in young (<0.39 myr) rejuvenated lavas from the Samoan island of Savai'i and 8 peridotite xenoliths from 6 to 10 myr old lavas from the Austral island of Tubuai have been examined to evaluate the history of the oceanic mantle in this region. Modal mineralogy, trace element compositions and 187Os/188Os ratios suggest that these peridotites are not cognate or residual to mantle plumes but rather samples of Pacific oceanic lithosphere created at the ridge. Savai'i and Tubuai islands lie along a flow line in the Pacific plate, and provide two snapshots (separated by over 40 Ma in time) of Pacific mantle that originated in the same region of the East Pacific rise. Tubuai xenoliths exhibit 187Os/188Os from 0.1163 to 0.1304, and Savai'i (Samoa) xenoliths span a smaller range from 0.1173 to 0.1284. The 187Os/188Os ratios measured in Tubuai xenoliths are lower than (and show no overlap with) basalts from Tubuai. The 187Os/188Os of the Savai'i xenoliths overlap the isotopic compositions of lavas from the island of Savai'i, but also extend to lower 187Os/188Os than the lavas. 3He/4He measurements of a subset of the xenoliths range from 2.5 to 6.4 Ra for Tubuai and 10.8 to 12.4 Ra for Savai'i. Like abyssal peridotites and xenoliths from oceanic hotspots that sample the convecting mantle, Os isotopes from the Savai'i and Tubuai xenolith suites are relatively unradiogenic, but do not preserve a record of depleted early-formed (Hadean and Archean) mantle domains expected from earlier cycles of ridge-related depletion, continent extraction, or subcontinental lithospheric mantle erosion. The lack of preservation of early-formed, geochemically-depleted Os-isotopic and 142Nd/144Nd domains in the modern convecting mantle contrasts with the preservation of early-formed (early-Hadean) 129Xe/130Xe isotopic heterogeneities in the convecting mantle. This can be explained if the initial isotopic signatures in Re-Os and Sm-Nd systems are erased by recycling because the parent and daughter elements are retained in subducting slabs and more efficiently returned to the mantle during subduction than Xe. In this way, early-formed Os and Nd-isotopic heterogeneities could have been overprinted with, and diluted by, younger isotopic signatures. In contrast, preservation of early-formed heterogeneities in the modern convecting mantle is possible for other elements, such as Xe, that are not as efficiently recycled back into the mantle, owing to greater fluid mobility that concentrates such elements in the near-surface. Differing recycling efficiencies for Os, Nd and Xe lead to wide differences in the preservation of Hadean isotopic signatures of these elements in the modern convecting mantle. In general, incompatible elements that are fluid mobile (e.g., Xe) concentrate in surface reservoirs and are more likely to preserve Hadean geochemical signatures in the convecting mantle than compatible elements (e.g., Os) and fluid immobile incompatible elements (e.g., Nd).

Chromium isotope variations (δ53/52Cr) in mantle-derived sources and their weathering products: Implications for environmental studies and the evolution of δ53/52Cr in the Earth’s mantle over geologic time

NASA Astrophysics Data System (ADS)

Farkaš, Juraj; Chrastný, Vladislav; Novák, Martin; Čadkova, Eva; Pašava, Jan; Chakrabarti, Ramananda; Jacobsen, Stein B.; Ackerman, Lukáš; Bullen, Thomas D.

2013-12-01

Here we report chromium isotope compositions, expressed as δ53/52Cr in per mil (‰) relative to NIST 979, measured in selected Cr-rich minerals and rocks formed by the primary magmatic as well as the secondary metamorphic and weathering processes. The main objectives of this study were: (i) to further constrain the isotope composition of the Earth’s mantle Cr inventory and its possible variation during geological history, based on the analysis of globally distributed and stratigraphically constrained mantle-derived chromites; and (ii) to investigate the magnitude and systematics of Cr isotope fractionation during oxidative weathering and secondary alteration (i.e., hydration, serpentinization) of the magmatic Cr sources. Specifically, we analyzed δ53/52Cr in a set of globally distributed mantle-derived chromites (FeMgCr2O4, n = 30) collected from various locations in Europe, Asia, Africa and South America, and our results confirm that a chromite-hosted Earth’s mantle Cr inventory is uniform at -0.079 ± 0.129‰ (2SD), which we named here as a ‘canonical’ mantle δ53/52Cr signature. Furthermore our dataset of stratigraphically constrained chromites, whose crystallization ages cover most of the Earth’s geological history, indicate that the bulk Cr isotope composition of the chromite-hosted mantle inventory has remained uniform, within about ±0.100‰, since at least the Early Archean times (∼3500 million years ago, Ma). To investigate the systematics of Cr isotope fractionation associated with alteration processes we analyzed a number of secondary Cr-rich minerals and variably altered ultramafic rocks (i.e., serpentinized harzburgites, lherzolites) that revealed large positive δ53/52Cr anomalies that are systematically shifted to higher values with an increasing degree of alteration and serpentinization. The degree of aqueous alteration and serpentinization was quantified by the abundances of fluid-mobile (Rb, K) elements, and by the Loss On Ignition (LOI) parameter, which determines the amount of structurally bound water (OH/H2O) present in secondary hydrated minerals like serpentine. Overall, we observed that altered ultramafic rocks that yielded the highest LOI values, and the lowest amounts of fluid mobile elements, also yielded the heaviest δ53/52Cr signatures. Therefore, we conclude that secondary alteration (i.e., hydration, serpentinization) of ultramafic rocks in near-surface oxidative environments tend to shift the bulk Cr isotope composition of the weathered products to isotopically heavier values, pointing to a dynamic redox cycling of Cr in the Earth’s crustal and near-surface environments. Hence, if validated by future studies, this would suggest that Cr isotopes could be used to trace the recycling of altered oceanic lithosphere through subduction zones, and to detect the sources of dehydrated and previously serpentinized oceanic crust carrying ‘heavy’ δ53/52Cr signatures in island arc systems. Finally, the fact that the geogenic Cr sources may locally exhibit anomalous (non-canonical) δ53/52Cr signatures has also implications for environmental studies that use δ53/52Cr as a tracer to quantify the amount of the hexavalent Cr reduction in waters.

Can We Monitor Ecosystem Function Using Keeling Plot Analyses of Nocturnal Cold-Air Drainage?

NASA Astrophysics Data System (ADS)

Bond, B. J.; Ocheltree, T.; Pypker, T.; Unsworth, M. H.; Mix, A. C.; William, R.

2003-12-01

The carbon isotope signature of ecosystem respiration, δ 13CR, as measured by the Keeling Plot approach, has been related to short-term variations in weather and ecosystem function in several recent studies. In order to obtain an adequate range of [CO2] and to sample a consistent vegetation type, investigators typically select sampling locations in relatively flat terrain and uniform canopy cover, but these are unusual conditions for many forested ecosystems. In a pilot study, we are collecting samples for Keeling Plot analyses in cold-air drainage systems in small (60-100 ha), deeply-incised watersheds, one covered with old-growth (ca 450-years-old) Douglas-fir/hemlock forest and one covered with young (ca 45-years-old) Douglas-fir forest. We found that the nightly range of [CO2] was typically 380-460 ppm, sufficient to develop good estimates of δ 13CR. At any point in time there was little variation in [CO2] with height through the canopy (0.5-30m), so the required range was obtained by sampling over several hours. There was no indication that samples taken from different heights or at different times of night represented sources with different isotopic signatures. The isotopic signature of respired CO2 in the older watershed averaged about 1 per mil greater than that of the young watershed, and δ 13CR of both locations correlated with modeled stomatal conductance 6 days prior to flask sampling.

