Sample records for carbon isotope geochemistry

  1. Carbon isotope geochemistry and geobiology (United States)

    Desmarais, D.


    Carbon isotope fractionation values were used to understand the history of the biosphere. For example, plankton analyses confirmed that marine extinctions at the end of the Cretaceous period were indeed severe (see Hsu's article in Sundquist and Broeker, 1984). Variations in the isotopic compositions of carbonates and evaporitic sulfates during the Paleozoic reflect the relative abundances of euxinic (anoxic) marine environments and organic deposits from terrestrial flora. The carbon isotopic composition of Precambrian sediments suggest that the enzyme ribulose bisphosphate carboxylase has existed for perhaps 3.5 billion years.

  2. Carbon isotope geochemistry in the Yalujiang estuary

    Institute of Scientific and Technical Information of China (English)

    吴莹; 张经


    The distribution of particulate organic carbon (POC) along the lower reaches is similar between the dry season and the flood season in the Yalujiang Estuary, North China. However, the values of particulate organic carbon of the upperstream in the dry season are one magnitude lower than the concentrations in the flood season. Stable carbon isotope ratios have been used to study the sources of particulate organic carbon in the Yalujiang Estuary. The isotopic composition of POC shows a range from -23.1‰ to -29.4‰ with a little seasonal variation. The isotopic evidence indicates that the POC in the Yalujiang Estuary is predominantly of terrestrial origin rather than a result of in situ plankton. The study of the ratio of POC: Chla shows that the turbidity maximum plays an important role in POC cycle in the Yalujiang Estuary. Organic detritus and soil erosion are the main contributions to POC in the turbidity maximum, especially in the flood season.

  3. Carbon isotope geochemistry of the Santa Clara River



    The Santa Clara River is a prototypical small mountainous river, with a headwater height greater than 1000 m and a basin area smaller than 10,000 m 2. Although individual small mountainous rivers export trivial amounts of sediment and carbon to the ocean, as a group these rivers may export a major fraction (as much as 50%) of the total global river sediment flux [Milliman and Syvitski, 1992], making their geochemistry relevant the study of the ocean's carbon cycle. In addition, many small riv...

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  5. The combined application of organic sulphur and isotope geochemistry to assess multiple sources of palaeobiochemicals with identical carbon skeletons

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Kohnen, M.E.L.; Schouten, S.; Leeuw, J.W. de; Merrit, D.; Hayes, J.M.


    Five immature sediments from a Messinian evaporitic basin, representing one evaporitic cycle, were studied using molecular organic sulphur and isotope geochemistry. It is shown that a specific carbon skeleton which is present in different 'modes of occurrence' ('free' hydrocarbon, alkylthiophene, al

  6. Calcium stable isotope geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Gausonne, Nikolaus [Muenster Univ. (Germany). Inst. fuer Mineralogie; Schmitt, Anne-Desiree [Strasbourg Univ. (France). LHyGeS/EOST; Heuser, Alexander [Bonn Univ. (Germany). Steinmann-Inst. fuer Geologie, Mineralogie und Palaeontologie; Wombacher, Frank [Koeln Univ. (Germany). Inst. fuer Geologie und Mineralogie; Dietzel, Martin [Technische Univ. Graz (Austria). Inst. fuer Angewandte Geowissenschaften; Tipper, Edward [Cambridge Univ. (United Kingdom). Dept. of Earth Sciences; Schiller, Martin [Copenhagen Univ. (Denmark). Natural History Museum of Denmark


    This book provides an overview of the fundamentals and reference values for Ca stable isotope research, as well as current analytical methodologies including detailed instructions for sample preparation and isotope analysis. As such, it introduces readers to the different fields of application, including low-temperature mineral precipitation and biomineralisation, Earth surface processes and global cycling, high-temperature processes and cosmochemistry, and lastly human studies and biomedical applications. The current state of the art in these major areas is discussed, and open questions and possible future directions are identified. In terms of its depth and coverage, the current work extends and complements the previous reviews of Ca stable isotope geochemistry, addressing the needs of graduate students and advanced researchers who want to familiarize themselves with Ca stable isotope research.

  7. Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume. (United States)

    van Breukelen, Boris M; Griffioen, Jasper; Röling, Wilfred F M; van Verseveld, Henk W


    The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH4, Fe(II), SO4, Cl, CH4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.

  8. The combined application of organic sulphur and isotope geochemistry to assess multiple sources of palaeobiochemicals with identical carbon skeletons (United States)

    Kohnen, M. E.; Schouten, S.; Sinninghe Damste, J. S.; de Leeuw, J. W.; Merrit, D.; Hayes, J. M.


    Five immature sediments from a Messinian evaporitic basin, representing one evaporitic cycle, were studied using molecular organic sulphur and isotope geochemistry. It is shown that a specific carbon skeleton which is present in different "modes of occurrence" ("free" hydrocarbon, alkylthiophene, alkylthiolane, alkyldithiane, alkylthiane, and sulphur-bound in macromolecules) may have different biosynthetic precursors which are possibly derived from different biota. It is demonstrated that the mode of occurrence and the carbon isotopic composition of a sedimentary lipid can be used to "reconstruct" its biochemical precursor. This novel approach of recognition of the suite of palaeobiochemicals present during the time of deposition allows for identification of the biological sources with an unprecedented specificity.

  9. Elemental geochemistry and strontium-isotope stratigraphy of Cenomanian to Santonian neritic carbonates in the Zagros Basin, Iran (United States)

    Navidtalab, Amin; Rahimpour-Bonab, Hossain; Huck, Stefan; Heimhofer, Ulrich


    A Neo-Tethyan upper Cenomanian-Santonian neritic carbonate ramp succession (Sarvak and Ilam formations), drilled in the Zagros Basin in southwest Iran, was investigated via detailed sedimentology, microfacies analysis, elemental geochemistry and Sr-isotope stratigraphy (SIS). The succession contains two exposure surfaces, which are known as the CT-ES and mT-ES (Cenomanian-Turonian and middle Turonian, respectively), and associated prominent negative carbon-isotope excursions that represent important regional stratigraphic marker horizons. Precise knowledge about the onset of platform exposure and the duration of the exposure-related hiatus, however, is currently lacking due to a rather low-resolved shallow-water biostratigraphic framework and a bulk carbonate carbon-isotope pattern that clearly differs from global Late Cretaceous reference curves. Therefore, the existing bio-chemostratigraphic framework was complemented by bulk carbonate strontium-isotope stratigraphy (SIS). As bulk carbonate material is in particular prone to diagenetic alteration, a careful selection of least altered samples has been carried out by means of elemental geochemistry and petrography. In contrast to what could be expected, the meteoric alteration of limestones beneath both exposure surfaces is not clearly expressed by increasing iron and manganese and coeval decreasing strontium contents. On the contrary, the impact of meteoric diagenesis is well illustrated via pronounced increases in Rb concentrations and concomitant prominent positive shifts to radiogenic strontium-isotope values, an observation that clearly reflects the decay of continentally derived 87Rb into 87Sr. Rubidium corrected strontium-isotope values place the CT-ES around the Cenomanian-Turonian boundary and point to an exposure duration of less than 0.4 Myr. This rather short-term CT-ES related hiatus is supported by petrographic evidence, which indicates a youth karstification stage of strata beneath the CT

  10. Carbon and oxygen isotope geochemistry of Ediacaran outer platform carbonates, Paraguay Belt, central Brazil

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    Claudio Riccomini


    Full Text Available After the late Cryogenian glaciation the central region of Brazil was the site of extensive deposition of platformal carbonates of the Araras Group. This group includes a basal cap carbonate sequence succeeded by transgressive, deep platform deposits of bituminous lime mudstone and shale. Facies and stratigraphic data combined with carbon and oxygen isotopic analyses of the most complete section of the transgressive deposits, exposed in the Guia syncline, were used to evaluate the depositional paleoenvironment and to test the correlation of these deposits along the belt and with other units worldwide. The studied succession consists of 150 m thick tabular beds of black to grey lime mudstone and shale with predominantly negative delta13C PDB values around -2.5 to -1‰ . The delta13C PDB profile of Guia syncline shows a clear correlation with the upper portion of Guia Formation in the Cáceres region, about 200 km to the southwest. The delta13C PDB profile of the Araras Group is comparable with delta13C PDB profiles of Ediacaran units of the southern Paraguay Belt, western Canada, and the Congo and Kalahari cratons. Moreover, facies distribution, stratigraphy and the carbon isotopic profile of the Araras Group match the middle Tsumeb Subgroup in Namibia, which reinforces the Ediacaran age assigned to the Araras Group.Após a glaciação do final do Criogeniano, a região central do Brasil foi palco de extensa deposição de carbonatos plataformais do Grupo Araras. Este grupo inclui na sua base uma seqüência de capa carbonática sucedida por depósitos transgressivos de calcilutitos betuminosos e folhelhos de plataforma profunda. Dados de fácies e estratigráficos combinados com análises isotópicas de carbono e oxigênio da seção mais completa desses depósitos transgressivos, expostos no sinclinal da Guia, foram empregados para avaliar o paleambiente deposicional e para testar a correlação desses depósitos ao longo da faixa e tamb

  11. Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt (United States)

    Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.


    Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

  12. Geochemistry of brachiopods: Oxygen and carbon isotopic records of Paleozoic oceans (United States)

    Veizer, Ján; Fritz, Peter; Jones, Brian


    Combined trace element and isotope studies of 319 brachiopods, covering the Ordovician to Permian time span, show that δ 13C and δ 18O in well preserved specimens varied during the Paleozoic. The overall δ 13C secular trend is in accord with the previously published observations, but its details are obscured by vital isotopic fractionation effects at generic level. Nonetheless, the results suggest that the negative correlation between marine δ 13C carbonate and δ 34S sulphate deteriorates at time scales of ⩽ 10 6 years, due to the long residence time, and thus slow response, of SO 42- in the ocean. For oxygen isotopes, all Devonian and older specimens have δ 18O of ⩽ -4%, while the well preserved Permian samples have near-present day δ 18O of about -1% (PDB). This isotopic dichotomy is probably not due to post-depositional phenomena, salinity, or biogenic fractionation effects. This leaves open the perennial arguments for a change in 18O /16O of sea water versus warmer ancient oceans. The present data are difficult to explain solely by the temperature alternative. The coincidence of the proposed shift in δ 18O with the large Late Paleozoic changes in marine 87Sr /86Sr , 13C /12C , 34S /32S , and "sea level stands" argues for a tectonic cause and for a change in 18O /16O of sea water, although such explanation is difficult to reconcile with global balance considerations and with isotopic patterns observed in alteration products of ancient basalts and ophiolites. Whatever the precise cause, or combination of causes, the implications for tectonism and/or paleoclimatology are of first order significance.

  13. Organic Geochemistry of the Hamersley Province: Relationships Among Organic Carbon Isotopes, Molecular Fossils, and Lithology (United States)

    Eigenbrode, Jennifer L.


    Molecular fossils are particularly valuable ancient biosignatures that can provide key insight about microbial sources and ecology in early Earth studies. In particular, hopanes carrying 2-methyl or 3-methyl substituents are proposed to be derived from cyanobacteria and oxygen-respiring methanotrophs, respectively, based on both their modem occurrences and their Proterozoic and Phanerozoic sedimentary distributions. Steranes are likely from ancestral eukaryotes. The distribution of methylhopanes, steranes, and other biomarkers in 2.72-2.56 billion-year-old rocks from the Hamersley Province, Western Australia show relationships to lithology, facies, and isotopes of macromolecular carbon, and other biomarkers. These observations support biomarker syngenicity and thermal maturity. Moreover, ecological signatures are revealed, including a surprising relationship between isotopic values for bulk macromolecular carbon and the biomarker for methanotrophs. The record suggests that cyanobacteria were likely key organisms of shallow-water microbial ecosystems providing molecular oxygen, fixed carbon, and possibly fixed nitrogen, and methanotrophs were not alone in recycling methane and other C-13-depleted substrates.

  14. Fluid Composititon and Carbon & Oxygen Isotope Geochemistry of Cenozoic Alkali Basalts in Eastern China

    Institute of Scientific and Technical Information of China (English)

    张铭杰; 王先彬; 等


    The fluid compositions of Cenozoic alkali basalts in eastern China have been determined by the pyrolysis-MS method,meanwhile the carbon and oxygen isotopic compositions of CO2 released from these samples at different heating temperatures have been analyzed by the vacuum step-heating method.The data show the volatiole heterogeneity in upper-mantle sources and different evolution trends of alkali basaltic magmas in eastern China,and these alkali basaltic magmas may be generated in the oxidizing milieu,as compared with mantle-derived xenoliths in these alkali basalts,and exotic volatile components were mixed into these magmas in the process of their formation and development.

  15. Annual and seasonal distribution of intertidal foraminifera and stable carbon isotope geochemistry, Bandon Marsh, Oregon, USA (United States)

    Milker, Yvonne; Horton, Benjamin; Vane, Christopher; Engelhart, Simon; Nelson, Alan R.; Witter, Robert C.; Khan, Nicole S.; Bridgeland, William


    We investigated the influence of inter-annual and seasonal differences on the distribution of live and dead foraminifera, and the inter-annual variability of stable carbon isotopes (d13C), total organic carbon (TOC) values and carbon to nitrogen (C/N) ratios in bulk sediments from intertidal environments of Bandon Marsh (Oregon, USA). Living and dead foraminiferal species from 10 stations were analyzed over two successive years in the summer (dry) and fall (wet) seasons. There were insignificant inter-annual and seasonal variations in the distribution of live and dead species. But there was a noticeable decrease in calcareous assemblages (Haynesina sp.) between live populations and dead assemblages, indicating that most of the calcareous tests were dissolved after burial; the agglutinated assemblages were comparable between constituents. The live populations and dead assemblages were dominated by Miliammina fusca in the tidal flat and low marsh, Jadammina macrescens, Trochammina inflata and M. fusca in the high marsh, and Trochamminita irregularis and Balticammina pseudomacrescens in the highest marsh to upland. Geochemical analyses (d13C, TOC and C/N of bulk sedimentary organic matter) show no significant influence of inter-annual variations but a significant correlation of d13C values (R = 20.820, p , 0.001), TOC values (R = 0.849, p , 0.001) and C/N ratios (R = 0.885, p , 0.001) to elevation with respect to the tidal frame. Our results suggest that foraminiferal assemblages and d13C and TOC values, as well as C/N ratios, in Bandon Marsh are useful in reconstructing paleosea-levels on the North American Pacific coast.

  16. Hydrology and isotope geochemistry; Hydrologie et geochimie isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Causse, Ch.; Gasse, F


    This book gathers recent works in hydrology and isotopic geochemistry. Part I exposes the general water cycle, from precipitations to deep aquifers, through the analysis of hydrogen, oxygen and carbon isotopic composition. Regional types are laid out from high latitudes (Spitzberg), through temperate regions (Parisian Basin), to the tropics (the Soudanian-Sahelian Niger Basin). The significance of isotopic techniques for Global Change analysis in shown in part II. Several case studies, mainly in Africa, reconstruct the hydro-climatic history through the pluri-proxy analysis of sediment profiles, where isotopic geochemistry is key. The last glacial maximum cooling is shown to have been homogeneous throughout middle and low latitudes, based upon noble gases isotopic analysis in groundwaters. The interpretation of some isotopic analysis could sometimes be questionable due to the organic origin of carbon in some sedimented carbonates. Part III refers to isotopes of cosmic origin and to in situ production of radionuclides. {sup 14}C dating is reminded to have contributed to our understanding of climate change mechanisms during the last glacial and post-glacial periods. Both the limitations and the recent improvements in this methodology are highlighted in a well documented synthesis. Isotopic data enable geochemistry to be the base for modelling stability conditions in the Oklo natural fossil nuclear fission reactor. (author)

  17. Carbon isotope geochemistry of hydrocarbons in the Cerro Prieto geothermal field, Baja California Norte, Mexico (United States)

    Des Marais, D. J.; Stallard, M. L.; Nehring, N. L.; Truesdell, A. H.


    Hydrocarbon abundances and stable-isotopic compositions were measured in wells M5, M26, M35 and M102, which represent a range of depths (1270-2000 m) and temperatures (275-330 degrees C) in the field. In order to simulate the production of the geothermal hydrocarbons, gases were collected from the pyrolysis of lignite in the laboratory. This lignite was obtained from a well which sampled rock strata which are identical to those occurring in the field, but which have experienced much lower subsurface temperatures. In both the well and the laboratory observations, high-temperature environments favored higher relative concentrations of methane, ethane and benzene and generally higher delta 13C-values in the individual hydrocarbons. The best correlation between the laboratory and well data is obtained when laboratory-produced gases from experiments conducted at lower (400 degrees C) and higher (600 degrees C) temperatures are mixed. This improved correlation suggests that the wells are sampling hydrocarbons produced from a spectrum of depths and temperatures in the sediments.

  18. Carbon isotope geochemistry of hydrocarbons in the Cerro Prieto geothermal field, Baja California Norte, Mexico. (United States)

    Des Marais, D J; Stallard, M L; Nehring, N L; Truesdell, A H


    Hydrocarbon abundances and stable-isotopic compositions were measured in wells M5, M26, M35 and M102, which represent a range of depths (1270-2000 m) and temperatures (275-330 degrees C) in the field. In order to simulate the production of the geothermal hydrocarbons, gases were collected from the pyrolysis of lignite in the laboratory. This lignite was obtained from a well which sampled rock strata which are identical to those occurring in the field, but which have experienced much lower subsurface temperatures. In both the well and the laboratory observations, high-temperature environments favored higher relative concentrations of methane, ethane and benzene and generally higher delta 13C-values in the individual hydrocarbons. The best correlation between the laboratory and well data is obtained when laboratory-produced gases from experiments conducted at lower (400 degrees C) and higher (600 degrees C) temperatures are mixed. This improved correlation suggests that the wells are sampling hydrocarbons produced from a spectrum of depths and temperatures in the sediments.

  19. Marine geochemistry ocean circulation, carbon cycle and climate change

    CERN Document Server

    Roy-Barman, Matthieu


    Marine geochemistry uses chemical elements and their isotopes to study how the ocean works. It brings quantitative answers to questions such as: What is the deep ocean mixing rate? How much atmospheric CO2 is pumped by the ocean? How fast are pollutants removed from the ocean? How do ecosystems react to the anthropogenic pressure? The book provides a simple introduction to the concepts (environmental chemistry, isotopes), the methods (field approach, remote sensing, modeling) and the applications (ocean circulation, carbon cycle, climate change) of marine geochemistry with a particular emphasis on isotopic tracers. Marine geochemistry is not an isolated discipline: numerous openings on physical oceanography, marine biology, climatology, geology, pollutions and ecology are proposed and provide a global vision of the ocean. It includes new topics based on ongoing research programs such as GEOTRACES, Global Carbon Project, Tara Ocean. It provides a complete outline for a course in marine geochemistry. To favor a...

  20. Ca isotope stratigraphy across the Cenomanian-Turonian OAE 2: Links between volcanism, seawater geochemistry, and the carbonate fractionation factor (United States)

    Du Vivier, Alice D. C.; Jacobson, Andrew D.; Lehn, Gregory O.; Selby, David; Hurtgen, Matthew T.; Sageman, Bradley B.


    The Ca isotope composition of marine carbonate rocks offers potential to reconstruct drivers of environmental change in the geologic past. This study reports new, high-precision Ca isotope records (δ44/40Ca; 2σSD = ± 0.04 ‰) for three sections spanning a major perturbation to the Cretaceous ocean-climate system known as Ocean Anoxic Event 2 (OAE 2): central Colorado, USA (Portland #1 core), southeastern France (Pont d'Issole), and Hokkaido, Japan (Oyubari, Yezo Group). In addition, we generated new data for selected samples from Eastbourne, England (English Chalk), where a previous Ca isotope study was completed using different methodology (Blättler et al., 2011). Strata of the Yezo Group contain little carbonate (∼1 wt.% on average) and accordingly did not yield a clear δ44/40Ca signal. The Portland core and the Pont d'Issole section display comparable δ44/40Ca values, which increase by ∼ 0.10- 0.15 ‰ at the onset of OAE 2 and then decrease to near-initial values across the event. The Eastbourne δ44/40Ca values are higher than previously reported. They are also higher than the δ44/40Ca values for the Portland core and the Pont d'Issole section but define a similar pattern. According to a numerical model of the marine Ca cycle, elevated hydrothermal inputs have little impact on seawater δ44/40Ca values. Elevated riverine (chemical weathering) inputs produce a transient negative isotope excursion, which significantly differs from the positive isotope excursions observed in the Portland, Pont d'Issole, and Eastbourne records. A decrease in the magnitude of the carbonate fractionation factor provides the best explanation for a positive shift in δ44/40Ca values, especially given the rapid nature of the excursion. Because a decrease in the fractionation factor corresponds to an increase in the Ca/CO3 ratio of seawater, we tentatively attribute the positive Ca isotope excursion to transient ocean acidification, i.e., a reduction in the concentration of

  1. Handbook of environmental isotope geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Baskaran, Mark (ed.) [Wayne State Univ., Detroit, MI (United States). Dept. Geology


    Applications of radioactive and stable isotopes have revolutionized our understanding of the Earth and near-earth surface processes. The utility of the isotopes are ever-increasing and our sole focus is to bring out the applications of these isotopes as tracers and chronometers to a wider audience so that they can be used as powerful tools to solve environmental problems. New developments in this field remain mostly in peer-reviewed journal articles and hence our goal is to synthesize these findings for easy reference for students, faculty, regulators in governmental and non-governmental agencies, and environmental companies. While this volume maintains its rigor in terms of its depth of knowledge and quantitative information, it contains the breadth needed for wide variety problems and applications in the environmental sciences. This volume presents all of the newer and older applications of isotopes pertaining to the environmental problems in one place that is readily accessible to readers. This book not only has the depth and rigor that is needed for academia, but it has the breadth and case studies to illustrate the utility of the isotopes in a wide variety of environments (atmosphere, oceans, lakes, rivers and streams, terrestrial environments, and sub-surface environments) and serves a large audience, from students and researchers, regulators in federal, state and local governments, and environmental companies. (orig.)

  2. Geochemistry and sedimentary environments Deep-water carbonate dissolution in the northern South China Sea during Marine Isotope Stage 3

    Institute of Scientific and Technical Information of China (English)

    Na Wang; Bao-Qi Huang; He Li


    The production, transportation, deposition, and dissolution of carbonate profoundly form part of the global carbon cycle and affect the amount and distribution of dissolved inorganic carbon (DIC) and alkalinity (ALK), which drive atmospheric CO2 changes during glacial/interglacial cycles. These processes may provide significant clues for better understanding of the mechanisms that control the global climate system. In this study, we calculate and analyze the foraminiferal dissolution index (FDX) and the fragmentation ratios of planktonic foraminifera for the 60-25 ka B.P. time-span, based on samples from Core 17924 and ODP Site 1144 in the northeastern South China Sea (SCS), so as to reconstruct the deep-water car-bonate dissolution during Marine Isotope Stage 3 (MIS 3). Our analysis shows that the dissolution of carbonate increases gradually in Core 17924, whereas it remains stable at ODP Site 1144. This difference is caused by the deep-sea carbonate ion concentration﹙[CO32-]﹚that affected the dissolution in Core 17924 where the depth of 3440 m is below the saturation horizon. However, the depth of ODP Site 1144 is 2037 m, which is above the lysocline where the water is always saturated with calcium carbonate; the dissolution is therefore less dependent of chemical changes of the seawater. The combined effect of the productivity and the deep-water chemical evolution may decrease deep-water [CO32-] and accelerate car-bonate dissolution. The fall of the sea-level increased the input of DIC and ALK to the deep ocean and deepened the carbonate saturation depth, which caused an increase of the deep-water [CO32-]. The elevated [CO32-] partially neutralized the reduced [CO32-] contributed by remineralization of organic matter and slowdown of thermohaline. These consequently are the fundamental reasons for the difference in dissolution rate between these two sites.

  3. Gas isotopes and geochemistry of hot springs in Hengjing,Jiangxi Province

    Institute of Scientific and Technical Information of China (English)

    周文斌; 张卫民


    With emphasis on gas isotopes and geochemistry as well as hydrogeochemistry, a field investigation has been carried out in Hengjing geothermal area, south Jiangxi Province of south-eastern China. The water chemistry of the geothermal waters indicates their local meteoric water origin, whereas their gas composition and carbon and helium isotopes reveal that some gases in the geothermal waters have mantle origin.

  4. Mineralization, geochemistry, fluid inclusion and sulfur stable isotope studies in the carbonate hosted Baqoroq Cu-Zn-As deposit (NE Anarak

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Jazi


    bacterial sulfate reduction or by nonbacterial sulfate reduction through a reaction with organic materialin the sedimentary rocks (thermochemical sulfate reduction. However, the narrow range of δ34S and positive values indicates that they were not produced by bacterial sulfate reduction.Partial thermochemical reduction of sulfates has apparently produced light sulfurvalues (~ 21‰ lighter and it has been effective inthe deposition of ore minerals. Organic matter occurs as graphite in the Baqoroq formation in proximity of Baqoroq deposit (Cherepovsky et al., 1982. Discussion Epigenetic, stratabound and discordant Cu-Zn-As mineralization in the Baqoroq deposit occurs as open space filling of upper Cretaceous rocks. Host rock is partially dolomitized by ascending warm, saline fluids. Seawater sulfates were the source of the sulfidesulfur and the sulfate in the barite. The reduced sulfur was generated by partial thermochemical reduction and it was effective inthe deposition ofthe ore minerals. Based onthe evidence of carbonate host rocks, the absence of igneous activity, the open space filling texture, mineralogy, dolomite alteration, ore geochemistry (As and Sb high content and absence of Bi, microthermometric data of ore bearing fluid and sulfur isotope values, the Baqoroq deposit is very similar to the carbonate hosted copper deposits in Africa and in particular the Tsumeb deposit in Namibia. The Baqoroqdepositmay have been produced bymetamorphicfluids during orogenyrelated to theclosureof the Neo-Tethys ocean. References Cherepovsky, N., Plyaskin, V., Zhitinev, N., Kokorin, Y., Susov, M., Melnikov, B. and Aistov, L., 1982. Report on detailed geological prospecting in Anarak area (Central Iran Nakhlak locality. Geological Survey of Iran and Technoexport Company, Tehran. Report 14, 196 pp. Jazi, M.A., Karimpour, M.H., Malekzadeh, A. and Rahimi, B., 2015. Stratigraphic, lithological and structural controls in placement of Nakhlak deposit (northeast of Esfahan. Advanced

  5. The geochemistry of stable chlorine and bromine isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Eggenkamp, Hans [Onderzock and Beleving, Bussum (Netherlands)


    First book solely dedicated to the geochemistry of chlorine and bromine isotopes. Detailed description of analytical techniques, including their advantages and disadvantages. Indication of research fields where measurement of these isotopes is especially useful. This book provides detailed information on the history, analysis and applications of chlorine and bromine isotope geochemistry. Chlorine and bromine are geochemically unique as they prefer to exist as single charged negative ions. For this reason isotope fractionation reflects mostly processes that are not related to changes in the redox state and this fractionation is generally modest. The book will describe the processes that are most easily detected using these isotopes. Also isotope variations, and processes that cause them, measured in oxidised species such as perchlorates and in organic molecules will be described in this book.


    Institute of Scientific and Technical Information of China (English)


    20150115Guo Haifeng(State Key Laboratory of Isotope Geochemistry,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,Guangzhou 510640,China);Xia Xiaoping LA-MC-ICPMS In-Situ Boron Isotope Analyses of Tourmalines from the Shangbao Granites(Southern Hunan Province)and Its Geological Significance(Geochimica,ISSN0379-1726,CN44-1398/P,43(1),2014,p.11-19,3illus.,1table,66refs.)Key words:micro-zone analysis,boron isotopes,Hunan Province LA-MC-ICPMS tourmaline in-situ

  7. Clumped isotope geochemistry of mid-Cretaceous (Barremian-Aptian) rudist shells: paleoclimatic and paleoenvironmental implications (United States)

    Huck, S.; Steuber, T.; Bernasconi, S.; Weissert, H.


    The Cretaceous period is generally considered to have been a time of climate warmth, but there is an ongoing dispute about the existence of Cretaceous cool episodes - including the short-termed installation of polar ice caps. The Late Barremian-Early Aptian represents a Cretaceous key interval in terms of paleoclimate and paleoceanography, as it provides evidence for (i) a cooler climate (Pucéat et al., 2003) and (ii) a considerable seasonality of sea surface temperatures (SSTs) at low latitudes (Steuber et al., 2005). The timing and significance of these cool episodes, however, are not well constrained. Recently published TEX86 data, in contrast to oxygen isotope paleotemperature estimates, now are in support of a climate scenario with equable hot (~30° C) tropical SSTs from the Early Cretaceous onwards. The aim of this project is to reconstruct the evolution of Barremian-Aptian sea-surface temperatures (SSTs) in the tropical Tethyan realm by use of a combined geochemical approach including oxygen isotope analysis and carbonate clumped-isotope thermometry. Paleotemperature proxies are based on the isotope geochemistry of low-Mg calcite of pristine rudist bivalve shells (Toucasia, Requienia) collected from different carbonate platform settings, including the Provence platform in SE France and the Adriatic Carbonate platform in Croatia. Carbonate clumped-isotope geochemistry deals with the state of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes (13C-18O) rather than with the most abundant ones. Carbonate clumped-isotope thermometry has been shown to allow for reconstructing (i) the temperature of carbonate mineral formation and calculating (ii) the isotopic composition of the water from which carbonate minerals were formed (by using the δ18O of the analysed carbonate sample). Our approach seeks to provide insights into possible biases in temperature estimates of different paleothermometers

  8. Magnesium isotope geochemistry in arc volcanism (United States)

    Teng, Fang-Zhen; Hu, Yan; Chauvel, Catherine


    Incorporation of subducted slab in arc volcanism plays an important role in producing the geochemical and isotopic variations in arc lavas. The mechanism and process by which the slab materials are incorporated, however, are still uncertain. Here, we report, to our knowledge, the first set of Mg isotopic data for a suite of arc lava samples from Martinique Island in the Lesser Antilles arc, which displays one of the most extreme geochemical and isotopic ranges, although the origin of this variability is still highly debated. We find the δ26Mg of the Martinique Island lavas varies from -0.25 to -0.10, in contrast to the narrow range that characterizes the mantle (-0.25 ± 0.04, 2 SD). These high δ26Mg values suggest the incorporation of isotopically heavy Mg from the subducted slab. The large contrast in MgO content between peridotite, basalt, and sediment makes direct mixing between sediment and peridotite, or assimilation by arc crust sediment, unlikely to be the main mechanism to modify Mg isotopes. Instead, the heavy Mg isotopic signature of the Martinique arc lavas requires that the overall composition of the mantle wedge is buffered and modified by the preferential addition of heavy Mg isotopes from fluids released from the altered subducted slab during fluid-mantle interaction. This, in turn, suggests transfer of a large amount of fluid-mobile elements from the subducting slab to the mantle wedge and makes Mg isotopes an excellent tracer of deep fluid migration.

  9. Magnesium isotope geochemistry in arc volcanism. (United States)

    Teng, Fang-Zhen; Hu, Yan; Chauvel, Catherine


    Incorporation of subducted slab in arc volcanism plays an important role in producing the geochemical and isotopic variations in arc lavas. The mechanism and process by which the slab materials are incorporated, however, are still uncertain. Here, we report, to our knowledge, the first set of Mg isotopic data for a suite of arc lava samples from Martinique Island in the Lesser Antilles arc, which displays one of the most extreme geochemical and isotopic ranges, although the origin of this variability is still highly debated. We find the δ(26)Mg of the Martinique Island lavas varies from -0.25 to -0.10, in contrast to the narrow range that characterizes the mantle (-0.25 ± 0.04, 2 SD). These high δ(26)Mg values suggest the incorporation of isotopically heavy Mg from the subducted slab. The large contrast in MgO content between peridotite, basalt, and sediment makes direct mixing between sediment and peridotite, or assimilation by arc crust sediment, unlikely to be the main mechanism to modify Mg isotopes. Instead, the heavy Mg isotopic signature of the Martinique arc lavas requires that the overall composition of the mantle wedge is buffered and modified by the preferential addition of heavy Mg isotopes from fluids released from the altered subducted slab during fluid-mantle interaction. This, in turn, suggests transfer of a large amount of fluid-mobile elements from the subducting slab to the mantle wedge and makes Mg isotopes an excellent tracer of deep fluid migration.

  10. Infrared Spectroscopy and Stable Isotope Geochemistry of Hydrous Silicate Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Stolper, Edward


    The focus of this DOE-funded project has been the study of volatile components in magmas and the atmosphere. Over the twenty-one year period of this project, we have used experimental petrology and stable isotope geochemistry to study the behavior and properties of volatile components dissolved in silicate minerals and melts and glasses. More recently, we have also studied the concentration and isotopic composition of CO2 in the atmosphere, especially in relation to air quality issues in the Los Angeles basin.

  11. Magnesium isotope geochemistry in arc volcanism (United States)

    Teng, Fang-Zhen; Hu, Yan


    Incorporation of subducted slab in arc volcanism plays an important role in producing the geochemical and isotopic variations in arc lavas. The mechanism and process by which the slab materials are incorporated, however, are still uncertain. Here, we report, to our knowledge, the first set of Mg isotopic data for a suite of arc lava samples from Martinique Island in the Lesser Antilles arc, which displays one of the most extreme geochemical and isotopic ranges, although the origin of this variability is still highly debated. We find the δ26Mg of the Martinique Island lavas varies from −0.25 to −0.10, in contrast to the narrow range that characterizes the mantle (−0.25 ± 0.04, 2 SD). These high δ26Mg values suggest the incorporation of isotopically heavy Mg from the subducted slab. The large contrast in MgO content between peridotite, basalt, and sediment makes direct mixing between sediment and peridotite, or assimilation by arc crust sediment, unlikely to be the main mechanism to modify Mg isotopes. Instead, the heavy Mg isotopic signature of the Martinique arc lavas requires that the overall composition of the mantle wedge is buffered and modified by the preferential addition of heavy Mg isotopes from fluids released from the altered subducted slab during fluid−mantle interaction. This, in turn, suggests transfer of a large amount of fluid-mobile elements from the subducting slab to the mantle wedge and makes Mg isotopes an excellent tracer of deep fluid migration. PMID:27303032

  12. Isotope geochemistry. Biological signatures in clumped isotopes of O₂. (United States)

    Yeung, Laurence Y; Ash, Jeanine L; Young, Edward D


    The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of "clumped" isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2—and not formation temperatures. Photosynthetic O2 is depleted in (18)O(18)O and (17)O(18)O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling.

  13. Oxygen and hydrogen isotope geochemistry of zeolites (United States)

    Karlsson, Haraldur R.; Clayton, Robert N.


    Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

  14. Metal stable isotope signatures as tracers in environmental geochemistry. (United States)

    Wiederhold, Jan G


    The biogeochemical cycling of metals in natural systems is often accompanied by stable isotope fractionation which can now be measured due to recent analytical advances. In consequence, a new research field has emerged over the last two decades, complementing the traditional stable isotope systems (H, C, O, N, S) with many more elements across the periodic table (Li, B, Mg, Si, Cl, Ca, Ti, V, Cr, Fe, Ni, Cu, Zn, Ge, Se, Br, Sr, Mo, Ag, Cd, Sn, Sb, Te, Ba, W, Pt, Hg, Tl, U) which are being explored and potentially applicable as novel geochemical tracers. This review presents the application of metal stable isotopes as source and process tracers in environmental studies, in particular by using mixing and Rayleigh model approaches. The most important concepts of mass-dependent and mass-independent metal stable isotope fractionation are introduced, and the extent of natural isotopic variations for different elements is compared. A particular focus lies on a discussion of processes (redox transformations, complexation, sorption, precipitation, dissolution, evaporation, diffusion, biological cycling) which are able to induce metal stable isotope fractionation in environmental systems. Additionally, the usefulness and limitations of metal stable isotope signatures as tracers in environmental geochemistry are discussed and future perspectives presented.


    Institute of Scientific and Technical Information of China (English)


    <正>20140115 Bian Youyan(Key Laboratory of Marginal Sea Geology,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,Guangzhou 510640,China);Chen Duofu Cold Seep Activities Recorded by Geochemical Characteristics of Authigenic Carbonates from Green Canyon 140,Gulf of Mexico(Geochimica,ISSN0379-1726,CN44-1398/P,42(3),2013,p.212-220,4illus.,2tables,49refs.)Key words:carbonate rocks,lithogeochemistry,Mexico

  16. TSR versus non-TSR processes and their impact on gas geochemistry and carbon stable isotopes in Carboniferous, Permian and Lower Triassic marine carbonate gas reservoirs in the Eastern Sichuan Basin, China (United States)

    Liu, Q. Y.; Worden, R. H.; Jin, Z. J.; Liu, W. H.; Li, J.; Gao, B.; Zhang, D. W.; Hu, A. P.; Yang, C.


    The Palaeozoic and lowermost Mesozoic marine carbonate reservoirs of the Sichuan Basin in China contain variably sour and very dry gas. The source of the gas in the Carboniferous, Permian and Lower Triassic reservoirs is not known for certain and it has proved difficult to discriminate and differentiate the effects of thermal cracking- and TSR-related processes for these gases. Sixty-three gas samples were collected and analysed for their composition and carbon stable isotope values. The gases are all typically very dry (alkane gases being >97.5% methane), with low (cracking of sapropelic kerogen-derived oil and primary gas and is highly mature. Carboniferous (and non-sour Triassic and Permian) gas has unusual carbon isotopes with methane and propane being isotopically heavier than ethane (a reversal of typical low- to moderate-maturity patterns). The gas in the non-sour Triassic and Permian reservoirs has the same geochemical and isotopic characteristics (and therefore the same source) as the Carboniferous gas. TSR in the deepest Triassic reservoirs altered the gas composition reaching 100% dryness in the deepest, most sour reservoirs showing that ethane and propane react faster than methane during TSR. Ethane evolves to heavier carbon isotope values than methane during TSR leading to removal of the reversed alkane gas isotope trend found in the Carboniferous and non-sour Triassic and Permian reservoirs. However, methane was directly involved in TSR as shown by the progressive increase in its carbon isotope ratio as gas souring proceeded. CO2 increased in concentration as gas souring proceeded, but typical CO2 carbon isotope ratios in sour gases remained about -4‰ V-PDB showing that it was not solely derived from the oxidation of alkanes. Instead CO2 may partly result from reaction of sour gas with carbonate reservoir minerals, such as Fe-rich dolomite or calcite, resulting in pyrite growth as well as CO2-generation.