New high resolution geochemistry of Lower Jurassic marine sections in western North America: A global positive carbon isotope excursion in the Sinemurian?

NASA Astrophysics Data System (ADS)

Porter, Sarah J.; Smith, Paul L.; Caruthers, Andrew H.; Hou, Pengfei; Gröcke, Darren R.; Selby, David

2014-07-01

Recognising variations in the carbon isotope compositions of marine organic-rich sedimentary rocks can provide insight into changes in ocean chemistry throughout geological time. Further, identification of global excursions in the carbon isotope record has proved to be valuable as a chronostratigraphic correlation tool. This investigation presents new high-resolution organic carbon isotope data (δCorg13) for marine sediments from 2 regions in North America (Last Creek, British Columbia, Canada and Five Card Draw, Nevada, USA). The carbon isotope profiles demonstrate that there were significant differences between the carbon reservoirs at Five Card Draw and Last Creek, notably in the upper part of the Leslei Zone. The δCorg13 values show a gradual positive CIE (∼2‰) at Last Creek in the upper part of the Leslei Zone. This corresponds to a coeval positive CIE of similar duration in Dorset, UK (upper Turneri Zone; Jenkyns and Weedon, 2013), suggesting that this may be a global marine carbon isotope signature, and likely reflects a widespread increase in primary productivity during the Early Sinemurian. In addition, a brief negative CIE is observed in the uppermost Lower Sinemurian at Last Creek. This negative excursion is not recorded in the Dorset section, suggesting localised upwelling of 12C-rich bottom-waters at Last Creek. Further, the signals identified at Last Creek are not present in coeval sections at Five Card Draw, thus highlighting a significant difference between these localities. Osmium (Os) isotope data (initial 187Os/188Os values) provide a quantitative determination of the contrasting depositional environments of Five Card Draw and Last Creek (at least partially restricted with high levels of continental inundation and open-ocean, respectively). This demonstrates that basinal restriction may act as a major factor that controls isotopic stratigraphic signatures, thus preventing the identification of global or widespread regional excursions.

The effects of magmatic processes and crustal recycling on the molybdenum stable isotopic composition of Mid-Ocean Ridge Basalts

NASA Astrophysics Data System (ADS)

Bezard, Rachel; Fischer-Gödde, Mario; Hamelin, Cédric; Brennecka, Gregory A.; Kleine, Thorsten

2016-11-01

Molybdenum (Mo) stable isotopes hold great potential to investigate the processes involved in planetary formation and differentiation. However their use is currently hampered by the lack of understanding of the dominant controls driving mass-dependent fractionations at high temperature. Here we investigate the role of magmatic processes and mantle source heterogeneities on the Mo isotope composition of Mid-Ocean Ridges Basalts (MORBs) using samples from two contrasting ridge segments: (1) the extremely fast spreading Pacific-Antarctic (66-41°S) section devoid of plume influence and; (2) the slow spreading Mohns-Knipovich segment (77-71°N) intercepted by the Jan Mayen Plume (71°N). We show that significant variations in Mo stable isotope composition exist in MORBs with δ98/95Mo ranging from - 0.24 ‰ to + 0.15 ‰ (relative to NIST SRM3134). The absence of correlation between δ98/95Mo and indices of magma differentiation or partial melting suggests a negligible impact of these processes on the isotopic variations observed. On the other hand, the δ98/95Mo variations seem to be associated with changes in radiogenic isotope signatures and rare earth element ratios (e.g., (La/Sm)N), suggesting mantle source heterogeneities as a dominant factor for the δ98/95Mo variations amongst MORBs. The heaviest Mo isotope compositions correspond to the most enriched signatures, suggesting that recycled crustal components are isotopically heavy compared to the uncontaminated depleted mantle. The uncontaminated depleted mantle shows slightly sub-chondritic δ98/95Mo, which cannot be produced by core formation and, therefore, more likely result from extensive anterior partial melting of the mantle. Consequently, the primitive δ98/95Mo composition of the depleted mantle appears overprinted by the effects of both partial melting and crustal recycling.

Zinc isotope investigation of surface and pore waters in a mountain watershed impacted by acid rock drainage.

PubMed

Aranda, Suzan; Borrok, David M; Wanty, Richard B; Balistrieri, Laurie S

2012-03-15

The pollution of natural waters with metals derived from the oxidation of sulfide minerals like pyrite is a global environmental problem. However, the metal loading pathways and transport mechanisms associated with acid rock drainage reactions are often difficult to characterize using bulk chemical data alone. In this study, we evaluated the use of zinc (Zn) isotopes to complement traditional geochemical tools in the investigation of contaminated waters at the former Waldorf mining site in the Rocky Mountains, Colorado, U.S.A. Geochemical signatures and statistical analysis helped in identifying two primary metal loading pathways at the Waldorf site. The first was characterized by a circumneutral pH, high alkalinity, and high Zn/Cd ratios. The second was characterized by acidic pHs and low Zn/Cd ratios. Zinc isotope signatures in surface water samples collected across the site were remarkably similar (the δ(66)Zn, relative to JMC 3-0749-L, for most samples ranged from 0.20 to 0.30‰±0.09‰ 2σ). This probably suggests that the ultimate source of Zn is consistent across the Waldorf site, regardless of the metal loading pathway. The δ(66)Zn of pore water samples collected within a nearby metal-impacted wetland area, however, were more variable, ranging from 0.20 to 0.80‰±0.09‰ 2σ. Here the Zn isotopes seemed to reflect differences in groundwater flow pathways. However, a host of secondary processes might also have impacted Zn isotopes, including adsorption of Zn onto soil components, complexation of Zn with dissolved organic matter, uptake of Zn into plants, and the precipitation of Zn during the formation of reduced sulfur species. Zinc isotope analysis proved useful in this study; however, the utility of this isotopic tool would improve considerably with the addition of a comprehensive experimental foundation for interpreting the complex isotopic relationships found in soil pore waters. Copyright © 2012 Elsevier B.V. All rights reserved.

Discrete stages of core formation survive the Moon-forming impact

NASA Astrophysics Data System (ADS)

Jackson, C.; Bennett, N.; Du, Z.; Fei, Y.