    Institute of Scientific and Technical Information of China (English)


    <正>20110070 Chen Gen(College of Earth Science,Chengdu University of Technology,Chengdu 610059,China);Zhu Zhengjie Advances in Research into Carbon and Oxygen Isotopes of Lacustrine Carbonate(Acta Geologica Sichuan,ISSN1006-0995,CN51-1273/P,30(1),2010,p.75-78,1 illus.,5 refs.)Key words:carbonate sediments,carbon isotopes,oxygen isotopes This paper deals with control factors and environment significance of δ13C and δ18O values of lacustrine authigenic carbonate and makes an

  18. Isotope geochemistry and fluxes of carbon and organic matter in tropical small mountainous river systems and adjacent coastal waters of the Caribbean (United States)

    Moyer, Ryan; Bauer, James; Grottoli, Andrea


    Recent studies have shown that small mountainous rivers (SMRs) may act as sources of aged and/or refractory carbon (C) to the coastal ocean, which may increase organic C burial at sea and subsidize coastal food webs and heterotrophy. However, the characteristics and spatial and temporal variability of C and organic matter (OM) exported from tropical SMR systems remain poorly constrained. To address this, the abundance and isotopic character (δ13C and Δ14C) of the three major C pools were measured in two Puerto Rico SMRs with catchments dominated by different land uses (agricultural vs. non-agricultural recovering forest). The abundance and character of C pools in associated estuaries and adjacent coastal waters were also examined. Riverine dissolved and particulate organic C (DOC and POC, respectively) concentrations were highly variable with respect to land use and sampling month, while dissolved inorganic C (DIC) was significantly higher at all times in the agricultural catchment. In both systems, riverine DOC and POC ranged from modern to highly aged (2,340 years before present), while DIC was always modern. The agricultural river and irrigation canals contained very old DOC (1,184 and 2,340 years before present, respectively), which is consistent with findings in temperate SMRs and indicates that these tropical SMRs provide a source of aged DOC to the ocean. During months of high river discharge, OM in estuarine and coastal waters had C isotope signatures reflective of direct terrestrial input, indicating that relatively unaltered OM is transported to the coastal ocean at these times. This is also consistent with findings in temperate SMRs and indicates that C transported to the coastal ocean by SMRs may differ from that of larger rivers because it is exported from smaller catchments that have steeper terrains and fewer land-use types.

  19. Environmental geochemistry of calcium isotopes: Applications of a new stable isotope approach

    Institute of Scientific and Technical Information of China (English)

    LIU Zhanmin; LIU Congqiang; HAN Guilin; WANG Zhongliang; XUE Zichen; SONG Zhaoliang; YANG Cheng


    This paper summarizes isotope fractionation mechanism, analytical method and applications in environmental geochemistry of calcium isotopes. Calcium isotopic composition can be used to constrain material sources and study geological and environmental processes as the isotopic composition of calcium (δ 44Ca) and fractionation processes depend on geochemical circumstances in nature. Recently, thanks to current advances in analytical technology of calcium isotopes, calcium isotopes are broadly used in biological and geochemical studies, such as the mechanism of plants imbibing nutrients through their roots, calcium transport in the environmental ecosystem, calcium cycle in oceans and paleo-oceans and paleo-climate. The elementary data show that δ44Ca values vary from -2.88‰ to 0.92‰ in natural samples.


    Stable carbon and hydrogen isotopes have been used for many decades in the petroleum industry, but the development of combined gas chromatography-isotope ratio mass spectrometry (GCIRMS) has led to a virtual explosion in application of this technique not only in petroleum explora...

  1. Ca isotopic geochemistry of an Antarctic aquatic system (United States)

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


    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.

  2. SPATIAL Short Courses Build Expertise and Community in Isotope Geochemistry (United States)

    Riggs, E. M.; Bowen, G. J.


    The SPATIAL short course at the University of Utah is designed for graduate students and professionals in the earth and environmental sciences from around the globe. An integral part of the broader, NSF-funded Inter-university Training for Continental-scale Ecology (ITCE) project, the course is an intensive two-week field, classroom and laboratory experience with internationally-known researchers as instructors. The course focuses on stable isotope geochemistry coupled with spatial analysis techniques. Participants do not typically know each other or this research community well upon entering. One of the stated goals of the overall project is to build a community of practice around these techniques. This design is common in many professional fields, but is not often applied at the graduate level nor formally assessed in the earth sciences. Paired pre- and post-tests were administered before the start and after the close of the short courses over 3 years. The survey is a set of instruments adapted from social-cognitive psychology measuring changes in identity and community with other items to measure content knowledge outcomes. We see a subtle, consistent convergence of identities between large-scale isotope geochemistry and participants' research areas. Results also show that the course generates an increase in understanding about stable isotopes' use and application. The data show the SPATIAL course is very effective at bringing students together socially with each other and with faculty to create an environment that fosters community and scientific cooperation. Semi-structured pre-and post- interviews were conducted to understand the program elements that generated gains in learning and community. Participants were selected based on initial responses on the pre-survey to capture the range of initial conditions for the group. Qualitative analysis shows that the major factors for participants were 1) ready access to researchers in an informal setting during the

  3. Geochemistry of organic carbon and nitrogen in surface sediments of coastal Bohai Bay inferred from their ratios and stable isotopic signatures. (United States)

    Gao, Xuelu; Yang, Yuwei; Wang, Chuanyuan


    Total organic carbon (TOC), total nitrogen (TN) and their δ(13)C and δ(15)N values were determined for 42 surface sediments from coastal Bohai Bay in order to determine the concentration and identify the source of organic matter. The sampling sites covered both the marine region of coastal Bohai Bay and the major rivers it connects with. More abundant TOC and TN in sediments from rivers than from the marine region reflect the situation that most of the terrestrial organic matter is deposited before it meets the sea. The spatial variation in δ(13)C and δ(15)N signatures implies that the input of organic matter from anthropogenic activities has a more significant influence on its distribution than that from natural processes. Taking the area as a whole, surface sediments in the marine region of coastal Bohai Bay are dominated by marine derived organic carbon, which on average accounts for 62±11% of TOC.


    Institute of Scientific and Technical Information of China (English)


    <正>20101501 Dou Chuanwei (State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, China); Lian Bin Microbial Weathering of Calcite by Rock-Inhabiting Fungi, biogenic processes

  5. Biogeochemistry and isotope geochemistry of a landfill leachate plume. (United States)

    van Breukelen, Boris M; Röling, Wilfred F M; Groen, Jacobus; Griffioen, Jasper; van Verseveld, Henk W


    The biogeochemical processes were identified which improved the leachate composition in the flow direction of a landfill leachate plume (Banisveld, The Netherlands). Groundwater observation wells were placed at specific locations after delineating the leachate plume using geophysical tests to map subsurface conductivity. Redox processes were determined using the distribution of solid and soluble redox species, hydrogen concentrations, concentration of dissolved gases (N(2), Ar, and CH(4)), and stable isotopes (delta15N-NO(3), delta34S-SO(4), delta13C-CH(4), delta2H-CH(4), and delta13C of dissolved organic and inorganic carbon (DOC and DIC, respectively)). The combined application of these techniques improved the redox interpretation considerably. Dissolved organic carbon (DOC) decreased downstream in association with increasing delta13C-DOC values confirming the occurrence of degradation. Degradation of DOC was coupled to iron reduction inside the plume, while denitrification could be an important redox process at the top fringe of the plume. Stable carbon and hydrogen isotope signatures of methane indicated that methane was formed inside the landfill and not in the plume. Total gas pressure exceeded hydrostatic pressure in the plume, and methane seems subject to degassing. Quantitative proof for DOC degradation under iron-reducing conditions could only be obtained if the geochemical processes cation exchange and precipitation of carbonate minerals (siderite and calcite) were considered and incorporated in an inverse geochemical model of the plume. Simulation of delta13C-DIC confirmed that precipitation of carbonate minerals happened.

  6. Geochemistry of Precambrian carbonates. IV - Early Paleoproterozoic (2.25 +/- 0.25 Ga) seawater (United States)

    Veizer, Jan; Clayton, R. N.; Hinton, R. W.


    The mineralogy, chemistry, and isotopic composition of the Malmani Dolomite, Duck Creek Dolomite, and Bruce 'Limestone' Member of the Espanola Formation are studied in an effort to restrict the first- and second-order variations in isotopic composition of Early Paleoproterozoic seawater. The diagenetic rank is found to increase in the order Duck Creek less than Bruce less than Malmani. The interpolation of alteration trends to 'best' value yields an estimate of 0.70550 for Sr-87/Sr-86. For delta C-13, the measured range of 0 +/- 1.5 percent PDB is similar to that observed for Phanerozoic marine carbonates, while the 'best' delta O-18 value for dolostones is -5 percent PDB, depleted in O-18 relative to Phanerozoic counterparts but comparable to estimates obtained for Archean facies. The isotope geochemistry and mineralogy of Bruce 'Limestone' Member is consistent with the proposition that the sequence was deposited in a lacustrine environment.

  7. Hydrogeochemistry and isotope geochemistry of Velenje Basin groundwater

    Directory of Open Access Journals (Sweden)

    Tjaša Kanduč


    Full Text Available The geochemical and isotopic composition of groundwater in the Velenje Basin, Slovenia, was investigated between the years 2014 to 2015 to identify the geochemical processes in the major aquifers (Pliocene and Triassic and the water–rock interactions. Thirty-eight samples of groundwater were taken from the aquifers, 19 in the mine and 19 from the surface. Groundwater in the Triassic aquifer is dominated by HCO3–, Ca2+ and Mg2+ with δ13C DIC values in the range from -19.3 to -2.8 ‰, indicating degradation of soil organic matter and dissolution of carbonate minerals. In contrast, groundwater in the Pliocene aquifers is enriched in Mg2+, Na+, Ca2+, K+, and Si, and has high alkalinity, with δ13CDIC values in the range of -14.4 to +4.6 ‰. Based on the δ13CDIC values in all the aquifers (Pliocene and Triassic, both processes inflence the dissolution of carbonate minerals and dissolution of organic matter and in the Pliocene aquifers, methanogenesis as well. Based on Principal Component Analysis (PCA, and on geochemical and isotopic data we conclude that the following types of groundwater in Velenje Basin are present: Triassic aquifers with higher pH and lower conductivity and chloride, Pliocene, Pliocene 1 and Pliocene 2 aquifers with lower pH and higher conductivity and chloride contents, and Pliocene 3 and Pliocene 2, 3 aquifers with the highest pH values and lowest conductivities and chloride contents. 87Sr/86Sr tracer was used for the fist time in Slovenia to determine geochemical processes (dissolution of silicate versus carbonate fraction in Velenje Basin groundwater of different aquifers dewatering Pliocene and Triassic strata. 87Sr/86Sr values range from 0.70820 to 0.71056 in groundwater of Pliocene aquifers and from 0.70808 to 0.70910 in groundwater of the Triassic aquifer. This indicates that dissolution of the carbonate fraction prevails in both aquifers, while in Pliocene aquifers, an additional silicate weathering prevails with


    Institute of Scientific and Technical Information of China (English)


    <正>20102226 Liu Congqiang(State Key Laboratory of Environmental Geochemistry,Institute of Geochemistry,Chinese Academy of Sciences,Guiyang 550002,China);Lang Yunchao Researches on Biogeochemical Processes and Nutrient Cycling in Karstic Ecological Systems,Southwest China:A review(Earth Science Frontiers,ISSN1005-2321,CN11-3370/P,16(6),2009,p.1-12,36 refs.)Key words:biogeochemistry,karst environmentBased on the previous studies,this paper introduces the researches on biogeochemical processes and nutrient cycling occurri


    Institute of Scientific and Technical Information of China (English)


    <正>20041015 Chen Ming (Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, Guangdong); Xie Xiande Geochemical Behavior of Alkaline Elements in the Deep Earth: Evidence from High -Pressure Minerals in Shocked Meteorites (Geochimica, ISSN 0379 - 1726, CN 44 -1398/P, 32(2), 2003, p. 161-166, 3 il-lus. , 30 refs. , with English abstract)

  10. Multiphase Sequestration Geochemistry: Model for Mineral Carbonation

    Energy Technology Data Exchange (ETDEWEB)

    White, Mark D.; McGrail, B. Peter; Schaef, Herbert T.; Hu, Jian Z.; Hoyt, David W.; Felmy, Andrew R.; Rosso, Kevin M.; Wurstner, Signe K.


    Carbonation of formation minerals converts low viscosity supercritical CO2 injected into deep saline reservoirs for geologic sequestration into an immobile form. Until recently the scientific focus of mineralization reactions with reservoir rocks has been those that follow an aqueous-mediated dissolution/precipitation mechanism, driven by the sharp reduction in pH that occurs with CO2 partitioning into the aqueous phase. For sedimentary basin formations the kinetics of aqueous-mediated dissolution/precipitation reactions are sufficiently slow to make the role of mineralization trapping insignificant over a century period. For basaltic saline formations aqueous-phase mineralization progresses at a substantially higher rate, making the role of mineralization trapping significant, if not dominant, over a century period. The overlooked mineralization reactions for both sedimentary and basaltic saline formations, however, are those that occur in liquid or supercritical CO2 phase; where, dissolved water appears to play a catalyst role in the formation of carbonate minerals. A model is proposed in this paper that describes mineral carbonation over sequestration reservoir conditions ranging from dissolved CO2 in aqueous brine to dissolved water in supercritical CO2. The model theory is based on a review of recent experiments directed at understanding the role of water in mineral carbonation reactions of interest in geologic sequestration systems occurring under low water contents.

  11. Isotopic and noble gas geochemistry in geothermal research

    Energy Technology Data Exchange (ETDEWEB)

    Kennedy, B.M.; DePaolo, D.J. [Lawrence Berkeley National Lab., CA (United States)


    The objective of this program is to provide, through isotopic analyses of fluids, fluid inclusions, and rocks and minerals coupled with improved methods for geochemical data analysis, needed information regarding sources of geothermal heat and fluids, the spatial distribution of fluid types, subsurface flow, water-rock reaction paths and rates, and the temporal evolution of geothermal systems. Isotopic studies of geothermal fluids have previously been limited to the light stable isotopes of H, C, and O. However, other isotopic systems such as the noble gases (He, Ne, Ar, Kr and Xe) and reactive elements (e.g. B, N, S, Sr and Pb) are complementary and may even be more important in some geothermal systems. The chemistry and isotopic composition of a fluid moving through the crust will change in space and time in response to varying chemical and physical parameters or by mixing with additional fluids. The chemically inert noble gases often see through these variations, making them excellent tracers for heat and fluid sources. Whereas, the isotopic compositions of reactive elements are useful tools in characterizing water-rock interaction and modeling the movement of fluids through a geothermal reservoir.

  12. The separation of stable isotopes of carbon (United States)

    Oziashvili, E. D.; Egiazarov, A. S.


    The present state of work on the separation of carbon isotopes by diffusion, fractional distillation, chemical isotopic exchange, and the selective excitation and dissociation of molecules in electrical discharges or in the field of laser radiation has been examined. The characteristics of new laboratory and industrial assemblies for separating carbon isotopes have been described. Promising directions of study aimed at developing effective technological processes for separating carbon isotopes have been noted. The bibliography contains 148 references.

  13. Invited review article: Recent developments in isotope-ratio mass spectrometry for geochemistry and cosmochemistry. (United States)

    Ireland, Trevor R


    Mass spectrometry is fundamental to measurements of isotope ratios for applications in isotope geochemistry, geochronology, and cosmochemistry. Magnetic-sector mass spectrometers are most common because these provide the best precision in isotope ratio measurements. Where the highest precision is desired, chemical separation followed by mass spectrometric analysis is carried out with gas (noble gas and stable isotope mass spectrometry), liquid (inductively coupled plasma mass spectrometry), or solid (thermal ionization mass spectrometry) samples. Developments in in situ analysis, including ion microprobes and laser ablation inductively coupled plasma mass spectrometry, have opened up issues concerning homogeneity according to domain size, and allow ever smaller amounts of material to be analyzed. While mass spectrometry is built solidly on developments in the 20th century, there are new technologies that will push the limits in terms of precision, accuracy, and sample efficiency. Developments of new instruments based on time-of-flight mass spectrometers could open up the ultimate levels of sensitivity per sample atom.


    Institute of Scientific and Technical Information of China (English)


    <正>20110807 Li Chao(National Research Center for Geoanalysis,Beijing 100037,China);Qu Wenjun Advances in the Study of the Re-Os Isotopic System of Organic-Rich Samples(Acta Petrologica et Mineralogica,ISSN1000-6524,CN11-1966/P,29(4),2010,p.421-430,3 illus.,1 table,45 refs.)Key words:organic compounds,rhenium isotopes,osmium isotopes This paper deals with the principles of Re-Os isotopic system applied to various organic-rich geological samples such as black shale,oil shale,asphalt,schungite,oil and coal.Moreover,the potential disturbances of the weathering-leaching and the hydrocarbon maturation to the closure of Re-Os isotopic system are analyzed.In the aspect of practical application,several cases are cited to illustrate the significance of this isotopic system in the organic-rich

  15. Strontium isotope geochemistry of groundwater affected by human activities in Nandong underground river system, China

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Yongjun, E-mail: [School of Geographical Sciences, Southwest University, Chongqing 400715 (China)] [Institute of Karst Environment and Rock Desertification Rehabilitation, Chongqing 400715 (China)


    Research highlights: {yields} Spatio-temporal variations of Sr concentrations and Sr isotopic composition of groundwater were investigated in a karst underground river system. {yields} Agricultural fertilizers and sewage effluents significantly modified the natural Sr isotopic signature of karst groundwater. {yields} Sr in the carbonate aquifers was relatively non-radiogenic, with low Sr concentrations, while anthropogenic Sr correlated with agricultural fertilizers and sewage effluents was relatively radiogenic, with higher Sr concentrations. {yields} {sup 87}Sr/{sup 86}Sr ratios can provide key information for natural and anthropogenic sources in karst groundwater. - Abstract: The Nandong Underground River System (NURS) is located in a typical karst area dominated by agriculture in SE Yunnan Province, China. Groundwater plays an important role in the social and economical development in the area. The effects of human activities (agriculture and sewage effluents) on the Sr isotope geochemistry were investigated in the NURS. Seventy-two representative groundwater samples, which were collected from different aquifers (calcite and dolomite), under varying land-use types, both in summer and winter, showed significant spatial differences and slight seasonal variations in Sr concentrations and {sup 87}Sr/{sup 86}Sr ratios. Agricultural fertilizers and sewage effluents significantly modified the natural {sup 87}Sr/{sup 86}Sr ratios signature of groundwater that was otherwise dominated by water-rock interaction. Three major sources of Sr could be distinguished by {sup 87}Sr/{sup 86}Sr ratios and Sr concentrations in karst groundwater. Two sources of Sr are the Triassic calcite and dolomite aquifers, where waters have low Sr concentrations (0.1-0.2 mg/L) and low {sup 87}Sr/{sup 86}Sr ratios (0.7075-0.7080 and 0.7080-0.7100, respectively); the third source is anthropogenic Sr from agricultural fertilizers and sewage effluents with waters affected having radiogenic {sup 87

  16. Atmospheric turbulence triggers pronounced diel pattern in karst carbonate geochemistry

    Directory of Open Access Journals (Sweden)

    M. Roland


    Full Text Available CO2 exchange between terrestrial ecosystems and the atmosphere is key to understanding the feedbacks between climate change and the land surface. In regions with carbonaceous parent material, CO2 exchange patterns occur that cannot be explained by biological processes, such as disproportionate outgassing during daytime or nighttime CO2 uptake during periods when all vegetation is senescent. Neither of these phenomena can be attributed to carbonate weathering reactions, since their CO2 exchange rates are too small. Soil ventilation induced by high atmospheric turbulence is found to explain atypical CO2 exchange between carbonaceous systems and the atmosphere. However, by strongly altering subsurface CO2 concentrations, ventilation can be expected to influence carbonate weathering rates. By imposing ventilation-driven CO2 outgassing in a carbonate weathering model, we show here that carbonate geochemistry is accelerated and does play a surprisingly large role in the observed CO2 exchange patterns. We found that by rapidly depleting soil CO2 during daytime, ventilation disturbs soil carbonate equilibria and therefore strongly magnifies daytime carbonate precipitation and associated CO2 production. At night, ventilation ceases and the depleted CO2 concentrations increase steadily. Dissolution of carbonate is now enhanced, which consumes CO2 and largely compensates for the enhanced daytime carbonate precipitation. This is why only a relatively small effect on global carbonate weathering rates is to be expected. On the short term, however, ventilation has a drastic effect on synoptic carbonate weathering rates, resulting in a pronounced diel pattern that exacerbates the non-biological behavior of soil-atmosphere CO2 exchanges in dry regions with carbonate soils.

  17. Isotope geochemistry of boron in mantle rocks, tektites and meteorites

    Energy Technology Data Exchange (ETDEWEB)

    Chaussidon, M. [Centre National de la Recherche Scientifique (CNRS), 54 - Nancy (France). Centre de Recherches Petrographiques et Geochimiques


    Recent ion microprobe studies of fresh oceanic basalt glasses and chondrules from primitive meteorites give an overview of the distribution of boron isotopes in the mantle and in extra-terrestrial rocks. After removal of secondary boron isotope variations due to interactions between mantle melts and the oceanic crust, the primitive mantle is found to have a constant {delta}{sup 11}B value of -10 {+-} 2 per mill, similar to that of the bulk continental crust. In contrast, large isotopic variations between -50 and +40 per mill are present at the micron scale in meteoritic chondrules which are among the most primitive objects of the solar system. These isotopic variations imply that a significant part of the boron of the solar system was synthesized in the presolar cloud, likely by spallation reactions between lo-energy cosmic rays and nebular hydrogen. These heterogeneities were partly preserved in chondrules which formed early in the evolution of the solar system but are not observed for the silicate Earth implying an efficient mixing just before or during the accretion of the Earth. (authors). 74 refs., 5 figs., 2 tabs.

  18. Geochemistry of Precambrian carbonates. I - Archean hydrothermal systems (United States)

    Veizer, Jan; Hoefs, Jochen; Ridler, R. H.; Jensen, L. S.; Lowe, D. R.


    Carbonate rocks from the Superior Province and the Slave Province of Canada, Kaapvaal Craton of South Africa, and the Pilbara Block of Australia were characterized mineralogically, isotopically, and chemically. Result on the bulk chemical composition suggest that the carbonate rocks originated by massive carbonatization, silicification, and sericitization via replacement and/or filling of void spaces of intermediate to ultramafic protoliths. Trace element chemistry of carbonates was found to be consistent with their precipitation from relatively low-salinity solutions and with the derivation of solutes from the contemporaneous volcano-sedimentary piles. On the basis of mineralogy and the chemical and isotopic findings, it is suggested that the carbonate component defines two partially overlapping populations, a ferroan dolomite-breunnerite series restricted mostly to extensive faults and shear zones, and a calcite-ferroan dolomite-siderite population associated with alteration halos of a larger regional extent.

  19. Iron isotope geochemistry in the Antarctic cryptoendolithic microbial ecosystem (United States)

    Sun, H.


    The stable isotope composition of iron is a potentially powerful tracer of biogeochemical cycles because iron is ubiquitous, it is required by all organisms, and it is resistant to alterations during diagenesis. Here we report evidence of biological iron isotope fractionation in the weathering process of sandstone in McMurdo Dry Valleys, Antarctica, caused by the cryptoendolithic lichen-dominated microbial community that live below the rock surface. The fungi secrete oxalic acid, which under the sunlight reduces and dissolves the iron in the colonized zone. The mobilized iron diffuses to the rock surface and the rock interior below the organisms where it is re-oxidized. This leaching process is shown to prefer lighter isotopes of iron, leaving the colonized layer enriched in del 56Fe by as much 0.8 per mil. Had endolithic microorganisms occurred on Mars as commonly believed, they might have left similar iron biosignatures, well preserved in rocks because of the absence of subsequent aqueous activities.

  20. Chromium Isotopes in Marine Carbonates - an Indicator for Climatic Change? (United States)

    Frei, R.; Gaucher, C.


    Chromium (Cr) stable isotopes experience an increased interest as a tracer of Cr (VI) reduction in groundwater and thus showed their potential as a monitor of remediation of anthropogenic and natural contamination in water (Berna et al., 2009; Izbicki et al., 2008). Chromium stable isotopes in Fe-rich chemical sediments (BIFs and Fe-cherts) have recently also been used as a tracer for Earth's atmospheric oxygenation through time (Frei et al., 2009). We have applied the Cr isotope system to organic-rich carbonates from a late Ediacaran succession in Uruguay (Polanco Formation), from which we have previously analyzed BIFs with extremely fractionated (δ53Cr up to 5.0 ‰) Cr isotope signatures that are part of an underlying deep water clastic sediment (shale-dominated) sequence (Yerbal Formation) deposited in a glacio-marine environment (Gaucher et al.,2004). δ53Cr values of organic rich carbonates correlate with positive and negative carbon isotope excursions (δ13C PDB between -3 and +3 ‰) and with systematic changes in strontium isotope compositions, commonly interpreted as to reflect fluctuations in organic (photosynthetic algae) production related to fluctuations in atmospheric oxygen and weathering intensities, respectively. Slightly positively fractioned δ53Cr values (up to +0.25‰), paralleling positive (δ13C PDB and 87Sr/86Sr ratio excursions would thereby trace elevated atmospheric oxygen levels/pulses possibly related to glacier retreat/melting stages that caused bioproductivity to increase. While the causal link between these multiple isotopic tracers and the mechanisms of Cr stripping into carbonates has to be further investigated in detail, the first indications from this study point to a potentially promising use of stable Cr isotopes in organic-rich carbonates to monitor fluctuations of atmospheric oxygen, particularly over the Neoproterozoic and Phanerozoic ice age periods. E.C. Berna et al. (2010) Cr stable isotopes as indicators of Cr


    Chapelle, Francis H.; Knobel, LeRoy L.


    Identifying sources and sinks of dissolved inorganic carbon species is an important step in understanding the geochemistry of ground-water systems. This is particularly important for Atlantic Coastal Plain aquifers because bicarbonate (HCO//3** minus ) is frequently the major dissolved anion. The purpose of this paper is to document the stable carbon isotope composition of dissolved inorganic carbon in the Aquia aquifer, Maryland, and to use this data to help identify sources and sinks of dissolved HCO//3** minus . Subjects covered include hydrogeology, ground-water chemistry, sources and sinks, and others. Refs.

  2. Carbon geochemistry of serpentinites in the Lost City Hydrothermal System (30°N, MAR) (United States)

    Delacour, Adélie; Früh-Green, Gretchen L.; Bernasconi, Stefano M.; Schaeffer, Philippe; Kelley, Deborah S.


    The carbon geochemistry of serpentinized peridotites and gabbroic rocks recovered at the Lost City Hydrothermal Field (LCHF) and drilled at IODP Hole 1309D at the central dome of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) was examined to characterize carbon sources and speciation in oceanic basement rocks affected by long-lived hydrothermal alteration. Our study presents new data on the geochemistry of organic carbon in the oceanic lithosphere and provides constraints on the fate of dissolved organic carbon in seawater during serpentinization. The basement rocks of the Atlantis Massif are characterized by total carbon (TC) contents of 59 ppm to 1.6 wt% and δ 13C TC values ranging from -28.7‰ to +2.3‰. In contrast, total organic carbon (TOC) concentrations and isotopic compositions are relatively constant (δ 13C TOC: -28.9‰ to -21.5‰) and variations in δ 13C TC reflect mixing of organic carbon with carbonates of marine origin. Saturated hydrocarbons extracted from serpentinites beneath the LCHF consist of n-alkanes ranging from C 15 to C 30. Longer-chain hydrocarbons (up to C 40) are observed in olivine-rich samples from the central dome (IODP Hole 1309D). Occurrences of isoprenoids (pristane, phytane and squalane), polycyclic compounds (hopanes and steranes) and higher relative abundances of n-C 16 to n-C 20 alkanes in the serpentinites of the southern wall suggest a marine organic input. The vent fluids are characterized by high concentrations of methane and hydrogen, with a putative abiotic origin of hydrocarbons; however, evidence for an inorganic source of n-alkanes in the basement rocks remains equivocal. We propose that high seawater fluxes in the southern part of the Atlantis Massif likely favor the transport and incorporation of marine dissolved organic carbon and overprints possible abiotic geochemical signatures. The presence of pristane, phytane and squalane biomarkers in olivine-rich samples associated with local faults at the central

  3. Lithium isotope geochemistry and origin of Canadian shield brines. (United States)

    Bottomley, D J; Chan, L H; Katz, A; Starinsky, A; Clark, I D


    Hypersaline calcium/chloride shield brines are ubiquitous in Canada and areas of northern Europe. The major questions relating to these fluids are the origin of the solutes and the concentration mechanism that led to their extreme salinity. Many chemical and isotopic tracers are used to solve these questions. For example, lithium isotope systematics have been used recently to support a marine origin for the Yellowknife shield brine (Northwest Territories). While having important chemical similarities to the Yellowknife brine, shield brines from the Sudbury/Elliot Lake (Ontario) and Thompson/Snow Lake (Manitoba) regions, which are the focus of this study, exhibit contrasting lithium behavior. Brine from the Sudbury Victor mine has lithium concentrations that closely follow the sea water lithium-bromine concentration trajectory, as well as delta6Li values of approximately -28/1000. This indicates that the lithium in this brine is predominantly marine in origin with a relatively minor component of crustal lithium leached from the host rocks. In contrast, the Thompson/Snow Lake brine has anomalously low lithium concentrations, indicating that it has largely been removed from solution by alteration minerals. Furthermore, brine and nonbrine mine waters at the Thompson mine have large delta6Li variations of approximately 30/1000, which primarily reflects mixing between deep brine with delta6Li of -35 +/- 2/1000 and near surface mine water that has derived higher delta6Li values through interactions with their host rocks. The contrary behavior of lithium in these two brines shows that, in systems where it has behaved conservatively, lithium isotopes can distinguish brines derived from marine sources.

  4. Oxygen isotope geochemistry of the second HSDP core


    WANG, ZHENGRONG; Kitchen, Nami E.; Eiler, John M.


    Oxygen isotope ratios were measured in olivine phenocrysts (~1 mm diameter), olivine microphenocrysts (generally ~100–200 µm diameter), glass, and/or matrix from 89 samples collected from depths down to 3079.7 m in the second, and main, HSDP core (HSDP-2). Olivine phenocrysts from 11 samples from Mauna Loa and 34 samples from the submarine section of Mauna Kea volcano have delta18O values that are similar to one another (5.11 ± 0.10‰, 1sigma, for Mauna Loa; 5.01 ± 0.07‰, for submarine Mauna K...

  5. Geochemistry: how well can Pb isotopes date core formation? (United States)

    Kamber, Balz S; Kramers, Jan D


    Timescale and the physics of planetary core formation are essential constraints for models of Earth's accretion and early differentiation. Wood and Halliday use the apparent mismatch in core-formation dates determined from tungsten (W) and lead (Pb) chrono-meters to argue for a two-stage core formation, involving an early phase of metal segregation followed by a protracted episode of sulphide melt addition. However, we show here that crust-;mantle Pb isotope systematics do not require diachronous core formation. Our observations indicate that very early (< or = 35 Myr) core formation and planet accretion remain the most plausible scenario.

  6. Roman road pollution assessed by elemental and lead isotope geochemistry in East Belgium

    Energy Technology Data Exchange (ETDEWEB)

    Renson, Virginie [U.R. Argiles et Paleoclimats, University of Liege, Allee du 6 Aout, B18, Sart Tilman, 4000 Liege (Belgium)], E-mail:; Fagel, Nathalie [U.R. Argiles et Paleoclimats, University of Liege, Allee du 6 Aout, B18, Sart Tilman, 4000 Liege (Belgium); Mattielli, Nadine [Departement des Sciences de la Terre et de l' Environnement, Universite Libre de Bruxelles, CP160/02, Avenue F.D. Roosevelt, 1050 Brussels (Belgium); Nekrassoff, Serge [Station Scientifique des Hautes Fagnes 137, Rue de Botrange, 4950 Robertville (Belgium); Streel, Maurice [U.R.P.P.M., University of Liege, Allee du 6 Aout, B18, Sart Tilman, 4000 Liege (Belgium); De Vleeschouwer, Francois [U.R. Argiles et Paleoclimats, University of Liege, Allee du 6 Aout, B18, Sart Tilman, 4000 Liege (Belgium)


    The ability of inorganic geochemistry to record environmental change and especially human impact has been evidenced by several studies across Europe, especially in peat, where it is possible to record the impact of agriculture, mining and other industries. However, despite the numerous investigations on the impact of ancient human activities such as ore mining and smelting, little attention has been paid to geochemistry as a tool to solve problems of palaeopollution in the surroundings of archaeological sites. This paper presents geochemical evidence of the impact of a possible early Roman road built in SE Belgian peatland. Increased Zn and Pb concentrations suggest that Pb-Zn ores were transported on the road. Lead isotope analyses suggest that these ores are locally derived, being compatible with those found in the nearby Pb-Zn ore deposits from East Belgium. Present results provide direct evidence that East Belgian Pb-Zn ores were already being mined during Roman times, i.e. earlier than previously suspected (i.e. 14th century) and that Zn appears to be relatively immobile here. On a broader scale, it also demonstrates that such an early road already had an impact on the environment in terms of metal pollution. This paper enlarges on the range of possibilities offered by geochemistry in the field of geoarchaeology.

  7. Chromium isotope uptake in carbonates

    DEFF Research Database (Denmark)

    Rodler, Alexandra

    composition of contemporaneous seawater. Marine carbonates are ubiquitous throughout Earth’s rock record rendering them a particularly interesting archive for constraining past changes in ocean chemistry. This thesis includes an investigation of the fractionation behavior of Cr isotopesduring coprecipitation......Chromium (Cr) is a redox sensitive element potentially capable of tracing fine-scale fluctuations of the oxygenation of Earth’s early surface environments and seawater. The Cr isotope composition of carbonates could perhaps be used as paleo-redox proxy to elucidate changes in the geological past...... related to the rise of oxygen and the evolution of the biosphere. However, before the Cr isotopesystem can be applied to faithfully delineate paleo-environmental changes, careful assessment of the signal robustness and a thorough understanding of the Cr cycle in Earth system processes is necessary...

  8. Re-Os isotope geochemistry of three Chinese chondrites

    Institute of Scientific and Technical Information of China (English)

    ZHI XiaChen; QIN Xie; SHI RenDeng; HONG JiAn


    Three Chinese ordinary chondrites, including Jilin (H5), Boxian (LL3.8) and Lujiang (LL6), have been studied for their Re and Os abundances and Os isotopic composition in whole-chondrite samples, separated magnetic and nonmagnetic fractions, and nodules.The results indicate that the Re and Os abundances of the whole-chondrite samples are in the ranges of corresponding H- and LL-Groups, respectively.The Re and Os abundances of magnetic fraction from Boxian and Lujiang are within the range of high-Os IIAB and IIIAB irons, whereas those of nonmagnetic fractions of Boxian and Lujiang are lower than the whole-chondrite values.The Re and Os abundances of nodules in Jilin are in the range of the LL-Group.187Re/188Os and 187Os/188Os ratios of the three whole chondrites are in the range of ordinary chondrites which locate around the isochron of IIAB+IIIAB irons.187Re/188Os and 187Os/188Os ratios of the magnetic and nonmagnetic fractions from Boxian have a larger difference.The nonmagnetic fraction of Lujiang may contain a recent addition of Re, which causes deviation of the 187Re/188Os ratio from the irons isochron.The Re and Os abundances of nodules in Jilin are lower than those of the whole-chondrite, but their 187Os/188Os ratios are higher than that of the whole chondrite.

  9. Thermal Water's Isotope Geochemistry Study of Evros Area, NE Greece (United States)

    Elissavet, Dotsika; Paraskevi, Chantzi


    Thermal waters from Evros area were collected and subjected to chemical and isotopic analysis in order to understand all the physicochemical mechanisms (mixing, dilution, precipitating) that contribute to the shallow and deep geothermal water tables and determine the origin of these fluids as well as their mineralization. Physicochemical characteristics EC, T°C, pH was determined at the field. The ionic concentrations of samples indicate solutions with high salinity. Two chemical water types were arisen: Na-SO4 concerning low temperatures and shallow aquifers and Na- Cl concerning high temperatures and deeper geothermal circulation. The ratio Br/Cl definitely considered marine origin indicator is the same as the sea confirming the involvement of the seawater in the geothermal system. The marine component and water-rock interaction process under high temperatures seem to contribute to the mineralization of thermal waters. Moreover, water-rock interaction process is also responsible for the alternation of δ18O values. Geothermometers concluded to a middle enthalpy geothermal field.

  10. Robust optical carbon dioxide isotope analyzer Project (United States)

    National Aeronautics and Space Administration — Isotopic analysis of carbon dioxide is an important tool for characterization of the exchange and transformation of carbon between the biosphere and the atmosphere....

  11. Sr, Nd, Pb Isotope geochemistry and magma evolution of the potassic volcanic rocks, Wudalianchi, Northeast China (United States)

    Junwen, W.; Guanghong, X.; Tatsumoto, M.; Basu, A.R.


    Wudalianchi volcanic rocks are the most typical Cenozoic potassic volcanic rocks in eastern China. Compositional comparisons between whole rocks and glasses of various occurrences indicate that the magma tends to become rich in silica and alkalis as a result of crystal differentiation in the course of evolution. They are unique in isotopic composition with more radiogenic Sr but less radiogenic Pb.87Sr /86 Sr is higher and143Nd/144Nd is lower than the undifferentiated global values. In comparison to continental potash volcanic rocks, Pb isotopes are apparently lower. These various threads of evidence indicate that the rocks were derived from a primary enriched mantle which had not been subjected to reworking and shows no sign of incorporation of crustal material. The correlation between Pb and Sr suggests the regional heterogeneity in the upper mantle in terms of chemical composition. ?? 1989 Institute of Geochemistry, Chinese Academy of Sciences.

  12. Geochemistry of Precambrian carbonates. V - Late Paleoproterozoic seawater (United States)

    Veizer, Jan; Plumb, K. A.; Clayton, R. N.; Hinton, R. W.; Grotzinger, J. P.


    A study of mineralogy, chemistry, and isotopic composition of the Coronation Supergroup (about 1.9 Ga, NWT), Canada, and the McArthur Group (about 1.65 NT), Australia, is reported in order to obtain better constrained data for the first- and second-order variations in the isotopic composition of late Paleoproterozoic (1.9 +/- 0.2 Ga) seawater. Petrologically, both carbonate sequences are mostly dolostones. The McArthur population contains more abundant textural features that attest to the former presence of sulfates and halite, and the facies investigated represent ancient equivalents of modern evaporitic sabkhas and lacustrine playa lakes. It is suggested that dolomitization was an early diagenetic event and that the O-18 depletion of the Archean to late Paleoproterozoic carbonates is not an artifact of postdepositional alteration.

  13. Trace element and isotope geochemistry of Cretaceous-Tertiary boundary sediments: identification of extra-terrestrial and volcanic components (United States)

    Margolis, S. V.; Doehne, E. F.