2016-12-01

There is mounting evidence that Earth contains isotopic variations produced by short-lived systems, namely Hf-W and I-Xe. The lifetimes of these systems are 50 Ma and 80 Ma, respectively, requiring that chemical heterogeneities that were formed extremely early in solar system history and have survived within Earth's mantle to the modern day. The isotopic heterogeneity observed within Earth's mantle contrasts the isotopic similarity of bulk silicate Earth and bulk silicate Moon. This suggests the process(es) responsible for the isotopic variations within Earth predate the Moon-forming impact. Here, we focus on the potential role of core-formation in generating coupled isotopic variations associated with the Hf-W and I-Xe systems. We present metal-silicate partitioning data for W and I from experiments employing laser-heated diamond anvil cells. Experiments were conducted up to the pressure and temperature conditions directly relevant to core formation at GSECARS, APS. Samples were prepared using focused ion beam milling and analyzed by field emission electron microbeam techniques (EDS & WDS). These analyses demonstrate that W and I preferentially partition into the core under a wide range of conditions. In combination with literature data, this suggests that core formation left the residual mantle with an increased Hf/W ratio and a decreased I/Xe ratio. These parent-daughter fractionations lead to radiogenic W and unradiogenic Xe isotopic signatures compared to mantle that experienced the extraction of core material at a later date, on average. Relatively radiogenic W and unradiogenic Xe isotopic signatures are associated with plume rocks, potentially linking the plume source to mantle reservoirs that experienced early core extraction relative to the bulk mantle. Compositional variables, pressure, and temperature also affect the magnitude of Hf/W and I/Xe fractionation associated with core formation. The interplay of these variables will be evaluated alongside the timing of core formation in the context of generating short-lived isotopic variations associated with plume mantle.

Mycobacterium tuberculosis strains exhibit differential and strain-specific molecular signatures in pulmonary epithelial cells.

PubMed

Mvubu, Nontobeko Eunice; Pillay, Balakrishna; Gamieldien, Junaid; Bishai, William; Pillay, Manormoney

2016-12-01

Although pulmonary epithelial cells are integral to innate and adaptive immune responses during Mycobacterium tuberculosis infection, global transcriptomic changes in these cells remain largely unknown. Changes in gene expression induced in pulmonary epithelial cells infected with M. tuberculosis F15/LAM4/KZN, F11, F28, Beijing and Unique genotypes were investigated by RNA sequencing (RNA-Seq). The Illumina HiSeq 2000 platform generated 50 bp reads that were mapped to the human genome (Hg19) using Tophat (2.0.10). Differential gene expression induced by the different strains in infected relative to the uninfected cells was quantified and compared using Cufflinks (2.1.0) and MeV (4.0.9), respectively. Gene expression varied among the strains with the total number of genes as follows: F15/LAM4/KZN (1187), Beijing (1252), F11 (1639), F28 (870), Unique (886) and H37Rv (1179). A subset of 292 genes was commonly induced by all strains, where 52 genes were down-regulated while 240 genes were up-regulated. Differentially expressed genes were compared among the strains and the number of induced strain-specific gene signatures were as follows: F15/LAM4/KZN (138), Beijing (52), F11 (255), F28 (55), Unique (186) and H37Rv (125). Strain-specific molecular gene signatures associated with functional pathways were observed only for the Unique and H37Rv strains while certain biological functions may be associated with other strain signatures. This study demonstrated that strains of M. tuberculosis induce differential gene expression and strain-specific molecular signatures in pulmonary epithelial cells. Specific signatures induced by clinical strains of M. tuberculosis can be further explored for novel host-associated biomarkers and adjunctive immunotherapies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Early Detection of NSCLC Using Stromal Markers in Peripheral Blood

DTIC Science & Technology

2017-11-01

transcriptionally altered and the alteration is tumor dependent . The specific transcriptomic signature of circulating myeloid cells may provide us unique...signature, which may be useful for early lung cancer diagnosis. The specific aims are: Aim 1. To identify a NSCLC- dependent transcriptomic signature in...circulating myeloid cells are transcriptionally altered and the alteration is tumor dependent . The specific transcriptomic signature of circulating

IsoNose - Isotopic Tools as Novel Sensors of Earth Surfaces Resources - A new Marie Curie Initial Training Network

NASA Astrophysics Data System (ADS)

von Blanckenburg, Friedhelm; Bouchez, Julien; Bouman, Caludia; Kamber, Balz; Gaillardet, Jérôme; Gorbushina, Anna; James, Rachael; Oelkers, Eric; Tesmer, Maja; Ashton, John

2015-04-01

The Marie Curie Initial Training Network »Isotopic Tools as Novel Sensors of Earth Surfaces Resources - IsoNose« is an alliance of eight international partners and five associated partners from science and industry. The project is coordinated at the Helmholtz Centre Potsdam GFZ German Research Centre for Geosciences and will run until February 2018. In the last 15 years advances in novel mass-spectrometric methods have opened opportunities to identify "isotopic fingerprints" of virtually all metals and to make use of the complete information contained in these fingerprints. The understanding developed with these new tools will ultimately guide the exploitation of Earth surface environments. However, progress in bringing these methods to end-users depends on a multi transfer of knowledge between (1) isotope Geochemistry and Microbiology, Environmental Sciences (2), Economic Geology and (3) instrument developers and users in the development of user-friendly and new mass spectrometric methods. IsoNose will focus on three major Earth surface resources: soil, water and metals. These resources are currently being exploited to an unprecedented extent and their efficient management is essential for future sustainable development. Novel stable isotope techniques will disclose the processes generating (e.g. weathering, mineral ore formation) and destroying (e.g. erosion, pollution) these resources. Within this field the following questions will be addressed and answered: - How do novel stable isotope signatures characterize weathering processes? - How do novel stable isotope signatures trace water transport? - How to use novel stable isotope as environmental tracers? - How to use novel stable isotope for detecting and exploring metal ores? - How to improve analytical capabilities and develop robust routine applications for novel stable isotopes? Starting from the central questions mentioned above the IsoNose activities are organized in five scientific work packages: 1. Making soil from rock 2. Dissolved metals in the global water cycle 3. Human influence on metal cycling 4. Innovations in metal ore exploration 5. New analytical tools Acknowledgement: The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/2007-2013/ under REA grant agreement n° [608069].

High-resolution analysis of Quaternary calcretes: a coupled stable isotope and micromorphological approach

NASA Astrophysics Data System (ADS)

Adamson, Kathryn; Candy, Ian; Whitfield, Liz

2015-04-01

Pedogenic calcretes are abundant in arid and semi-arid regions, and they are widely used as proxy records of palaeoclimatic change. Calcrete oxygen (δ18O) and carbon (δ13C) isotopic signatures are indicative of temperature, aridity, or vegetation at the time of calcrete formation. Their microfabrics also reflect carbonate formation mechanisms in response to the prevailing environmental conditions. Many studies have explored calcrete micromorphology or stable isotope composition, but these techniques have not yet been applied simultaneously. This co-analysis is important as it allows us to establish whether calcrete morphology directly reflects environmental change. This study tests the potential of combining these analyses to examine the relationships between calcrete microfabrics, their isotopic signals, and Quaternary climate change. Calcretes from four river terraces of the Rio Alias in southeast Spain have been analysed in detail. On the basis of morphostratigraphic correlation (Maher et al., 2007) and Uranium-series ages (Candy et al., 2005), these span the period from 304 ± 26 ka (MIS 9) to the Holocene. The oldest profiles have therefore been exposed to multiple glacial-interglacial cycles. A total of 37 micromorphological profiles have been used to extract stable oxygen and carbon isotopic indicators from 77 microfacies. The morphological and isotopic complexity of the calcrete profiles increases with progressive age. The oldest samples display multiple calcretisation phases, and their microfabrics have a larger isotopic range than the younger samples. Alpha (non-biogenic) fabrics have higher δ13C and δ18O values than beta (biogenic) fabrics. Strong positive covariance between δ13C and δ18O within all profiles suggests that both isotopes are responding to the same environmental parameter. We suggest that this is relative aridity. The study demonstrates that the detailed co-analysis of calcrete micromorphology and stable isotope signatures allows calcrete formation patterns to be placed into a wider palaeoclimatic context. Importantly, this technique provides a level of detail that is not possible through bulk isotope sampling alone. It demonstrates the potential of this technique to more reliably constrain the palaeoenvironmental significance of secondary carbonates in dryland settings where other proxy records may be poorly preserved.