    Trace element and stable isotope analyses were performed on a series of sediment samples crossing the Cretaceous-Tertiary (K-T) boundary from critical sections at Aumaya and Sopelano, Spain. The aim is to possibly distinguish extraterrestrial vs. volcanic or authigenic concentration of platinum group and other elements in K-T boundary transitional sediments. These sediments also have been shown to contain evidence for step-wise extinction of several groups of marine invertebrates, associated with negative oxygen and carbon isotope excursions occurring during the last million years of the Cretaceous. These isotope excursions have been interpreted to indicate major changes in ocean thermal regime, circulation, and ecosystems that may be related to multiple events during latest Cretaceous time. Results to date on the petrographic and geochemical analyses of the Late Cretaceous and Early Paleocene sediments indicate that diagenesis has obviously affected the trace element geochemistry and stable isotope compositions at Zumaya. Mineralogical and geochemical analysis of K-T boundary sediments at Zumaya suggest that a substantial fraction of anomalous trace elements in the boundary marl are present in specific mineral phases. Platinum and nickel grains perhaps represent the first direct evidence of siderophile-rich minerals at the boundary. The presence of spinels and Ni-rich particles as inclusions in aluminosilicate spherules from Zumaya suggests an original, non-diagenetic origin for the spherules. Similar spherules from southern Spain (Caravaca), show a strong marine authigenic overprint. This research represents a new approach in trying to directly identify the sedimentary mineral components that are responsible for the trace element concentrations associated with the K-T boundary.

  14. Geochemistry of fossiliferous carbonate concretions from the Cretaceous Santana Formation - assessing the role of microbial processes (United States)

    Heimhofer, Ulrich; Schwark, Lorenz; Ariztegui, Daniel; Martill, David M.; Immenhauser, Adrian


    Exceptional fossil preservation (incl. soft-tissue phosphatization) within organic-rich black shales is often associated with the formation of a protective carbonate shell surrounding the fossil specimen. Whereas the mechanisms controlling soft-tissue mineralization during the earliest stage of fossilization are considerably well understood (e.g. Briggs and Kear, 1993), only limited information is currently available on the complex biogeochemical processes which lead to the precipitation of the concretionary carbonate mantle around the fossils. This study focuses on the organic and inorganic geochemistry of carbonate concretions derived from black shale deposits of the Early Cretaceous Santana Formation, Araripe Basin, NE Brazil (Martill, 1993; Heimhofer et al. 2008). This konservat-type fossil lagerstätte is world famous for its fossiliferous concretions hosting an exceptionally preserved fish and reptile fauna. The principle aim is twofold including (1) identification of the type and source of organic matter trapped within the Santana concretions and (2) assessment of the different microbial or microbially-mediated processes associated with successive concretion growth during early burial. Based on sedimentological evidence and palaeoenvironmental considerations, the involvement of a prokaryotic mat in early fossilization of the Santana biota has been proposed (Martill, 1988). At this stage, 3 different carbonate concretions hosting fossil fish remains (incl. Notelops brama, Calamopleurus sp. und an unknown specimen) have been analysed with a combined approach including organic molecular geochemistry, high-resolution stable isotope analysis, micro-XRF scanning and sedimentary petrography. Petrographic inspection shows a distinct zonal pattern of the carbonate shell surrounding the fossils. The innermost zone I shows an undulating and discontinuous lamination superimposed on a clotted fabric. Zone II is characterized by the frequent abundance of finely dispersed

  15. Isotope Geochemistry of Possible Terrestrial Analogue for Martian Meteorite ALH84001 (United States)

    Mojzsis, Stephen J.


    We have studied the microdomain oxygen and carbon isotopic compositions by SIMS of complex carbonate rosettes from spinel therzolite xenoliths, hosted by nepheline basanite, from the island of Spitsbergen (Norway). The Quaternary volcanic rocks containing the xenoliths erupted into a high Arctic environment and through relatively thick continental crust containing carbonate rocks. We have attempted to constrain the sources of the carbonates in these rocks by combined O-18/O-16 and C-13/C-12 ratio measurements in 25 micron diameter spots of the carbonate and compare them to previous work based primarily on trace-element distributions. The origin of these carbonates can be interpreted in terms of either contamination by carbonate country rock during ascent of the xenoliths in the host basalt, or more probably by hydrothermal processes after emplacement. The isotopic composition of these carbonates from a combined delta.18O(sub SMOW) and delta.13C(sub PDB) standpoint precludes a primary origin of these minerals from the mantle. Here a description is given of the analysis procedure, standardization of the carbonates, major element compositions of the carbonates measured by electron microprobe, and their correlated C and O isotope compositions as measured by ion microprobe. Since these carbonate rosettes may represent a terrestrial analogue to the carbonate "globules" found in the martian meteorite ALH84001 interpretations for the origin of the features found in the Spitsbergen may be of interest in constraining the origin of these carbonate minerals on Mars.

  16. Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology (United States)

    Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis


    Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

  17. Mineralogy and geochemistry of secondary carbonates from NanTroSEIZE reference sites C0011 and C0012 (United States)

    Fisher, A. J.; Sample, J. C.; Tripati, A.; Torres, M. E.


    Two reference sites were drilled seaward of the Nankai Trough subduction system to characterize properties of materials before entering the zone of deformation. Secondary carbonates can increase sediment strength and record variations in pore water characteristics over time. For this study, we analyzed up to 86 carbonates for mineralogy, major element geochemistry, and stable isotope geochemistry. Carbonate cement abundances range from 2 % to 79 %. In order from most to least abundant, the carbonate mineralogy is calcite, Mn-Fe bearing calcites, magnesium calcite, and dolomite. Total carbonate abundances show no trend with depth, and Mn-Fe calcites with abundances of 2-5%, are common. High-Mg calcite and dolomite are scarce and are most abundant in the upper 500 m at site C0011. Calcite abundance maxima (14.49% and 13.36%) occur at two depths at site C0012 corresponding with sandier volcanic units in the Shikoku basin facies (Unit II 151-220 mbsf) and Unit V (416-529 mbsf). Calcite abundance maxima (14 % and 10 %) occur at two depths at site C0011 (Unit I (0-340 mbsf) and Unit IV (529-538 mbsf)), but do not appear related to sedimentary lithology. General textural relationships obtained from scanning electron microscopy display primarily calcite and Mn-Fe calcite pore-filling cements with less abundant secondary Fe- and Mg-rich clay cements. Carbon isotope delta values (vs. VPDB) range from -23.36 ‰ to 0.26 ‰ at Site C0011 and from -22.48 ‰ to 0.09‰ at Site C0012. The values are consistent with mixtures of seawater dissolved inorganic carbon and contributions from oxidized methane. Carbon isotope values become depleted starting at ~400 mbsf at site C0011 and ~180 mbsf at site C0012. Oxygen isotope values (vs. VPDB) range from -11.88 ‰ to 1.65 ‰ at Site C0011 and from -15.96 ‰ to 5.70 ‰ at Site C0012. The strongest 18O depletions occur below a depth of 420 mbsf at C0011 and 330 mbsf at C0012. Carbonate clumped isotope thermometry of samples from C

  18. Genesis of hydrothermal alterations using stable isotope geochemistry in Takestan area (Tarom zone

    Directory of Open Access Journals (Sweden)

    Batool Taghipou


    Full Text Available Hydrothermal alteration processes are extensively took place on volcanic and pyroclstics of Takestan area. Existence of abundant, deep fracturing and subvolcanic intrusions are enhanced extend hydrothermal alteration zones. The following alteration zones are determined: propylitic, argillic, advanced argillic and sillicic. There are outcropped and widespread in different size and limit. Formation of siliceous sinter, silicified tuffs with preserved primary sedimentary layering including pure mineralized alunite patches are most outstanding. Quartz, sussoritic plagioclase, chlorite, sericite and alunite are main mineral constituents in the volcanics. On the basis of geochemical data volcanic rocks are rhyolite, dacite, andesite, andesitic-basalt and basalt in composition. Acid-sulfate zone is the type of alteration in Tarom area and alunite is an index mineral of this zone. Results of 18O, D and 34S stable isotope geochemistry on altered minerals (muscovite, kaolinite and alunite, revealed that alteration fluids are magmatic in origin.

  19. Carbon isotopic fractionation in heterotrophic microbial metabolism (United States)

    Blair, N.; Leu, A.; Munoz, E.; Olsen, J.; Kwong, E.; Des Marais, D.


    Differences in the natural-abundance carbon stable isotopic compositions between products from aerobic cultures of Escherichia coli K-12 were measured. Respired CO2 was 3.4 percent depleted in C-13 relative to the glucose used as the carbon source, whereas the acetate was 12.3 percent enriched in C-13. The acetate C-13 enrichment was solely in the carboxyl group. Even though the total cellular carbon was only 0.6 percent depleted in C-13, intracellular components exhibited a significant isotopic heterogeneity. The protein and lipid fractions were -1.1 and -2.7 percent, respectively. Aspartic and glutamic acids were -1.6 and +2.7 percent, respectively, yet citrate was isotopically identical to the glucose. Probable sites of carbon isotopic fractionation include the enzyme, phosphotransacetylase, and the Krebs cycle.

  20. The modeling of carbon isotope kinetics and its application to the evaluation of natural gas

    Institute of Scientific and Technical Information of China (English)

    Xianqing LI; Xianming XIAO; Yongchun TANG; Hui TIAN; Qiang ZHOU; Yunfeng YANG; Peng DONG; Yan WANG; Zhihong SONG


    The modeling of carbon isotope kinetics of natural gas is an issue driving pioneering research in the oil and gas geochemistry in China and internationally.Combined with the sedimentary burial history and basin geothermal history,the modeling of carbon isotope kinetics provides a new and effective means for the determination of the origin and accumulation history of natural gas pools.In this paper,we introduce the modeling of carbon isotope kinetics of natural gas formation and its applications to the assessment of natural gas maturity,the determination of the gas source,the history of gas accumulation,and the oil-gas ratio.It is shown that this approach is of great value for these applications.The carbon isotopic characteristics of natural gas are not only affected by the gas source and maturity of the source rock,but also are related to the accumulation condition and geothermal gradient in a basin.There are obvious differences in the characteristics of carbon isotope ratios between instantaneous gas and cumulative gas.Different basins have different kinetic models of carbon isotope fractionation,which depends on the gas source condition,the accumulation history and the sedimentary-tectonic history.Since the origin of natural gas in the superimposed basin in China is very complicated,and the natural gas pool is characterized by multiphase and variable gas-sources,this paper may provide a new perspective on the study and evaluation of natural gas.

  1. Lunar carbon chemistry - Relations to and implications for terrestrial organic geochemistry. (United States)

    Eglinton, G.; Maxwell, J. R.; Pillinger, C. T.


    Survey of the various ways in which studies of lunar carbon chemistry have beneficially affected terrestrial organic geochemistry. A lunar organic gas-analysis operating system is cited as the most important instrumental development in relation to terrestrial organic geochemistry. Improved methods of analysis and handling of organic samples are cited as another benefit derived from studies of lunar carbon chemistry. The problem of controlling contamination and minimizing organic vapors is considered, as well as the possibility of analyzing terrestrial samples by the techniques developed for lunar samples. A need for new methods of analyzing carbonaceous material which is insoluble in organic solvents is indicated.

  2. Sulfur and carbon geochemistry of the Santa Elena peridotites: Comparing oceanic and continental processes during peridotite alteration (United States)

    Schwarzenbach, Esther M.; Gill, Benjamin C.; Gazel, Esteban; Madrigal, Pilar


    Ultramafic rocks exposed on the continent serve as a window into oceanic and continental processes of water-peridotite interaction, so called serpentinization. In both environments there are active carbon and sulfur cycles that contain abiogenic and biogenic processes, which are eventually imprinted in the geochemical signatures of the basement rocks and the calcite and magnesite deposits associated with fluids that issue from these systems. Here, we present the carbon and sulfur geochemistry of ultramafic rocks and carbonate deposits from the Santa Elena ophiolite in Costa Rica. The aim of this study is to leverage the geochemistry of the ultramafic sequence and associated deposits to distinguish between processes that were dominant during ocean floor alteration and those dominant during low-temperature, continental water-peridotite interaction. The peridotites are variably serpentinized with total sulfur concentrations up to 877 ppm that is typically dominated by sulfide over sulfate. With the exception of one sample the ultramafic rocks are characterized by positive δ34Ssulfide (up to + 23.1‰) and δ34Ssulfate values (up to + 35.0‰). Carbon contents in the peridotites are low and are isotopically distinct from typical oceanic serpentinites. In particular, δ13C of the inorganic carbon suggests that the carbon is not derived from seawater, but rather the product of the interaction of meteoric water with the ultramafic rocks. In contrast, the sulfur isotope data from sulfide minerals in the peridotites preserve evidence for interaction with a hydrothermal fluid. Specifically, they indicate closed system abiogenic sulfate reduction suggesting that oceanic serpentinization occurred with limited input of seawater. Overall, the geochemical signatures preserve evidence for both oceanic and continental water-rock interaction with the majority of carbon (and possibly sulfate) being incorporated during continental water-rock interaction. Furthermore, there is

  3. Carbon isotope anomalies in carbonates of the Karelian series (United States)

    Iudovich, Ia. E.; Makarikhin, V. V.; Medvedev, P. V.; Sukhanov, N. V.


    Results are presented on carbon isotope distributions in carbonates of the Karelian complex. A highly anomalous isotopic composition was found in carbonate rocks aged from 2.6 to 1.9 b.y. In the stromatolitic carbonates of the Onega water table, delta-(C-13) reaches a value of +18 percent, while the shungite layer of the Zaonega horizon is characterized by a wide dispersion (from +7.9 to -11.8 percent). These data are in good agreement with the known geochemical boundary (about 2.2 b.y. ago) in the history of the earth.

  4. Exotic Structure of Carbon Isotopes

    CERN Document Server

    Suzuki, T; Hagino, K; Suzuki, Toshio; Sagawa, Hiroyuki; Hagino, Kouichi


    We studied firstly the ground state properties of C-isotopes using a deformed Hartree-Fock (HF)+ BCS model with Skyrme interactions. Shallow deformation minima are found in several neutron$-$rich C-isotopes. It is shown also that the deformation minima appear in both the oblate and the prolate sides in $^{17}$C and $^{19}$C having almost the same binding energies. Secondly, we carried out shell model calculations to study electromagnetic moments and electric dipole transitions of the C-isotopes. We point out the clear configuration dependence of the quadrupole and magnetic moments in the odd C-isotopes, which will be useful to find out the deformations and the spin-parities of the ground states of these nuclei. We studied electric dipole states of C-isotopes focusing on the interplay between low energy Pigmy strength and giant dipole resonances. Reasonable agreement is obtained with available experimental data for the photoreaction cross sections both in the low energy region below $\\hbar \\omega $=14 MeV and ...

  5. Evidence from isotopic geochemistry as an indicator of eutrophication of Meiliang Bay in Lake Taihu, China

    Institute of Scientific and Technical Information of China (English)


    In this paper, Lake Taihu, a large shallow freshwater lake in China, is chosen as an example of reconstruction of eutrophication through the comparison between stable isotopes from dissolved nutrients and plants and water column nutrient parameters and integration of multiple proxies in a sediment core from Meiliang Bay including TN, TP, TOC, C/N, δ15N, δ13C, etc. Differences in aquatic plant species and trophic status between East Taihu Bay and Meiliang Bay are indicated by their variations in δ13C and δ15N of aquatic plants and δ15N of NH4+. A significant influence ofexternal nutrient inputs on Meiliang Bay is reflected in temporal changes in δ 15N of NH4+ and hydro-environmental parameters. The synchronous change between δ13C and δ15N values of sedimented organic matter (OM) has been attributed to elevated primary production at the beginning of eutrophication between 1950 and 1990, then recent inverse correlation between them has been caused by the uptake of 15N-enriched inorganic nitrogen by phytoplankton grown under eutrophication and subsequent OM decomposition and denitrification in surface sediments, indicating that the lake has suffered from progressive eutrophication since 1990. Based on the use of a combination of stable isotopes and elemental geochemistry, the eutrophication of Meiliang Bay in Lake Taihu could be better traced. These transitions of the lake eutrophication respectively occurring in the 1950s and 1990s have been suggested as a reflection of growing impacts of human activities, which is coincident with the instrumental data.

  6. The growth of the continental crust: Constraints from radiogenic isotope geochemistry (United States)

    Taylor, Paul N.


    Most models for evolution of continental crust are expressed in the form of a diagram illustrating the cumulative crustal mass (normalized relative to the present crustal mass) as a function of time. Thus, geochronological data inevitably play a major role in either constructing or testing crustal growth models. For all models, determining the start-time for effective crustal accretion is of vital importance. To this end, the continuing search for, and reliable characterization of, the most ancient crustal rock-units remains a worthy enterprise. Another important role for geochronology and radiogenic isotope geochemistry is to assess the status of major geological events as period either of new crust generation or of reworking of earlier formed continental crust. For age characterization of major geological provinces, using the critieria outined, the mass (or volume) of crust surviving to the present day should be determinable as a function of crust formation age. More recent developments, however, appear to set severe limitations on recycling of crust, at least by the process of sediment subduction. In modeling crustal growth without recycling, valuable constaints on growth rate variations through time can be provided if variations in the average age of the continental crust can be monitored through geological history. The question of the average age of the exposed continental crust was addressed by determining Sm-Nd crustal residence model ages (T-CR) for fine-grained sediment loads of many of the world's major rivers.

  7. Isotope and elemental geochemistry of Cretaceous fossiliferous concretions (Santana Formation, Brazil) (United States)

    Heimhofer, Ulrich; Meister, Patrick; Bernasconi, Stefano M.; Ariztegui, Daniel; Martill, David M.; Schwark, Lorenz


    Exceptional three-dimensional fossil preservation (incl. phosphatization of soft-tissues) within organic carbon-rich mudstones is often associated with the formation of a protective carbonate shell surrounding the fossil specimen. Examples for this type of preservation are the Early Cretaceous fishes, turtles and pterosaurs from the Brazilian Santana Formation. Numerous studies proposed different conceptual models for concretion formation. Having new state-of-the-art geochemical tools at hand we revisited these models for the Santana Formation as an exemplary case. Differential compaction clearly indicates early precipitation of micritic calcite surrounding a central cavity containing the still decomposing fossil. The presence of pyrite forming a circular rim around the fossil and carbonate with negative carbon isotope compositions suggest intense sulphate reduction whereby the production of ammonium from the decay of proteins led to an increased alkalinity, which induced early carbonate precipitation. By means of micro-XRF scanning we found that pyrite is absent from the interior part of the concretions and that total iron content is very low, which indicate absence of sulphate reduction at the center of the concretions and possibly local onset of methanogenesis. We postulate that the central cavity may even have been filled with methane gas that evolved from the decaying animal. Methane diffusing outward was anaerobically oxidized in the surrounding sulphate reduction zone. Carbonate clumped isotopes revealed that micritic calcite formed early, but that these early precipitates are overprinted by two different late diagenetic cements precipitated at elevated temperatures. The occurrence of an outermost "cone-in-cone" calcite rim can be associated with burial showing temperatures of up to 60°C. Strontium-isotope ratios of matrix calcite and cement phases show radiogenic values (0.710416 to 0.712465), which are significantly higher than typical marine Cretaceous

  8. An automated method for 'clumped-isotope' measurements on small carbonate samples. (United States)

    Schmid, Thomas W; Bernasconi, Stefano M


    Clumped-isotope geochemistry deals with the state of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes rather than with the most abundant ones. Among its possible applications, carbonate clumped-isotope thermometry is the one that has gained most attention because of the wide potential of applications in many disciplines of earth sciences. Clumped-isotope thermometry allows reconstructing the temperature of formation of carbonate minerals without knowing the isotopic composition of the water from which they were formed. This feature enables new approaches in paleothermometry. The currently published method is, however, limited by sample weight requirements of 10-15 mg and because measurements are performed manually. In this paper we present a new method using an automated sample preparation device coupled to an isotope ratio mass spectrometer. The method is based on the repeated analysis (n = 6-8) of 200 microg aliquots of sample material and completely automated measurements. In addition, we propose to use precisely calibrated carbonates spanning a wide range in Delta(47) instead of heated gases to correct for isotope effects caused by the source of the mass spectrometer, following the principle of equal treatment of the samples and standards. We present data for international standards (NBS 19 and LSVEC) and different carbonates formed at temperatures exceeding 600 degrees C to show that precisions in the range of 10 to 15 ppm (1 SE) can be reached for repeated analyses of a single sample. Finally, we discuss and validate the correction procedure based on high-temperature carbonates instead of heated gases.

  9. Soil Carbon: Compositional and Isotopic Analysis

    Energy Technology Data Exchange (ETDEWEB)

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


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

  10. Carbon isotopes as indicators of peatland growth? (United States)

    Alewell, Christine; Krüger, Jan Paul; von Sengbusch, Pascal; Szidat, Sönke; Leifeld, Jens


    As undisturbed and/or growing peatlands store considerable amounts of carbon and are unique in their biodiversity and species assemblage, the knowledge of the current status of peatlands (growing with carbon sequestration, stagnating or degrading with carbon emissions) is crucial for landscape management and nature conservation. However, monitoring of peatland status requires long term measurements and is only feasible with expert knowledge. The latter determination is increasingly impeded in a scientific world, where taxonomic expert knowledge and funding of long term monitoring is rare. Stable carbon and nitrogen isotopes depth profiles in peatland soils have been shown to be a useful tool to monitor the degradation of peatlands due to permafrost thawing in Northern Sweden (Alewell et al., 2011; Krüger et al., 2014), drainage in Southern Finland (Krüger et al., 2016) as well as land use intensification in Northern Germany (Krüger et al., 2015). Here, we tackle the questions if we are able to differentiate between growing and degrading peats with the use of a combination of carbon stable (δ13C) and radiogenic isotope data (14C) with peat stratification information (degree of humification and macroscopic plant remains). Results indicate that isotope data are a useful tool to approximate peatland status, but that expert taxonomic knowledge will be needed for the final conclusion on peatland growth. Thus, isotope tools might be used for landscape screening to pin point sites for detailed taxonomic monitoring. As the method remains qualitative future research at these sites will need to integrate quantitative approaches to determine carbon loss or gain (soil C balances by ash content or C accumulation methods by radiocarbon data; Krüger et al., 2016). Alewell, C., R. Giesler, J. Klaminder, J. Leifeld, and M. Rollog. 2011. Stable carbon isotopes as indicators for micro-geomorphic changes in palsa peats. Biogeosciences, 8, 1769-1778. Krüger, J. P., Leifeld, J

  11. Fractionation behavior of chromium isotopes during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

    Rodler, Alexandra; Sánchez-Pastor, Nuria; Fernández-Díaz, Lurdes;


    Interest in chromium (Cr) isotope incorporation into carbonates arises from the observation that Cr isotopic composition of carbonates could be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenviro......Interest in chromium (Cr) isotope incorporation into carbonates arises from the observation that Cr isotopic composition of carbonates could be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track...

  12. Deciphering Carbon Isotope Excursions in Separated Biogenic and Diagenetic Carbonates (United States)

    Hermoso, M.; Minoletti, F.; Hesselbo, S.; Jenkyns, H.; Rickaby, R.; Diester-Haass, L.; Delsate, D.


    The long-term evolution of the carbon-isotope ratio in the sedimentary archive is classically linked with changes in primary productivity and organic matter burial. There have been sudden and pronounced shifts, so-called Carbon Isotope Excursions (CIEs) in the long-term trends as evidenced by synchronous shifts from various basins. These geochemical perturbations may have various explanations such as changes of the efficiency of the carbon sink; sudden infusion of isotopically-light carbon into the Ocean-Atmosphere system; or advection of 12C-rich source from bottom water in a stratified water column. Beside the record of primary changes in seawater chemistry, a possible diagenetic overprint may also mime such CIEs in the sedimentary record. The aim of this contribution is to illustrate through three critical intervals (the Early Toarcian, the K-P boundary and the Mid-Miocene Montery Event) how the various micron-sized sedimentary particles specifically record these CIEs, which are respectively associated with major paleoceanographical events. New techniques for getting monotaxic calcareous nannofossil assemblages from the sediment (Minoletti et al., accepted) enable the isotopic measurement at various depths within the surface water and from bottom water by analyzing early diagenetic precipitations (rhombs and micarbs). The integration of these high-resolution isotopic signals in terms of amplitudes affords to recognize diagenetic artifacts in some sections displaying coeval decrease in the carbonate content. For both Early Toarcian and K-P events, corroborative records of CIE records in both primary calcite and bottom water carbonate indicate a global C-isotope perturbation of the water column. For the Monterey event, the evolution of calcareous nannoplankton and the foraminifera isotopic records are in overall agreement, but in detail, the coccolith-discoaster and foraminifer ratio in the sediment, related to environmental changes, is likely to produce isotopic

  13. Strontium isotope geochemistry of alluvial groundwater: a tracer for groundwater resources characterisation

    Directory of Open Access Journals (Sweden)

    P. Négrel


    Full Text Available This study presents strontium isotope and major ion data of shallow groundwater and river water from the Ile du Chambon catchment, located on the Allier river in the Massif Central (France. There are large variations in the major-element contents in the surface- and groundwater. Plotting of Na vs. Cl contents and Ca, Mg, NO3, K, SO4, HCO3, Sr concentrations reflect water–rock interaction (carbonate dissolution for Ca, Mg, HCO3 and Sr because the bedrock contains marly limestones, agricultural input (farming and fertilising and sewage effluents (for NO3, K, SO4, although some water samples are unpolluted. Sr contents and isotope ratios (87Sr/86Sr vary from 0.70892 to 0.71180 along the hydrological cycle in the groundwater agree with previous work on groundwater in alluvial aquifers in the Loire catchment. The data plot along three directions in a 87Sr/86Sr v. 1/Sr diagram as a result of mixing, involving at least three geochemical signatures–Allier river water, and two distinct signatures that might be related to different water-rock interactions in the catchment. Mixing proportions are calculated and discussed. The alluvial aquifer of the Ile du Chambon catchment is considered, within the Sr isotope systematic, in a larger scheme that includes several alluvial aquifers of the Loire Allier catchment. Keywords: : Loire river, major and trace elements, Sr isotopic ratio, alluvial aquifer, hydrology

  14. Strontium isotope geochemistry of soil and playa deposits near Yucca Mountain, Nevada

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, B.D.; Mahan, S.A.


    The isotopic composition of strontium contained in the carbonate fractions of soils provides an excellent tracer which can be used to test models for their origin. This paper reports data on surface coatings and cements, eolian sediments, playas and alluvial fan soils which help to constrain a model for formation of the extensive calcretes and fault infilling in the Yucca Mountain region. The playas contain carbonate with a wide range of strontium compositions; further work will be required to fully understand their possible contributions to the pedogenic carbonate system. Soils from an alluvial fan to the west of Yucca Mountain show that only small amounts of strontium are derived from weathering of silicate detritus. However, calcretes from a fan draining a carbonate terrane have strontium compositions dominated locally by the limestone strontium component. Although much evidence points to an eolian source for at least some of the strontium in the pedogenic carbonates near Yucca Mountain, an additional component or past variation of strontium composition in the eolian source is required to model the pedogenic carbonate system.

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

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


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

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

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


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

  17. Strontium isotope geochemistry of the Lemachang independent silver ore deposit, northeastern Yunnan, China

    Institute of Scientific and Technical Information of China (English)


    Sr isotope geochemical studies (the 87Sr/86Sr and ?18O-87Sr/86Sr systems) on the wall rocks and ores from the Lemachang independent Ag deposit in northeastern Yunnan provide strong evidence that the ore-forming fluids had flown through radiogenetically Sr-enriched rocks or strata prior to their entry into the locus of ore precipitation, and water-rock interaction is the main mechanism of Ag ore precipitation. The radiogenetically Sr-enriched source region may be the Proterozoic basement (the Kunyang and Hekou groups). Moreover, the theoretical modeling of the Sr isotopic system indicates that the ore-forming fluids contain as much as 3×10?6 Sr with isotopic composition of Sr being 0.750 and that of oxygen 7.0‰. The ore-forming temperatures were estimated at 150-250℃ for the carbonate rock-type ores and at 200-260℃ for the clastic rock-type.

  18. Strontium isotope geochemistry of the Lemachang independent silver ore deposit, northeastern Yunnan, China

    Institute of Scientific and Technical Information of China (English)

    邓海琳; 李朝阳; 涂光炽; 周云满; 王崇武


    Sr isotope geochemical studies (the 87Sr/86Sr and δ18O-87Sr/86Sr systems) on the wall rocks and ores from the Lemachang independent Ag deposit in northeastern Yunnan provide strong evidence that the ore-forming fluids had flown through radiogenetically Sr-enriched rocks or strata prior to their entry into the locus of ore precipitation, and water-rock interaction is the main mechanism of Ag ore precipitation. The radiogenetically Sr-enriched source region may be the Proterozoic basement (the Kunyang and Hekou groups). Moreover, the theoretical modeling of the Sr isotopic system indicates that the ore-forming fluids contain as much as 3×10-6 Sr with isotopic composition of Sr being 0.750 and that of oxygen 7.0‰. The ore-forming temperatures were estimated at 150-250℃ for the carbonate rock-type ores and at 200-260℃ for the clastic rock-type.

  19. Major, trace element and stable isotope geochemistry of synorogenic breccia bodies, Ellsworth Mountains, Antarctica (United States)

    Craddock, J.P.; McGillion, M.S.; Webers, G.F.


    Cambrian carbonates in the Heritage Range of the Ellsworth Mountains, West Antarctica host a series of carbonate-rich breccia bodies that formed contemporaneously with the Permian Gondwanide orogen. The breccia bodies had a three-stage genesis, with the older breccias containing Cambrian limestone (and marble) clasts supported by calcite, whereas the younger breccias are nearly clast-free and composed entirely of matrix calcite. Breccia clasts, calcite matrix and detrital matrix samples were analyzed using x-ray fluorescence (major and trace elements), x-ray diffraction, and stable isotopes (C, O) and suggest that the breccias formed as part of a closed geochemical system, at considerable depth, within the Cambrian limestone host as the Ellsworth Mountains deformed into a fold-and-thrust belt along the margin of Gondwana

  20. Carbon Isotope Chemistry in Molecular Clouds (United States)

    Robertson, Amy N.; Willacy, Karen


    Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

  1. Infrared spectroscopy and hydrogen isotope geochemistry of hydrous silicate glasses. Progress report, June 1, 1996--May 31, 1999

    Energy Technology Data Exchange (ETDEWEB)

    Epstein, S.; Stolper, E.


    This DOE-funded project (DE-FG03-ER13445, 6/1/96-5/31/99) emphasizes study of the behavior of volatiles in magmatic systems. The project is explicitly focused on the combined application of IR spectroscopy, experimental petrology, and stable isotope geochemistry to understanding the behavior and properties of the volatile components dissolved in silicate melts and glasses, although in recent years, our emphasis has broadened to include non-volatile aspects of stable isotope geochemistry. Results obtained during the current grant and previous grant periods confirm that when applied to study of well-chosen synthetic and natural systems, the combination of these approaches and techniques can yield insights of general petrological and volcanological value and of practical value to DOE. In particular, the results of our DOE-funded work has led to a deeper understanding of the physical chemistry of silicate melts as well as specific constraints on the thermal and chemical evolution of high-level magmatic systems of the sort being evaluated as potential geothermal and magmathermal energy sources. Moreover, our work has also contributed to understanding the behavior of H-, C-, and O-bearing species in amorphous and crystalline silicates, including the kinetics of their interactions; we believe these results will contribute to efforts to use silicates in the development of nuclear waste disposal strategies.

  2. Minor-element and Sr-isotope geochemistry of tertiary stocks, Colorado mineral belt (United States)

    Simmons, E.C.; Hedge, C.E.


    Rocks of the northeast portion of the Colorado mineral belt form two petrographically, chemically and geographically distinct rock suites: (1) a silica oversaturated granodiorite suite; and (2) a silica saturated, high alkali monzonite suite. Rocks of the granodiorite suite generally have Sr contents less than 1000 ppm, subparallel REE patterns and initial 87Sr/ 86Sr ratios greater than 0.707. Rocks of the monzonite suite are restricted to the northeast part of the mineral belt, where few rocks of the granodiorite suite occur, and generally have Sr contents greater than 1000 ppm, highly variable REE patterns and 87Sr/86Sr initial ratios less than 0.706. Despite forming simple, smooth trends on major element variation diagrams, trace element data for rocks of the granodiorite suite indicate that they were not derived from a single magma. These rocks were derived from magmas having similar REE patterns, but variable Rb and Sr contents, and Rb/Sr ratios. The preferred explanation for these rocks is that they were derived by partial melting of a mixed source, which yielded pyroxene granulite or pyroxenite residues. The monzonite suite is chemically and petrographically more complex than the granodiorite suite. It is subdivided here into alkalic and mafic monzonites, and quartz syenites, based on the textural relations of their ferromagnesian phases and quartz. The geochemistry of these three rock types require derivation from separate and chemically distinct magma types. The preferred explanation for the alkalic monzonites is derivation from a heterogeneous mafic source, leaving a residue dominated by garnet and clinopyroxene. Early crystallization of sphene from these magmas was responsible for the severe depletion of the REE observed in the residual magmas. The lower Sr content and higher Rb/Sr ratios of the mafic monzonites requires a plagioclase-bearing source. The Sr-isotope systematics of the majority of these rocks are interpreted to be largely primary, and not

  3. 四川拉拉IOCG矿床方解石REE与C,O同位素地球化学特征及意义%REE and carbon-oxygen isotope geochemistry of calcite from Lala IOCG deposit, Sichuan and its significance

    Institute of Scientific and Technical Information of China (English)

    黄从俊; 李泽琴


    calcite, and the features and source of ore-forming fluids were discussed through systematic investigation of REE and C-O isotope geochemistry of calcites. The results show that the average åwREE ,δ(13CPDB) andδ(18OSMOW) of calcite (Ⅰ) are 75.98×10−6, −3.84‰−0‰ and 9.45‰−12.2‰, respectively, while the calcite (Ⅱ) are 313.85×10−6,−3.98‰~−1.40‰and 8.1‰~11.6‰, respectively. The results show that calcite (Ⅰ) is not the main carrier of REE in the MMS, and its ore-forming fluid has very low åwREE . Calcite (Ⅱ) is the dominate REE carrier of HMS, and its ore-forming fluid has higher åwREE than calcite (Ⅰ). Both calcite (Ⅰ) and calcite (Ⅱ) are hydrothermal origin,water-rock interaction and cooling effect the precipitation of calcite, but their ore-forming fluids have different sources. REE distribution pattern of calcite (Ⅰ) is flat type. There are both positive and negative Eu anomalies, and no Ce anomaly, which is controlled by the stability of REE complexes in the fluid. The ore-forming fluid of calcite(Ⅰ) is a kind of high temperature residual fluid after the precipitation of a large number of LREE, and has inherited characteristics of the surrounding marine eruption volcanic rock. REE distribution pattern of calcite (Ⅱ) is leftist type, with significant positive Eu anomaly and no Ce anomaly, which is controlled by crystal chemical factors. The ore-forming fluid of calcite (Ⅱ) is a kind of hot brine originated from the reaction between meteoric water and surrounding rocks, which has a feature of low temperature and high oxygen fugacity. C of calcite (Ⅰ) is derived from mantle fluids and marine carbonates, while C of calcite (Ⅱ) is sourced from CO2 which is released by gabbro magma. O isotope obviously has negative drift being affected by meteoric water.

  4. Geochemistry and Stable Isotopes of Tacana Volcano-Hydrothermal System, Mexico-Guatemala (United States)

    Rouwet, D. /; Inguaggiato, S.; Taran, Y. /; Varley, N. /


    Tacana volcano (4100 m.s.n.m.), situated on the border between Chiapas (Mexico) and Guatemala is considered an active volcano. In May 1986, after a minor phreatic explosion, a fumarole field was formed at an altitude between 3200 and 3600 m.a.s.l. Around the volcano, at altitudes between 1500 and 2000 m.a.s.l., exist several thermal springs, with temperatures up to 63 degrees C. Incomplete chemical composition of the Agua Caliente thermal waters in the period 1986-1993 were presented by Medina (1986), De la Cruz-Reyna et al. (1989) and Armienta and De la Cruz-Reyna (1995), a chemical analysis of fumarole gases were published by Martini et al. (1986). This study presents the first series of isotope data of water and gases: hydrogen, oxygen, carbon and helium. Data on gas and water chemistry of several thermal spring waters and gases are presented in more detail than ever. Hydrogen and oxygen isotopes of Tacana thermal spring waters show that meteoric water is the main contribution for the thermal waters. Cation geothermometry of the spring waters confirm these meteoric contribution, as all waters are immature in a dynamic system of water-rock interaction with a constant infiltration of fresh meteoric waters (precipitation of 6000 mm per year). The relatively high bicarbonate (up to 1100 ppm) and sulphate (up to 1200 ppm) concentrations in the thermal waters suggest an important degassing up to 2500 m below the volcano summit, which indicates the presence of a extended and complex volcano-hydrothermal system. Helium isotopes of free and dissolved gases confirm the existence of a magmatic contribution, so as for fumarole gases (6.6 R/Ra) as for gases sampled at the thermal springs (5.7-6.2 R/Ra for free gases and between 0.50 and 5.55 R/Ra for dissolved gases). These values are typical for gases liberated at volcanoes in clasic volcanic arcs. The lower values for the dissolved He is probably due to an interaction with the granitic basement, which can be found at

  5. Helium and carbon isotopes in Indian diamonds (United States)

    Wiens, R.; Lal, D.; Craig, H.


    Helium and carbon isotope measurements in Indian diamonds (from Andhra Pradesh) were carried out using samples that included mined diamonds from primary kimberlite source rocks and alluvial diamonds from river gravel. The He and C isotope concentrations in diamonds from these two sources were compared, and the Indian diamonds were compared to those from other regions. Results indicate that most of the He-3 in the alluvial diamonds is of cosmogenic origin and that the alluvial diamonds may also have a significant He-4 component due to alpha particles implanted during storage in a secondary matrix. One diamond, a mined kimberlite specimen, was found to have the lowest He-4 content (0.018 microcc/g) so far recorded in diamonds.