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.

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.

Interstellar and Solar Nebula Materials in Cometary Dust

NASA Technical Reports Server (NTRS)

Messenger, Scott; Nakamura-Messenger, Keiko; Keller, Lindsay; Nguyen, Ann; Clemett, Simon

2017-01-01

Laboratory studies of cometary dust collected in the stratosphere and returned from comet 81P/Wild 2 by the Stardust spacecraft have revealed ancient interstellar grains and molecular cloud organic matter that record a range of astrophysical processes and the first steps of planetary formation. Presolar materials are rarer meteorites owing to high temperature processing in the solar nebula and hydrothermal alteration on their asteroidal parent bodies. The greater preservation of presolar materials in comets is attributed to their low accretion temperatures and limited planetary processing. Yet, comets also contain a large complement of high temperature materials from the inner Solar System. Owing to the limited and biased sampling of comets to date, the proportions of interstellar and Solar System materials within them remains highly uncertain. Interstellar materials are identified by coordinated isotopic, mineralogical, and chemical measurements at the scale of individual grains. Chondritic porous interplanetary dust particles (CP IDPs) that likely derive from comets are made up of 0.1 - 10 micron-sized silicates, Fe-Ni-sulfides, oxides, and other phases bound by organic material. As much as 1% of the silicates are interstellar grains that have exotic isotopic compositions imparted by nucleosynthetic processes in their parent stars. Crystalline silicates in CP IDPs dominantly have normal isotopic compositions and probably formed in the Solar System. 81P samples include isotopically normal refractory minerals that resemble Ca-Al rich inclusions and chondrules common in meteorites. The origins of sub-micron amorphous silicates in IDPs are not certain, but at least a few % of them are interstellar grains. The remainder have isotopic compositions consistent with Solar System origins and elemental compositions that are inconsistent with interstellar grain properties, thus favoring formation in the solar nebula [4]. The organic component in comets and primitive meteorites has large enrichments in D/H and N-15/N-14 relative to terrestrial materials. These isotopic signatures are probably due to low temperature chemical processes in cold molecular clouds or the outermost reaches of the protoplanetary disk. The greatest isotopic anomalies are found in sub-micron organic nanoglobules that show chemical signatures of interstellar chemistry. The observation that cometary dust is mostly composed of isotopically normal minerals within isotopically anomalous organic matter is difficult to reconcile with the formation models of each component. The mineral component likely formed in high temperature processes in the inner Solar System, while the organic fraction shows isotopic and chemical signatures of formation near 10 K. Studying more primitive remnants of the Solar System starting materials would help in resolving this paradox. Comets formed across a vast expanse of the outer disk under differing thermal and collisional regimes, and some are likely to be better preserved than others. Finding truly pristine aggregates of presolar materials may require return of a pristine sample of comet nucleus material.

Steady state or non-steady state? Identifying driving mechanisms of oxygen isotope signatures of leaf transpiration in functionally distinct plant species

NASA Astrophysics Data System (ADS)

Dubbert, Maren; Kübert, Angelika; Cuntz, Matthias; Werner, Christiane

2015-04-01

Isotope techniques are widely applied in ecosystem studies. For example, isoflux models are used to separate soil evaporation from transpiration in ecosystems. These models often assume that plant transpiration occurs at isotopic steady state, i.e. that the transpired water shows the same isotopic signature as the source water. Yet, several studies found that transpiration did not occur at isotopic steady state, under both controlled and field conditions. Here we focused on identifying the internal and external factors which drive the isotopic signature of leaf transpiration. Using cavity ring-down spectroscopy (CRDS), the effect of both environmental variables and leaf physiological traits on δ18OT was investigated under controlled conditions. Six plant species with distinct leaf physiological traits were exposed to step changes in relative air humidity (RH), their response in δ18OT and gas exchange parameters and their leaf physiological traits were assessed. Moreover, two functionally distinct plant types (tree, i.e. Quercus suber, and grassland) of a semi-arid Mediterranean oak-woodland where observed under natural conditions throughout an entire growth period in the field. The species differed substantially in their leaf physiological traits and their turn-over times of leaf water. They could be grouped in species with fast (<60 min.), intermediate (ca. 120 min.) and slow (>240 min.) turn-over times, mostly due to differences in stomatal conductance, leaf water content or a combination of both. Changes in RH caused an immediate response in δ18OT, which were similarly strong in all species, while leaf physiological traits affected the subsequent response in δ18OT. The turn-over time of leaf water determined the speed of return to the isotopic steady or a stable δ18OT value (Dubbert & Kübert et al., in prep.). Under natural conditions, changes in environmental conditions over the diurnal cycle had a huge impact on the diurnal development of δ18OT in both observed plant functional types. However, in accordance with our findings in the lab, species specific differences in the leaf water turn over time, significantly influenced the amount of time plants transpired at non-steady state during the day (Dubbert et al., 2013, 2014). Our results emphasize the significance of considering isotopic non-steady state of transpiration and specifically to account for the specific differences of plant species resulting from distinct physiological traits of their leaves when applying isoflux models in ecosystem studies. Dubbert, M; Cuntz, M; Piayda, A; Maguas, C; Werner, C: Partitioning evapotranspiration - Testing the Craig and Gordon model with field measurements of oxygen isotope ratios of evaporative fluxes. J Hydrol (2013) Dubbert, M; Piayda, A; Cuntz, M; Correia, AC; Costa e Silva, F; Pereira, JS; Werner, C: Stable oxygen isotope and flux partitioning demonstrates understory of an oak savanna contributes up to half of ecosystem carbon and water exchange, Frontiers in Plant Science (2014a)

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].

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

NASA Astrophysics Data System (ADS)

Kiczka, Mirjam; Wiederhold, Jan G.; Frommer, Jakob; Voegelin, Andreas; Kraemer, Stephan M.; Bourdon, Bernard; Kretzschmar, Ruben

2011-10-01

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ 56Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ 56Fe. For all soils the lightest isotopic composition was observed in a 1 M NH 2OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.

The Austrian Network of Isotopes in Precipitation and Surface water: more than 50 years applications and interpretations of basic isotope-hydrological data for Central Europe

NASA Astrophysics Data System (ADS)

Wyhlidal, S.; Rank, D.; Kralik, M.