  6. Isotope geochemistry reveals ontogeny of dispersal and exchange between main-river and tributary habitats in smallmouth bass Micropterus dolomieu. (United States)

    Humston, R; Doss, S S; Wass, C; Hollenbeck, C; Thorrold, S R; Smith, S; Bataille, C P


    Radiogenic strontium isotope ratios ((87) Sr:(86) Sr) in otoliths were compared with isotope ratios predicted from models and observed in water sampling to reconstruct the movement histories of smallmouth bass Micropterus dolomieu between main-river and adjacent tributary habitats. A mechanistic model incorporating isotope geochemistry, weathering processes and basin accumulation reasonably predicted observed river (87) Sr:(86) Sr across the study area and provided the foundations for experimental design and inferring fish provenance. Exchange between rivers occurred frequently, with nearly half (48%) of the 209 individuals displaying changes in otolith (87) Sr:(86) Sr reflecting movement between isotopically distinct rivers. The majority of between-river movements occurred in the first year and often within the first few months of life. Although more individuals were observed moving from the main river into tributaries, this pattern did not necessarily reflect asymmetry in exchange. Several individuals made multiple movements between rivers over their lifetimes; no patterns were found, however, that suggest seasonal or migratory movement. The main-river sport fishery is strongly supported by recruitment from tributary spawning, as 26% of stock size individuals in the main river were spawned in tributaries. The prevailing pattern of early juvenile dispersal documented in this study has not been observed previously for this species and suggests that the process of establishing seasonal home-range areas occurs up to 2 years earlier than originally hypothesized. Extensive exchange between rivers would have substantial implications for management of M. dolomieu populations in river-tributary networks.

  7. The Precambrian marine carbonate isotope database: version 1.1.


    G. A. Shields; Veizer, J.


    We present a compilation of strontium, carbon, and oxygen isotope compositions of roughly 10,000 marine carbonate rocks of Archean - Ordovician age (3800 Ma – 450 Ma). The Precambrian Marine Carbonate Isotope Database (PMCID) has been compiled from 152 published and 3 unpublished articles and books of the past 40 years. Also included are 30 categories of relevant “metadata” that allow detailed comparisons and quality assessments of the isotope data to be made. The PMCID will be updated period...

  8. Geochemistry of Precambrian carbonates - 3-shelf seas and non-marine environments of the Archean (United States)

    Veizer, Jan; Clayton, R. N.; Hinton, R. W.; Von Brunn, Victor; Mason, T. R.


    Samples from the Pangola and Ventersdorp Supergroups (Kaapvaal Craton, South Africa) and from the Fortescue and Hamersley Groups (Pilbara Block, Australia) were analyzed, using XRF, AAS, and isotope-analysis techniques to investigate the mineralogical, chemical, and isotopic features of these representatives of contemporary shelf carbonates (Pangola and Hamersley samples) and nonmarine carbonates (the Ventersdorp and Fortescue samples). Results show that, mineralogically, the shelf carbonates are almost exclusively dolostones, while the lacustrine facies are predominantly limestones. Geological, trace-element, and oxygen-isotope results of the shelf carbonates suggest that their original mineralogy may have been aragonite, and that the Pangola dolostones may represent a direct dolomitization product of this precursor. By contrast, the stabilization of the Hamersley carbonates may have involved an additional step of transformation of a metastable precursor into limestone.

  9. Origin and time-space distribution of hydrothermal systems in east-central Australian sedimentary basins: Constraints from illite geochronology and isotope geochemistry. (United States)

    Uysal, I. Tonguç


    Some well-known precious mineral deposits and hydrocarbon resources occur extensively in east-central Australian sedimentary Basins. The metal occurrences are abundant in northwestern and eastern part of Queensland, whereas no significant deposits are known in large areas further south, which may, however, be hidden beneath the Jurassic-Cretaceous sedimentary basins. Important hydrocarbon resources exist within the Jurassic-Cretaceous sedimentary rocks at relatively shallow depths, of which the distribution represent zones of high paleo-geothermal gradients. This study examines the time-space distribution in relation to the regional tectonic history of concealed metal deposits and areas of high paleo-geothermal gradient leading to hydrocarbon maturation. To this end, authigenic illitic clay minerals representing various locations and stratigraphic depths in east-central Australia were investigated, of which the Rb-Sr and Ar-Ar geochronology and stable isotope geochemistry assist in delineating zones of hydrothermal systems responsible for hydro-carbon maturation/migration and potentially ore deposition. The Late Carboniferous - Early Permian crustal extension that affected large areas of eastern Australia and led to the epithermal mineralisations (e.g., the Drummond Basin) is also recorded in northern South Australia and southwest Queensland. A Late Triassic - Early Jurassic tectonic event being responsible for coal maturation and gas generation in the Bowen Basin and the epithermal mineralisation in the North Arm goldfield in SE Queensland likewise affected the areas much further west in Queensland. Some illites from the basement in outback Queensland and fault gouges from the Demon Fault in NE New South Wales yield younger Rb-Sr and Ar-Ar ages indicating the effect of hydrothermal processes as a result of a Middle-Upper Jurassic tectonic event. The majority of illite samples from the crystalline basement rocks, Permian Cooper Basin, and Jurassic

  10. Carbon-isotopic analysis of dissolved acetate. (United States)

    Gelwicks, J T; Hayes, J M


    Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degrees C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4% for acetate samples larger than 5 micromoles. A full treatment of uncertainties is outlined.

  11. Investigation of Chemical and Physical Changes to Bioapatite During Fossilization Using Trace Element Geochemistry, Infrared Spectroscopy and Stable Isotopes (United States)

    Suarez, C. A.; Kohn, M. J.


    Bioapatite in the form of vertebrate bone can be used for a wide variety of paleo-proxies, from determination of ancient diet to the isotopic composition of meteoric water. Bioapatite alteration during diagenesis is a constant barrier to the use of fossil bone as a paleo-proxy. To elucidate the physical and chemical alteration of bone apatite during fossilization, we analyzed an assortment of fossil bones of different ages for trace elements, using LA-ICP-MS, stable isotopes, and reflected IR spectroscopy. One set of fossil bones from the Pleistocene of Idaho show a diffusion recrystallization profile, however, rare earth element (REE) profiles indicate diffusion adsorption. This suggests that REE diffusion is controlled by changing (namely decreasing) boundary conditions (i.e. decreasing concentration of REE in surrounding pore fluids). Reflected IR analysis along this concentration profile reveal that areas high in U have lost type A carbonate from the crystal structure in addition to water and organics. Stable isotopic analysis of carbon and oxygen will determine what, if any, change in the isotopic composition of the carbonate component of apatite has occurred do to the diffusion and recrystallization process. Analysis of much older bone from the Cretaceous of China reveal shallow REE and U concentration profiles and very uniform reflected IR spectra with a significant loss of type A carbonate throughout the entire bone cortex. Analysis of stable isotopes through the bone cortex will be compared to the stable isotopes collected from the Pleistocene of Idaho.

  12. The Oxidant Budget of Dissolved Organic Carbon Driven Isotope Excursions (United States)

    Bristow, T. F.; Kennedy, M. J.


    Negative carbon isotope values, falling below the mantle average of about -5 per mil, in carbonate phases of Ediacaran age sedimentary rocks are widely regarded as reflecting negative excursions in the carbon isotopic composition of seawater lasting millions of years. These isotopic signals form the basis of chemostratigraphic correlations between Ediacaran aged sections in different parts of the world, and have been used to track the oxidation of the biosphere. However, these isotopic values are difficult to accommodate within limits prescribed by the current understanding of the carbon cycle, and a hypothetical Precambrian ocean dissolved organic carbon (DOC) pool 100 to 1000 times the size of the modern provides a potential source of depleted carbon not considered in Phanerozoic carbon cycle budgets. We present box model results that show the remineralization of such a DOC pool to drive an isotope excursion of the magnitude observed in the geological record exhausts global budgets of free oxygen and sulfate in 800 k.y. These results are incompatible with the estimated duration of late Ediacaran isotope excursions of more than 10 m.y., as well as geochemical and biological indicators that oceanic sulfate and oxygen levels were maintained or even increased at the same time. Therefore the carbon isotope record is probably not a useful tool for monitoring oxygen levels in the atmosphere and ocean. Covariation between the carbon and oxygen isotope records is often observed during negative excursions and is indicative of local processes or diagenetic overprinting.

  13. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation (United States)

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


    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

  14. Geochemistry, Nd Isotopic Characteristics of Metamorphic Complexes in Northern Hebei: Implications for Crustal Accretion

    Institute of Scientific and Technical Information of China (English)

    LIU Shuwen; TIAN Wei; L(U) Yongjun; LI Qiugen; FENG Yonggang; K. H. PARK; Y. S. SONG


    Ma Late Paleozoic metamorphic mafic rocks and related granitic rocks show a medium-potassium calc-alkaline magmatic evolution series, characterized by high Mg#,obviously negative Th, Nb, Ta anomalies and positive Sr anomalies, from no to strongly negative Ti anomalies and fiat REE patterns with εNd(t) = +8.42, implying that the mafic magma was derived from the depleted mantle. However the other granitic rocks are characterized by right-declined REE patterns with no to evidently positive Eu anomalies, significantly low εNd(t) = -13.37 to -14.04, and TDM=1.97-1.96 Ga, revealing that the granitoid magma was derived from hybrid between mafic magma that came from ~311 Ma depleted mantle and granitoid magma from Archean to Early Paleoproterozoic ancient crustal recycling. The geochemistry and Nd isotopic characteristics as well as the above geological and geochronological results indicate that the middle segment of the northern margin of the NCC mainly experienced four crustal growth episodes from Archean to Late Paleozoic,which were dominated by three continental marginal arc accretions (~2.49, ~2.44 and 311 Ma), except the 1.76-1.68 Ga episode related to post-collisional extension, revealing that the crustal accretion of this segment was chiefly generated from arc accretion and amalgamation to the NCC continental block.

  15. The Itataia phosphate-uranium deposit (Ceará, Brazil) new petrographic, geochemistry and isotope studies (United States)

    Veríssimo, César Ulisses Vieira; Santos, Roberto Ventura; Parente, Clóvis Vaz; Oliveira, Claudinei Gouveia de; Cavalcanti, José Adilson Dias; Nogueira Neto, José de Araújo


    The Itataia phosphate-uranium deposit is located in Santa Quitéria, in central Ceará State, northeastern Brazil. Mineralization has occurred in different stages and involves quartz leaching (episyenitization), brecciation and microcrystalline phase formation of concretionary apatite. The last constitutes the main mineral of Itatiaia uranium ore, namely collophane. Collophanite ore occurs in massive bodies, lenses, breccia zones, veins or episyenite in marble layers, calc-silicate rocks and gneisses of the Itataia Group. There are two accepted theories on the origin of the earliest mineralization phase of Itataia ore: syngenetic (primary) - where the ore is derived from a continental source and then deposited in marine and coastal environments; and epigenetic (secondary) - whereby the fluids are of magmatic, metamorphic and meteoric origin. The characterization of pre- or post-deformational mineralization is controversial, since the features of the ore are interpreted as deformation. This investigation conducted isotopic studies and chemical analyses of minerals in marbles and calc-silicate rocks of the Alcantil and Barrigas Formations (Itataia Group), as well as petrographic and structural studies. Analysis of the thin sections shows at least three phosphate mineral phases associated with uranium mineralizaton: (1) A prismatic fluorapatite phase associated with chess-board albite, arfvedsonite and ferro-eckermannite; (2) a second fluorapatite phase with fibrous radial or colloform habits that replaces calcium carbonate in marble, especially along fractures, with minerals such as quartz, chlorite and zeolite also identified in calc-silicate rocks; and (3) an younger phosphate phase of botryoidal apatite (fluorapatite and hydroxyapatite) related with clay minerals and probably others calcium and aluminum phosphates. Detailed isotopic analysis carried out perpendicularly to the mineralized levels and veins in the marble revealed significant variation in isotopic

  16. New Results on the Palaeobiology of Bears on the Swabian Alb (Chronology, Isotopic Geochemistry and Palaeogenetics) (United States)

    Muenzel, Susanne


    Paleogenetic investigations at three geographically close caves in the Ach Valley near Blaubeuren have revealed two different cave bear haplogroups. These two haplogroups correspond to Ursus spelaeus (haplogroup 1) and Ursus ingressus (haplogroup 4) (Rabeder & Hofreiter 2004, Die Höhle 55, 58-77). This genetic variability was first attested for Geißenklösterle and Sirgenstein cave, but the new genetic data attest them also for Hohle Fels. In all three caves Ursus ingressus replaced Ursus spelaeus around 28 000 B.P. The carbon and nitrogen isotopes of the two genetic types do not vary significantly, meaning that there is no dietary difference between them and Ursus spelaeus were in dietary competition with Ursus ingressus in the Ach valley. The radiocarbon dates suggested a sudden replacement (Hofreiter et al. 2007, Current Biology 17(4): R1-R3), which must have been accompanied by local extinction of the older cave bear, according to the dietary competition with the younger bear. The possible reasons for this replacement are not clear yet. Climatic changes are unlikely, since the faunal composition remains the same and the environmental data do not differ significantly. But we cannot exclude human impact on the cave bear population, since a cave bear vertebra with an embedded fragment of a flint projectile was recovered in the Gravettian layer AH IIcf dated to 27 830+150-140 B.P. and gives indisputable proof of the hunting of cave bears. Numerous cut marks proof an ongoing exploitation of this species. In this context, new radiocarbon dates and isotopic results on cave bears and coeval brown bears will help us to refine the possible scenarios of this complex evolutionary and ecological process. These results will be used to test hypotheses of competitive exclusion between the different bear species. This study will exemplify how combining evidence from different approaches can provide invaluable clues about palaeobiology of late Pleistocene large mammals such as

  17. Petrology,Chronology and Isotope Geochemistry of the Proterozoic Amphibolites from Xiangshan,Central Jiangxi Province,China

    Institute of Scientific and Technical Information of China (English)

    胡恭任; 章邦桐; 等


    On the basis of a comprehensive study on the petrology,trace elements and isotopic geochemistry of the Xiangshan amphibolites,we suggest that the protoliths of the amphibolites were basalts formed in an island-arc tectonic setting.The basaltic magma was derived from a slightly depleted mantle source with a small amount of crustal contamination.Assemblage of the rock-froming minerals indicates that these amphibolites underwent a low-grade metamorphism of amphibolite facies.According to the formation age(1113Ma) and subsequent metamophic age(726.6Ma) of the basalts aw well as the geological and gochemical features of these amphibolites,a tectonic model of Proterozoic oceanic island-arc setting is proposed for central Jiangxi.

  18. Elucidating the magmatic history of the Austurhorn silicic intrusive complex (southeast Iceland) using zircon elemental and isotopic geochemistry and geochronology (United States)

    Padilla, A. J.; Miller, C. F.; Carley, T. L.; Economos, R. C.; Schmitt, A. K.; Coble, M. A.; Wooden, J. L.; Fisher, C. M.; Vervoort, J. D.; Hanchar, J. M.


    The Austurhorn intrusive complex (AIC) in southeast Iceland comprises large bodies of granophyre and gabbro, and a mafic-silicic composite zone (MSCZ) that exemplifies magmatic interactions common in Icelandic silicic systems. Despite being one of Iceland's best-studied intrusions, few studies have included detailed analyses of zircon, a mineral widely recognized as a valuable tracer of the history and evolution of its parental magma(s). In this study, we employ high spatial resolution zircon elemental and isotopic geochemistry and U-Pb geochronology as tools for elucidating the complex construction and magmatic evolution of Austurhorn's MSCZ. The trace element compositions of AIC zircon crystals form a broad but coherent array that partly overlaps with the geochemical signature for zircons from Icelandic silicic volcanic rocks. Typical of Icelandic zircons, Hf concentrations are relatively low (mush-like material and a prolonged lifetime for the complex.

  19. Organic geochemistry, stable isotopes, and facies analysis of the Early Aptian OAE—New records from Spain (Western Tethys)


    Quijano López, María Luisa; Castro Jiménez, Jose Manuel; Pancost, Richard D.; Gea Guillén, Ginés Alfonso; Najarro, María; Aguado Merlo, Roque; Rosales, Idoia; Martín Chivelet, Javier


    The Early Aptian Oceanic Anoxic Event (OAE1a) is a time interval characterized by increased organic carbon accumulation in marine sediments, notable sedimentary and biotic changes, and abrupt carbon-isotope excursions indicative of significant major palaeoenvironmental changes linked to a perturbation in the global carbon cycle. Here we present the study of four sections recording the OAE1a (Early Aptian) in Spain, which are located in two broad basins respectively located in the ...

  20. A Clumped Isotope Calibration for Lacustrine Carbonates (United States)

    Mitsunaga, B. A.; Mering, J. A.; Petryshyn, V. A.; Dunbar, R. B.; Cohen, A. S.; Liu, X.; Kaufman, D. S.; Eagle, R.; Tripati, A.


    Our capacity to understand Earth's environmental history is highly dependent on the accuracy of past climate reconstructions. Unfortunately, many terrestrial proxies—tree rings, speleothems, leaf margin analyses, etc.—are influenced by the effects of both temperature and precipitation. Methods that can isolate the effects of temperature alone are needed, and clumped isotope thermometry has the potential to be a useful tool for determining terrestrial climates. Multiple studies have shown that the fraction of 13C—18O bonds in carbonates is inversely related to the temperature at which the rocks formed and may be a useful proxy for reconstructing temperatures on land. An in-depth survey of lacustrine carbonates, however, has not yet been published. Therefore we have been measuring the abundance of 13C18O16O in the CO2 produced by the dissolution of modern lake samples' carbonate minerals in phosphoric acid and comparing results to independently known estimates of lake water temperature and air temperature. Some of the sample types we have investigated include endogenic carbonates, freshwater gastropods, bivalves, microbialites, and ooids.

  1. A Teaching Exercise to Introduce Stable Isotope Fractionation of Metals into Geochemistry Courses (United States)

    Weiss, Dominik J.; Harris, Caroline; Maher, Kate; Bullen, Thomas


    Variations in the isotopic composition of elements have been widely used to study earth's climate, biosphere, and interior, and more recently to track the fate of contaminants. Within the broad range of elements that exhibit measureable isotopic variations, metal stable isotopes are increasingly applied across the biological, geological,…

  2. Elemental and Sm-Nd isotopic geochemistry on detrital sedimentary rocks in the Ganzi-Songpan block and Longmen Mountains

    Institute of Scientific and Technical Information of China (English)

    CHEN Yuelong; LIU Fei; ZHANG Hongfei; NIE Lanshi; JIANG Liting


    Systematic results of major and trace element geochemistry and Sm-Nd isotopic geochemistry on detrital sedimentary rocks of Precambrian to Triassic in the Ganzi-Songpan block and Longmen Mountains are presented. The rocks are classified into greywaekes or feldspar sandstones,grains of which are the mixtures of mafic rocks, felsic rocks,and quartz + calcite. Total rare earth elements (REE) contents of the rocks increase gradually and negative Eu anomalies become more obvious from Precambrian to Triassic, which may indicate intensifying crustal anatexis. Tectonic setting was stable during the Late Paleozoic, the refore there are obvious negative Ce anomalies. Nd model ages are between 1.6 Ga and 2.4 Ga, which are very similar to those of the Yangtze croton, South Qinling and North Qinling belts and quite different from those of the North China craton. There-fore, provenance of the sedimentary rocks in the Ganzi-Songpan block and Longmen Mountains was the Yangtze craton and/or the Qinling orogen, which evolved on the basis of the Yangtze craton. The correlation between provenances and tectonostratigraphic strata of the western Yangtze craton shows that the source materials should be primarily from Neoproterozoic. Secondary sources were Archean and Paleoproterozoic strata. Triassic clastic sedimentary rocks contain Late Paleozoic mantle-derived materials, represented by the Emeishan Permian flood basalts. Spatial distribution of initial Nd isotopic compositions indicates that denudating areas were in the east and the north and depositing areas of deep water were in the west and the south for the Ganzi-Songpan basin during Triassic.

  3. Degradation changes stable carbon isotope depth profiles in palsa peatlands

    Directory of Open Access Journals (Sweden)

    J. P. Krüger


    Full Text Available Palsa peatlands are a significant carbon pool in the global carbon cycle and are projected to change by global warming due to accelerated permafrost thaw. Our aim was to use stable carbon isotopes as indicators of palsa degradation. Depth profiles of stable carbon isotopes generally reflect organic matter dynamics in soils with an increase of δ13C values during aerobic decomposition and stable or decreasing δ13C values with depth during anaerobic decomposition. Stable carbon isotope depth profiles of undisturbed and degraded sites of hummocks as well as hollows at three palsa peatlands in northern Sweden were used to investigate the degradation processes. The depth patterns of stable isotopes clearly differ between intact and degraded hummocks at all sites. Erosion and cryoturbation at the degraded sites significantly changes the stable carbon isotope depth profiles. At the intact hummocks the uplifting of peat material by permafrost is indicated by a turning in the δ13C depth trend and this assessment is supported by a change in the C / N ratios. For hollows isotope patterns were less clear, but some hollows and degraded hollows in the palsa peatlands show differences in their stable carbon isotope depth profiles indicating enhanced degradation rates. We conclude that the degradation of palsa peatlands by accelerated permafrost thawing could be identified with stable carbon isotope depth profiles. At intact hummocks δ13C depth patterns display the uplifting of peat material by a change in peat decomposition processes.

  4. Phanerozoic and Neoproterozoic Negative Carbon Isotope Excursions, Diagenesis and Terrestrialization (United States)

    Paul, K.; Kennedy, M. J.


    Comprehensive data sets of Phanerozoic and late Precambrian carbon isotope data derived from carbonate rocks show a similar positive relation when cross-plotted with oxygen isotope values. The range and slope between the time periods is identical and the processes responsible for the relation have been well documented in Quaternary sediments. These processes include the stabilization of isotope values to ambient meteoric water values during shallow burial and flushing of carbonate sediments. Both data sets show strongly depleted carbon (-9 per mil PDB) and oxygen isotope values that retain seemingly systematic stratigraphic patterns with the Quaternary and Phanerozoic examples that demonstrably record meteroric water values. Similar values and patterns in the Precambrian are interpreted as primary marine in origin with significant implications for an ocean carbon mass balance not possible in the Phanerozoic carbon cycle. A similar compilation of carbonates older than one billion years do not show a relation between carbon and oxygen isotopes, lacking the negative carbon values evident in the younger record. We hypothesize that this difference records the onset of significant organic carbon on the land surface and the alteration of meteoric waters toward Phanerozoic values. We demonstrate the meteoric affinities of Neoproterozoic carbonates containing prominent negative isotope excursions recorded in the Shuram and Wonoka Formations of Oman and South Australia commonly attributed to whole ocean isotope variation. The conspicuous absence of negative carbon isotope values with normal marine oxygenisotope values in the Phanerozoic and Neoproterozic identifies a consistent relation between these time intervals and suggests that, as well accepted in the Phanerozoic, negative carbon isotope excursions less than -3 per mil are not a record of marine processes, but rather the later terrestrial biotic influence on meteoric water values.

  5. Isotope geochemistry and modelling of the multi-aquifer system in the eastern part of Lithuania (United States)

    Mokrik, Robert; Juodkazis, Vytautas; Štuopis, Anicetas; Mažeika, Jonas


    A steady-state groundwater flow model of three Quaternary intertill aquifers in the eastern part of Lithuania has been compiled. The distinction of separate modelled layers is based on hydraulic and isotope-hydrochemistry data criteria. 3H data were used to estimate the corrected groundwater age and were coupled with a groundwater-flow-dynamics model of the Quaternary aquifer system along a cross-section flow pathway from the Baltic Upland recharge area in eastern Lithuania towards the discharge area in the lowlands near the city of Kaunas in central Lithuania. The bicarbonate content in groundwater (214-462 mg/l) increases downgradient towards the lowland area. The other major constituents and total dissolved solids (TDS) have a trend analogous to the bicarbonate. The 14C activity of dissolved inorganic carbon (DIC) in the groundwater ranges from 41.4 to 85.7 pMC. With aquifer-system depth, active precipitation of aqueous solution takes place by dissolving minerals of calcite and dolomite and leakage of "old" groundwater from lower aquifers; the process is also traced by lower 14C and 3H activities and by more positive δ18O values in lowland areas.

  6. Time-series analysis of ion and isotope geochemistry of selected springs of the Nevada Test Site, Nye County, Nevada

    Energy Technology Data Exchange (ETDEWEB)

    Lyles, B.F.; Edkins, J.; Jacobson, R.L.; Hess, J.W.


    The temporal variations of ion and isotope geochemistry were observed at six selected springs on the Nevada Test Site, Nye County, Nevada and included: Cane, Whiterock, Captain Jack, Topopah, Tippipah, and Oak Springs. The sites were monitored from 1980 to 1982 and the following parameters were measured: temperature, pH, electrical conductance, discharge, cations (Ca{sup 2+}, Mg{sup 2+}. Na{sup +}, K{sup +}), anions Cl{sup {minus}}, SO{sub 4}{sup 2{minus}}. HCO{sub 3}{sup {minus}}, silica, stable isotopes ({delta}{sup 18}O, {delta}D, {delta}{sup 13}C), and radioactive isotopes ({sup 3}H, {sup 14}C). A more detailed study was continued from 1982 to 1988 at Cane and Whiterock Springs. Field microloggers were installed at these sites in 1985 to measure the high frequency response of temperature, electrical conductance, and discharge to local precipitation. Stage fluctuations near the discharge point dissolve minerals/salts as groundwater inundates the mineralized zone immediately above the equilibrium water table. This phenomena was most noticeable at Whiterock Spring and lagged the discharge response by several hours. Stable isotope analysis of precipitation and groundwater suggests a 1.5 to 2 month travel time for meteoric water to migrate from the recharge area to the discharge point. Groundwater age determinations suggest a mean age of approximately 30 years at Whiterock Spring and possibly older at Cane Spring. However, the short travel time and geochemical integrity of recharge pulses suggest that the waters are poorly mixed along the flow paths. 25 refs., 25 figs., 24 tabs.

  7. Carbon isotope fractionation in protoplanetary disks

    CERN Document Server

    Woods, Paul M


    We investigate the gas-phase and grain-surface chemistry in the inner 30 AU of a typical protoplanetary disk using a new model which calculates the gas temperature by solving the gas heating and cooling balance and which has an improved treatment of the UV radiation field. We discuss inner-disk chemistry in general, obtaining excellent agreement with recent observations which have probed the material in the inner regions of protoplanetary disks. We also apply our model to study the isotopic fractionation of carbon. Results show that the fractionation ratio, 12C/13C, of the system varies with radius and height in the disk. Different behaviour is seen in the fractionation of different species. We compare our results with 12C/13C ratios in the Solar System comets, and find a stark contrast, indicative of reprocessing.

  8. Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine (United States)

    Moynier, Frédéric; Fujii, Toshiyuki


    Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000 ppm for the 44Ca/40Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000 ppm. We show that the Ca isotopic fractionation between soil solutions and plant roots can be explained by the difference of isotopic fractionation between the different first shell hydration degree of Ca2+ and that the isotopic fractionation between roots and leaves is controlled by the precipitation of Ca-oxalates. The isotopic fractionation between blood and urine is due to the complexation of heavy Ca with citrate and oxalates in urine. Calculations are presented for additional Ca species that may be useful to interpret future Ca isotopic measurements. PMID:28276502

  9. Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine. (United States)

    Moynier, Frédéric; Fujii, Toshiyuki


    Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000 ppm for the (44)Ca/(40)Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000 ppm. We show that the Ca isotopic fractionation between soil solutions and plant roots can be explained by the difference of isotopic fractionation between the different first shell hydration degree of Ca(2+) and that the isotopic fractionation between roots and leaves is controlled by the precipitation of Ca-oxalates. The isotopic fractionation between blood and urine is due to the complexation of heavy Ca with citrate and oxalates in urine. Calculations are presented for additional Ca species that may be useful to interpret future Ca isotopic measurements.

  10. One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite (United States)

    Hoehler, Tori M.; Mccollom, Tom; Schrenk, Matt; Cardace, Dawn


    Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

  11. One-carbon (bio?)geochemistry in subsurface waters of the serpentinizing Coast Range Ophiolite (United States)

    Hoehler, T. M.; McCollom, T.; Schrenk, M. O.; Kubo, M.; Cardace, D.


    Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

  12. Mass transfer and carbon isotope evolution in natural water systems (United States)

    Wigley, T.M.L.; Plummer, L.N.; Pearson, F.J.


    This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

  13. Intramolecular carbon isotope distribution of acetic acid in vinegar. (United States)

    Hattori, Ryota; Yamada, Keita; Kikuchi, Makiko; Hirano, Satoshi; Yoshida, Naohiro


    Compound-specific carbon isotope analysis of acetic acid is useful for origin discrimination and quality control of vinegar. Intramolecular carbon isotope distributions, which are each carbon isotope ratios of the methyl and carboxyl carbons in the acetic acid molecule, may be required to obtain more detailed information to discriminate such origin. In this study, improved gas chromatography-pyrolysis-gas chromatography-combustion-isotope ratio mass spectrometry (GC-Py-GC-C-IRMS) combined with headspace solid-phase microextraction (HS-SPME) was used to measure the intramolecular carbon isotope distributions of acetic acid in 14 Japanese vinegars. The results demonstrated that the methyl carbons of acetic acid molecules in vinegars produced from plants were mostly isotopically depleted in (13)C relative to the carboxyl carbon. Moreover, isotopic differences (δ(13)C(carboxyl) - δ(13)C(methyl)) had a wide range from -0.3 to 18.2‰, and these values differed among botanical origins, C3, C4, and CAM plants.

  14. Clumped-isotope thermometry of magnesium carbonates in ultramafic rocks (United States)

    García del Real, Pablo; Maher, Kate; Kluge, Tobias; Bird, Dennis K.; Brown, Gordon E.; John, Cédric M.


    Magnesium carbonate minerals produced by reaction of H2O-CO2 with ultramafic rocks occur in a wide range of paragenetic and tectonic settings and can thus provide insights into a variety of geologic processes, including (1) deposition of ore-grade, massive-vein cryptocrystalline magnesite; (2) formation of hydrous magnesium carbonates in weathering environments; and (3) metamorphic carbonate alteration of ultramafic rocks. However, the application of traditional geochemical and isotopic methods to infer temperatures of mineralization, the nature of mineralizing fluids, and the mechanisms controlling the transformation of dissolved CO2 into magnesium carbonates in these settings is difficult because the fluids are usually not preserved. Clumped-isotope compositions of magnesium carbonates provide a means to determine primary mineralization or (re)equilibration temperature, which permits the reconstruction of geologic processes that govern magnesium carbonate formation. We first provide an evaluation of the acid fractionation correction for magnesium carbonates using synthetic magnesite and hydromagnesite, along with natural metamorphic magnesite and low-temperature hydromagnesite precipitated within a mine adit. We show that the acid fractionation correction for magnesium carbonates is virtually indistinguishable from other carbonate acid fractionation corrections given current mass spectrometer resolution and error. In addition, we employ carbonate clumped-isotope thermometry on natural magnesium carbonates from various geologic environments and tectonic settings. Cryptocrystalline magnesite vein deposits from California (Red Mountain magnesite mine), Austria (Kraubath locality), Turkey (Tutluca mine, Eskişehir district) and Iran (Derakht-Senjed deposit) exhibit broadly uniform Δ47 compositions that yield apparent clumped-isotope temperatures that average 23.7 ± 5.0 °C. Based on oxygen isotope thermometry, these clumped-isotope temperatures suggest

  15. Assessment of pollution aerosols sources above the Straits of Dover using lead isotope geochemistry. (United States)

    Deboudt, K; Flament, P; Weis, D; Mennessier, J P; Maquinghen, P


    We assess the capability of lead isotopes to study the transport of pollution aerosols above the Straits of Dover by collecting atmospheric aerosols above the Eastern Channel and the Southern Bight of the North Sea. During the same period, we characterized the lead isotopic signature of the main industrial sources on the French coast near the Straits of Dover. Urban and automobile-derived aerosols were also collected. Due to the phasing out of lead in gasoline, the urban isotopic composition (206Pb/207Pb = 1.158 +/- 0.003) has become more radiogenic, although it is highly variable. On a regional scale, major industrial emissions have a well-defined isotopic composition (1.13 isotopic compositions, it can be shown that lead aerosols originating from eastern Europe have an isotopic signature (1.145 isotopic composition of west-European lead aerosols (1.111 < 206Pb/207Pb < 1.142). The influence of remote North American sources is suggested, with caution, due to uncertainties in meteorological calculations.

  16. Carbon isotopes in otolith amino acids identify residency of juvenile snapper (Family: Lutjanidae) in coastal nurseries (United States)

    McMahon, K. W.; Berumen, M. L.; Mateo, I.; Elsdon, T. S.; Thorrold, S. R.


    This study explored the potential for otolith geochemistry in snapper (Family: Lutjanidae) to identify residency in juvenile nursery habitats with distinctive carbon isotope values. Conventional bulk otolith and muscle stable isotope analyses (SIA) and essential amino acid (AA) SIA were conducted on snapper collected from seagrass beds, mangroves, and coral reefs in the Red Sea, Caribbean Sea, and Pacific coast of Panama. While bulk stable isotope values in otoliths showed regional differences, they failed to distinguish nursery residence on local scales. Essential AA δ13C values in otoliths, on the other hand, varied as a function of habitat type and provided a better tracer of residence in different juvenile nursery habitats than conventional bulk otolith SIA alone. A strong linear relationship was found between paired otolith and muscle essential AA δ13C values regardless of species, geographic region, or habitat type, indicating that otolith AAs recorded the same dietary information as muscle AAs. Juvenile snapper in the Red Sea sheltered in mangroves but fed in seagrass beds, while snapper from the Caribbean Sea and Pacific coast of Panama showed greater reliance on mangrove-derived carbon. Furthermore, compound-specific SIA revealed that microbially recycled detrital carbon, not water-column-based new phytoplankton carbon, was the primary carbon source supporting snapper production on coastal reefs of the Red Sea. This study presented robust tracers of juvenile nursery residence that will be crucial for reconstructing ontogenetic migration patterns of fishes among coastal wetlands and coral reefs. This information is key to determining the importance of nursery habitats to coral reef fish populations and will provide valuable scientific support for the design of networked marine-protected areas.

  17. Carbon isotopes in otolith amino acids identify residency of juvenile snapper (Family: Lutjanidae) in coastal nurseries

    KAUST Repository

    McMahon, Kelton


    This study explored the potential for otolith geochemistry in snapper (Family: Lutjanidae) to identify residency in juvenile nursery habitats with distinctive carbon isotope values. Conventional bulk otolith and muscle stable isotope analyses (SIA) and essential amino acid (AA) SIA were conducted on snapper collected from seagrass beds, mangroves, and coral reefs in the Red Sea, Caribbean Sea, and Pacific coast of Panama. While bulk stable isotope values in otoliths showed regional differences, they failed to distinguish nursery residence on local scales. Essential AA δ13C values in otoliths, on the other hand, varied as a function of habitat type and provided a better tracer of residence in different juvenile nursery habitats than conventional bulk otolith SIA alone. A strong linear relationship was found between paired otolith and muscle essential AA δ13C values regardless of species, geographic region, or habitat type, indicating that otolith AAs recorded the same dietary information as muscle AAs. Juvenile snapper in the Red Sea sheltered in mangroves but fed in seagrass beds, while snapper from the Caribbean Sea and Pacific coast of Panama showed greater reliance on mangrove-derived carbon. Furthermore, compound-specific SIA revealed that microbially recycled detrital carbon, not water-column-based new phytoplankton carbon, was the primary carbon source supporting snapper production on coastal reefs of the Red Sea. This study presented robust tracers of juvenile nursery residence that will be crucial for reconstructing ontogenetic migration patterns of fishes among coastal wetlands and coral reefs. This information is key to determining the importance of nursery habitats to coral reef fish populations and will provide valuable scientific support for the design of networked marine-protected areas. © 2011 Springer-Verlag.

  18. Precambrian organic geochemistry - Preservation of the record (United States)

    Hayes, J. M.; Wedeking, K. W.; Kaplan, I. R.


    A review of earlier studies is presented, and new results in Precambrian organic geochemistry are discussed. It is pointed out that two lines of evidence can be developed. One is based on structural organic chemistry, while the other is based on isotopic analyses. In the present investigation, the results of both structural and isotopic investigations of Precambrian organic matter are discussed. Processes and products related to organic geochemistry are examined, taking into account the carbon cycle, an approximate view of the principal pathways of carbon cycling associated with organic matter in the present global ecosystem, processes affecting sedimentary organic matter, and distribution and types of organic matter. Attention is given to chemical fossils in Precambrian sediments, kerogen analyses, the determination of the structural characteristics of kerogen, and data concerning the preservation of the Precambrian organic geochemical record.

  19. Stable isotope geochemistry of calcrete nodules and septarian concretions in a Quaternary 'red clay' paleovertisol from Hungary. (United States)

    Bajnóczi, Bernadett; Horváth, Zoltán; Demény, Attila; Mindszenty, Andrea


    Calcrete nodules and concretions in unusually large amounts are embedded in the Quaternary clay-rich (Vertisol-type) 'red clay' soil-sedimentary complex at the pediment of the Mátra Mountains (Hungary). Stable isotope signatures were studied in nodules and septarian concretions, uncommon due to their several millimeter sized calcite crystals filling voids and fractures, to reveal their origin. The isotope composition of calcrete covers a wide range: delta18O=-5.9 to-10.4 per thousand and delta13C=-8.9 to-12.3 per thousand (vs. V-PDB). Isotope compositions support pedogenic (sensu stricto) and/or shallow groundwater origin for the calcrete nodules and concretions, the role of 'evolved' (isotopically modified) groundwaters in the formation of secondary carbonate was possibly subordinate. Late-stage, large, Mn-rich euhedral calcite crystals in concretions have the lowest delta13C values, which are interpreted as a result of larger contribution of isotopically light organic carbon due to decomposition of organic matter under reducing conditions. Precipitation of late calcite crystals in concretions occurred in early diagenetic environment after shallow burial of the 'red clay' paleovertisol.

  20. Investigation on primary and secondary processes in Nasirabad manganese deposit, south of Neyriz: using mineralogy and Pb isotope geochemistry

    Directory of Open Access Journals (Sweden)

    Ali Reza Zarasvandi


    Full Text Available The Nasirabad manganese deposit is located 5 km south of Nasirabad, 8 km SW of Neyriz in the Fars province. Structurally, the area is placed in the southeastern part of Zagros thrust belt. In this area, the manganese mineralization occurred as ore layers and nodules, interlayered with Pichakun radiolarite chert deposits. In this study, mineralogy and geochemistry of uranium, thorium and lead isotopes were used to investigate the primary and secondary processes. In this way, in addition to petrographic and XRD studies, ICP-MS analysis was carried out in order to measure the U, Th and Pb isotopes. The strong fractionation of Fe and Mn phases and also the absence of Fe-bearing minerals in the XRD results, presence of syngenetic todorokite and quartz crystals, high U/Th ratios in some samples and Th versus U diagrams, all indicate entrance of Mn-bearing hydrothermal fluids into the sedimentary basin of the Nasirabad manganese deposit. The pyrolusites in radiolarites tests as replacement textures, host rock space filling and fracture filling pyrolusites, indicates the influence of secondary exogenic processes on primary hydrothermal mineralization. Non-homogenous 206Pb/Pb204, 207Pb/Pb204 and 208Pb/Pb204 values show non-steady hydrothermal processes in the sedimentary basin and indicate mixing of hydrothermal lead isotopes with another secondary source. Strong positive correlation between absolute values of radiogenic lead isotopes and insoluble High Field Strength Elements (HFSE such as 207Pb vs Nb (r=0.81, 207Pb vs TiO2 (r=0.93, 207Pb vs Th (r=0.79 and strong correlation between these elements and some mafic components like 208Pb vs Fe2O3 (r=0.94 and Th vs MgO (r=0.86 represent entrance of radiogenic lead with mafic detrital materials into the sedimentary basin. Similar linear trend among 206Pb/Pb204 vs 208Pb/Pb204 and 207Pb/Pb204 ratios in nodules and manganese layers show the same geochemical condition in Mn-nodules and layers formation and

  1. Chlorine isotopic geochemistry of salt lakes in the Qaidam Basin, China

    Digital Repository Service at National Institute of Oceanography (India)

    Liu, W.G.; Xiao, Y.K.; Wang, Q.Z.; Qi, H.P.; Wang, Y.H.; Zhou, Y.M.; Shirodkar, P.V.

    and halite precipitation and with the hydrochemistry of the input water. The chlorine isotopic composition may reflect the degree of evaporation of the salt lake brine and may be used to distinguish brine that are in equilibrium with precipitating salts...

  2. Carbon isotopic characteristics of hydrocarbon gases from coal-measure source rocks--A thermal simulation experiment

    Institute of Scientific and Technical Information of China (English)

    ZHENG Jianjing; HU Huifang; SUN Guoqiang; JI Limin


    Gaseous hydrocarbon geochemistry research through a thermal simulation experiment in combination with the natural evolution process in which natural gases were formed from coal-measure source rocks revealed that the δ13C1 values of methane vary from light to heavy along with the increase of thermal evolution degree of coal-measure source rocks, and the δ13C2 values of ethane range from -28.3‰ to -20‰ (PDB). δ13C2 value was -28‰± ( Ro= 0.45% - 0.65%) at the lower thermal evolution stage of coal-measure source rocks. After the rocks entered the main hydrocarbon-generating stage (Ro=0.65% - 1.50%), δ13C2 values generally varied within the range of -26‰ - -23‰±; with further thermal evolution of the rocks the carbon isotopes of ethane became heavier and heavier, but generally less than - 20‰.The partial carbon isotope sequence inversion of hydrogen gases is a characteristic feature of mixing of natural gases of different origins. Under the condition of specially designated type of organic matter, hydrogen source rocks may show this phenomenon via their own evolution.In the lower evolution stages of the rocks, it is mainly determined by organic precursors that gaseous hydrocarbons display partial inversion of the carbon isotope sequence and the carbon isotopic values of ethane are relatively low. These characteristic features also are related to the geochemical composition of primary soluble organic matter.

  3. Rb-Sr and Nd-Sr isotope geochemistry and petrogenesis of the Misho Mountains mafic dikes (NW Iran

    Directory of Open Access Journals (Sweden)

    Maryam Ahankoub


    Full Text Available Introduction There are some theories about the Paleotethys event during the Paleozoic that have been proposed by geologists (Metcalfe, 2006. Some scientist offered some pieces of evidence about the northern margin of Gondwana (Zhu et al., 2010. The Paleotethys Ocean and Hercynian orogenic report first in Iran, have been Offered from the Morrow and Misho Mountain (Eftekharnejad, 1981. Misho Mountains is located between the north and south Misho faults and cause the formation of a positive flower structure (Moayyed and Hossainzade, 2011. There is theory about Misho southern fault as the best candidate of the Paleotethys suture zone (Moayyed and Hossainzade, 2011. Geochemistry and Sr –Nd isotopic data of the A2 granitic and Synite rocks of the East Misho, indicate that the magmatism post collision has occurred in the active continental margin by extensional zones of the following the closure of the Paleotethys (Ahankoub, 2012. Granite and syenite rocks have been cut by mafic dikes. Mafic dikes are often formed in extensional tectonic settings related to mantle plume or continental break –up (Zhu et al., 2009. In this paper, we use the geochemistry and Nd-Sr isotope data to determined petrogenesis, tectono-magmatic setting and age of Misho mafic dikes. Materials and methods After petrography study of 30 thin sections of mafic dike rocks, 8 samples were selected for whole-rock chemical analyses using ICP-MS and ICP-AES instruments by ACME Company in Vancouver, Canada. We prepared 6 sample For Sm-Nd and Rb-Sr analysis. Sr and Nd isotope ratios were measured with a thermal ionization mass spectrometer, VG Sector 54–30 at the Nagoya University. The isotope abundances of Rb, Sr, Nd, and Sm were measured by the ID method with a Finnigan MAT Thermoquad THQ thermal ionization quadrupole mass spectrometer at the Nagoya University. NBS987 and JNdi-1 were measured as natural Sr and Nd isotope ratio standards (Tanaka et al., 2000. Averages and 2σ errors


    The measurement of stable isotope ratios of carbon (d13C values) was investigated as a viable technique to monitor the intrinsic bioremediation of polycyclic aromatic hydrocarbons (PAHs). Biometer-flask experiments were conducted in which the bacterium, Sphingomonas paucimobilis,...

  5. Microbial sulfur metabolism evidenced from pore fluid isotope geochemistry at Site U1385 (United States)

    Turchyn, Alexandra V.; Antler, Gilad; Byrne, David; Miller, Madeline; Hodell, David A.


    At Site U1385, drilled during IODP Expedition 339 off the coast of Portugal on the continental slope, high-resolution sulfate concentration measurements in the pore fluids display non-steady-state behavior. At this site there is a zone of sulfate reduction in the uppermost seven meters of sediment, followed by a 38-meter interval where sulfate concentrations do not change, and finally sulfate concentrations are depleted to zero between 45 and 55 meters below seafloor. Below the sulfate minimum zone, there is abundant methane, suggesting that the lower sulfate consumption zone is coupled to anaerobic methane oxidation. We analyze pore water samples from IODP Site U1385 for sulfur and oxygen isotope ratios of dissolved sulfate, as well as the sulfur isotope composition of sedimentary pyrite. The sulfur isotopes in pore fluid sulfate display similar non-steady-state behavior similar to that of the sulfate concentrations, increasing over the uppermost zone of sulfate reduction and again over the lower zone of sulfate-driven anaerobic methane oxidation. The oxygen isotopes in sulfate increase to the 'apparent equilibrium' value in the uppermost zone of sulfate reduction and do not change further. Our calculations support the idea that sulfite to sulfide reduction is the limiting step in microbial sulfate reduction, and that the isotope fractionation expressed in the residual pore water sulfate pool is inversely proportional to the net sulfate reduction rate. The sulfur isotope composition of pyrite acquires one value in the uppermost sediments, which may be overprinted by a second value in the deeper sediments, possibly due to iron release during anaerobic methane oxidation or iron diffusion from a higher zone of bacterial iron reduction. Our results have implications for modeling the sulfur isotope composition of the pyrite burial flux in the global biogeochemical sulfur cycle.

  6. CCQM-K140: carbon stable isotope ratio delta values in honey (United States)

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


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

  7. Variation of stable silicon isotopes. Analytical developments and applications in Precambrian geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Abraham, Kathrin


    The work presented in this thesis predominantly deals with bulk-rock measurements of silicon stable isotopes on a Multi Collector-ICP-MS. Analyses were performed in cooperation with the Royal Museum for Central Africa, Belgium. The first section describes how the first analysis of δ{sup 30}Si on a conventional Nu PlasmaTM Multi-Collector ICP-MS instrument can be enabled by the elimination of 14N16O interference overlying the 30Si peak. The determination of δ{sup 30}Si was rendered possible owing to new instrumental upgrades that facilitate the application of a higher mass resolution. The careful characterisation of appropriate reference materials is indispensable for the assessment of the accuracy of a measurement. The determination of U.S. Geological Survey (USGS) reference materials represents the second objective of this section. The analysis of two Hawaiian standards (BHVO-1 and BHVO-2) demonstrates precise and accurate δ{sup 30}Si determinations and provides cross-calibration data as a quality control for other laboratories. The second section focuses on coupled silicon-oxygen isotopic evidences for the origin of silicification in mafic volcanic rocks of the Barberton Greenstone Belt, South Africa. In contrast to the modern Earth, silicification of near-surface layers, including chert formation, were widespread processes on the Precambrian ocean floor, and demonstrate the ubiquity of extreme silica mobilization in the early Earth. This section outlines the investigation of silicon and oxygen isotopes on three different stratigraphic sections of variably silicified basalts and overlying bedded cherts from the 3.54 Ga, 3.45 Ga and 3.33 Ga Theespruit, Kromberg and Hooggenoeg Formations, respectively. Silicon isotopes, oxygen isotopes and the variable SiO{sub 2}-contents demonstrate a positive correlation with silicification intensity in all three sections, with varying gradients of δ{sup 30}Si vs. δ{sup 18}O arrays for different sections. Seawater has been

  8. Mineral chemistry and isotope geochemistry of pyrite from the Heilangou gold deposit, Jiaodong Peninsula, Eastern China

    Institute of Scientific and Technical Information of China (English)

    Yutong Yan; Na Zhang; Shengrong Li; Yongsheng Li


    The Heilangou gold deposit is located in the northern QixiaePenglai gold belt, which is one amongst the three large gold belts in the eastern Shandong Province (Jiaodong Peninsula). The ore body has formed within the Guojialing granite. In this study, we report the mineral chemistry of pyrite, as well as the S, Pb, and HeO isotope data of the Heilangou gold deposit. The chemical composition of pyrite in the Heilangou gold deposit indicates that the associated gold deposit is a typical magmatic hydrothermal one. The geochemical signatures and crystal structure of pyrite show that the ore-forming materials have been derived from the crust. The S isotope data of the pyrites from Heilangou show an overall range from 5.5 to 7.8&and an average of 6.7&. The S isotope data in this deposit are similar to those from the deposits in the Jiaodong gold belt. The Pb and S isotope variations are small in the Heilangou gold deposit. The 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios are 17.4653e17.5958, 15.5105e15.5746 and 38.0749e38.4361, respec-tively. These data plot between the lower crust and the orogenic belt. The Pb isotope data in the Heilangou gold deposit are similar to those in the Linglong gold deposit. From the Qixia gold area (the Liukou and Majiayao gold deposits) to the MupingeRushan gold belt (Rushan gold deposit) to the ZhaoeYe gold belt (the Linglong, Sanshandao and Jiaojia gold deposits), the 206Pb/204Pb ratios progressively increase. The DeO isotope data obtained from quartz separates suggest that the ore-forming fluid was similar to a mixture of magmatic and meteoric waters. These results suggest that the ore-forming elements were primarily from source fluids derived from the lower crust.

  9. Petrogenesis and origin of modern Ethiopian rift basalts: Constraints from isotope and trace element geochemistry (United States)

    Ayalew, D.; Jung, S.; Romer, R. L.; Kersten, F.; Pfänder, J. A.; Garbe-Schönberg, D.


    The source of continental rift-related basalts and their relation to rifting processes is a continuous matter of debate. We present major and trace element and Sr, Nd, Hf and Pb isotope data for axial rift basalts from eight volcanic centres (Ayelu, Hertali, Dofan, Fantale, Kone, Bosetti and Gedemsa, from NE to SW) in Afar and Main Ethiopian Rift (MER) to assess their source regions and their genetic relationships. These lavas have geochemical characteristics, i.e., a peak at Ba, Nb and troughs at K and Rb in primitive mantle-normalised multielement diagrams, which are consistent with predominant melting of an amphibole-bearing lithospheric mantle. However, the isotopic compositions for these lavas are heterogeneous (87Sr/86Sr = 0.70354-0.70431, 143Nd/144Nd = 0.51280-0.51294, 176Hf/177Hf = 0.28301-0.28315, 206Pb/204Pb = 18.48-19.31, 207Pb/204Pb = 15.53-15.62, 208Pb/204Pb = 38.61-39.06) and require various mantle reservoirs with distinctive isotopic signatures. The range of isotopic compositions requires the involvement of three distinct source components from the asthenospheric and veined lithospheric mantle. Progressive rifting leads to lithosperic thinning and upwelling of hot asthenospheric mantle, which induces melting of the veined lithospheric mantle. The trace element characteristics of the lavas are dominated by the vein material, which has a higher trace element content than the surrounding mantle. The isotopic composition of the vein material, however, is not very different from the ambient mantle, giving rise of apparent uncoupling of trace element and isotope constraints for the melt source. The uprising basaltic liquids in part inherit a lithospheric trace element signature, while their isotopic compositions are mostly unaffected due to short residence times within the lithosphere in context with progressive rifting and lithospheric thinning. Thus, the geochemical and isotope data are consistent with a multi-component source prevailing beneath the Afar

  10. Sm-Nd isotope geochemistry and U/Pb geochronological data of the Campina Grande complex, Paraiba State, NE Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Almeida, C.N. [Pernambuco Univ., Recife, PE (Brazil). Pos-Graduacao em Geociencias; Guimaraes, I.P.; Silva Filho, A.F. da [Pernambuco Univ., Recife, PE (Brazil). Dept. de Geologia; Beurlen, H. [Pernambuco Univ., Recife, PE (Brazil). Dept. de Engenharia de Minas


    The Campina Grande Complex (CCG) constitutes a 250 Km{sup 2} intrusion within the high grade gneiss-migmatitic terrain, in the contact zone between the Mesoproterozoic Pajeu-Paraiba Fold Belt and the Archean Caldas Brandao Massif of the Borborema Province, NE Brazil. The contact of the complex is made by the Guarabira Shear Zone (west) and the Campina Grande Shear Zone in the south. The CCG is composed of coarse grained porphyritic quartz-monzonites, quartz-monzodiorites and medium grained porphyritic granodiorites. Mafic enclaves are common and show composition ranging from diorites to quartz diorites. Field and petrographic features point out to magma mixing and mingling processes involved in the CCG evolution. Basalts of probably Cretaceous age occur as dykes cutting in the CCG. This work presents and discusses the Sm-Nd isotope geochemistry of the CCG and a gabro which occur very close to the south contact of the CCG. This also presents the U/Pb in zircon geochronological data for the CCG. (author) 4 refs., 2 figs.

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

    Romanek, C.


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

  12. Chlorine isotope geochemistry of Icelandic thermal fluids: Implications for geothermal system behavior at divergent plate boundaries (United States)

    Stefánsson, Andri; Barnes, Jaime D.


    The chlorine isotope composition of thermal fluids from Iceland were measured in order to evaluate the source of chlorine and possible chlorine isotope fractionation in geothermal systems at divergent plate boundaries. The geothermal systems studied have a wide range of reservoir temperatures from 40 to 437 °C and in-situ pH of 6.15 to 7.15. Chlorine concentrations range from 5.2 to 171 ppm and δ37 Cl values are -0.3 to + 2.1 ‰ (n = 38). The δ37 Cl values of the thermal fluids are interpreted to reflect the source of the chlorine in the fluids. Geothermal processes such as secondary mineral formation, aqueous and vapor speciation and boiling were found to have minimal effects on the δ37 Cl values. However, further work is needed on incorporation of Cl into secondary minerals and its effect on Cl isotope fractionation. Results of isotope geochemical modeling demonstrate that the range of δ37 Cl values documented in the natural thermal fluids can be explained by leaching of the basaltic rocks by meteoric source water under geothermal conditions. Magmatic gas partitioning may also contribute to the source of Cl in some cases. The range of δ37 Cl values of the fluids result mainly from the large range of δ37 Cl values observed for Icelandic basalts, which range from -0.6 to + 1.2 ‰.

  13. The Use of Lead Isotope and Rare Earth Element Geochemistry for Forensic Geographic Provenancing (United States)

    Carey, A.; Darrah, T.; Harrold, Z.; Prutsman-Pfeiffer, J.; Poreda, R.


    Lead isotope and rare earth element composition of modern human bones are analyzed to explore their utility for geographical provenancing. DNA analysis is the standard for identification of individuals. DNA analysis requires a DNA match for comparison. Thus, DNA analysis is of limited use in cases involving unknown remains. Trace elements are incorporated into bones and teeth during biomineralization, recording the characteristics of an individual's geochemical environment. Teeth form during adolescence, recording the geochemical environment of an individual's youth. Bones remodel throughout an individual's lifetime. Bones consist of two types of bone tissue (cortical and trabecular) that remodel at different rates, recording the geochemical environment at the time of biomineralization. Cortical bone tissue, forming the outer surface of bones, is dense, hard tissue that remodels in 25-30 yrs. Conversely, trabecular bone tissue, the inner cavity of bones, is low density, porous and remodels in 2-5 years. Thus, analyzing teeth and both bone tissues allows for the development of a geographical time line capable of tracking immigration patterns through time instead of only an individual's youth. Geochemical isotopic techniques (Sr, O, C, N) have been used for geographical provenancing in physical anthropology. The isotopic values of Sr, C, O, N are predominantly a function of soil compositions in areas where food is grown or water is consumed. Application of these provenancing techniques has become difficult as an individual's diet may reflect the isotopic composition of foods obtained at the local grocer as opposed to local soil compositions. Thus, we explore the use of REEs and Pb isotopes for geographical provenancing. Pb and REEs are likely more reliable indicators of modern geographical location as their composition are high in bio-available sources such as local soils, atmospheric aerosols, and dust as opposed to Sr, C, O, N that are controlled by food and

  14. Isotopic and trace element geochemistry of alkalic-mafic-ultramafic-carbonatitic complexes and flood basalts in NE India: Origin in a heterogeneous Kerguelen plume (United States)

    Ghatak, Arundhuti; Basu, Asish R.


    , nephelinites, sovites, melteigite in the first group and syenites and ijolites in the second. The Nd-Sr-Pb-isotopic and trace element geochemistry of the first group of carbonatitic-ultrabasic rocks are consistent with similar data of the RBST lavas of the present and previous studies, and are modeled as derived from a relatively primitive carbonated garnet peridotite source in the KP. In contrast, the syenites and ijolites of the second group show a wide range of Nd-Sr-Pb isotopic compositions, modeled by low-degree melts of an ancient recycled carbonated eclogite also in the KP. The KP thus reflects heterogeneities in the lower mantle-derived plume with carbonated components yielding ultrabasic melts at greater depths with low-degree melting, followed by rise of the plume at shallower depths causing tholeiitic flood basalt volcanism. Collectively, these data imply a zone of influence of the plate-motion-reconstructed KP head for ˜1000 km around the Bengal Basin, as represented by the widely scattered and diverse rock types of the RBST.

  15. Cu isotope geochemistry of volcanogenic massive sulphide deposits of the eastern Pontides, Turkey

    Energy Technology Data Exchange (ETDEWEB)

    Housh, T B [Department of Geological Sciences, University of Texas at Austin, 1 University Station C1100, Austin, TX 78712 (United States); Ciftci, E [Department of Geological Engineering, Nigde University, 51245 Nigde (Turkey)], E-mail:


    A large number of volcanogenic massive sulfide (VMS) deposits are associated with Late Cretaceous to Eocene arc-like volcanic rocks in the eastern Pontides of NE Turkey. Cu isotope studies on thirteen VMS and two vein deposits were undertaken to examine the nature of copper isotope variations and to compare these with other VMS and black smoker deposits. {phi}{sup 65}Cu of chalcopyrite from these deposits range between +0.34 and -0.62 per mille . Chalcopyrite from the VMS deposits of the eastern Pontides have a mean {phi}{sup 65}Cu = -0.13 per mille . {phi}{sup 65}Cu of chalcopyrite is generally heavier than that of corresponding bornite. The range of {phi}{sup 65}Cu for chalcopyrite from VMS deposits in the eastern Pontides is larger than that observed from Alexandrinka, a Devonian VMS deposit in the southern Urals, but is significantly smaller than the up to 3 per mille variations observed from individual modern sea-floor hydrothermal fields along modern mid-ocean ridges. The range of Cu isotope variation in VMS deposits from the eastern Pontides is interpreted to result from processes related to both oxidation and leaching of previously deposited copper by seawater and to its subsequent deposition elsewhere in the hydrothermal system.

  16. Carbon isotopic studies of organic matter in Precambrian rocks. (United States)

    Oehler, D. Z.; Schopf, J. W.; Kvenvolden, K. A.


    A survey has been undertaken of the carbon composition of the total organic fraction of a suite of Precambrian sediments to detect isotopic trends possibly correlative with early evolutionary events. Early Precambrian cherts of the Fig Tree and upper and middle Onverwacht groups of South Africa were examined for this purpose. Reduced carbon in these cherts was found to be isotopically similar to photosynthetically produced organic matter of younger geological age. Reduced carbon in lower Onverwacht cherts was found to be anomalously heavy; it is suggested that this discontinuity may reflect a major event in biological evolution.

  17. Geochemistry and mineralogy of the carbonates of the Creede mining district, Colorado (United States)

    Wetlaufer, Pamela Heald


    hematite) followed by (3) low-calcium siderite deposition without hematite. The composition of the high-calcium siderite lies well outside of the recognized stability field for siderite at 250?C and, therefore, is considered either a metastable phase or possibly a new mineral. Carbon and oxygen isotopic compositions of the carbonates together with the hydrogen isotopic composition of inclusion fluids suggest that the fluids depositing the carbonates either were deep-seated in origin, or, less likely, were meteoric waters which came in contact with a large volume of magmatic rock with which it exchanged isotopes. The oxygen and hydrogen isotopic compositions of the fluids that deposited the carbonates are significantly different from those that yielded the other vein minerals (sphalerite, chlorite, sericite, quartz, adularla). The latter minerals appear to-have been deposited from two distinctive fluids of meteoric origin. The stability fields of minerals present during the carbonate stages have been calculated for 250?Co The results indicate that conditions during carbonate deposition were not drastically different from those suggested by Barton and others (1977) for main-stage ore deposition, although little ore, if any, was deposited during the carbonate stages. A new value for the free energy of formation of siderite was calculated since all of the most recently published values predict too small a stability field for the siderite based on the occurrence of siderite at Creede, The change to the more iron-rich composition of the later stage carbonate was probably controlled by the pyrite-chlorite buffer which was not present during early-stage carbonate deposition.

  18. Carbon isotopic study of individual alcohol compounds in modern sediments from Nansha Islands sea area, China

    Institute of Scientific and Technical Information of China (English)

    段毅; 文启彬; 郑国东; 罗斌杰


    Carbon isotopic compositions of individual n-alkanols and sterols in modern sediments from the Nan-sha Islands sea area are measured after derivatization to trimethylsilyl ethers by the new isotopic analytical technique of GC/C/IRMS. The effects of the three added silyl carbon atoms in every alcohol molecule on these compound isotopic compositions and the characteristics of their carbon isotopic compositions are studied. Then their biological sources are discussed using their carbon isotopic compositions.

  19. 江西省兴源冲铜矿床同位素地球化学特征及成矿机制探讨%Carbon, oxygen and sulfur isotopic geochemistry and metallogenic mechanism of Xingyuanchong copper deposit in Jiangxi Province

    Institute of Scientific and Technical Information of China (English)

    刘婷; 刘成东; 严兆彬; 陈益平; 吴旭铃; 凡秀君


    The Xingyuanchong copper deposit of Huangmao area is located in the west segment of the South Jiuling large copper polymetallic ore concentration area.In combination with the metallogenic characteristics of the ore deposit,the authors mainly studied stable isotopes of the ores to probe into the sources of metallogenic materials and metallogenic mechanism of the deposit.δ13 CVPDB values of carbonates in this area vary in the range of -5.4‰~1.9‰,0.6‰ on average,whereas δ18OsMow values range from 9.0‰ to 13.8‰,10.9‰ on average,indicating that carbonates were mainly marine carbonates.The δ18O-δ13C diagram shows that carbon in the region probably came from the deep earth,and experienced metamorphism at high temperatures and alteration at low temperatures.Except two higher values of δ34S,most δ34S values in this deposit vary in the range of 1.0‰ ~6.2‰ ; in comparison with other similar deposits,sulfur of this deposit is characterized by submarine exhalation sedimentation and hydrothermal superimposition.In combination with isotopic data and geological setting,it is proposed that the ore-forming processes of the Xingyuanchong copper deposit could be divided into two stages.At the first stage,submarine volcanic sediments or protore layers were formed in Mesoproterozoic.At the second stage,the pre-existing protores were altered by the hydrothermal fluids and dynamic metamorphism mainly derived from Jinning orogenic period in Late Proterozoic.%兴源冲铜矿床地处九岭南缘铜多金属大型矿集区西段的黄茅地区.文章在成矿地质特征的基础上,通过对矿石进行稳定同位素地球化学研究,重点分析了成矿物质来源,探讨了矿床成矿机制.碳、氧同位素分析结果表明,矿区碳酸盐岩δ13 CVPDB为-5.4‰~ 1.9‰,平均为0.6‰,δ18 OSMOW变化范围为9.0‰~13.9‰,平均为10.9‰,主要为海相碳酸盐岩,碳、氧同位素图解表明碳可能主要来源于深部,且受高温变质作

  20. Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism. (United States)

    Kaufman, A J; Hayes, J M; Knoll, A H; Germs, G J


    The carbon isotope geochemistry of carbonates and organic carbon in the late Proterozoic Damara Supergroup of Namibia, including the Nama, Witvlei, and Gariep groups on the Kalahari Craton and the Mulden and Otavi groups on the Congo Craton, has been investigated as an extension of previous studies of secular variations in the isotopic composition of late Proterozoic seawater. Subsamples of microspar and dolomicrospar were determined, through petrographic and cathodoluminescence examination, to represent the "least-altered" portions of the rock. Carbon-isotopic abundances in these phases are nearly equal to those in total carbonate, suggesting that 13C abundances of late Proterozoic fine-grained carbonates have not been significantly altered by meteoric diagenesis, although 18O abundances often differ significantly. Reduced and variable carbon-isotopic differences between carbonates and organic carbon in these sediments indicate that isotopic compositions of organic carbon have been altered significantly by thermal and deformational processes, likely associated with the Pan-African Orogeny. Distinctive stratigraphic patterns of secular variation, similar to those noted in other, widely separated late Proterozoic basins, are found in carbon-isotopic compositions of carbonates from the Nama and Otavi groups. For example, in Nama Group carbonates delta 13C values rise dramatically from -4 to +5% within a short stratigraphic interval. This excursion suggests correlation with similar excursions noted in Ediacaran-aged successions of Siberia, India, and China. Enrichment of 13C (delta 13C> +5%) in Otavi Group carbonates reflects those in Upper Riphean successions of the Akademikerbreen Group, Svalbard, its correlatives in East Greenland, and the Shaler Group, northwest Canada. The widespread distribution of successions with comparable isotopic signatures supports hypotheses that variations in delta 13C reflect global changes in the isotopic composition of late

  1. Applications of isotope geochemistry to the reconstruction of Yucca Mountain, Nevada, paleohydrology -- Status of investigations: June 1996

    Energy Technology Data Exchange (ETDEWEB)

    Whelan, J.F.; Moscati, R.J.; Allerton, S.B.M.; Marshall, B.D.


    Tunneling of the Exploratory Studies Facility has offered the opportunity to sample and examine occurrences of secondary mineralization found in the unsaturated-zone tuffs of Yucca Mountain, nevada. Petrographic and paragenetic analyses, calcite and silica-phase stable isotopic analyses, and preliminary strontium tracer isotope and radiocarbon age analyses of these samples indicate that (1) an early stage of secondary mineralization consisting largely of chalcedony and quartz, but possibly with or slightly preceded by calcite, probably formed at warmer than ambient temperatures; (2) later secondary mineralization consisting of calcite and opal appears completely consistent with formation from percolation of surface infiltration whose solute load and carbon isotopic compositions reflect passage through the overlying soils; (3) based on textural studies, all unsaturated-zone secondary mineral occurrences exposed within the Exploratory Studies Facility tunnel, with the exception of the vapor-phase assemblages that formed at high temperatures during cooling of the tuffs, probably formed in unsaturated settings; and (4) calcite radiocarbon ages, based on preliminary results, have not been compromised by post-depositional exchange with carbon-bearing water and gases in the unsaturated zone.

  2. Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study (United States)

    Warwick, Peter; Ruppert, Leslie F.


    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 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

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

    Indian Academy of Sciences (India)

    S Banerjee; S K Bhattacharya; S Sarkar


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

  4. Petrogenesis of Paleoproterozoic Luyashan charnockitic rocks in Shanxi Province: Constraints from Geochemistry and Nd isotope

    Institute of Scientific and Technical Information of China (English)


    Luyashan charnockite pluton mainly consists of monzonite, adamellite, charnockite and syenogranite, which are characterized by the enrichment of TiO2, P2O5, K2O, Zr, Nb, Y, Pb, La, Ce, Ba and a higher K2O/Na2O and depletion of MgO, CaO,Mg#, Th, U and lower Sr/Ba and Rb/Ba. The negative correlations between Zr, Nb, Ce and SiO2 are distinct from Ⅰ-type granites. Isotopically Luyashan charnockite plutons are relatively uniform in Nd isotope, displaying initial εNd( t ) ( - 5.93 to - 6.97) and Nd depleted mantle model ages (2.67 Ga to 2.78 Ga). These features indicate that Luyashan charnockitic magma derived from pre-existing late Archean crustal sources and the partial melting of mafic granulites probably under exceptionally high temperature with CO2-rich fluid. The garnet is a main residual phase during the partial melting. The original dry charnockitic magma experienced crystal fractionation of pyroxene, plagioclase, apatite and ilmenite during early crystallization. The geochemical evidence suggests that the Luyashan charnockitic magma was probably generated in the post-collision thermal relaxation and uplift tectonic setting after the main collision ( - 1850 Ma) between the Eastern and Western continental blocks.

  5. Geochemistry of trace elements and Sr- Nd isotopes of foraminifera shell from the Okinawa Trough

    Institute of Scientific and Technical Information of China (English)


    Trace elemental associations and Sr - Nd isotopic compositions are of important to recognition of biogenic material from mixed marine sediments. The foraminifera shell from the Okinawa Trough strongly enrichesSr, P, Mn andBa, enriches Li, U, Th, Sc, Co, Cu, Pb, Zn, Cr, Rb, Y, Sb and light rare earth elements, slightly enriches V, Ga, Zr, Nb, Cd and middle rare earth elements,is short of Mo, In, Sn, Cs, Hf, Ta, W, Ti, Bi and heavy rare earth elements. The mechanism of elemental enrichment in forminifera is the concentrations of trace elements in sea water and selective absorption of trace elements during foraminifera living, as well as the geochemical affinity between major elements and trace elements. The REE (rare earth elements) partition pattern of foraminifera shell of the Okinawa Trough shows enrichment of middle rare earth elements with slightly negative Ce anomaly,which are different from those of foraminifera of the Pacific Ocean. The Sr, Nd isotopic ratios of the Okinawa Trough foraminifera are 0.709 769 and 0.512 162, respectively, which are different not only from those of oceanic water, but also from those of river water of China's Mainland, the former is slightly higher than those of oceanic water, but much lower than those of river water; the latter is slightly lower than those of oceanic water, but higher than those of river water, demonstrating that the Okinawa Trough sea water has been influenced by river water of China's Mainland.

  6. Mineralogy, Geochemistry and Stable Isotope Studies of the Dopolan Bauxite Deposit, Zagros Mountain, Iran

    Directory of Open Access Journals (Sweden)

    Somayeh Salamab Ellahi


    Full Text Available The Dopolan deposit is a Mediterranean-type bauxite located in the Zagros Fold-Thrust Zone, Iran. This deposit consists of five lithological members including iron-rich, clay-rich, oolitic, pisolitic and organic matter-containing bauxites. The mineralogy of the deposit includes diaspore, boehmite, and kaolinite, nacrite, with minor pyrite, anatase and rutile. Geochemical studies show that light rare earth elements (LREEs are enriched relative to heavy rare earth elements (HREEs in all members, supporting an authigenic origin. Mass changes based on Ti as an immobile element indicate that conventionally-immobile elements (Al, Nb, Ta, Zr, Hf are enriched in situ in the residual units, whereas mobile elements (K, Ca, Si were depleted during bauxitization. This study shows that the Khaneh–Kat argillitic dolomite is the likely parent rock. The δ18O (7.63‰to 9.35‰ and D values (49.91‰to 66.49‰ for kaolinite in the bauxite samples suggest equilibration with meteoric waters which supports a supergene origin. Bauxitization occurred in a warm climate with relatively constant isotopic composition suggesting climate stability during the development of bauxite horizons and remobilization of Al (with formation of secondary boehmite. The δ13C values of calcite (7.3‰ in the bauxite support the idea that the Khaneh–Kat Formation has experienced post-depositional isotope exchange with meteoric waters during the karstification process.

  7. Magnesian anorthosites from the western highlands of the Moon: Isotope geochemistry and petrogenesis (United States)

    Snyder, Gregory A.; Taylor, Lawrence A.; Halliday, Alex N.


    Breccias from the Apollo 14 landing site have provided a wealth of information on the genesis of the lunar highlands. Various pristine rock-types have been discovered in relative abundance including rare ferroan anorthosites and alkali-suite and magnesian-suite rocks. Mineral-chemical and radiogenic isotopic data are reported here for a newly discovered Mg-suite anorthosite from Apollo 14, sample 14303,347. Meyer et al. reported U-Pb zircon analyses of Mg-suite highlands rocks from the western limb of the Moon. We have compiled these ages and generated a weighted average age of 4211 = 6 Ma; some 200 Ma younger than ferroan anorthosites. Utilizing this age for Mg-anorthosite 14303,347, our data results in an initial epsilon(sub Nd) value of -1.0 and initial Sr-87/Sr-86 of 0.69915. Based on trace-element, isotopic, and mineral-chemical data, the western highlands Mg-suite is interpreted to be crustal precipitates of a picritic magma, which assimilated KREEPy trapped liquid from upper-mantle cumulates during its transport to the crust.

  8. Isotope Geochemistry of Gold Ore Deposits in the Gezhen Shear Zone, Qiongxi, Hainan Island

    Institute of Scientific and Technical Information of China (English)



    Gold deposits hosted in the Gezhen shear zone at Qingxi, Hainan Island occur in the Precambrian metamorphic rock series and are regionally developed in the N-E direction along the tectonic zone. From northeast to southwest are distributed the Tuwaishan-Baoban gold mining district, the Erjia gold mining district and the Bumo gold mining district, making up the most industrially important gold metallogenesis zone on the Hainan Island. Isotope geochemical studies of the typical gold deposits in this metallogenesis zone indicate that their ore-forming materials stemmed largely from the Baoban Group migmatite series, though the involvement of some plutonic materials could not be ruled out. The ore fluids are the mixture of migmatitized hydrothermal solutions and meteoric waters in addition to the involvement of local magmatic hydrothermal solutions. The superimposition of plutonic materials and magmatic hydrothermal solutions is controlled by the deformation environment of the shear zone and later magmatic activities. Obvious variations are noticed in isotopic composition in the region studied, probably related to tectonic deformation, metamorphism and other evolutionary characteristics. This study is of great significance in understanding the relationship between the shear zone and gold metallogenesis, the rules of gold metallogenesis and gold ore prognosis.

  9. Carbon and Oxygen Isotope Ratios in Rona Limestone, Romania

    Directory of Open Access Journals (Sweden)

    Stela Cuna


    Full Text Available The carbon and oxygen isotopic compositions of limestones provide criteria for the evaluation of the depositional environment. For Jurassic and younger samples, the best discrimination between marine and fresh-water limestones is given by Z parameter, calculated as a linear correlation between δ13C and δ18O (‰ PDB. Rona Limestone (Upper Paleocene - Lower Eocene, outcropping on a small area in NW Transylvania (Meseş area is a local lacustrine facies. There, it divides Jibou Formation into the Lower Red Member and the Upper Variegated Member, respectively. Recently, a sequence containing a marine nannoplankton assemblage was identified in the base of Rona deposits. The main goal of our study was to characterize, based on the isotopic record, the primary environment of formation of the deposit, as well as that in which some diagenetic processes (the formation of dolomite and of green clay around the siliceous chert nodules took place. Ten samples representing limestones, dolomitic limestone, marls and the green carbonate-rich clay were studied from petrographical and mineralogical points of view, and the carbon and oxygen isotopic ratios from the carbonate (calcite component were measured. In conclusion, it was found that the procedure of extraction of CO2 we used enabled the discrimination between the isotopic prints of calcite vs. dolomite. This pleads for considering our results as a primary isotopic pattern in the bulk rock. The oxygen and carbon isotope data indicate a fresh-water depositional environment with Z<120. The δ13C mean value (-4.96 ‰ PDB is, generally, representative for fresh-water carbonates of the Tertiary period. The same environment characterized also the formation of carbonates within the green clay.

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


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


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

  11. Stable carbon isotope ratios of ambient aromatic volatile organic compounds (United States)

    Kornilova, Anna; Huang, Lin; Saccon, Marina; Rudolph, Jochen


    Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, ∫ [OH]dt) of the different VOC. It is found that ∫ [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform ∫ [OH]dt for VOC with different reactivity is not justified and that the observed values for ∫ [OH]dt are the result of mixing of VOC from air masses with different values for ∫ [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine ∫ [OH]dt would result in values for ∫ [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform ∫ [OH]dt for an air mass has to be replaced by the concept of individual values of an average ∫ [OH]dt for VOC with different reactivity.