2017-12-01

Austria runs one of the longest-standing and most dense isotope precipitation collection networks worldwide, resulting in a unique isotope time series. Stable isotope variations in precipitation are a consequence of isotope effects accompanying each step of the water cycle. Therefore, stable isotope ratios of oxygen (18O/16O) and hydrogen (2H/1H) in precipitation provide important information about the origin and atmospheric transport of water vapour. The separation of a remote moisture source signals from local influences is thereby challenging. The amount of precipitation in Austria is highly influenced by the Alpine mountain range (400-3.000 mm/a). The amount of annual precipitation increases towards the mountain ranges. However, strong regional differences exist between the north and south of the Austrian Alps because the Alpine range functions as weather divide. The isotope time series of the stations of the Austrian precipitation network show significant but not uniform long-term trends. While the 10-year running mean of some mountain stations exhibit a highly significant increase in δ18O of about 1 ‰ since 1975, the change of δ18O at the valley stations is less pronounced. The increasing δ18O values can be correlated to an increase mean air temperature in the Alpine area and can be used as an additional indicator of climate change in this region. The differences in δ18O-values of sampling stations at similar altitudes can be explained by the origin of the air moisture. An Atlantic influence causes lower δ18O-values than sources from the Mediterranean. This can be explained by the different distances to the sea. Deuterium excess is a second-order isotopic parameter which is often interpreted as a tracer of the evaporation conditions of water vapor at the moisture source in terms of relative humidity, wind speed, and sea surface temperature, but can also be modified by local influences, such as below-cloud evaporation and equilibrium fractionation under very cold conditions. The long-term variations of d-excess in precipitation at selected stations show a significant difference in the behavior of the d-excess at mountain and valley stations. Deuterium excess and δ18O will be used to explore climate effects on precipitation signatures observed and elicit how they can be integrated in to global climate models.

Partitioning net ecosystem carbon exchange into net assimilation and respiration using 13CO2 measurements: A cost-effective sampling strategy

NASA Astrophysics Data System (ADS)

OgéE, J.; Peylin, P.; Ciais, P.; Bariac, T.; Brunet, Y.; Berbigier, P.; Roche, C.; Richard, P.; Bardoux, G.; Bonnefond, J.-M.

2003-06-01

The current emphasis on global climate studies has led the scientific community to set up a number of sites for measuring the long-term biosphere-atmosphere net CO2 exchange (net ecosystem exchange, NEE). Partitioning this flux into its elementary components, net assimilation (FA), and respiration (FR), remains necessary in order to get a better understanding of biosphere functioning and design better surface exchange models. Noting that FR and FA have different isotopic signatures, we evaluate the potential of isotopic 13CO2 measurements in the air (combined with CO2 flux and concentration measurements) to partition NEE into FR and FA on a routine basis. The study is conducted at a temperate coniferous forest where intensive isotopic measurements in air, soil, and biomass were performed in summer 1997. The multilayer soil-vegetation-atmosphere transfer model MuSICA is adapted to compute 13CO2 flux and concentration profiles. Using MuSICA as a "perfect" simulator and taking advantage of the very dense spatiotemporal resolution of the isotopic data set (341 flasks over a 24-hour period) enable us to test each hypothesis and estimate the performance of the method. The partitioning works better in midafternoon when isotopic disequilibrium is strong. With only 15 flasks, i.e., two 13CO2 nighttime profiles (to estimate the isotopic signature of FR) and five daytime measurements (to perform the partitioning) we get mean daily estimates of FR and FA that agree with the model within 15-20%. However, knowledge of the mesophyll conductance seems crucial and may be a limitation to the method.

Using small mammals to understand the effects of urbanization in Southern California over the last 100 years

NASA Astrophysics Data System (ADS)

Loza, E.; Cotton, J. M.; Smiley, T. M.; Terry, R. C.

2017-12-01

Environmental and climate change due to urbanization has been occurring for the last 100 years, but we do not yet know the full extent of these impacts on ecosystems at local to regional scales. To investigate these impacts, we leverage extensive historical collections of small mammals, which can serve as indicators of past and modern ecosystem change. Here, we use the stable isotopic composition of hair from Peromyscus maniculatus, a widespread generalist rodent, to better understand the influence of urbanization over the last 100 years. The stable isotopic composition of small-mammal diets are recorded in the hair of these historical specimens, thereby providing a long-term record of climate and environmental change. Carbon isotopes (δ13C) can inform about the vegetation composition of an animal's diet, while nitrogen isotopes (δ15N) offer a view into agriculture signatures and atmospheric deposition of nitrogen-based pollutants through time. We focus on Los Angeles and southern California, which has experienced a population increase of 15 million people and dramatic land-use change over the past century. We have collected hair from historical P. maniculatus specimens found in natural history museums across the county to investigate spatial and temporal changes in δ13C and δ15N in southern California. We also use specimens from nearby and relatively pristine Channel Islands as a comparison to assess the impacts of anthropogenic land-use change on the mainland. We will present `isoscapes', or isotope landscape models for the δ13C and δ15N of P. maniculatus, in southern California through time. Understanding the isotopic signatures of urbanization provides better insight to the ecosystem response to urbanization and climate change and is useful for guiding future conservation and management decisions.

Genetic link between EMI and EMII: An adakite connection

NASA Astrophysics Data System (ADS)

Shimoda, Gen

2009-10-01

Geochemical modeling of the origin of enriched mantle I (EMI) and enriched mantle II (EMII) is conducted from the perspective of adakite production. For the model, the average composition of adakites is re-estimated from published data for eighteen trace elements. Although the concentrations determined for highly incompatible elements are very high (about 100 times of primitive mantle), these high concentrations can be explained by melting of oceanic crust without sediment contribution. The compiled data further suggest that the mantle-slab melt reaction would play a major role in the production of basic adakites. In addition, crystal fractionation in the magma chamber should produce additional chemical variations in adakites, in particular for acidic adakites. To examine the effect of chemical variations on the isotopic composition of recycled adakites, broad correlations between trace elements and SiO 2 concentrations, and the MELTS program are employed. The results suggest that recycling of a basic adakite (SiO 2 = 55%) can account for EMI isotopic signatures with storage times of about 2.0 Gyr. The isotopic compositions of less-basic adakites and their evolved magmas shift towards EMII values with increasing SiO 2 concentrations. In particular, evolved acidic adakite can yield EMII isotopic signatures. These lines of evidence suggest that the recycling of adakites at various stages of evolution can conceivably produce the entire isotopic range between EMI and EMII reservoirs. Consequently, adakite recycling via sediment subduction or subduction erosion can account for the origins of EMI and EMII reservoirs. In this context, residual garnet under high pressure and plagioclase fractionation at low pressure might play an essential role in producing the chemical variations among adakites that ultimately govern the isotopic compositions of these geochemical reservoirs.

Identification of energy consumption and nutritional stress by isotopic and elemental analysis of urine in bonobos (Pan paniscus).