  12. Carbon isotope biogeochemistry of plant resins and derived hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Murray, A.P.; Edwards, D.; Hope, J.M.; Boreham, C.J. [Australian Geological Survey Organisation, Canberra (Australia)] [and others


    Hydrocarbons derived from plant resins are major components of some terrigenous oils and bitumens. These compounds are structurally distinct and this makes then useful biomarkers applicable in petroleum exploration as well as sources of biogeochemical information about palaeoenvironment and palaeobotany. Although recent studies have elucidated the molecular structure of resinites, very little information has been available for the carbon isotope composition of resinites and no studies of resin-derived compounds in oils had been performed prior to the present study. Hence, carbon stable isotope analyses were carried out on a suite of modern and fossil resins of diverse origins, including compound specific isotope analysis of individual hydrocarbons produced during resin pyrolysis. Oils derived from resinite source organic matter were also analysed. The results showed that ``Class I`` resinites derived from gymnosperms were enriched in the heavy carbon isotope compared with those from angiosperms (``Class I`` resinites). Furthermore, both fossil resinites themselves and individual hydrocarbons derived from them were isotopically heavy compared with modern plant resins. The isotopic signatures of diterpanes and triterpanes in various early Tertiary oils from Australasia and Southeast Asia reflect their origins from gymnosperms and angiosperms, respectively. (author)

  13. Detrital zircon geochronology and Nd isotope geochemistry of an early Paleozoic succession in Korea: (United States)

    Lee, Yong Il; Choi, Taejin; Lim, Hyoun Soo; Orihashi, Yuji


    This study reports the results of an analysis of U-Pb ages of detrital zircons and Nd isotope compositions from the well-established lower Paleozoic platform succession developed on the Precambrian gneiss and metasedimentary rocks in South Korea. The three stratigraphic units in the basal part of the succession are the Jangsan, Myeonsan, and Myobong Formations. The unfossiliferous Jangsan (white­to­pink quartz sandstone) and Myeonsan (dark-gray ilmenite-rich sandstone/shale) Formations are in fault contact and are generally considered to be coeval (Early Cambrian). Both formations are also generally considered to be conformably overlain by the dark­ gray, fossiliferous, fine-grained Myobong Formation (late Early-early Middle Cambrian). We here report U-Pb ages of detrital zircons and Nd isotopic data from the Jangsan, Myeonsan, and Myobong Formations. The Jangsan and Myeonsan Formations provide Archean-Paleoproterozoic U-Pb ages, but the former is characterized by Archean Sm-Nd model ages and the latter by late Paleoproterozoic Sm-Nd model ages, which is indicative of a significant change in provenance. This suggests that the Jangsan Formation predates the Myeonsan Formation. The Myobong Formation provides dominantly Meso- to Neoproterozoic U-Pb ages and Sm-Nd model ages that are slightly younger than those of the Myeonsan Formation. Contrary to the conventional wisdom, the combined evidence of unconformable contact and marked changes in zircon U-Pb ages and Nd isotopic compositions suggests that the Myobong Formation overlies the Jangsan and Myeonsan Formations unconformably. Considering the metamorphic age of the immediately underlying Precambrian basement metasediments (0.8 to 0.9 Ga), this stratigraphic relationship strongly suggests that the Jangsan Formation may be Neoproterozoic in age and that the Myeonsan Formation may be latest Neoproterozoic to Early Cambrian and calls for reevaluation of Precambrian-Paleozoic history of the Korean Peninsula. The

  14. Geochemistry and Sr, Nd isotopic composition of the Hronic Upper Paleozoic basic rocks (Western Carpathians, Slovakia) (United States)

    Vozár, Jozef; Spišiak, Ján; Vozárová, Anna; Bazarnik, Jakub; Krái, Ján


    The paper presents new major and trace element and first Sr-Nd isotope data from selected lavas among the Permian basaltic andesite and basalts of the Hronicum Unit and the dolerite dykes cutting mainly the Pennsylvanian strata. The basic rocks are characterized by small to moderate mg# numbers (30 to 54) and high SiO2 contents (51-57 wt. %). Low values of TiO2 (1.07-1.76 wt. %) span the low-Ti basalts. Ti/Y ratios in the dolerite dykes as well as the basaltic andesite and basalt of the 1st eruption phase are close to the recommended boundary 500 between high-Ti and low-Ti basalts. Ti/Y value from the 2nd eruption phase basalt is higher and inclined to the high-Ti basalts. In spite of this fact, in all studied Hronicum basic rocks Fe2O3* is lower than 12 wt. % and Nb/La ratios (0.3-0.6) are low, which is more characteristic of low-Ti basalts. The basic rocks are characterized by Nb/La ratios (0.56 to 0.33), and negative correlations between Nb/La and SiO2, which point to crustal assimilation and fraction crystallization. The intercept for Sr evolution lines of the 1st intrusive phase basalt is closest to the expected extrusions age (about 290 Ma) with an initial 87Sr/86Sr ratio of about 0.7054. Small differences in calculated values ISr document a partial Sr isotopic heterogeneity source (0.70435-0.70566), or possible contamination of the original magma by crustal material. For Nd analyses of the three samples, the calculated values ɛCHUR (285 Ma) are positive (from 1.75 to 3.97) for all samples with only subtle variation. Chemical and isotopic data permit us to assume that the parental magma for the Hronicum basic rocks was generated from an enriched heterogeneous source in the subcontinental lithospheric mantle.

  15. DOE workshop: Sedimentary systems, aqueous and organic geochemistry

    Energy Technology Data Exchange (ETDEWEB)


    A DOE workshop on sedimentary systems, aqueous and organic geochemistry was held July 15-16, 1993 at Lawrence Berkeley Laboratory. Papers were organized into several sections: Fundamental Properties, containing papers on the thermodynamics of brines, minerals and aqueous electrolyte solutions; Geochemical Transport, covering 3-D imaging of drill core samples, hydrothermal geochemistry, chemical interactions in hydrocarbon reservoirs, fluid flow model application, among others; Rock-Water Interactions, with presentations on stable isotope systematics of fluid/rock interaction, fluid flow and petotectonic evolution, grain boundary transport, sulfur incorporation, tracers in geologic reservoirs, geothermal controls on oil-reservoir evolution, and mineral hydrolysis kinetics; Organic Geochemistry covered new methods for constraining time of hydrocarbon migration, kinetic models of petroleum formation, mudstones in burial diagenesis, compound-specific carbon isotope analysis of petroleums, stability of natural gas, sulfur in sedimentary organic matter, organic geochemistry of deep ocean sediments, direct speciation of metal by optical spectroscopies; and lastly, Sedimentary Systems, covering sequence stratigraphy, seismic reflectors and diagenetic changes in carbonates, geochemistry and origin of regional dolomites, and evidence of large comet or asteroid impacts at extinction boundaries.

  16. The Ellsworth terrane, coastal Maine: Geochronology, geochemistry, and Nd-Pb isotopic composition - Implications for the rifting of Ganderia (United States)

    Schulz, K.J.; Stewart, D.B.; Tucker, R.D.; Pollock, J.C.; Ayuso, R.A.


    The Ellsworth terrane is one of a number of fault-bounded blocks that occur along the eastern margin of Ganderia, the western-most of the peri-Gondwanan domains in the northern Appalachians that were accreted to Laurentia in the Paleozoic. Geologic relations, detrital zircon ages, and basalt geochemistry suggest that the Ellsworth terrane is part of Ganderia and not an exotic terrane. In the Penobscot Bay area of coastal Maine, the Ellsworth terrane is dominantly composed of bimodal basalt-rhyolite volcanic sequences of the Ellsworth Schist and unconformably overlying Castine Volcanics. We use new U-Pb zircon geochronology, geochemistry, and Nd and Pb isotopes for these volcanic sequences to constrain the petrogenetic history and paleotectonic setting of the Ellsworth terrane and its relationship with Ganderia. U-Pb zircon geochronology for rhyolites indicates that both the Ellsworth Schist (508.6 ?? 0.8 Ma) and overlying Castine Volcanics (503.5 ?? 2.5 Ma) are Middle Cambrian in age. Two tholefitic basalt types are recognized. Type Tb-1 basalt, present as pillowed and massive lava flows and as sills in both units, has depleted La and Ce ([La/Nd]N = 0.53-0.87) values, flat heavy rare earth element (REE) values, and no positive Th or negative Ta anomalies on primitive mantle-normalized diagrams. In contrast, type Th-2 basalt, present only in the Castine Volcanics, has stightly enriched LREE ([La/Yb]N = 1.42-2.92) values and no Th or Th anomalies. Both basalt types have strongly positive ??Nd (500) values (Th-1 = +7.9-+8.6; Th-2 = +5.6-+7.0) and relatively enriched Pb isotopic compositions (206Ph/204Pb = 18.037-19.784; 207/204Pb = 15.531-15.660; 2088Pb/204Pb = 37.810-38.817). The basalts have compositions transitional between recent normal and enriched mid-ocean-ridge basalt, and they were probably derived by partial melting of compositionatly heterogeneous asthenosphenc mantle. Two types of rhyolite also are present. Type R-1 rhyolite, which mostly occurs as tuffs

  17. Isotope geochemistry of mercury in source rocks, mineral deposits and spring deposits of the California Coast Ranges, USA (United States)

    Smith, Christopher N.; Kesler, Stephen E.; Blum, Joel D.; Rytuba, James J.


    We present here the first study of the isotopic composition of mercury in rocks, ore deposits, and active spring deposits from the California Coast Ranges, a part of Earth's crust with unusually extensive evidence of mercury mobility and enrichment. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of mercury deposits, hot-spring deposits that form at shallow depths (geothermal areas continue to precipitate Hg and Au and are modern analogues to the fossil hydrothermal systems preserved in the ore deposits. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of mercury than volcanic rocks of the Clear Lake Volcanic Field. Mean mercury isotopic compositions ( δ202Hg) for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate mercury deposits have similar average mercury isotopic compositions that are indistinguishable from averages for the three rock units, although δ202Hg values for the mercury deposits have a greater variance than the country rocks. Precipitates from spring and geothermal waters in the area have similarly large variance and a mean δ202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate that there is little or no isotopic fractionation (< ± 0.5‰) during release of mercury from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of mercury in deposits, however, especially in their uppermost parts. Boiling of hydrothermal fluids, separation of a mercury-bearing CO 2 vapor or reduction and volatilization of Hg (0) in the near-surface environment are likely the

  18. Carbonate Geochemistry and Organic Biomarkers Evolutions During the Early Toarcian in the Paris Basin (United States)

    Hermoso, M.; Le Callonnec, L.; Hautevelle, Y.; Minoletti, F.; Renard, M.


    Within the Early Toarcian Oceanic Anoxic event, isotopic perturbations (C, O, Sr, Os, Mo and S) are now well described. Their worldwide occurrences and synchronicity are still under debate and oppose locally controlled mechanisms to global events such as methane hydrates release. We present an integrated study for understanding palaeoceanographical records in the Paris Basin. In order to test the influence of the redox status of the environment, the sedimentological, mineralogical and geochemical (carbonate and organic biomarkers) evolutions of two Early Toarcian sites are studied: Bascharage (Luxemburg) and Sancerre (center of France. A sedimentary particles isolation technique was performed to quantify the contribution of primary calcite (calcareous nannoflora) and diagenetic calcareous particles. The respective isotopic signatures of these particles enable to validate the bulk record and discuss the link between photic-zone and interstitial fluids (water-mass stratification, intensity of DIC remineralization, interstitial fluid migrations). It is demonstrated that both biogenic calcareous particles and early diagenetic macrocrystals record the C-isotope negative shift with similar magnitudes. Molecular biomarkers of the organic matter studied by GC-MS enable to characterize the paleoredox conditions in the photic-zone and the bottom water. The Bascharage section is characterized by permanant anoxic conditions in the photic zone (as shown by the presence of gammacerane, 2,3,6- trimethylalkylbenzenes and isorenieratane typical of Chlorobiaceae and reducing conditions in the sediment: Pr/PhC 34hopanes. The Earliest Toarcian Sancerre deposits are dysoxic and transient euxinic conditions are observed from the second step of the C-isotope decrease in carbonates. This level is also highlighted by generalized reducing conditions (Mn- rich carbonate) due to oxides phase destabilization, beginning of Black Shales deposits and disappearance of benthic life. The biomarker

  19. BOREAS TE-5 Tree Ring and Carbon Isotope Ratio Data (United States)

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


    The BOREAS TE-5 team collected several data sets to investigate the vegetation-atmosphere CO2 and H2O exchange processes. These data include tree ring widths and cellulose carbon isotope data from coniferous trees collected at the BOREAS NSA and SSA in 1993 and 1994 by the BOREAS TE-5 team. Ring width data are provided for both Picea mariana and Pinus banksiana. The carbon isotope data are provided only for Pinus banksiana. The data are provided in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

  20. The hydro- and multi-isotope geochemistry of iron-rich ground waters emerging at the southern Baltic Sea coast line (United States)

    Lipka, Marko; Wu, Zijun; Escher, Peter; Struck, Ulrich; Dellwig, Olaf; Schafmeister, Maria; Böttcher*, Michael E.


    Iron-rich groundwater springs emerging at the shore zone of the southern Baltic Sea (BS; Site Meschendorf) were examined on a seasonal base for a period of about two years. Besides major, minor, and trace elements, stable isotopes of water (H-2, O-18), dissolved inorganic carbon (DIC; C-13), and sulfate (S-34) were analyzed. The stream bed sediment was extracted for the geochemistry of the newly formed precipitates and further characterized via SEM-EDAX. Subsequently, the hydrogeochemical results were subjected to a thermodynamic analysis via the PHREEQC speciation model. The springs emerge from small pits (about 60 cm diameter; up to 15cm depth). Surrounding sediments are sandy with gravels found at depth and corresponding high permeabilities. The positions of different springs on the shore zone were stable during the investigation period while the shape of the pits and the stream beds may vary due to wind- and wave-driven forces. Selected measurements of spring yield discharges close to 10 L/min. The H-2 and O-18 contents of the spring waters indicate the ground water to originate from relatively young mixed meteoric waters. The hydrochemistry of the springs was similar and showed some variability in between which indicates that the genetic processes for the ground water before reaching the surface may slightly differ. The springs are characterized by dissolved Ca, Mg, Na, DIC and sulfate, mainly reflecting the interaction with soils and bedrocks in the recharge area that is dominated by marly till. The oxygen-free ground water is rich in Fe, P, and DIC. Iron and dissolved sulfate originate from the oxidation of pyrite, as further confirmed by the 34-S signature of sulfate. The carbon isotope signature of DIC indicates a mixture of biogenic CO2 from the soil zone with some water-rock interaction with carbonate minerals. The streams flow towards the BS and, in contact with the atmosphere, outgas carbon dioxide and takes up oxygen. Upon CO2-degassing, C-12 is

  1. Helium and neon isotope geochemistry of some ground waters from the Canadian Precambrian Shield (United States)

    Bottomley, D. J.; Ross, J. D.; Clarke, W. B.


    Ground waters in a Precambrian granitic batholith at the Whiteshell Nuclear Research Establishment (WNRE) in Pinawa, Manitoba contain between 5 × 10 -5 and 10 -1 cc STP/g H 2O of radiogenic helium-4 but have relatively uniform 3He/ 4He ratios of between 0.6 × 10 -8 and 2.3 × 10 3. The highest helium samples also contain radiogenic 21,22Ne produced by (α, n) or ( n,α) reactions with other isotopes. As much as 1.8 × 10 -9ccSTP/ gH2O of excess 21Ne and 3.8 × 10 -9ccSTP/ gH2O of excess 22Ne have been measured. Helium and 21Ne ages of these ground waters, calculated on the basis of known crustal production rates of 4He and 21Ne, are unreasonably high (up to 2 × 10 5 years) and incompatible with the 14C ages and other isotopic and hydrogeologic data. Uranium enrichment in the flow porosity of the granite may dominate 4He and 21,22Ne production in this granite and mask the contributions from more typical U and Th concentrations in the rock matrix. At the Chalk River Nuclear Laboratories in Ontario helium concentrations in ground waters in a Precambrian monzonitic gneiss range from 1.5 × 10 -7 to 8.7 × 10 -4ccSTP/ gH2O with the 3He/ 4He ratios ranging from 2.0 × 10 -3 to 1.5 × 10 -7. The highest helium concentrations may be attributable to the presence of a thick uraniferous pegmatite vein and yield helium ages more than two orders of magnitude higher than the 14C ages. Application of He age dating equations to ground waters from Precambrian granitic rocks requires knowledge of the nature of uranium and thorium enrichment in the subsurface in order to select appropriate values for porosity and uranium and thorium concentration in the rock.

  2. Fluid inclusion and isotope geochemistry of the Yangla copper deposit, Yunnan, China (United States)

    Yang, Xi-An; Liu, Jia-Jun; Yang, Long-Bo; Han, Si-Yu; Sun, Xiao-Ming; Wang, Huan


    The Yangla copper deposit, with Cu reserves of 1.2 Mt, is located between a series of thrust faults in the Jinshajiang-Lancangjiang-Nujiang region, Yunnan, China, and has been mined since 2007. Fluid inclusion trapping conditions ranged from 1.32 to 2.10 kbar at 373-409 °C. Laser Raman spectroscopy confirms that the vapour phase in these inclusions consists of CO2, CH4, N2 and H2O. The gas phases in the inclusions are H2O and CO2, with minor amounts of N2, O2, CO, CH4, C2H2, C2H4, and C2H6. Within the liquid phase, the main cations are Ca2+ and Na+ while the main anions are SO4 2- and Cl-. The oxygen and hydrogen isotope compositions of the ore-forming fluids (-3.05‰ ≤ δ18OH2O ≤ 2.5‰; -100‰ ≤ δD ≤ -120‰) indicate that they were derived from magma and evolved by mixing with local meteoric water. The δ34S values of sulfides range from -4.20‰ to 1.85‰(average on -0.85‰), supporting a magmatic origin. Five molybdenite samples taken from the copper deposit yield a well-constrained 187Re-187Os isochron age of 232.8 ± 2.4 Ma. Given that the Yangla granodiorite formed between 235.6 ± 1.2 Ma and 234.1 ± 1.2 Ma, the Cu metallogenesis is slightly younger than the crystallization age of the parent magma. A tectonic model that combines hydrothermal fluid flow and isotope compositions is proposed to explain the formation of the Yangla copper deposit. At first, westward subduction of the Jinshajiang Oceanic Plate in the Early Permian resulted in the development of a series of thrust faults. This was accompanied by fractional melting beneath the overriding plate, triggering magma ascent and extensive volcanism. The thrust faults, which were then placed under tension during a change in tectonic mode from compression to extension in the Late Triassic, formed favorable pathways for the magmatic ore-forming fluids. These fluids precipitated copper-sulfides to form the Yangla deposit.

  3. Paradox of the peak-PCIM (Paleocene Carbon Isotope Maxima; ~57.8Ma) and Abrupt Global Warming (United States)

    Harper, D. T.; Hoenisch, B.; Zachos, J. C.


    The Paleocene Carbon Isotope Maxima (PCIM; ~57.8Ma) represents a major transition in global δ13C during the late Paleocene, when the long-term positive trend in δ13C reversed from positive to negative. The peak-PCIM (~57.7Ma) has been tightly resolved in new high-resolution, astronomically-tuned benthic isotope records from IODP Sites 1209 (Pacific) and 1262 (Atlantic), which show the final phase of δ13C enrichment as abrupt (~1‰ in warming, effectively marking the onset of a gradual 8Myr long warming trend [Littler et al., EPSL 2014]. Typically, during the Paleogene on orbital time scales, warming is observed during intervals of δ13C depletion, consistent with release of isotopically light carbon to the atmosphere. This event, which has the appearance of a bifurcation in the long-term coupling of climate system and the carbon cycle, poses an interesting paradox as any rapid carbon release to the atmosphere should, in theory, create a negative excursion because all of the major carbon sources are isotopically light, whether volcanic outgassing, weathering/oxidation of organic carbon, or methane release [Dunkley-Jones et al., Phil. Trans. R. Soc. A 2010]. If global, there are several testable mechanisms that may explain the shift including increase in burial flux of light carbon, a reduction in heavy carbon burial flux, or a large-scale circulation change perhaps associated with the transition of a major oceanic gateway. Using trace metal (B/Ca and Mg/Ca) and stable isotope (δ11B, δ18O, and δ13C) geochemistry, here we establish the nature of the peak-PCIM at sites from 3 different ocean basins (IODP Sites 690, 1209, and 1262) and begin to test several of the possible mechanisms for change. Mg/Ca in mixed-layer planktonic foraminifera show 2-3°C of sea surface warming coinciding with, and abrupt as, the benthic carbon isotope enrichment at all sites. Bottom water ∆[CO32-], as indicated by B/Ca in benthic foraminifera, abruptly increases by 30-40µmol

  4. The clumped isotopic record of Neoproterozoic carbonates, Sultanate of Oman (United States)

    Bergmann, K. D.; Eiler, J. M.; Fischer, W. W.; Osburn, M. R.; Grotzinger, J. P.


    The Huqf Supergroup of the Sultanate of Oman records several important events in latest Precambrian time, including two glaciations in the Abu Mahara Group (ca. 725 - isotope excursion in the Nafun Group (ca. isotopic excursions, hypothesized to record perturbations of the surficial Earth carbon cycle or post-depositional diagenetic processes. Rigorous interpretation of these records requires a more thorough assessment of diagenetic processes. To better understand the significance and cause of these large amplitude isotopic excursions, we employed carbonate clumped isotope thermometry. This method allows us to estimate the absolute temperature of carbonate precipitation, including recrystallization, based on the temperature dependent abundance of carbonate ions containing both 13C and 18O. These estimates are accompanied by a measurement of carbonate δ18O, which in conjunction with temperature, can be used to calculate the oxygen isotopic composition of the fluid from which the carbonate precipitated. We analyzed stratigraphically constrained samples from a range of paleoenvironments with differing burial histories (1 - >10km maximum burial depth) to constrain the temperature and fluid composition of recrystallization. Clumped isotope temperatures from Huqf Supergroup samples range from 35-175°C. The isotopic composition of the fluid these rocks equilibrated with ranges from -3.7 to 15.7% VSMOW. This large range in temperature and fluid composition separates into distinct populations that differ systematically with independent constraints on petrography, stratigraphy and burial history. The data indicate the Abu Mahara, Nafun and Ara groups have unique diagenetic histories. In central Oman, the post-glacial Abu Mahara cap dolostone shows high temperature, rock buffered diagenesis (Tavg = 176°C; δ18Ofluid = 15% VSMOW), the Nafun Group generally experienced lower temperature, fluid buffered diagenesis (Tavg = 69°C; δ18Ofluid = 1% VSMOW) and the Ara Group

  5. Photosynthetic carbon isotope discrimination and its relationship to the carbon isotope signals of stem, soil and ecosystem respiration. (United States)

    Wingate, Lisa; Ogée, Jérôme; Burlett, Régis; Bosc, Alexandre; Devaux, Marion; Grace, John; Loustau, Denis; Gessler, Arthur


    • Photosynthetic carbon (C) isotope discrimination (Δ(Α)) labels photosynthates (δ(A) ) and atmospheric CO(2) (δ(a)) with variable C isotope compositions during fluctuating environmental conditions. In this context, the C isotope composition of respired CO(2) within ecosystems is often hypothesized to vary temporally with Δ(Α). • We investigated the relationship between Δ(Α) and the C isotope signals from stem (δ(W)), soil (δ(S)) and ecosystem (δ(E)) respired CO(2) to environmental fluctuations, using novel tuneable diode laser absorption spectrometer instrumentation in a mature maritime pine forest. • Broad seasonal changes in Δ(Α) were reflected in δ(W,) δ(S) and δ(E). However, respired CO(2) signals had smaller short-term variations than Δ(A) and were offset and delayed by 2-10 d, indicating fractionation and isotopic mixing in a large C pool. Variations in δ(S) did not follow Δ(A) at all times, especially during rainy periods and when there is a strong demand for C allocation above ground. • It is likely that future isotope-enabled vegetation models will need to develop transfer functions that can account for these phenomena in order to interpret and predict the isotopic impact of biosphere gas exchange on the C isotope composition of atmospheric CO(2).

  6. CO2-dependent carbon isotope fractionation in dinoflagellates relates to their inorganic carbon fluxes

    NARCIS (Netherlands)

    Hoins, M.; Eberlein, T.; Van de Waal, D.B.; Sluijs, A.|info:eu-repo/dai/nl/311474748; Reichart, G.-J.|info:eu-repo/dai/nl/165599081; Rost, B.


    Carbon isotope fractionation (εp) between the inorganic carbon source and organic matter has been proposed to be a function of pCO2. To understand the CO2-dependency of εp and species-specific differences therein, inorganic carbon fluxes in the four dinoflagellate species Alexandrium fundyense, Scri

  7. Geochemistry of Precambrian carbonates: II. Archean greenstone belts and Archean sea water. (United States)

    Veizer, J; Hoefs, J; Lowe, D R; Thurston, P C


    Carbonate rocks with geological attributes of marine sediments are a minor component of the Archean greenstone belts. Despite their relative scarcity, these rocks are important because they record chemical and isotopic properties of coeval oceans. The greenstones containing such carbonates appear to cluster at approximately 2.8 +/- 0.2 and approximately 3.5 +/- 0.1 Ga ago. The samples for the younger group are from the Abitibi, Yellowknife, Wabigoon (Steep Rock Lake), Michipicoten and Uchi greenstone belts of Canada and the "Upper Greenstones" of Zimbabwe. The older group includes the Swaziland Supergroup of South Africa, Warrawoona Group of Australia and the Sargur marbles of India. Mineralogically, the carbonates of the younger greenstones are mostly limestones and of the older ones, ferroan dolomites (ankerites); the latter with some affinities to hydrothermal carbonates. In mineralized areas with iron ores, the carbonate minerals are siderite +/- ankerite, irrespective of the age of the greenstones. Iron-poor dolomites represent a later phase of carbonate generation, related to post-depositional tectonic faulting. The original mineralogy of limestone sequences appears to have been an Sr-rich aragonite. The Archean carbonates yield near-mantle Sr isotopic values, with (87Sr/86Sr)o of 0.7025 +/- 0.0015 and 0.7031 +/- 0.0008 for younger and older greenstones, respectively. The best preserved samples give delta 13C of +1.5 +/- 1.5% PDB, comparable to their Phanerozoic counterparts. In contrast, the best estimate for delta 18O is -7% PDB. Archean limestones, compared to Phanerozoic examples, are enriched in 16O as well as in Mn2+ and Fe2+, and these differences are not a consequence of post-depositional alteration phenomena. The mineralogical and chemical attributes of Archean carbonates (hence sea water) are consistent with the proposition that the composition of the coeval oceans may have been buffered by a pervasive interaction with the "mantle", that is, with

  8. Martian carbon dioxide: Clues from isotopes in SNC meteorites (United States)

    Karlsson, H. R.; Clayton, R. N.; Mayeda, T. K.; Jull, A. J. T.; Gibson, E. K., Jr.


    Attempts to unravel the origin and evolution of the atmosphere and hydrosphere on Mars from isotopic data have been hampered by the impreciseness of the measurements made by the Viking Lander and by Earth-based telescopes. The SNC meteorites which are possibly pieces of the Martian surface offer a unique opportunity to obtain more precise estimates of the planet's volatile inventory and isotopic composition. Recently, we reported results on oxygen isotopes of water extracted by pyrolysis from samples of Shergotty, Zagami, Nakhla, Chassigny, Lafayette, and EETA-79001. Now we describe complementary results on the stable isotopic composition of carbon dioxide extracted simultaneously from those same samples. We will also report on C-14 abundances obtained by accelerator mass spectrometry (AMS) for some of these CO2 samples.

  9. The origin of carbon isotope vital effects in coccolith calcite (United States)

    McClelland, H. L. O.; Bruggeman, J.; Hermoso, M.; Rickaby, R. E. M.


    Calcite microfossils are widely used to study climate and oceanography in Earth's geological past. Coccoliths, readily preserved calcite plates produced by a group of single-celled surface-ocean dwelling algae called coccolithophores, have formed a significant fraction of marine sediments since the Late Triassic. However, unlike the shells of foraminifera, their zooplankton counterparts, coccoliths remain underused in palaeo-reconstructions. Precipitated in an intracellular chemical and isotopic microenvironment, coccolith calcite exhibits large and enigmatic departures from the isotopic composition of abiogenic calcite, known as vital effects. Here we show that the calcification to carbon fixation ratio determines whether coccolith calcite is isotopically heavier or lighter than abiogenic calcite, and that the size of the deviation is determined by the degree of carbon utilization. We discuss the theoretical potential for, and current limitations of, coccolith-based CO2 paleobarometry, that may eventually facilitate use of the ubiquitous and geologically extensive sedimentary archive. PMID:28262764

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

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


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

  11. Geology of Precambrian rocks and isotope geochemistry of shear zones in the Big Narrows area, northern Front Range, Colorado (United States)

    Abbott, Jeffrey T.


    Rocks within the Big Narrows and Poudre Park quadrangles located in the northern Front Range of Colorado are Precambrian metasedimentary and metaigneous schists and gneisses and plutonic igneous rocks. These are locally mantled by extensive late Tertiary and Quaternary fluvial gravels. The southern boundary of the Log Cabin batholith lies within the area studied. A detailed chronology of polyphase deformation, metamorphism and plutonism has been established. Early isoclinal folding (F1) was followed by a major period of plastic deformation (F2), sillimanite-microcline grade regional metamorphism, migmatization and synkinematic Boulder Creek granodiorite plutonism (1.7 b.y.). Macroscopic doubly plunging antiformal and synformal structures were developed. P-T conditions at the peak of metamorphism were probably about 670?C and 4.5 Kb. Water pressures may locally have differed from load pressures. The 1.4 b.y. Silver Plume granite plutonism was post kinematic and on the basis of petrographic and field criteria can be divided into three facies. Emplacement was by forcible injection and assimilation. Microscopic and mesoscopic folds which postdate the formation of the characteristic mineral phases during the 1.7 b.y. metamorphism are correlated with the emplacement of the Silver Plume Log Cabin batholith. Extensive retrograde metamorphism was associated with this event. A major period of mylonitization postdates Silver Plume plutonism and produced large E-W and NE trending shear zones. A detailed study of the Rb/Sr isotope geochemistry of the layered mylonites demonstrated that the mylonitization and associated re- crystallization homogenized the Rb87/Sr 86 ratios. Whole-rock dating techniques applied to the layered mylonites indicate a probable age of 1.2 b.y. Petrographic studies suggest that the mylonitization-recrystallization process produced hornfels facies assemblages in the adjacent metasediments. Minor Laramide faulting, mineralization and igneous activity

  12. Pb isotope geochemistry of lead, zinc, gold and silver deposit clustered region, Liaodong rift zone,northeastern China

    Institute of Scientific and Technical Information of China (English)

    CHEN; Jiangfeng; YU; Gang; XUE; Chunji; QIAN; Hui; HE; Jian


    33 Pb isotopic analyses were reported for sulfide and hydrothermal carbonate minerals and marble of the Xiquegou lead-zinc, the Zhenzigou zinc-lead and the Gaojiapuzi silver deposits from the Qingchengzi ore field and the Beiwagou zinc-lead deposit in the west, Proterozoic Liaodong rift zone. Pb isotopic ratios of the marble from the Qingchengzi ore field range from 18.24 to 30.63 for 206Pb/204Pb, 15.59 to 17.05 for 207Pb/204Pb and 37.43 to 38.63 for 208Pb/204Pb. The marble gives a Pb-Pb isochron age of 1822±92 Ma, which is interpreted as the age of the metamorphism of the marble. Ore Pb, including Pb of sulfide and hydrothermal carbonate minerals, from the Qingchengzi ore field shows limited variation with 206Pb/204Pb=17.66-17.96, 207Pb/204Pb=15.60-15.74 and 208Pb/204Pb=37.94-38.60. In contrast, ore Pb from the Beiwagou deposit gives different Pb isotopic ratios with 206Pb/204Pb=15.68-15.81, 207Pb/204Pb= 15.34-15.45 and 208Pb/204Pb=35.30-35.68. Pb of all deposits from the Liaodong rift zone is derived from the upper crust. Ore Pb of the Qingchengzi deposits is derived from a young upper crust. The model Th/U ratios of 4.40 to 4.74 for ore Pb are significantly different from that of 1.7 to 4.4 given by the marble of the Qingchengzi ore field, suggesting that marble is not the source of the ore Pb. Ore Pb of the Beiwagou deposit is extracted from its source and the deposit is formed at the Paleoproterozoic era. Different Pb isotopic ratios of the Qingchengzi ore field and the Beiwagou deposit are due to different ages of the deposits and suggest that the two types of deposits are derived from different sources and are possibly formed by different ore-forming processes.

  13. Modeling stable isotope and organic carbon in hillslope stormflow (United States)

    Dusek, Jaromir; Vogel, Tomas; Dohnal, Michal; Marx, Anne; Jankovec, Jakub; Sanda, Martin; Votrubova, Jana; Barth, Johannes A. C.; Cislerova, Milena


    Reliable prediction of water movement and fluxes of dissolved substances (such as stable isotopes and organic carbon) at both the hillslope and the catchment scales remains a challenge due to complex boundary conditions and soil spatial heterogeneity. In addition, microbially mediated transformations of dissolved organic carbon (DOC) are known to affect balance of DOC in soils, hence the transformations need to be included in a conceptual model of a DOC transport. So far, only few studies utilized stable isotope information in modeling and even fewer linked dissolved carbon fluxes to mixing and/or transport models. In this study, stormflow dynamics of oxygen-18 isotope and dissolved organic carbon was analyzed using a physically based modeling approach. One-dimensional dual-continuum vertical flow and transport model, based on Richards and advection-dispersion equations, was used to simulate the subsurface transport processes in a forest soil during several observed rainfall-runoff episodes. The transport of heat in the soil profile was described by conduction-advection equation. Water flow and transport of solutes and heat were assumed to take place in two mutually communicating porous domains, the soil matrix and the network of preferential pathways. The rate of microbial transformations of DOC was assumed to depend on soil water content and soil temperature. Oxygen-18 and dissolved organic carbon concentrations were observed in soil pore water, hillslope stormflow (collected in the experimental hillslope trench), and stream discharge (at the catchment outlet). The modeling was used to analyze the transformation of input solute signals into output hillslope signals observed in the trench stormflow. Signatures of oxygen-18 isotope in hillslope stormflow as well as isotope concentration in soil pore water were predicted reasonably well. Due to complex nature of microbial transformations, prediction of DOC rate and transport was associated with a high uncertainty.

  14. Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS (United States)

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


    We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V

  15. Preliminary Nanosims Analysis of Carbon Isotope of Carbonates in Calcium-Aluminum-Rich Inclusions


    Guan, Y.; Paque, J. M.; Burnett, D.S.; Eiler, J. M.


    Carbonate minerals observed in primitive meteorites are products of either terrestrial weathering or aqueous alteration in the early solar system. Most of the carbonate minerals in carbonaceous chondrites occur primarily as isolated grains in matrix, as crosscutting veins, or as replacement minerals in chondrules [e.g., 1, 2]. A few calcium-aluminum-rich inclusions (CAIs) have been reported containing carbonate minerals as well [2, 3]. The C and O isotopes of carbonates in c...

  16. Geochemical monitoring using noble gases and carbon isotopes: study of a natural reservoir; Monitoring geochimique par couplage entre les gaz rares et les isotopes du carbone: etude d'un reservoir naturel

    Energy Technology Data Exchange (ETDEWEB)

    Jeandel, E


    To limit emissions of greenhouse gases in the atmosphere, CO{sub 2} geological sequestration appears as a solution in the fight against climate change. The development of reliable monitoring tools to ensure the sustainability and the safety of geological storage is a prerequisite for the implementation of such sites. In this framework, a geochemical method using noble gas and carbon isotopes geochemistry has been tested on natural and industrial analogues. The study of natural analogues from different geological settings showed systematic behaviours of the geochemical parameters, depending on the containment sites, and proving the effectiveness of these tools in terms of leak detection and as tracers of the behaviour of CO{sub 2}. Moreover, an experience of geochemical tracing on a natural gas storage has demonstrated that it is possible to identify the physical-chemical processes taking place in the reservoir to a human time scale, increasing interest in the proposed tool and providing general information on its use. (author)

  17. Carbon isotope fluctuations in Precambrian carbonate sequences of several localities in Brazil

    Directory of Open Access Journals (Sweden)



    Full Text Available Carbon isotope fluctuations in Precambrian sedimentary carbonates between 2.8 Ga and 0.60 Ga in Brazil are examined in this study. The carbonate facies of the BIF of the 2.8 Ga-old Carajás Formation, state of Pará in northern Brazil, has rather homogeneous delta13C (-5 o/ooPDB, compatible with carbonatization of a silicate protolith by a CO2-rich fluid from mantle degassing. The Paleoproterozoic Gandarela Formation, state of Minas Gerais, displays a narrow delta13C variation (-1.5 to +0.5 o/oo compatible with carbon isotope signatures of carbonates deposited around 2.4 Ga worldwide. The Fecho do Funil Formation has probably recorded the Lomagundi delta13C positive anomaly (+6.4 to +7.1 o/ooPDB. The magnesite-bearing carbonates of the Orós mobile belt, state of Ceará, exhibit carbon isotope fluctuation within the range for carbonates deposited at 1.8 Ga. The C-isotope record of the Frecheirinha Formation, northwestern state of Ceará, shows negative delta13C values in its lower portion (-2 o/oo and positive values up section (+1 to +3 o/oo, which suggests this sequence is a cap carbonate deposited after a glacial event around 0.95 Ga. The Jacoca and Acauã sedimentary carbonate Formations, state of Sergipe, NE Brazil, show carbon isotope fluctuations very similar to each other (average around -5 o/oo, compatible with a deposition around 0.76 Ga. The younger Olho D'Água carbonate Formation, however, also in the state of Sergipe, displays negative delta13C values at the lower portion of the Formation, changing dramatically up section to positive values as high as +10 o/oo, a characteristic compatible with a Sturtian cap carbonate deposited around 0.69 Ga. On the light of the C isotope data discussed in this study, it seems that delta13C fluctuations in Paleoproterozoic carbonates in Brazil are within the range found globally for metasedimentary carbonates of this age. Carbon isotope data proved to be very useful in establishing relative

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

    Institute of Scientific and Technical Information of China (English)



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

  19. Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments (United States)

    Parkinson, I. J.; Pearce, C. R.; Polacskek, T.; Cockell, C.; Hammond, S. J.


    Magnesium is an essential component of life, with pivotal roles in the generation of cellular energy as well as in plant chlorophyll [1]. The bio-geochemical cycling of Mg is associated with mass dependant fractionation (MDF) of the three stable Mg isotopes [1]. The largest MDF of Mg isotopes has been recorded in carbonates, with foraminiferal tests having δ26Mg compositions up to 5 ‰ lighter than modern seawater [2]. Magnesium isotopes may also be fractionated during bacterially mediated carbonate precipitation and such carbonates are known to have formed in both modern and ancient Earth surface environments [3, 4], with cyanobacteria having a dominant role in carbonate formation during the Archean. In this study, we aim to better constrain the extent to which Mg isotope fractionation occurs during cellular processes, and to identify when, and how, this signal is transferred to carbonates. To this end we have undertaken biologically-mediated carbonate precipitation experiments that were performed in artificial seawater, but with the molar Mg/Ca ratio set to 0.6 and with the solution spiked with 0.4% yeast extract. The bacterial strain used was marine isolate Halomonas sp. (gram-negative). Experiments were run in the dark at 21 degree C for two to three months and produced carbonate spheres of various sizes up to 300 μm in diameter, but with the majority have diameters of ~100 μm. Control experiments run in sterile controls (`empty` medium without bacteria) yielded no precipitates, indicating a bacterial control on the precipitation. The carbonate spheres are produced are amenable to SEM, EMP and Mg isotopic analysis by MC-ICP-MS. Our new data will shed light on tracing bacterial signals in carbonates from the geological record. [1] Young & Galy (2004). Rev. Min. Geochem. 55, p197-230. [2] Pogge von Strandmann (2008). Geochem. Geophys. Geosys. 9 DOI:10.1029/2008GC002209. [3] Castanier, et al. (1999). Sed. Geol. 126, 9-23. [4] Cacchio, et al. (2003

  20. Application of stable carbon isotopes in long term mesocosm studies for carbon cycle investigation (United States)

    Esposito, Mario


    Carbon dioxide (CO2) is an effective greenhouse gas. The Oceans absorb ca. 30% of the anthropogenic CO2 emissions and thereby partly attenuate deleterious climate effects. A consequence of the oceanic CO2 uptake is a decreased seawater pH and planktonic community shifts. The quantification of the anthropogenic perturbation was investigated through stable carbon isotope analysis in three "long term" mesocosm experiments (Sweden 2013, Gran Canaria 2014, Norway 2015) which reproduced near natural ecosystem conditions under both controlled and modified future CO2 level (up to 2000 ppm) scenarios. Parallel measurements of the stable isotope composition of dissolved inorganic carbon (δ13CDIC) dissolved organic carbon (δ13CDOC) and particulate carbon (δ13CTPC) both from the mesocosms water column and sediment traps showed similar trends in all the three experiments. A CO2 response was noticeable in the isotopic dataset, but increased CO2 levels had only a subtle effect on the concentrations of the dissolved and particulate organic carbon pool. Distinctive δ13C signatures of the particulate carbon pool both in the water column and the sediments were detectable for the different CO2 treatments and they were strongly correlated with the δ13CDIC signatures but not with the δ13CDOC pool. The validity of the isotopic data was verified by cross-analyses of multiple substances of known isotopic signatures on a GasBench, Elemental Analyser (EA) and on an in-house TOC-IRMS setup for the analysis of δ13CDIC, δ13CTPC and δ13CDOC, respectively. Results from these mesocosm experiments proved the stable carbon isotope approach to be an effective tool for quantifying the uptake and carbon transfer among the various compartments of the marine carbon system.

  1. Carbon isotope composition of the Lower Triassic marine carbonates, Lower Yangtze Region, South China

    Institute of Scientific and Technical Information of China (English)

    ZUO; Jingxun; TONG; Jinnan; QIU; Haiou; ZHAO; Laishi


    Studies on three Lower Triassic sections located on the shallow water platform, the deep water slope and in the deep water basin in the Lower Yangtze Region, South China, show the similar trend of carbon isotope evolution. Biostratigraphic correlations among the Lower Triassic sections on the basis of standard conodont zones indicate that three negative shifts occurred in the Griesbachian, the Smithian and the late Spathian stages respectively, and one distinctly positive shift occurred in the early Spathian stage. Trend of carbon isotope evolution of the Lower Triassic reflects some significant changes in the global carbon cycle. Moreover, δ13C background values are intensively controlled by palaeogeographic environment. In general, δ13C values from deep-water slope carbonates are lighter than those from carbonate platform and heavier than those from deep-water basin carbonates. The positive carbon isotope excursion may be induced by a significant amount of organic carbon burial in marine sediments and increase in primary productivity. The large negative carbon isotope excursions during the Early Triassic in Lower Yangtze Region are interpreted to relate to volcano eruptions based on tuffaceous claystone interlayers observed near the Permian-Triassic boundary, the Induan- Olenekian boundary and the Lower Triassic-Middle Triassic boundary.

  2. Carbon and Noble Gas Isotope Banks in Two-Phase Flow: Changes in Gas Composition During Migration (United States)

    Sathaye, K.; Larson, T.; Hesse, M. A.


    In conjunction with the rise of unconventional oil and gas production, there has been a recent rise in interest in noble gas and carbon isotope changes that can occur during the migration of natural gas. Natural gas geochemistry studies use bulk hydrocarbon composition, carbon isotopes, and noble gas isotopes to determine the migration history of gases from source to reservoir, and to trace fugitive gas leaks from reservoirs to shallow groundwater. We present theoretical and experimental work, which helps to explain trends observed in gas composition in various migration scenarios. Noble gases are used as tracers for subsurface fluid flow due to distinct initial compositions in air-saturated water and natural gases. Numerous field studies have observed enrichments and depletions of noble gases after gas-water interaction. A theoretical two-phase gas displacement model shows that differences in noble gas solubility will cause volatile gas components will become enriched at the front of gas plumes, leaving the surrounding residual water stripped of dissolved gases. Changes in hydrocarbon gas composition are controlled by gas solubility in both formation water and residual oil. In addition to model results, we present results from a series of two-phase flow experiments. These results demonstrate the formation of a noble gas isotope banks ahead of a main CO2 gas plume. Additionally, we show that migrating hydrocarbon gas plumes can sweep biogenic methane from groundwater, significantly altering the isotope ratio of the gas itself. Results from multicomponent, two-phase flow experiments qualitatively agree with the theoretical model, and previous field studies. These experimentally verified models for gas composition changes can be used to aid source identification of subsurface gases.

  3. Gas and Isotope Geochemistry of 81 Steam Samples from Wells in The Geysers Geothermal Field, Sonoma and Lake Counties, California (United States)

    Lowenstern, Jacob B.; Janik, Cathy J.; Fahlquist, Lynne; Johnson, Linda S.


    geothermal field, the carbon-isotopic composition of CO2 is consistent with derivation of carbon from Franciscan metasedimentary rocks. NH3 concentrations are high in most Geysers well fluids, and are 2-3 orders of magnitude greater than would be expected in a the gas phase exhibiting homogeneous equilibrium at normal reservoir temperatures and pressures. Evidently, NH3 is flushed from the Franciscan host rocks at a rate that exceeds the reaction rate for NH3 breakdown. Many wells show clear influence by fluids from reinjection wells where steam condensate has been pumped back into the geothermal reservoir. Six wells were resampled over the time period of this study. One of these six wells was strongly affected by a nearby injection well. Three of the six resampled wells showed some signs of decreasing liquid/ steam within the geothermal reservoir, consistent with 'drying out' of the reservoir due to steam withdrawal. However, two wells exhibited little change. Analyses of gases from five surface manifestations (fumaroles and bubbling pools) are roughly similar to the deeper geothermal samples in both chemical and isotopic composition, but are lower in soluble gases that dissolve in groundwater during transit toward the surface.

  4. Simultaneous tracing of carbon and nitrogen isotopes in human cells. (United States)

    Nilsson, Roland; Jain, Mohit


    Stable isotope tracing is a powerful method for interrogating metabolic enzyme activities across the metabolic network of living cells. However, most studies of mammalian cells have used (13)C-labeled tracers only and focused on reactions in central carbon metabolism. Cellular metabolism, however, involves other biologically important elements, including nitrogen, hydrogen, oxygen, phosphate and sulfur. Tracing stable isotopes of such elements may help shed light on poorly understood metabolic pathways. Here, we demonstrate the use of high-resolution mass spectrometry to simultaneously trace carbon and nitrogen metabolism in human cells cultured with (13)C- and (15)N-labeled glucose and glutamine. To facilitate interpretation of the complex isotopomer data generated, we extend current methods for metabolic flux analysis to handle multivariate mass isotopomer distributions (MMIDs). We find that observed MMIDs are broadly consistent with known biochemical pathways. Whereas measured (13)C MIDs were informative for central carbon metabolism, (15)N isotopes provided evidence for nitrogen-carrying reactions in amino acid and nucleotide metabolism. This computational and experimental methodology expands the scope of metabolic flux analysis beyond carbon metabolism, and may prove important to understanding metabolic phenotypes in health and disease.

  5. Shear heating and clumped isotope reordering in carbonate faults (United States)

    Siman-Tov, Shalev; Affek, Hagit P.; Matthews, Alan; Aharonov, Einat; Reches, Ze'ev


    Natural faults are expected to heat rapidly during seismic slip and to cool quite quickly after the slip event. Here we examine clumped isotope thermometry for its ability to identify such short duration elevated temperature events along frictionally heated carbonate faults. Our approach is based on measured Δ47 values that reflect the distribution of oxygen and carbon isotopes in the calcite lattice, measuring the abundance of 13Csbnd 18O bonds, which is affected by temperature. We examine three types of calcite rock samples: (1) crushed limestone grains that were rapidly heated and then cooled in static laboratory experiments, simulating the temperature cycle experienced by fault rock during an earthquake slip; (2) limestone samples that were experimentally sheared to simulate earthquake slip events; and (3) samples from Fault Mirrors (FMs) collected from principle slip surfaces of three natural carbonate faults. Extensive FM surfaces are believed to form during earthquake slip. Our experimental results show that Δ47 values decrease rapidly (in the course of seconds) with increasing temperature and shear velocity. On the other hand, carbonate shear zones from natural faults do not show such Δ47 decrease. We suggest that the Δ47 response may be controlled by nano-size grains, the high abundance of defects, and highly stressed/strained grain boundaries within the carbonate fault zone that can reduce the activation energy for diffusion, and thus lead to an increased rate of isotopic disordering during shear experiments. In our laboratory experiments the high stress and strain on grain contacts and the presence of nanograins thus allows for rapid disordering so that a change in Δ47 occurs in a very short and relatively low intensity heating events. In natural faults it may also lead to isotopic ordering after the cessation of frictional heating thus erasing the high temperature signature of Δ47.




    The presented studies were carried out in order to check the usefulness of subfossil wood for stable isotope analysis. The aim of research was also to define the optimal method of subfossil samples preparation. Subfossil samples used during the presented studies are a part of the multi-century dendrochronological scale. This chronology originates in an area situated around a small mountain lake — Schwarzersee, in Austria. The obtained results of stable carbon isotope measurements confirmed that the method of α-cellulose extraction by the application of acidic sodium chlorite and sodium hydroxide solutions removes resins and other mobile compounds from wood. Therefore, in the case of the analysed samples, the additional chemical process of extractives removing was found to be unnecessary. Studied wood samples contained an adequate proportion of α-cellulose similar to the values characteristic for the contemporary trees. This proved an adequate wood preservation which is essential for the conduction of isotopic research. PMID:26346297

  7. Carbon and Oxygen Isotope Stratigraphy of the Oxfordian Carbonate Rocks in Amu Darya Basin

    Institute of Scientific and Technical Information of China (English)

    Rongcai Zheng; Yanghui Pan; Can Zhao; Lei Wu; Renjin Chen; Rui Yang


    Based on the detailed research on petrologic and geochemical characteristics of deposition and diagenesis of Oxfordian carbonate rocks in Amu Darya Basin,Turkmenistan,carbon and oxygen isotopes were analyzed.The results show that the paleoenvironmental evolution reflected by the samples with well-preserved original carbon isotopes coincides with the carbon-isotope stratigraphic carve and is almost consistent with the global sea-level curve,the Mid-Oxfordian wide transgression,and the positive carbon-isotope excursion event.The Mid-Oxfordian continuing transgression not only laid the foundation for the development of the Oxfordian reef and shoal reservoirs in Amu Darya Basin but also provided an example for the Oxfordian global transgression and the resulting development of reefs and banks and high-speed organic carbon burial events.The response of oxygen isotopes in diagenetic environment showed that micrite limestones and granular limestones underwent weak diagenetic alteration,and the samples largely retained the original seawater features.Dolomitization and the precipitation of hydrothermal calcites tilling solution vugs and fractures before hydrocarbon accumulation occurred in a closed diagenetic environment where the main controlling factor is the temperature,and the diagenetic fluids were from the deep hot brine.The chalkification of the limestones after hydrocarbon accumulation occurred in the oiltield water systems.

  8. A supercritical oxidation system for the determination of carbon isotope ratios in marine dissolved organic carbon

    NARCIS (Netherlands)

    Le Clercq, Martijn; Van der Plicht, Johannes; Meijer, Harro A.J.


    An analytical oxidation system employing supercritical oxidation has been developed. It is designed to measure concentration and the natural carbon isotope ratios (C-13, C-14) Of dissolved organic carbon (DOC) and is especially suited for marine samples. The oxidation takes place in a ceramic tube a

  9. Boron isotope fractionation in magma via crustal carbonate dissolution. (United States)

    Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela


    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

  10. Carbon isotope systematics of a mantle 'hotspot': A comparison of Loihi Seamount and MORB glasses

    Energy Technology Data Exchange (ETDEWEB)

    Exley, R.A.; Mattey, D.P.; Pillinger, C.T.; Clague, D.A.


    The carbon isotope geochemistry of glasses from Loihi Seamount has been compared with that of MORB glasses. Stepped heating shows two carbon components in both sample suites: 1. isotopically light carbon (avg. delta/sup 13/C=-26.3per mille) released <600/sup 0/C, ascribed to surficial contamination, and 2. isotopically heavy carbon released >600/sup 0/C, regarded as indigenous. The high-temperature component in MORB samples varied from 52 to 169 ppm C, average delta/sup 13/C=-6.6per mille, consistent with previous studies (overall MORB average delta/sup 13/C=-6.4 +- 0.9per mille), and new results for Indian Ocean glasses are similar to Atlantic and Pacific Ocean samples. Carbon release profiles produced by stepped heating may be typical of locality, but there are no significant differences in delta/sup 13/C values between MORB samples from different areas. Lower yields (17-110 ppm C) correlated with depth in the Loihi samples suggest that they are partially degassed. This degassing has not affected delta/sup 13/C values significantly (avg. -5.8per mille). Loihi tholeiites have higher delta/sup 13/C (avg. -5.6per mille) than the alkali basalts (avg. -7.1per mille). Carbon abundances correlate well with He concentration data. Comparison of the delta/sup 13/C values with trace element and He, Sr, Nd, and Pb isotope data from the literature suggests that the Loihi samples with highest delta/sup 13/C have high /sup 3/He//sup 4/He and possibly the least depleted /sup 143/Nd//sup 144/Nd and /sup 87/Sr//sup 86/Sr. The carbon isotope data are consistent with previous models for Loihi involving several mantle sources, lithospheric contamination, and mixing. The slightly higher delta/sup 13/C of Loihi tholeiites suggests that the undegassed ''plume'' component manifested by high /sup 3/He//sup 4/He values might have delta/sup 13/C about 1per mille higher than the MORB average.

  11. Carbon isotope stratigraphy and palynology of an eastern Tethyan Cretaceous-Paleogene boundary section from Sumbar, Turkmenistan (United States)

    Gilmour, I.; Pearce, C. A.; Jolley, D.; Sephton, M. A.; Widdowson, M.; Gilmour, M. A.


    A number of marine sequences across the K/Pg boundary have been identified that offer reasonably continuous records and relatively high sedimentation rates, most notably those near Tethyan continental margins. However, few Eastern Tethys K/Pg localities have been studied compared to the well-known North African and Southern European sites. Here we present a high-resolution stable carbon isotope and palynological record of a 2m thick section across the K/Pg boundary from the eastern Tethys at Sumbar in Turkmenistan (38°28'N, 56°14'E). The stratigraphy and inorganic geochemistry of the section used in this study, SM-4, has been described in detail by [1]. A moderately diverse series of palynofloras were recovered from the samples spanning the K/Pg boundary with a late Maastrichtian assemblage comparable to that described from Tunisia [2]. Above the K/Pg boundary a dinocyst assemblage dominated by Areoligera is observed, reinforcing the similarity with Tunisia, that we interpret as representing a marine transgression by eutrophic water masses with the levels of Areoligera decreasing up section with a decline in nutrient availability. Carbon isotope stratigraphy of bulk carbonate and bulk organic matter reveal correlated negative carbon isotope excursions (CIEs) across the K/Pg boundary. The extent of the CIE and the concomitant drop in carbonate content parallels that observed for bulk and fine fraction carbonate isotopic analyses from other K/Pg sections. The negative CIE of bulk organic matter is similar in magnitude to CIEs for organic matter that have been observed at only a few other marine K/Pg sections. In contrast, the marked CIE observed in bulk organic matter is not evident in the carbon isotopic compositions of algal lipids. We interpret this as a geochemical signature of post-K/Pg algal blooms. Recent analysis identified the K/Pg boundary in the Boltysh meteorite crater sediment fill and reported evidence of a marine incursion into the crater during the

  12. The geochemistry characteristic and dating of cold seepage carbonates of the Pearl River Mouth Basin, eastern of South China Sea (United States)

    Fang, Yunxin; Fu, Shaoying


    Cold seepage carbonates are usually formed by the interaction of methane oxidizing archaea, sulfate reducing bacteria and cold seepage which contain abundant venting hydrocarbon gases. The presence of cold seepage carbonates on the seabed is one of the evidences that the area exist venting hydrocarbon gases, which are usually result by the dissociation of gas hydrate. The cold seepage property and fluid flow rate can influence the oxidation-deoxidation environment of the bottom water and sediment. Many previous studies focused on the mineral composition, microstructure, elemental composition, isotope composition of the cold seepage carbonates and isotopic dating for the cold seepage carbonates. The isotopic dating for the cold seepage carbonates can provide the information of the gas hydrate formation and dissociation in some area of the South China Sea. High precision TIMS-U dating and 14C dating are used as routine method for the dating of the Quaternary carbonates and fossils. The cold seepage carbonates in the study include the samples collected by ROV on the seabed and the drilling for gas hydrate in the Pearl River Mouth Basin, eastern of the South China Sea. The authigenic carbonate occurred in different depth in the A, B and C drilling site. They may be represent different events of gas hydrate formation and dissociation in the Quaternary. The dating study for all the cold seepage carbonates can provide the relative accurate eras of the gas hydrate dissociation events in certain area of the South China Sea.

  13. Dissolved Organic Carbon Cycling in Forested Watersheds: A Carbon Isotope Approach (United States)

    Schiff, S. L.; Aravena, R.; Trumbore, S. E.; Dillon, P. J.


    Dissolved organic carbon (DOC) is important in the acid-base chemistry of acid-sensitive freshwater systems; in the complexation, mobility, persistence, and toxicity of metals and other pollutants; and in lake carbon metabolism. Carbon isotopes (13C and 14C) are used to study the origin, transport, and fate of DOC in a softwater catchment in central Ontario. Precipitation, soil percolates, groundwaters, stream, beaver pond, and lake waters, and lake sediment pore water were characterized chemically and isotopically. In addition to total DOC, isotopic measurements were made on the humic and fulvic DOC fractions. The lake is a net sink for DOC. Δ14C results indicate that the turnover time of most of the DOC in streams, lakes, and wetlands is fast, less than 40 years, and on the same time scale as changes in acidic deposition. DOC in groundwaters is composed of older carbon than surface waters, indicating extensive cycling of DOC in the upper soil zone or aquifer.

  14. Descriptions of carbon isotopes within the energy density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Ismail, Atef [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia and Department of Physics, Al-Azhar University, 71524 Assiut (Egypt); Cheong, Lee Yen; Yahya, Noorhana [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Tammam, M. [Department of Physics, Al-Azhar University, 71524 Assiut (Egypt)


    Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in {sup 15}C, {sup 17}C and {sup 19}C, and the two-neutron halo structures in {sup 16}C and {sup 22}C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly the blocking effect plays a significant role in the shell model configurations.

  15. SRP baseline hydrogeologic investigation: Aquifer characterization. Groundwater geochemistry of the Savannah River Site and vicinity

    Energy Technology Data Exchange (ETDEWEB)

    Strom, R.N.; Kaback, D.S.


    An investigation of the mineralogy and chemistry of the principal hydrogeologic units and the geochemistry of the water in the principal aquifers at Savannah River Site (SRS) was undertaken as part of the Baseline Hydrogeologic Investigation. This investigation was conducted to provide background data for future site studies and reports and to provide a site-wide interpretation of the geology and geochemistry of the Coastal Plain Hydrostratigraphic province. Ground water samples were analyzed for major cations and anions, minor and trace elements, gross alpha and beta, tritium, stable isotopes of hydrogen, oxygen, and carbon, and carbon-14. Sediments from the well borings were analyzed for mineralogy and major and minor elements.

  16. Investigating controls on boron isotope ratios in shallow marine carbonates (United States)

    Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.


    The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives

  17. Late Carboniferous to Late Permian carbon isotope stratigraphy

    DEFF Research Database (Denmark)

    Buggisch, Werner; Krainer, Karl; Schaffhauser, Maria;


    . Negative δ13C excursions are related to low-stand deposits and caused by diagenetic processes during subaerial exposure. The comparison with δ13C records from other parts of the world demonstrate that δ13C values are high in most unaltered samples, an overall negative trend during the Permian, as recently...... published, is not obvious and negative excursions related to changes in the carbon isotope composition of the global oceanic carbon pool cannot be confirmed, except for the Permian–Triassic boundary interval....

  18. Provenance of late Oligocene to quaternary sediments of the Ecuadorian Amazonian foreland basin as inferred from major and trace element geochemistry and Nd-Sr isotopic composition (United States)

    Roddaz, Martin; Christophoul, Frédéric; Burgos Zambrano, José David; Soula, Jean-Claude; Baby, Patrice


    Oligocene to Quaternary deposits from the Oriente Amazonian foreland basin (Ecuador and Peru) were analyzed for major and trace element geochemistry (46 and 32 samples respectively) and Nd-Sr isotopic systematics (n = 10). Chemical Index of Alteration values lower than those of other Amazonian foreland basin sediments and scattering along the AK join in the A-CN-K diagram indicate that the Oriente foreland basin has been continuously fed by poorly to moderately weathered sediments having an overall Andesitic composition since the Oligocene. Chemical ratios such as Cr/Th and Th/Sc as well as Eu anomaly and Nd-Sr isotopic compositions indicate that most of the analyzed sediments contained a greater proportion of volcanic arc rock material than the other Amazonian foreland basin sediments. When compared with the older sediments The Quaternary sediments are characterized by a greater contribution of the volcanic arc source. The composition of the sediments deposited in the Ecuadorian Amazonian foreland basin is mainly controlled by geodynamic processes. We suspect the Late Pliocene-Pleistocene subduction of the Carnegie ridge to be responsible for the back arc volcanism feeding the Amazonian foreland with more basic materials. Input of young Ecuadorian volcanic rocks may explain the difference in Sr and Nd isotopic ratios of suspended sediments between the Solimoes and the Madeira rivers.

  19. Sedimentary process control on carbon isotope composition of sedimentary organic matter in an ancient shallow-water shelf succession (United States)

    Davies, S. J.; Leng, M. J.; Macquaker, J. H. S.; Hawkins, K.


    Source and delivery mechanisms of organic matter are rarely considered when interpreting changing δ13C through sedimentary successions even though isotope excursions are widely used to identify and correlate global perturbations in the carbon cycle. Combining detailed sedimentology and geochemistry we demonstrate how organic carbon abundance and δ13C values from sedimentary organic matter from Carboniferous-aged mudstones are influenced by the proportion of terrestrial versus water column-derived organic matter. Silt-bearing clay-rich shelf mudstones that were deposited by erosive density flows are characterized by 1.8-2.4% organic carbon and highδ13C values (averaging -22.9 ± 0.3‰, n = 12). Typically these mudstones contain significant volumes of terrestrial plant-derived material. In contrast, clay-rich lenticular mudstones, with a marine macrofauna, are the products of the transport of mud fragments, eroded from pre-existing water-rich shelfal muds, when shorelines were distant and biological productivity in the water column was high. Higher organic carbon (2.1-5.2%) and lowerδ13C values (averaging -24.3 ± 0.5‰, n = 11) characterize these mudstones and are interpreted to reflect a greater contribution by (isotopically more negative) amorphous organic matter derived from marine algae. Differences in δ13C between terrestrial and marine organic matter allow the changing proportions from different sources to be tracked through this succession. Combining δ13C values with zirconium (measured from whole rock), here used as a proxy for detrital silt input, provides a novel approach to distinguishing mudstone provenance and ultimately using δ13C to identify oil-prone organic matter in potential source rocks. These results have important implications for using bulk organic matter to identify and characterize global C-isotope excursions.

  20. The Re-Os Isotopic System: Geochemistry and Methodology at the Geochronological Research Center (CPGeo of the University of São Paulo, Brazil

    Directory of Open Access Journals (Sweden)

    Ciro Teixeira Correia


    Full Text Available The Re-Os isotopic system is an important tool for the study of mantle-crust processes, geochronology and the tracingof source reservoirs for metal deposition. Rhenium and osmium differ fundamentally from other lithophile isotopic systemswith regards to their behavior during partial melting processes, coupled with the chalcophile/siderophile nature of bothelements. These differences make the system extremely useful for a number of novel applications not traditionally addressedby lithophile isotopic systems. A low-blank technique for the analysis of Re-Os isotopes in geological materials has beenestablished at the Geochronological Research Center (CPGeo of the Geosciences Institute of the University of São Paulo,Brazil, with the aim of furthering knowledge of regional geology, tectonic evolution, petrology and ore deposition in SouthAmerica. The techniques described here use isotope dilution to simultaneously determine the concentration of Os and Re aswell the Os isotopic composition of geologic materials. Sample digestion and sample-isotopic spike equilibration are achievedin sealed borosilicate glass tubes at high temperature. Osmium is separated and purified by carbon tetrachloride solventextraction and micro-distillation techniques. Rhenium is separated and purified by anion exchange chromatography. Accuracyof the concentration and isotopic determinations is monitored by the analysis of a certified reference material (WPR-1 andthe use of the Department of Terrestrial Magnetism (DTM Os isotopic standard. Measured values and precision of thesestandards is within error and comparable to established Re-Os laboratories.

  1. Environmental impact and magnitude of paleosol carbonate carbon isotope excursions marking five early Eocene hyperthermals in the Bighorn Basin, Wyoming

    NARCIS (Netherlands)

    Abels, H.A.|info:eu-repo/dai/nl/304848018; Lauretano, V.; van Yperen, Anna E.; Hopman, Tarek; Zachos, J.C.; Lourens, L.J.|info:eu-repo/dai/nl/125023103; Gingerich, P.D.; Bowen, G.J.


    Transient greenhouse warming events in the Paleocene and Eocene were associated with the addition of isotopically light carbon to the exogenic atmosphere–ocean carbon system, leading to substantial environmental and biotic change. The magnitude of an accompanying carbon isotope excursion (CIE) can b

  2. C isotope fractionation during heterotrophic activity driven carbonate precipitation (United States)

    Balci, Nurgul; Demirel, Cansu


    Stable carbon isotopic fractionation during carbonate precipitation induced by environmentally enriched heterotrophic halophilic microorganims was experimentally investigated under various salinity (% 4.5, %8, %15) conditions at 30 °C. Halophilic heterotrophic microorganims were enriched from a hypersaline Lake Acigöl located in SW Turkey (Balci et al.,2015) and later used for the precipitation experiments (solid and liquid medium). The carbonate precipitates had relatively high δ13C values (-4.3 to -16.9 ‰) compared to the δ13C values of the organic compounds that ranged from -27.5 to -25.4 ‰. At salinity of 4.5 % δ13C values of carbonate ranged from -4.9 ‰ to -10.9 ‰ with a 13C-enrichment factor of +20 to +16 ‰ higher than the δ13C values of the associated DOC (-27.5) . At salinity 8 % δ13C values of carbonate ranged from -16.3 ‰ to -11.7 ‰ with a 13C-enrichment factor of+11.3 to+15.9 ‰ higher than the δ13C values of the associated DOC. The respected values for 15 % salinity ranged from -12.3 ‰ to -9.7 ‰ with a 13C-enrichment factor of +15.2 to+16.8 ‰ higher than the δ13C values of the associated DOC. The carbonate precipitates produced in the solid medium are more enriched in 13C relative to liquid culture experiments. These results suggest that the carbon in the solid was derived from both the bacterial oxidation of organic compounds in the medium and from the atmospheric CO2. A solid medium used in the experiments may have suppressed convective and advective mass transport favouring diffusion-controlled system. This determination suggests that the rate and equilibration of CO2 exchange with the atmosphere is the major control on C isotope composition of carbonate minerals precipitated in the experiments. Key words: Lake Acıgöl, halophilic bacteria, carbonate biomineralization, C isotopes References Nurgul Balci, Meryem Menekşe, Nevin Gül Karagüler, M. Şeref Sönmez,Patrick Meister 2015.Reproducing authigenic carbonate

  3. Carbon and nitrogen isotope systematics in diamond: Different sensitivities to isotopic fractionation or a decoupled origin? (United States)

    Hogberg, K.; Stachel, T.; Stern, R. A.


    Using stable isotope data obtained on multiple aliquots of diamonds from worldwide sources, it has been argued that carbon and nitrogen in diamond are decoupled. Here we re-investigate the carbon-nitrogen relationship based on the most comprehensive microbeam data set to date of stable isotopes and nitrogen concentrations in diamonds (n = 94) from a single locality. Our diamond samples, derived from two kimberlites in the Chidliak Field (NE Canada), show large variability in δ13C (- 28.4 ‰ to - 1.1‰, mode at - 5.8‰), δ15N (- 5.8 to + 18.8‰, mode at - 3.0‰) and nitrogen contents ([N]; 3800 to less than 1 at.ppm). In combination, cathodoluminescence imaging and microbeam analyses reveal that the diamonds grew from multiple fluid pulses, with at least one major hiatus documented in some samples that was associated with a resorption event and an abrupt change from low δ13C and [N] to mantle-like δ13C and high [N]. Overall, δ13C appears to be uncorrelated to δ15N and [N] on both the inter- and intra-diamond levels. Co-variations of δ15N-log[N], however, result in at least two parallel, negatively correlated linear arrays, which are also present on the level of the individual diamonds falling on these two trends. These arrays emerge from the two principal data clusters, are characterized by slightly negative and slightly positive δ15N (about - 3 and + 2‰, respectively) and variable but overall high [N]. Using published values for the diamond-fluid nitrogen isotope fractionation factor and nitrogen partition coefficient, these trends are perfectly reproduced by a Rayleigh fractionation model. Overall, three key elements are identified in the formation of the diamond suite studied: (1.) a low δ13C and low [N] component that possibly is directly associated with an eclogitic diamond substrate or introduced during an early stage fluid event. (2.) Repeated influx of a variably nitrogen-rich mantle fluid (mildly negative δ13C and δ15N). (3.) In waning

  4. Late Holocene Multiproxy Record (Palynology, Stable Isotope and Multi-Element Geochemistry) of Lake Santa Maria del Oro, Western Mesoamerica. (United States)

    Lozano, S.; Caballero, M.; Rodriguez, A.; Roy, P.; Sosa, S.


    We present the palynological, stable isotope and major element (ITRAX X-Ray fluorescence) data from a 850-cm sediment sequence from the deepest part of lake Santa María del Oro (SMO) in order to document changes in the climatic and limnological conditions and in the vegetation for the last ca. 5000 yr. SMO is a crater lake of (750 m asl, 2 km diam.) located in a tropical sub-humid climate (1250 mm/yr, average annual temperature 21° C) at the transition between the temperate central Mexican highlands and the arid northern regions. Tropical deciduous forests which loose their leaves for 8 months in a year and the tropical oak forests are the main plant communities in the lake catchments. The western part of Mesoamerica is the cradle of maize (Zea mays ssp. mays ) agriculture; this region is probably one of the two centers of maize domestication based on the presence of one of its closets wild relative teosinte (Zea mays ssp. parviglumis ). Chronology was established with 8 AMS radiocarbon dates. Sediments are finely laminated, with some intervals dominated by black and brown clayey silt and others by brown clayey silt and calcareous silt. In some levels, laminae are characterized by silts and fine sands. Authigenic carbonate laminations are formed during the summer season, when the highest temperatures are reached in the area. Throughout the pollen analysis, teosinte pollen and maize pollen was recorded. The major element concentration (Ca and Ti) in the bulk sediments was analyzed by ITRAX multi-element scanner and the isotopic data (δ13C and δ18O) in authigenic carbonates by mass spectrometer. Ca and Ti ITRAX intensities were calibrated to mass % by using the linear relationship between ITRAX intensity and mass % obtained through conventional XRF analysis. Preliminary pollen data of SMO sediments indicates abundant pollen of teosinte from ca. 2000 to 100 BC and maize presence at ca. 1300 BC and ca. 900 BC along with high charcoal particle concentrations

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

    Institute of Scientific and Technical Information of China (English)

    LIU ZongXiu; GU ZhaoYan; WU NaiQin; XU Bing


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

  6. Photosynthetic fractionation of the stable isotopes of oxygen and carbon

    Energy Technology Data Exchange (ETDEWEB)

    Guy, R.D. (Carnegie Institution of Washington, Stanford, CA (United States)); Fogel, M.L.; Berry, J.A. (Carnegie Inst. of Washington, Washington, DC (United States))


    Isotope discrimination during photosynthetic exchange of O[sub 2] and CO[sub 2] was measured using enzyme, thylakoid, and whole cell preparations. Evolved oxygen from isolated spinach thylakoids was isotopically identical (within analytical error) to its source water. Similar results were obtained with Anacystis nidulans Richter and Phaeodactylum tricornutum Bohlin cultures purged with helium. For consumptive reactions, discrimination ([triangle], where 1 + [triangle]/1000 equals the isotope effect, k[sup 16]/k[sup 18] or k[sup 12]/k[sup 13]) was determined by analysis of residual substrate (O[sub 2] or CO[sub 2]). The [triangle] for the Mehler reaction, mediated by ferredoxin or methylviologen, was 15.3[per thousand]. Oxygen isotope discrimination during oxygenation of ribulose-1,5-bisphosphate (RuBP) catalyzed by RuBP carboxylase/oxygenase (Rubisco) was 21.3[per thousand] and independent of enzyme source, unlike carbon isotope dicrimination: 30.3[per thousand] for spinach enzyme and 19.6 to 23[per thousand] for Rhodospirillum rubrum and A. nidulans enzymes, depending on reaction conditions. The [triangle] for O[sub 2] consumption catalyzed by glycolate oxidase was 22.7[per thousand]. Consistent with this, when Asparagus sprengeri Regel mesopyll cells approached the compensation point within a sealed vessel, the [delta][sup 18]O of dissolved O[sub 2] came to a steady-state value of about 21.5[per thousand] relative to the source water. The results provide improved estimates of discrimination factors in several reactions prominent in the global oxygen cycle and indicate that photorespiration plays a significant part in determining the isotopic composition of atmospheric oxygen. 47 refs., 8 figs., 2 tabs.

  7. Organic carbon isotopes of the Sinian and Early Cambrian black shales on Yangtze Platform, China

    Institute of Scientific and Technical Information of China (English)

    李任伟; 卢家烂; 张淑坤; 雷加锦


    Organic matter of the Sinian and early Cambrian black shales on the Yangtze Platform belongs to the light carbon group of isotopes with the δ13C values from - 27 % to -35 % , which are lower than those of the contemporaneously deposited carbonates and phosphorites. A carbon isotope-stratified paleooceanographic model caused by upwelling is proposed, which can be used not only to interpret the characteristics of organic carbon isotopic compositions of the black shales, but also to interpret the paleogeographic difference in the organic carbon isotope compositions of various types of sedimentary rocks.

  8. Allochthonous carbon hypothesis for bulk OM and n-alkane PETM carbon isotope discrepancies (United States)

    Baczynski, A. A.; McInerney, F. A.; Wing, S. L.; Kraus, M. J.; Fricke, H. C.


    The Paleocene-Eocene Thermal Maximum (PETM), a period of abrupt, transient, and large-scale global warming fueled by a large release of isotopically light carbon, is a relevant analogue for episodes of rapid global warming and recovery. The PETM is recorded in pedogenic carbonate, bulk organic matter, and n-alkanes as a prominent negative carbon isotope excursion (CIE) in paleosols exposed in the Bighorn Basin, WY. Here we present a composite stable carbon isotope record from n-alkanes and dispersed soil organic δ13C records from five individual sections that span the PETM in the southeastern Bighorn Basin. Four sections are from a 10km transect in the Cabin Fork area and one section was collected at Sand Creek Divide. These five new dispersed organic carbon (DOC) isotope records are compared to the previously published Polecat Bench (Magioncalda et al. 2004) and Honeycombs (Yans et al. 2006) isotope records. The high-resolution n-alkane curve shows an abrupt, negative shift in δ13C values, an extended CIE body, and a rapid recovery to more positive δ13C values. Although the five DOC records show similarly abrupt negative shifts in δ13C values, the DOC CIEs are compressed, smaller in magnitude, and return to more positive δ13C values more gradually relative to the n-alkane record. Moreover, the stratigraphic thickness of the body of the excursion and the pattern of the recovery phase are not consistent among the five DOC records. We modeled predicted DOC δ13C values from the n-alkane record by applying enrichment factors based on modern plants to the n-alkane δ13C values. The anomaly, difference between the expected and observed DOC δ13C values, was calculated for the PETM records and compared to weight percent carbon and grain size. There is no correlation between pre- and post-PETM anomaly values and grain size or weight percent carbon. PETM anomaly values, however, do trend with both grain size and weight percent carbon. The largest PETM anomaly values

  9. Seagrass sediments as a global carbon sink: Isotopic constraints (United States)

    Kennedy, Hilary; Beggins, Jeff; Duarte, Carlos M.; Fourqurean, James W.; Holmer, Marianne; Marbã, Núria; Middelburg, Jack J.


    Seagrass meadows are highly productive habitats found along many of the world's coastline, providing important services that support the overall functioning of the coastal zone. The organic carbon that accumulates in seagrass meadows is derived not only from seagrass production but from the trapping of other particles, as the seagrass canopies facilitate sedimentation and reduce resuspension. Here we provide a comprehensive synthesis of the available data to obtain a better understanding of the relative contribution of seagrass and other possible sources of organic matter that accumulate in the sediments of seagrass meadows. The data set includes 219 paired analyses of the carbon isotopic composition of seagrass leaves and sediments from 207 seagrass sites at 88 locations worldwide. Using a three source mixing model and literature values for putative sources, we calculate that the average proportional contribution of seagrass to the surface sediment organic carbon pool is ˜50%. When using the best available estimates of carbon burial rates in seagrass meadows, our data indicate that between 41 and 66 gC m-2 yr-1 originates from seagrass production. Using our global average for allochthonous carbon trapped in seagrass sediments together with a recent estimate of global average net community production, we estimate that carbon burial in seagrass meadows is between 48 and 112 Tg yr-1, showing that seagrass meadows are natural hot spots for carbon sequestration.

  10. Control strategies for laser separation of carbon isotopes

    Indian Academy of Sciences (India)

    V Parthasarathy; A K Nayak; S K Sarkar


    Laser isotope separation (LIS) by infrared laser chemistry of polyatomic molecules has come a long way since its discovery. The last decade has seen considerable efforts in scaling up of the process for light elements like carbon, oxygen and silicon. These efforts aim at ways to improve both the enrichment factor and the throughput. The achievement is quite significant especially for carbon isotope separation wherein macroscopic operating scales have been realized. We report our studies on the IR laser chemistry of two promising systems, viz. neat CF2HCl and CF3Br/Cl2. We have investigated conditions for optimizing the dissociation yield and selectivity using natural samples containing 1.1 % C-13. We also highlight our current efforts for scaling up the process. These include the design aspects of a photochemical reactor with multipass refocusing Herriott optics for efficient photon utilization, development of a cryogenic distillation set up and a preparative gas chromatograph for large scale separation/collection of the isotopically enriched photoproduct in the post-irradiation stage.