PubMed

Deschner, Tobias; Fuller, Benjamin T; Oelze, Vicky M; Boesch, Christophe; Hublin, Jean-Jacques; Mundry, Roger; Richards, Michael P; Ortmann, Sylvia; Hohmann, Gottfried

2012-01-15

A mounting body of evidence suggests that changes in energetic conditions like prolonged starvation can be monitored using stable isotope ratios of tissues such as bone, muscle, hair, and blood. However, it is unclear if urinary stable isotope ratios reflect a variation in energetic condition, especially if these changes in energetic condition are accompanied by shifts in dietary composition. In a feeding experiment conducted on captive bonobos (Pan paniscus), we monitored urinary δ(13)C, δ(15)N, total C (carbon), total N (nitrogen), and C/N ratios and compared these results with glucocorticoid levels under gradually changing energy availability and dietary composition. Measurements of daily collected urine samples over a period of 31 days showed that while shifts in urinary isotope signatures of δ(13)C and δ(15)N as well as total C were best explained by changes in energy consumption, urinary total N excretion as well as the C/N ratios matched the variation in dietary composition. Furthermore, when correcting for fluctuations in dietary composition, the isotope signatures of δ(13)C and δ(15)N as well as total C correlated with urinary glucocorticoid levels; however, the urinary total N and the C/N ratio did not. These results indicate for the first time that it is possible to non-invasively explore specific longitudinal records on animal energetic conditions and dietary compositions with urinary stable isotope ratios and elemental compositions, and this research provides a strong foundation for investigating how ecological factors and social dynamics affect feeding habits in wild animal populations such as primates. Copyright © 2011 John Wiley & Sons, Ltd.

Lead concentration and isotope chronology in two coastal environments in Western and South East Asia

NASA Astrophysics Data System (ADS)

Carrasco, G. G.; Chen, M.; Boyle, E. A.; Zhao, N.; Nurhati, I. S.; Gevao, B.; al Ghadban, A.; Switzer, A.; Lee, J. M.

2014-12-01

Lead is a trace metal that is closely related to anthropogenic activity, mainly via leaded gasoline and coal combustion. The study of lead concentrations and isotopes in seawater, sediments, corals and aerosols allows for a systematic look at its sources and their time evolution in a natural environment. We will discuss results from two projects in Western and South East Asia, regions that have seen dramatic socio-economical changes over the past half-century that may have left environmental signals. These results highlight the usefulness of the method, indicate the degree of complexity of these systems, and point to the need for a continuous monitoring of anthropogenic trace metals in the small-medium coastal scale to be able to asses the larger scale effects of human activity. On the one hand, coastal Kuwait is heavily influenced by the Shat al-Arab river and shows a clear anthropogenic signature from Kuwait city. A mix of two sources can be tracked through the coral and sediment chronological records, with Pb206/Pb207 ratios (1.202 and 1.151) that approach the suspected source values (1.21 and 1.12) and eliminate the possibility of other sources. Through a wide sediment geographic distribution, the strength of the anthropogenic signature is modulated. On the other hand, Singapore offers a more complex system, where an apparent mix of two sources (extreme isotope ratios 1.215 and ~1.14) occurs also, but where either an unresolved potentially important third source (isotope ratio ~1.18), or an isotope exchange process should be invoked. The sediment and coral records allows us to track the changes through time; however, there seems to be incongruence with the aerosol isotope record. Further potential sources are being explored currently and will be discussed.

Stable isotope composition of cocoa beans of different geographical origin.

PubMed

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

2016-09-01

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

27 CFR 73.3 - What terms must I know to understand this part?

Code of Federal Regulations, 2010 CFR

2010-04-01

... and/or actions are both unique to that individual and measurable. Digital signature. An electronic... verified. A signer creates a digital signature by using public-key encryption to transform a message digest of an electronic message. If a recipient of the digital signature has an electronic message, message...

27 CFR 73.3 - What terms must I know to understand this part?

Code of Federal Regulations, 2011 CFR

2011-04-01

... and/or actions are both unique to that individual and measurable. Digital signature. An electronic... verified. A signer creates a digital signature by using public-key encryption to transform a message digest of an electronic message. If a recipient of the digital signature has an electronic message, message...

A renewed search for short-lived 126Sn in the early Solar System: Hydride generation MC-ICPMS for high sensitivity Te isotopic analysis

NASA Astrophysics Data System (ADS)

Brennecka, Gregory A.; Borg, Lars E.; Romaniello, Stephen J.; Souders, Amanda K.; Shollenberger, Quinn R.; Marks, Naomi E.; Wadhwa, Meenakshi

2017-03-01

Although there is limited direct evidence for supernova input into the nascent Solar System, many models suggest it formed by the gravitational collapse of a molecular cloud that was triggered by a nearby supernova. Existing lines of evidence, mostly in the form of short-lived radionuclides present in the early Solar System, are potentially consistent with this hypothesis, but still allow for alternative explanations. Since the natural production of 126Sn is thought to occur only in supernovae and this isotope has a short half-life (126Sn→126Te, t1/2 = 235 ky), the discovery of extant 126Sn would provide unequivocal proof of supernova input to the early Solar System. Previous attempts to quantify the initial abundance of 126Sn by examining Sn-Te systematics in early solids have been hampered by difficulties in precisely measuring Te isotope ratios in these materials. Thus, here we describe a novel technique that uses hydride generation to dramatically increase the ionization efficiency of Te-an approximately 30-fold increase over previous work. This introduction system, when coupled to a MC-ICPMS, enables high-precision Te isotopic analyses on samples with <10 ng of Te. We used this technique to analyze Te from a unique set of calcium-aluminum-rich inclusions (CAIs) that exhibit an exceptionally large range in Sn/Te ratios, facilitating the search for the short-lived isotope 126Sn. This sample set shows no evidence of live 126Sn, implying at most minor input of supernova material during the time at which the CAIs formed. However, based on the petrology of this sample set combined with the higher than expected concentrations of Sn and Te, as well as the lack of nucleosynthetic anomalies in other isotopes of Te suggest that the bulk of the Sn and Te recovered from these particular refractory inclusions is not of primary origin and thus does not represent a primary signature of Sn-Te systematics of the protosolar nebula during condensation of CAIs or their precursors. Although no evidence of supernova input was found based on Sn-Te systematics in this sample set, hydride generation represents a powerful tool that can now be used to further explore Te isotope systematics in less altered materials.

A renewed search for short-lived 126 Sn in the early Solar System: Hydride generation MC-ICPMS for high sensitivity Te isotopic analysis

DOE PAGES

Brennecka, Gregory A.; Borg, Lars E.; Romaniello, Stephen J.; ...

2017-03-01

Although there is limited direct evidence for supernova input into the nascent Solar System many models suggest it formed by the gravitational collapse of a molecular cloud that was triggered by a nearby supernova. Existing lines of evidence mostly in the form of short lived radionuclidespresent in the early Solar System are potentially consistent with this hypothesis but still allow for alternative explanations. Since the natural production of Sn-126 is thought to occur only in supernovae and this isotope has a short half-life (Sn-126 -> Te-126 t(1/2) = 235 ky) the discovery of extant Sn-126 would provide unequivocal proof ofmore » supernova input to the early Solar System. Previous attempts to quantify the initial abundance of Sn-126 by examining Sn-Te systematics in early solids have been hampered by difficulties in precisely measuring Te isotope ratios in these materials. Thus here we describe a novel technique that uses hydride generation to dramatically increase the ionization efficiency of Te-an approximately 30-fold increase over previous work. This introduction system when coupled to a MC-ICPMS enables highprecision Te isotopic analyses on samples with < 10 ng of Te. We used this technique to analyze Te from a unique set of calcium-aluminum-rich inclusions (CAIs) that exhibit an exceptionally large range in Sn/Te ratios facilitating the search for the short-lived isotope Sn-126. This sample set shows no evidence of live Sn-126 implying at most minor input of supernova material during the time at which the CAIs formed. However based on the petrology of this sample set combined with the higher than expected concentrations of Sn and Te as well as the lack of nucleosynthetic anomalies in other isotopes of Te suggest that the bulk of the Sn and Te recovered from these particular refractory inclusions is not of primary origin and thus does not represent a primary signature of Sn-Te systematics of the protosolar nebula during condensation of CAIs or their precursors. Although no evidence of supernova input was found based on Sn-Te systematics in this sample set hydride generation represents a powerful tool that can now be used to further explore Te isotope systematics in less altered materials.« less

Combined use of 15N and 18O of nitrate and 11B to evaluate nitrate contamination in groundwater

USGS Publications Warehouse

Seiler, R.L.

2005-01-01

Isotopic composition of NO3 (??15NNO3 and ??18ONO3) and B (??11B) were used to evaluate NO3 contamination and identify geochemical processes occurring in a hydrologically complex Basin and Range valley in northern Nevada with multiple potential sources of NO3. Combined use of these isotopes may be a useful tool in identifying NO3 sources because NO3 and B co-migrate in many environmental settings, their isotopes are fractionated by different environmental processes, and because wastewater and fertilizers may have distinct isotopic signatures for N and B. The principal cause of elevated NO3 concentrations in residential parts of the study area is wastewater and not natural NO3 or fertilizers. This is indicated by some samples with elevated NO3 concentrations plotting along ??15NNO3 and NO3 mixing lines between natural NO3 from the study area and theoretical septic-system effluent. This conclusion is supported by the presence of caffeine in one sample and the absence of samples with elevated NO3 concentrations that fall along mixing lines between natural NO3 and theoretical percolate below fertilized lawns. Nitrogen isotopes alone could not be used to determine NO3 sources in several wells because denitrification blurred the original isotopic signatures. The range of ??11B values in native ground water in the study area (-8.2??? to +21.2???) is large. The samples with the low ??11B values have a geochemical signature characteristic of hydrothermal systems. Physical and chemical data suggest B is not being strongly fractionated by adsorption onto clays. ??11B values from local STP effluent (-2.7???) and wash water from a domestic washing machine (-5.7???) were used to plot mixing lines between wastewater and native ground water. In general, wells with elevated NO3 concentrations fell along mixing lines between wastewater and background water on plots of ??11B against 1/B and Cl/B. Combined use of ??15N and ??11B in the study area was generally successful in identifying contaminant sources and processes that are occurring, however, it is likely to be more successful in simpler settings with a well-characterized ??11B value for background wells.

Nitrous oxide nitrification and denitrification 15N enrichment factors from Amazon forest soils.

PubMed

Pérez, Tibisay; Garcia-Montiel, Diana; Trumbore, Susan; Tyler, Stanley; de Camargo, Plínio; Moreira, Marcelo; Piccolo, Marisa; Cerri, Carlos

2006-12-01

The isotopic signatures of 15N and 18O in N2O emitted from tropical soils vary both spatially and temporally, leading to large uncertainty in the overall tropical source signature and thereby limiting the utility of isotopes in constraining the global N2O budget. Determining the reasons for spatial and temporal variations in isotope signatures requires that we know the isotope enrichment factors for nitrification and denitrification, the two processes that produce N2O in soils. We have devised a method for measuring these enrichment factors using soil incubation experiments and report results from this method for three rain forest soils collected in the Brazilian Amazon: soil with differing sand and clay content from the Tapajos National Forest (TNF) near Santarém, Pará, and Nova Vida Farm, Rondônia. The 15N enrichment factors for nitrification and denitrification differ with soil texture and site: -111 per thousand +/- 12 per thousand and -31 per thousand +/- 11 per thousand for a clay-rich Oxisol (TNF), -102 per thousand +/- 5 per thousand and -45 per thousand +/- 5 per thousand for a sandier Ultisol (TNF), and -10.4 per thousand +/- 3.5 per thousand (enrichment factor for denitrification) for another Ultisol (Nova Vida) soil, respectively. We also show that the isotopomer site preference (delta15Nalpha - delta15Nbeta, where alpha indicates the central nitrogen atom and beta the terminal nitrogen atom in N2O) may allow differentiation between processes of production and consumption of N2O and can potentially be used to determine the contributions of nitrification and denitrification. The site preferences for nitrification and denitrification from the TNF-Ultisol incubated soils are: 4.2 per thousand +/- 8.4 per thousand and 31.6 per thousand +/- 8.1 per thousand, respectively. Thus, nitrifying and denitrifying bacteria populations under the conditions of our study exhibit significantly different 15N site preference fingerprints. Our data set strongly suggests that N2O isotopomers can be used in concert with traditional N2O stable isotope measurements as constraints to differentiate microbial N2O processes in soil and will contribute to interpretations of the isotopic site preference N2O values found in the free troposphere.

The impact of sedimentary coatings on the diagenetic Nd flux

NASA Astrophysics Data System (ADS)

Abbott, April N.; Haley, Brian A.; McManus, James

2016-09-01

Because ocean circulation impacts global heat transport, understanding the relationship between deep ocean circulation and climate is important for predicting the ocean's role in climate change. A common approach to reconstruct ocean circulation patterns employs the neodymium isotope compositions of authigenic phases recovered from marine sediments. In this approach, mild chemical extractions of these phases is thought to yield information regarding the εNd of the bottom waters that are in contact with the underlying sediment package. However, recent pore fluid studies present evidence for neodymium cycling within the upper portions of the marine sediment package that drives a significant benthic flux of neodymium to the ocean. This internal sedimentary cycling has the potential to obfuscate any relationship between the neodymium signature recovered from the authigenic coating and the overlying neodymium signature of the seawater. For this manuscript, we present sedimentary leach results from three sites on the Oregon margin in the northeast Pacific Ocean. Our goal is to examine the potential mechanisms controlling the exchange of Nd between the sedimentary package and the overlying water column, as well as the relationship between the εNd composition of authigenic sedimentary coatings and that of the pore fluid. In our comparison of the neodymium concentrations and isotope compositions from the total sediment, sediment leachates, and pore fluid we find that the leachable components account for about half of the total solid-phase Nd, therefore representing a significant reservoir of reactive Nd within the sediment package. Based on these and other data, we propose that sediment diagenesis determines the εNd of the pore fluid, which in turn controls the εNd of the bottom water. Consistent with this notion, despite having 1 to 2 orders of magnitude greater Nd concentration than the bottom water, the pore fluid is still <0.001% of the total Nd reservoir in the upper sediment column. Therefore, the pore fluid reservoir is too small to maintain a unique signature, and instead must be controlled by the larger reservoir of Nd in the reactive coatings. In addition, to achieve mass balance, we find it necessary to invoke a cryptic radiogenic (εNd of +10) trace mineral source of neodymium within the upper sediment column at our sites. When present, this cryptic trace metal results in more radiogenic pore fluid.

Metamorphosis affects metal concentrations and isotopic signatures in a mayfly (Baetis tricaudatus): Implications for the aquatic-terrestrial transfer of metals

USGS Publications Warehouse

Wesner, Jeff S.; Walters, David; Schmidt, Travis S.; Kraus, Johanna M.; Stricker, Craig A.; Clements, William H.; Wolf, Ruth E.

2017-01-01

Insect metamorphosis often results in substantial chemical changes that can alter contaminant concentrations and fractionate isotopes. We exposed larval mayflies (Baetis tricaudatus) and their food (periphyton) to an aqueous zinc gradient (3-340 µg Zn/l) and measured zinc concentrations at different stages of metamorphosis: larval, subimago, and imago. We also measured changes in stable isotopes (δ15N and δ13C) in unexposed mayflies. Larval zinc concentrations were positively related to aqueous zinc, increasing 9-fold across the exposure gradient. Adult zinc concentrations were also positively related to aqueous zinc, but were 7-fold lower than larvae. This relationship varied according to adult substage and sex. Tissue concentrations in female imagoes were not related to exposure concentrations, but the converse was true for all other stage-by-sex combinations. Metamorphosis also increased δ15N by ~0.8‰, but not δ13C. Thus, the main effects of metamorphosis on insect chemistry were large declines in zinc concentrations coupled with increased δ15N signatures. For zinc, this change was largely consistent across the aqueous exposure gradient. However, differences among sexes and stages suggest that caution is warranted when using nitrogen isotopes or metal concentrations measured in one insect stage (e.g. larvae) to assess risk to wildlife that feed on subsequent life stages (e.g. adults).

Metamorphosis Affects Metal Concentrations and Isotopic Signatures in a Mayfly (Baetis tricaudatus): Implications for the Aquatic-Terrestrial Transfer of Metals.

PubMed

Wesner, Jeff S; Walters, David M; Schmidt, Travis S; Kraus, Johanna M; Stricker, Craig A; Clements, William H; Wolf, Ruth E

2017-02-21

Insect metamorphosis often results in substantial chemical changes that can alter contaminant concentrations and fractionate isotopes. We exposed larval mayflies (Baetis tricaudatus) and their food (periphyton) to an aqueous zinc gradient (3-340 μg Zn/l) and measured zinc concentrations at different stages of metamorphosis: larval, subimago, and imago. We also measured changes in stable isotopes (δ 15 N and δ 13 C) in unexposed mayflies. Larval zinc concentrations were positively related to aqueous zinc, increasing 9-fold across the exposure gradient. Adult zinc concentrations were also positively related to aqueous zinc, but were 7-fold lower than larvae. This relationship varied according to adult substage and sex. Tissue concentrations in female imagoes were not related to exposure concentrations, but the converse was true for all other stage-by-sex combinations. Metamorphosis also increased δ 15 N by ∼0.8‰, but not δ 13 C. Thus, the main effects of metamorphosis on insect chemistry were large declines in zinc concentrations coupled with increased δ 15 N signatures. For zinc, this change was largely consistent across the aqueous exposure gradient. However, differences among sexes and stages suggest that caution is warranted when using nitrogen isotopes or metal concentrations measured in one insect stage (e.g., larvae) to assess risk to wildlife that feed on subsequent life stages (e.g., adults).

Evidence for Tautomerisation of Glutamine in BLUF Blue Light Receptors by Vibrational Spectroscopy and Computational Chemistry

PubMed Central

Domratcheva, Tatiana; Hartmann, Elisabeth; Schlichting, Ilme; Kottke, Tilman

2016-01-01

BLUF (blue light sensor using flavin) domains regulate the activity of various enzymatic effector domains in bacteria and euglenids. BLUF features a unique photoactivation through restructuring of the hydrogen-bonding network as opposed to a redox reaction or an isomerization of the chromophore. A conserved glutamine residue close to the flavin chromophore plays a central role in the light response, but the underlying modification is still unclear. We labelled this glutamine with 15N in two representative BLUF domains and performed time-resolved infrared double difference spectroscopy. The assignment of the signals was conducted by extensive quantum chemical calculations on large models with 187 atoms reproducing the UV-vis and infrared signatures of BLUF photoactivation. In the dark state, the comparatively low frequency of 1,667 cm−1 is assigned to the glutamine C=O accepting a hydrogen bond from tyrosine. In the light state, the signature of a tautomerised glutamine was extracted with the C=N stretch at ~1,691 cm−1 exhibiting the characteristic strong downshift by 15N labelling. Moreover, an indirect isotope effect on the flavin C4=O stretch was found. We conclude that photoactivation of the BLUF receptor does not only involve a rearrangement of hydrogen bonds but includes a change in covalent bonds of the protein. PMID:26947391

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).

Oxygen isotopes in tree rings record variation in precipitation δ18O and amount effects in the south of Mexico.

PubMed

Brienen, Roel J W; Hietz, Peter; Wanek, Wolfgang; Gloor, Manuel

2013-12-01

[1] Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings ( δ 18 O tr ). Interannual variation in δ 18 O tr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ 13 C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ 18 O tr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18 O-depleted rain in the region and seem to have affected the δ 18 O tr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ 18 O tr of M . acantholoba can be used as a proxy for source water δ 18 O and that interannual variation in δ 18 O prec is caused by a regional amount effect. This contrasts with δ 18 O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in disentangling the processes influencing precipitation δ 18 O.

Using Sulfur Stable Isotopes to Understand Feeding Behavior and Selenium Concentrations in Yellow Perch (Perca flavescens).

PubMed

Ponton, Dominic E; Hare, Landis

2015-07-07

We measured selenium (Se) concentrations in yellow perch (Perca flavescens) muscle and their prey collected from four Se-contaminated lakes located near metal smelters in the eastern Canadian cities of Sudbury and Rouyn-Noranda. Yellow perch Se concentrations were related to their weight in two of the four lakes. Measurements of sulfur stable isotopes (δ(34)S) in yellow perch muscle and stomach contents showed that larger fish tended to feed less on zooplankton and more on benthic invertebrates than did smaller fish. Because Se concentrations are lower and δ(34)S signatures are higher in zooplankton than in sediment-feeding invertebrates, there was an inverse relationship between animal Se concentrations and δ(34)S signatures in all of our study lakes. δ(34)S signatures were highly effective in characterizing these food web relationships. Selenium concentrations in yellow perch were 1.6 times those of its prey, which indicates that Se is biomagnified by this fish in our study lakes. Estimated Se concentrations in yellow perch gonads suggest that in two of our study lakes one-third of fish are at risk of reproductive toxicity.