  11. Nature of the Precambrian metamorphic blocks in the eastern segment of Central Tianshan:Constraint from geochronology and Nd isotopic geochemistry

    Institute of Scientific and Technical Information of China (English)

    LIU; Shuwen; GUO; Zhaojie; ZHANG; Zhicheng; LI; Qiugen; ZH


    Granitoid gneisses are widespread in Precambrian metamorphic blocks of eastern segment of the Central Tianshan Tectonic Zone, and they have intrusive contact relationships with their metamorphic sedimentary country rocks of Proterozoic Xingxingxia and Kawabulag groups. Zircon U-Pb ages from a granodioritic gneiss (IW11-1) and a parametamorphic schist (W05-9) are determined at the Weiya area. Euhedral prismatic zircons from the granodioritic gneiss (IW11-1) provide U-Pb isotopic discordia intercept ages of 1218±17 Ma and 426±26 Ma, respectively, and euhedral prismatic zircons from the parametamorphic schist (W05-9) display U-Pb isotopic discordia intercept ages of 1216±74 Ma and 290±15 Ma, respectively. A whole-rock Sm-Nd isotopic isochron is determined in augen granitoid gneiss samples at the Ganggou-Kumishi area and we obtain the isochron age of 1142±120 Ma, and its εNd(t) = -4.3. These geochronological data suggest that these Precambrian metamorphic basement blocks within eastern segment of the Central Tianshan Tectonic Zone can be produced during 1140-1220 Ma, and occur a nearly homochronous metamorphism. Integrated to these geochronological data, Nd depleted mantle model ages (TDM) and epsilon Nd(t) values of these granitoid gneiss samples indicate that they can derive from mixing in various scales both magmas from mantle and crust sources at a late Mesoproterozoic active continental margin tectonic environment. Similarity in geochronology, Sm-Nd isotopic geochemistry between Weiya-Xingxingxia, Pargangtag and Ganggou-Kumishi areas suggests that they could be a bigger uniform metamorphic basement block, which could be formed by the assembly of the supercontinent Rodinia and be separated by late geological processes.

  12. An analytical system for stable isotope analysis on carbon monoxide using continuous-flow isotope-ratio mass spectrometry

    NARCIS (Netherlands)

    Pathirana, S. L.; Van Der Veen, C.; Popa, M. E.; Röckmann, T.


    A fully automated system for the determination of δ13C and δ18O in atmospheric CO has been developed. CO is extracted from an air sample and converted into carbon dioxide (CO2) using the Schütze reagent. The isotopic composition is determined with an isotope-ratio mass spectrometer (IRMS) technique.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  14. Provenance and sedimentary environments of the Proterozoic São Roque Group, SE-Brazil: Contributions from petrography, geochemistry and Sm-Nd isotopic systematics of metasedimentary rocks (United States)

    Henrique-Pinto, R.; Janasi, V. A.; Tassinari, C. C. G.; Carvalho, B. B.; Cioffi, C. R.; Stríkis, N. M.


    The Proterozoic metasedimentary sequences exposed in the São Roque Domain (Apiaí Terrane, Ribeira Belt, southeast Brazil) consist of metasandstones and meta-felspathic wackes with some volcanic layers of within-plate geochemical signature (Boturuna Formation), a passive margin turbidite sequence of metawackes and metamudstones (Piragibu Formation), and volcano-sedimentary sequences with MORB-like basalts (Serra do Itaberaba Group; Pirapora do Bom Jesus Formation). A combination of zircon provenance studies in metasandstones, whole-rock geochemistry and Sm-Nd isotopic systematics in metamudstones was used to understand the provenance and tectonic significance of these sequences, and their implications to the evolution of the Precambrian crust in the region. Whole-rock geochemistry of metamudstones, dominantly from the Piragibu Formation, points to largely granitic sources (as indicated for instance by LREE-rich moderately fractionated REE patterns and subtle negative Eu anomalies) with some mafic contribution (responding for higher contents of Fe2O3, MgO, V, and Cr) and were subject to moderate weathering (CIA - 51 to 85). Sm-Nd isotope data show three main peaks of Nd TDM ages at ca. 1.9, 2.1 and 2.4 Ga; the younger ages define an upper limit for the deposition of the unit, and reflect greater contributions from sources younger than the >2.1 Ga basement. The coincident age peaks of Nd TDM and U-Pb detrital zircons at 2.1-2.2 Ga and 2.4-2.5 Ga, combined with the possible presence of a small amount of zircons derived from mafic (gabbroid) sources with the same ages, as indicated by a parallel LA-ICPMS U-Pb dating study in metapsammites, are suggestive that these were major periods of crustal growth in the sources involving not only crust recycling but also some juvenile addition. A derivation from similar older Proterozoic sources deposited in a passive margin basin is consistent with the main sedimentary sequences in the São Roque Domain being broadly coeval and

  15. Sources of granite magmatism in the Embu Terrane (Ribeira Belt, Brazil): Neoproterozoic crust recycling constrained by elemental and isotope (Sr-Nd-Pb) geochemistry (United States)

    Alves, Adriana; Janasi, Valdecir de Assis; Campos Neto, Mario da Costa


    Whole rock elemental and Sr-Nd isotope geochemistry and in situ K-feldspar Pb isotope geochemistry were used to identify the sources involved in the genesis of Neoproterozoic granites from the Embu Terrane, Ribeira Belt, SE Brazil. Granite magmatism spanned over 200 Ma (810-580 Ma), and is dominated by crust-derived relatively low-T (850-750 °C, zircon saturation) biotite granites to biotite-muscovite granites. Two Cryogenian plutons show the least negative εNdt (-8 to -10) and highest mg# (30-40) of the whole set. Their compositions are strongly contrasted, implying distinct sources for the peraluminous (ASI ∼ 1.2) ∼660 Ma Serra do Quebra-Cangalha batholith (metasedimentary rocks from relatively young upper crust with high Rb/Sr and low Th/U) and the metaluminous (ASI = 0.96-1.00) ∼ 630 Ma Santa Catarina Granite. Although not typical, the geochemical signature of these granites may reflect a continental margin arc environment, and they could be products of a prolonged period of oceanic plate consumption started at ∼810 Ma. The predominant Ediacaran (595-580 Ma) plutons have a spread of compositions from biotite granites with SiO2 as low as ∼65% (e.g., Itapeti, Mauá, Sabaúna and Lagoinha granites) to fractionated muscovite granites (Mogi das Cruzes, Santa Branca and Guacuri granites; up to ∼75% SiO2). εNdT are characteristically negative (-12 to -18), with corresponding Nd TDM indicating sources with Paleoproterozoic mean crustal ages (2.0-2.5 Ga). The Guacuri and Santa Branca muscovite granites have the more negative εNdt, highest 87Sr/86Srt (0.714-0.717) and lowest 208Pb/206Pb and 207Pb/206Pb, consistent with an old metasedimentary source with low time-integrated Rb/Sr. However, a positive Nd-Sr isotope correlation is suggested by data from the other granites, and would be consistent with mixing between an older source predominant in the Mauá granite and a younger, high Rb/Sr source that is more abundant in the Lagoinha granite sample. The

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  17. A global deglacial negative carbon isotope excursion in speleothem calcite (United States)

    Breecker, D.


    δ13C values of speleothem calcite decreased globally during the last deglaciation defining a carbon isotope excursion (CIE) despite relatively constant δ13C values of carbon in the ocean-atmosphere system. The magnitude of the CIE varied with latitude, increasing poleward from ~2‰ in the tropics to as much as 7‰ at high latitudes. This recent CIE provides an interesting comparison with CIEs observed in deep time. A substantial portion of this CIE can be explained by the increase in atmospheric pCO2 that accompanied deglaciation. The dependence of C3 plant δ13C values on atmospheric pCO2 predicts a 2‰ δ13C decrease driven by the deglacial pCO2 increase. I propose that this signal was transferred to caves and thus explains nearly 100% of the CIE magnitude observed in the tropics and no less than 30% at the highest latitudes in the compilation. An atmospheric pCO2 control on speleothem δ13C values, if real, will need to be corrected for using ice core data before δ13C records can be interpreted in a paleoclimate context. The decrease in the magnitude of the equilibrium calcite-CO2 carbon isotope fractionation factor explains a maximum of 1‰ of the CIE at the highest northern latitude in the compilation, which experienced the largest deglacial warming. Much of the residual extratropical CIE was likely driven by increasing belowground respiration rates, which were presumably pronounced at high latitudes as glacial retreat exposed fresh surfaces and/or vegetation density increased. The largest increases in belowground respiration would have therefore occurred at the highest latitudes, explaining the meridional trend. This work supports the notion that increases in atmospheric pCO2 and belowground respiration rates can result in large CIEs recorded in terrestrial carbonates, which, as previously suggested, may explain the magnitude of the PETM CIE as recorded by paleosol carbonates.

  18. 镁同位素地球化学研究新进展及其应用%Advances and application in magnesium isotope geochemistry

    Institute of Scientific and Technical Information of China (English)

    柯珊; 刘盛遨; 李王晔; 杨蔚; 滕方振


    作为一种新兴的地质示踪剂,Mg同位素正受到国际地学界日益广泛的关注.Mg同位素地球化学研究已取得了巨大的进展,近期研究工作主要包括两个方面.首先,调查了地球各主要储库和陨石的Mg同位素组成特征,结果表明陨石和地球地幔具有均一并且相似的Mg同位素组成,平均δ26Mg值分别为-0.28±0.06‰和~0.25±0.07‰;相反,上地壳和水圈的Mg同位素组成很不均一,δ26Mg值变化范围分剐为-4.84‰~+0.92‰和-2.93‰~+1.13‰.其次,对一些地质和物理化学过程中Mg同位素的分馏行为进行研究,结果表明:(1)地表风化作用可以造成大的Mg同住素分馏,导致重Mg同位素残留在风化产物中而轻Mg同位素进入水圈;(2)岩浆分异过程中Mg同位素平衡分馏很小;(3)高温化学扩散和热扩散过程中Mg同位素会发生显著的动力学分馏.基于这些研究成果,Mg同位素体系已经被初步应用于示踪早期地球形成和壳内物质再循环等过程,并有望在不久的将来应用于示踪大陆地壳的化学演化和地质温度计等研究领域.%As new geological tracers, Mg isotopes attract more and more attentions from international geologists. Great achievements have been made in the Mg isotope geochemistry. Recent studies have been focusing on two aspects. First, Mg isotopic compositions of the major terrestrial reservoirs and chondrites have been investigated. Chondrites and the mantle have homogeneous and similar Mg isotopic compositions, with the average δ26Mg values of -0.28 ±0.06‰ and -0. 25 ±0.07‰, respectively. By contrast, the upper continental crust and hydrosphere are highly heterogeneous, with δ26Mg values varying from -4.84‰ to +0. 92‰ and from -2. 93‰ to + 1.13‰, respectively. Second, studies on behaviors of Mg isotopes during geological and physicochemical processes suggest that; (1) large Mg isotope fractionation occurs during continental weathering with heavy

  19. Silicate versus carbonate weathering in Iceland: New insights from Ca isotopes (United States)

    Jacobson, Andrew D.; Grace Andrews, M.; Lehn, Gregory O.; Holmden, Chris


    Several studies have measured riverine fluxes of Ca and carbonate alkalinity in Iceland with the aim of quantifying the role of basalt weathering in the long-term carbon cycle. A major assumption is that all of the Ca and alkalinity originates from the dissolution of Ca-bearing silicate minerals, such as plagioclase and clinopyroxene. However, hydrothermal calcite occurs throughout Iceland, and even trace levels are expected to impact river geochemistry owing to the mineral's high solubility and fast dissolution rate. To test this hypothesis, we used a new, high-precision Ca isotope MC-TIMS method (δ44/40Ca; 2σSD = ± 0.04 ‰) to trace sources of Ca in Icelandic rivers. We report elemental and Ca isotope data for rivers, high- and low-temperature groundwater, basalt, hydrothermal calcite (including Iceland Spar), and stilbite and heulandite, which are two types of zeolites commonly formed during low-grade metamorphism of basalt. In agreement with previous research, we find that rivers have higher δ44/40Ca values than basalt, with a maximum difference of ∼0.40‰. This difference may reflect isotope fractionation in the weathering zone, i.e., preferential uptake of 40Ca during clay mineral formation, adsorption, and other geochemical processes that cycle Ca. However, calcite δ44/40Ca values are also up to ∼0.40‰ higher than bedrock values, and on a diagram of δ44/40Ca versus Sr/Ca, nearly all waters plot within a plausible mixing domain bounded by the measured compositions of basalt and calcite, with glacial rivers plotting closer to calcite than non-glacial rivers. Calcite and heulandite form during hydrothermal alteration of basalt in the deep lava pile and often occur together in metabasalts now exposed at the surface. Because heulandite δ44/40Ca values are ∼1-2‰ lower than basalt, we suggest that 40Ca uptake by heudlandite explains the relatively high δ44/40Ca values of calcite and that calcite weathering in turn elevates riverine δ44/40Ca

  20. Carbon isotope excursions in paleosol carbonate marking five early Eocene hyperthermals in the Bighorn Basin, Wyoming

    Directory of Open Access Journals (Sweden)

    H. A. Abels


    Full Text Available Transient greenhouse warming events in the Paleocene and Eocene were associated with the addition of isotopically-light carbon to the exogenic atmosphere–ocean carbon pool, leading to substantial environmental and biotic change. The magnitude of an accompanying carbon isotope excursion (CIE can be used to constrain both the sources and amounts of carbon released during an event, as well as to correlate marine and terrestrial records with high precision. The Paleocene Eocene Thermal Maximum (PETM is well documented, but CIE records for the subsequent warming events are still rare especially from the terrestrial realm. Here, we provide new CIE records for two of the smaller hyperthermal events, I1 and I2, in paleosol carbonate, as well as two additional records of ETM2 and H2 in the Bighorn Basin. Stratigraphic comparison of this expanded, high-resolution terrestrial carbon isotope record to the deep-sea benthic foraminifera records from ODP Sites 1262 and 1263, Walvis Ridge, in the southern Atlantic Ocean corroborates that the Bighorn Basin fluvial sediments record global atmospheric change. The stratigraphic thicknesses of the eccentricity-driven hyperthermals in these archives are in line with precession-forcing of the 7 m thick fluvial overbank-avulsion sedimentary cycles. Using the CALMAG bulk oxide mean annual precipitation proxy, we reconstruct similar or slightly wetter than background soil moisture contents during the four younger hyperthermals, in contrast to drying observed during the PETM. Soil carbonate CIEs vary in magnitude proportionally with the marine CIEs for the four smaller early Eocene hyperthermals. This relationship breaks down for the PETM, with the soil carbonate CIE ~ 2–4‰ less than expected if all five linearly relate to marine CIEs. If the PETM CO2 forcing was similar but scaled to the younger hyperthermals, photosynthetic isotope fractionation or soil environmental factors are needed to explain this anomaly. We

  1. Carbon isotope excursions across the Permian-Triassic boundary in the Meishan section, Zhejiang Province, China

    Institute of Scientific and Technical Information of China (English)


    Both gradual and sharp decrease in organic and carbonate carbon isotope values were detected across the Permian-Triassic boundary in the Meishan section, Changxing, Zhejiang Province, China. The gradual decrease in organic carbon isotope values started at the bottom of Bed 23, coinciding with the strong oscillations of total organic carbon (TOC) contents, indicates increasing fluxes from carbonate to organic carbon reservoir during this interval. A 2.3‰ sharp drop of inorganic carbon isotope values occurred at the uppermost part of Bed 24e. A 3.7‰ sharp drop of organic carbon isotope values occurred in Bed 26. The dramatic drop of inorganic carbon isotope value of 8‰ reported previously is not confirmed from the unweathered carbonate samples in Bed 27. The large-scale fluctuation of organic carbon isotope values in the Yinkeng Formation reflects different extent of mixing of marine and terrestrial organic matters. The gradual depletion and subsequent sharp drop of carbon isotopes near the Permian-Triassic boundary might indicate complex causes of the end-Permian mass extinction.

  2. Geology, mineralization, U-Pb dating and Sr-Nd isotope geochemistry of intrusive bodies in northeast of Kashmar

    Directory of Open Access Journals (Sweden)

    Alireza Almasi


    Full Text Available Alireza Almasi1, Mohammad Hassan Karimpour1*, Khosrow Ebrahimi Nasrabadi1, Behnam Rahimi1, Urs KlÖtzli2 and Jose Francisco Santos3 Introduction The study area is located in central part of the Khaf- Kashmar-Bardeskan belt which is volcano-plutonic belt at the north of the Dorouneh fault in the north of Lut block. The north of the Lut block is affected by tectonic rotation and subduction processes which occur in the east of Iran (Tirrul et al., 1983. The magmatism of Lut block begins in Jurassic and continues in Tertiary (Aghanabati, 1995. Karimpour (Karimpour, 2006 pointed out the Khaf-Kashmar-Bardeskan belt has significant potential for IOCG type mineralization such as Kuh-e-Zar, Tannurjeh, and Sangan (Karimpour, 2006; Mazloumi, 2009. The data gathered on the I-type intrusive rocks include their field geology, petrography, U–Pb zircon dating and Sr–Nd isotope and also alteration and mineralization in the study area. Materials and methods - Preparation of 150 thin sections of rock samples for study of petrography and alteration of the intrusive rocks. - Magnetic susceptibility measuring of intrusive rocks. - U-Pb dating in zircon of I-type intrusive rocks by Laser-Ablation Multi Collector ICP-MS method. - Sr-Nd analysis on 5 samples of I-type intrusive rocks by Multi-Collector Thermal Ionization Mass Spectrometer (TIMS VG Sector 54 instrument. - Mineralography and paragenetic studies of ore-bearing quartz veins and geochemical analysis for 28 samples. - Production of the geology, alteration and mineralization maps by scale: 1:20000 in GIS. Results Oblique subduction in southern America initiated an arc-parallel fault and shear zones in the back of continental magmatic arc (Sillitoe, 2003. Because of this event, pull-apart basins were formed and high-K to shoshonitic calc-alkalineI- and A-type magmatism occur (Sillitoe, 2003. Most important deposits accompany with this magmatism are Au-Cu deposits types and Fe-Skarns (Sillitoe, 2003. We have

  3. Identifying microbial carbon sources during ethanol and toluene biodegradation in a pilot-scale experimental aquifer system using isotopic analysis (United States)

    Clay, S.; McLeod, H.; Smith, J. E.; Roy, J. W.; Slater, G. F.


    Combining ethanol with gasoline has become increasingly common in order to create more environmentally conscience transportation fuels. These blended fuels are favourable alternatives since ethanol is a non-toxic and highly labile renewable biomass-based resource which is an effective fuel oxygenate that reduces air pollution. Recent research however, has indicated that upon accidental release into groundwater systems, the preferential microbial metabolism of ethanol can cause progressively reducing conditions leading to slower biodegradation of petroleum hydrocarbons. Therefore, the presence of ethanol can result in greater persistence of BTEX compounds and longer hydrocarbon plumes in groundwater systems. Microbial biodegradation and community carbon sources coupled to aqueous geochemistry were monitored in a pilot-scale laboratory tank (80cm x 525cm x 175cm) simulating an unconfined sand aquifer. Dissolved ethanol and toluene were continuously injected into the aquifer at a controlled rate over 330 days. Carbon isotope analyses were performed on phospholipid fatty acid (PLFA) samples collected from 4 different locations along the aquifer. Initial stable carbon isotope values measured over days 160-185 in the bacterial PLFA ranged from δ13C = -10 to -21‰, which is indicative of dominant ethanol incorporation by the micro-organisms based on the isotopic signature of ethanol derived from corn, a C4 plant. A negative shift to δ13C = -10 to -30‰ observed over days 185-200, suggests a change in microbial metabolisms associated with less ethanol incorporation. This generally corresponds to a decrease in ethanol concentrations from day 40 to full attenuation at approximately day 160, and the onset of toluene depletion observed on day 120 and continuing thereafter. In addition, aqueous methane concentrations first detected on day 115 continued to rise to 0.38-0.70 mmol/L at all monitoring locations, demonstrating a significant redox shift to low energy methanogenic

  4. Mantle Degassing and Diamond Genesis:A Carbon Isotope Perspective

    Institute of Scientific and Technical Information of China (English)



    The effect of Co2 and CH4 degassing from the mantle on the carbon isotopic composition of diamond has been quantitatively modeled in terms of the principles of Rayleigh distillation.Assuming the δ13 C value of -5‰ for the mantle,the outgassing of CO2 can result in the large negative δ13 C values of diamond,whereas the outgassing of CH4 can drive the δ13C values of diamond in the positive direction.The theoretical expectations can be used to explain the full range of δ13 C values from-34.4‰5 to+5‰ observed for natural diamonds.It is possible that diamond formation was triggered by the degassing of Co2 and/or CH4 from the mantle and the associated fractional crystallization of carbonate-bearing melt.

  5. Carbon isotopes and water use efficiency in C4 plants. (United States)

    Ellsworth, Patrick Z; Cousins, Asaph B


    Drought is a major agricultural problem worldwide. Therefore, selection for increased water use efficiency (WUE) in food and biofuel crop species will be an important trait in plant breeding programs. The leaf carbon isotopic composition (δ(13)Cleaf) has been suggested to serve as a rapid and effective high throughput phenotyping method for WUE in both C3 and C4 species. This is because WUE, leaf carbon discrimination (Δ(13)Cleaf), and δ(13)Cleaf are correlated through their relationships with intercellular to ambient CO2 partial pressures (Ci/Ca). However, in C4 plants, changing environmental conditions may influence photosynthetic efficiency (bundle-sheath leakiness) and post-photosynthetic fractionation that will potentially alter the relationship between δ(13)Cleaf and Ci/Ca. Here we discuss how these factors influence the relationship between δ(13)Cleaf and WUE, and the potential of using δ(13)Cleaf as a meaningful proxy for WUE.

  6. Geochemistry of highly acidic mine water following disposal into a natural lake with carbonate bedrock

    Energy Technology Data Exchange (ETDEWEB)

    Wisskirchen, Christian, E-mail: [Institute of Mineralogy and Geochemistry, University of Lausanne, CH-1015 Lausanne (Switzerland); Dold, Bernhard [Institute of Mineralogy and Geochemistry, University of Lausanne, CH-1015 Lausanne (Switzerland)] [Instituto de Geologia Economica Aplicada, Universidad de Concepcion, Concepcion (Chile); Friese, Kurt [UFZ - Helmholtz Centre for Environmental Research, Department of Lake Research, D-39114 Magdeburg (Germany); Spangenberg, Jorge E. [Institute of Mineralogy and Geochemistry, University of Lausanne, CH-1015 Lausanne (Switzerland); Morgenstern, Peter [UFZ - Helmholtz Centre for Environmental Research, Department of Analytical Chemistry, D-04318 Leipzig (Germany); Glaesser, Walter [Institute of Geophysics and Geology, University of Leipzig, D-04211 Leipzig (Germany)


    Research highlights: {yields} Mean lake water element composition did not differ greatly from discharged AMD. {yields} Most elements showed increasing concentrations from the surface to lake bottom. {yields} Jarosite formed in the upper part, settled, and dissolved in the deeper part of the lake. {yields} Elements migrated into the underlying carbonates in the sequence As< Pb {approx} Cu < Cd < Zn = Mn. {yields} Gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks. - Abstract: Acid mine drainage (AMD) from the Zn-Pb(-Ag-Bi-Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of {approx}1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO{sub 3}, 4330 mg/L Fe and 29,250 mg/L SO{sub 4}. Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO{sub 4}). The variations in the H and O isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI {approx} 0.25) and anglesite (SI {approx} 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI {approx} 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI {approx} -0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material ({approx}90 wt.% water) of pH {approx}1 with a

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

    Institute of Scientific and Technical Information of China (English)

    李春园; 王先彬; 文启彬; 邵波


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

  8. Abundances in red giant stars - Carbon and oxygen isotopes in carbon-rich molecular envelopes (United States)

    Wannier, P. G.; Sahai, R.


    Millimeter-wave observations have been made of isotopically substituted CO toward the envelopes of 11 carbon-rich stars. In every case, C-13O was detected and model calculations were used to estimate the C-12/C-13 abundance ratio. C-17O was detected toward three, and possibly four, envelopes, with sensitive upper limits for two others. The CO-18 variant was detected in two envelopes. New results include determinations of oxygen isotopic ratios in the two carbon-rich protoplanetary nebulae CRL 26688 and CRL 618. As with other classes of red giant stars, the carbon-rich giants seem to be significantly, though variably, enriched in O-17. These results, in combination with observations in interstellar molecular clouds, indicate that current knowledge of stellar production of the CNO nuclides is far from satisfactory.

  9. Carbon isotope fluctuations in Precambrian carbonate sequences of several localities in Brazil




    Carbon isotope fluctuations in Precambrian sedimentary carbonates between 2.8 Ga and 0.60 Ga in Brazil are examined in this study. The carbonate facies of the BIF of the 2.8 Ga-old Carajás Formation, state of Pará in northern Brazil, has rather homogeneous delta13C (-5 o/ooPDB), compatible with carbonatization of a silicate protolith by a CO2-rich fluid from mantle degassing. The Paleoproterozoic Gandarela Formation, state of Minas Gerais, displays a narrow delta13C variation (-1.5 to +0.5 o/...

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

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


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

  11. Hydrogen isotope geochemistry of lherzolitic shergottite in Martian meteorite GRV99027 from the Grove Mountains in Antarctica

    Institute of Scientific and Technical Information of China (English)

    WANG Henan; HSU Weibiao; GUAN Yunbin; LIANG Ying


    Hydrogen isotopic composition was measured using an ion microprobe for lherzolitic shergottite in Martian meteorite GRV 99027 from the Grove Mountains in Antarctica. The D/H ratios of phosphate whitlockites were analyzed and water concentrations of tested points were calculated. The result show that their δD values vary from +1300‰ to +4700‰, and water contents from 0.04 wt% to 0.43 wt%. Comparing the results with the hydrogen isotopic compositions of whole rock, hydrous minerals and phosphates in SNC meteorites indicates that water highly enriched in deuterium is a unique feature of Martian meteorites, especially the phosphates prominent. It is interpreted as the result of isotopic exchange between magmatic water and Martian crustal fluids. The high D/H ratios observed in GRV 99027 phosphates indicate that they have hydrogen isotopic compositions similar to those of apatite in other Martian meteorites. The results further confirmed the association of GRV 99027 with the Martian meteorite group.

  12. Tunable Diode Laser Measurements of Leaf-scale Carbon Isotope Discrimination and Ecosystem Respired Carbon and Oxygen Isotope Ratios in a Semi-arid Woodland (United States)

    McDowell, N.; Chris, B.; Hanson, D.; Kern, S.; Meyer, C.; Pockman, W.; Powers, H.


    We present results and speculative interpretation of leaf-level carbon isotope discrimination and ecosystem respired carbon and oxygen isotope ratios from a semi-arid, C3/C4 woodland located in northern New Mexico, USA. Overstory leaf area index (LAI) is dominated by live juniper (Juniperus monosperma) trees with an LAI value of approximately 1.0 m2 per m2 ground area, and has a seasonally dynamic understory of mixed C3 forbs and C4 grasses and cacti, with a maximum LAI of 0.30 m2 per m2 ground area. Ecosystem respired carbon isotope ratios showed values characteristic of C3 dominated photosynthesis (Keeling plot intercepts of -35 to -22 per mil). Seasonal variation was typical of that found in wetter, C3 dominated forests, as was the dependence on climate (e.g. relationships with vapor pressure deficit, soil water content, and canopy conductance). Leaf-level carbon isotope discrimination of the junipers, measured by coupling a Li-Cor 6400 photosynthesis system to the TDL, provided discrimination-Ci and discrimination-vpd relationships consistent with measured ecosystem respired carbon isotope ratios. The oxygen isotope ratio of ecosystem respiration was dependent on rain water isotope composition, but was correlated with soil water content during rain-free periods. The cumulative effect of vapor pressure deficit after a rain event was tightly correlated with the oxygen isotope ratio of ecosystem respiration, suggesting the primary drivers are evaporative enrichment of soil water and perhaps nocturnal leaf enrichment. Instrument precision for carbon and oxygen isotope ratios of carbon dioxide is 0.06 to 0.18 per mil; however, overall precision is somewhat lower due to pressure and sampling effects.

  13. Sulfur and oxygen isotope geochemistry of acid mine drainage--the polymetallic sulfide deposit "himmelfahrt fundgrube" in Freiberg (Germany). (United States)

    Haubrich, F; Tichomirowa, M


    We investigated physical, chemical and isotope (S, O) parameters of sulfate from acid mine drainage from the polymetallic sulfide ore deposit Freiberg (Gennany), which was mined for more than eight hundred years. Two main groups of water were distinguished: 1. Flowing mine water with sulfate concentrations of less than 9,000 mg/l and pH values higher than 3.2, 2. Pore water in weathered low grade ores and pools with sulfate concentrations higher than 9000mg/l and pH values below 3.2. The sulfur and oxygen isotope composition of sulfate from flowing mine waters reflects mixing of sulfate from two sulfur sources: a) atmospheric sulfur from precipitation and b) sulfate formed as a result of sulfide oxidation processes. Sulfur isotope values of mine water sulfate were used to estimate the contribution of sulfate derived through oxidation of sulfides. The sulfur isotope composition of pore water sulfate and precipitated sulfate (jarosite) from weathered low grade ore samples is identical to the sulfur isotope composition of primary sulfides. The oxygen isotope composition of pore water sulfate from low grade ore samples indicates that the oxidation process proceeds relatively slowly in 02-depleted waters, probably without significant microbial catalysis.

  14. Carbon and strontium isotope variations and responses tosea-level fluctuations in the Ordovician of the Tarim Basin

    Institute of Scientific and Technical Information of China (English)

    JIANG; Maosheng


    [1]Arthur, M. A., The carbon cycle-controls of atmospheric CO2 and climate in the geologic past, in Climate in Earth History (eds., Berger, W. M., Crowell, J. C), Washington D C: U. S. National Academy Press, 1982, 55-67.[2]Kroopnick, P. M., Margolis, M. V., Wong, C. S., δ18C variations in marine carbonate sediments as indicators of the CO2 balance between atmosphere and ocean, in The Fate of Fossil Fuel CO2 in the Ocean (eds., Anderson, N. R., Malahoff. A.),New York: Plenum Press, 1977, 295-321.[3]Veizer, J., Fritz, P., Jones, B., Geochemistry of brachiopods: Oxygen and carbon isotopic records of Paleozoic oceans,Geochim. Cosmochim. Acta, 1986, 50: 1679- 1696.[4]Wadleigh, M. A., Veizer, J., 18O/16O and 13C/12C in Lower Paleozoic articulate brachiopods: Implications for the isotopic composition seawater, Geochim. Cosmochim. Acta, 1992, 56:431-443.[5]Goldberg, E. D., Minor elements in sea water, in Chemical Oceanography (eds., Riley, J. P., Skirrow, G.), Vol. l, New York: Academic Press, 1986.[6]Fanre, G., Principles ofIsotope Geology, New York: Wiley, 1986, 1 -589.[7]Ebneth, S., Diener, A., Buhl, D. et al., Strontium isotope systematics of conodonts: Middle Devonian, Eifel Mts. Germany,Paleogeogr. Paleoclimatol. Paleoecol, 1996, 119:201 - 214.[8]Martin, E. E., Macdougall, J. D., Sr and Nd isotopes at Permian / Triassic boundary: A record of climate change, Chem.Geol.. 1995. 125: 73-79.[9]Jones. C. E.. Jenkyns, H. C., Hesselbo, S. P., Strotium isotopic variations in Jurassic and Cretaceous seawater, Geochemica et Cosmochemica Acta. 1994, 58:3061 - 3074.[10]McArthur. J. M., Kennedy, W. J., Chen, M. et al., Staontium isotope stratigraphy for Late Cretaceous time: Drect numerical clibration of the Sr curve based on the U.S. western interior, Paleogeogr. Paleoclimatol. Paleoecol., 1994, 108:95-119.[11]McArthur, J. M., Thirlwall, M. F., Gale, A. S. et al., Strotium isotope stratigraphy for the Late Cretaceous: A new curve

  15. Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review (United States)

    Brüggemann, N.; Gessler, A.; Kayler, Z.; Keel, S. G.; Badeck, F.; Barthel, M.; Boeckx, P.; Buchmann, N.; Brugnoli, E.; Esperschütz, J.; Gavrichkova, O.; Ghashghaie, J.; Gomez-Casanovas, N.; Keitel, C.; Knohl, A.; Kuptz, D.; Palacio, S.; Salmon, Y.; Uchida, Y.; Bahn, M.


    The terrestrial carbon (C) cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual), including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. A further part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO2 diffusion and dissolution processes within the

  16. Geochemistry@BGS : a guide to geochemical data at the British Geological Survey


    Johnson, C C


    This report reviews the main activities in the British Geological Survey (and previously as the Institute of Geological Sciences) that have generated geochemical data. Included are; the mineral reconnaissance programme; regional geochemical mapping; groundwater geochemistry; marine and estuarine surveys; environmental geochemistry and health; radiometric surveys; isotopic geochemistry; lithogeochemical investigations; organic geochemistry laboratories; and many international activities involv...

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

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


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

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

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


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

  19. Long-range transport of continentally-derived particulate carbon in the marine atmosphere: evidence from stable carbon isotope studies


    Cachier, Héléne; BUAT-MÉNARD, PATRICK; Fontugne, Michel; Chesselet, Roger


    Since 1979, we have investigated marine and non-marine sources of particulate carbon in the marine atmosphere from measurements of carbon concentration and isotopic composition 13C/12C). Aerosol samples were collected, mostly during the Sea/Air Exchange (SEAREX) Program experiments, in the northern and southern hemispheres (Sargasso Sea, Enewetak Atoll, Peru upwelling, American Samoa, New Zealand, Amsterdam Island). The concentration and the isotopic composition of particulate carbon of marin...

  20. Isotope hydrology and baseflow geochemistry in natural and human-altered watersheds in the Inland Pacific Northwest, USA. (United States)

    Sánchez-Murillo, Ricardo; Brooks, Erin S; Elliot, William J; Boll, Jan


    This study presents a stable isotope hydrology and geochemical analysis in the inland Pacific Northwest (PNW) of the USA. Isotope ratios were used to estimate mean transit times (MTTs) in natural and human-altered watersheds using the FLOWPC program. Isotope ratios in precipitation resulted in a regional meteoric water line of δ(2)H = 7.42·δ(18)O + 0.88 (n = 316; r(2) = 0.97). Isotope compositions exhibited a strong temperature-dependent seasonality. Despite this seasonal variation, the stream δ(18)O variation was small. A significant regression (τ = 0.11D(-1.09); r(2) = 0.83) between baseflow MTTs and the damping ratio was found. Baseflow MTTs ranged from 0.4 to 0.6 years (human-altered), 0.7 to 1.7 years (mining-altered), and 0.7 to 3.2 years (forested). Greater MTTs were represented by more homogenous aqueous chemistry whereas smaller MTTs resulted in more dynamic compositions. The isotope and geochemical data presented provide a baseline for future hydrological modelling in the inland PNW.

  1. Using Carbon Isotopes in Cenozoic Soil Carbonates to Quantify Primary Productivity from Mid-Latitude Regions (United States)

    Caves, J. K.; Kramer, S. H.; Ibarra, D. E.; Chamberlain, C. P.


    The carbon isotope composition of pedogenic carbonates (δ13Ccarb) from paleosols has been extensively used as a proxy to estimate atmospheric pCO2 over the Phanerozoic. However, a number of other factors - including the concentration of plant-respired CO2 and the isotopic composition of both atmospheric and plant-respired carbon - influence the δ13C of pedogenic carbonates. For example, δ13Ccarb records from the mid-latitudes in central Asia and western North America show increasing trends in δ13Ccarb despite decreasing pCO2 during the late Cenozoic, which suggests that other factors play an important role in determining the isotopic composition of pedogenic carbonates. Instead, we suggest that these records are primarily recording changes in primary productivity rather than changes in atmospheric pCO2 and therefore propose a novel use of paleosol carbonate records to understand paleo-ecosystem dynamics. Here, we compile existing paleosol carbonate records, and present three new records from Wyoming, to estimate soil respiration and primary productivity in western North America during the Paleogene and early Neogene. We observe both an overall increase in δ13Ccarb after the early Eocene, and spatially heterogeneous δ13Ccarb values across western US basins. We combine this δ13Ccarb data with compilations of atmospheric pCO2 to estimate soil respiration and plant productivity. The long-term increase in δ13Ccarb indicates a decrease in plant productivity as conditions became more arid across much of the western US, congruent with both records of regional uplift and of global cooling. Furthermore, significant spatial heterogeneity in δ13Ccarb indicates that regional factors, such as the presence of paleolakes and/or local paleotopography may have provided a second-order control on local and regional productivity. Thus, our results provide a first-order estimate linking changes in primary productivity with regional tectonics and global climatic change.

  2. Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates (United States)

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


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

  3. Stable Carbon and Oxygen Isotopes of Pedogenic Carbonates in Ustic Vertisols: Implications for Paleoenvironmental Change

    Institute of Scientific and Technical Information of China (English)

    HUANG Cheng-Min; WANG Cheng-Shan; TANG Ya


    Pedogenic carbonates, found extensively in arid and semiarid regions, are important in revealing regional climatic and environmental changes as well as the carbon cycle. In addition, stable carbon and oxygen isotopic compositions of pedogenic carbonates have been used to rebuild paleoecology (biomass and vegetation) and to estimate paleotemperature and paleoprecipitation during past geological time. By utilizing the stable carbon and oxygen isotopic compositions (δ13C and δ18O) of secondary nodules in Ustic Vertisols, this study looked into the climatic and environmental changes in the dry valleys of the Yuanmou Basin, Yunnan Province, in southwestern China. The results showed that during the early Holocene, a warm-humid or hot-humid climate existed in the Yuanmou Basin, but since then fluctuations in climate have occurred, with a dry climate prevailing. A highly significant correlation (r = 0.92, n= 9) between δ13C and δ18O values of carbonates illustrated that there had been a continual shifting between cold-humid and warm-dry climates in southwestern China including the Yuanmou Basin since the early Holocene.

  4. Regional prediction of carbon isotopes in soil carbonates for Asian dust source tracer (United States)

    Chen, Bing; Cui, Xinjuan; Wang, Yaqiang


    Dust particles emitted from deserts and semi-arid lands in northern China cause particulate pollution that increases the burden of disease particularly for urban population in East Asia. The stable carbon isotopes (δ13C) of carbonates in soils and dust aerosols in northern China were investigated. We found that the δ13C of carbonates in surface soils in northern China showed clearly the negative correlation (R2 = 0.73) with Normalized Difference Vegetation Index (NDVI). Using Moderate Resolution Imaging Spectroradiometer (MODIS) satellite-derived NDVI, we predicted the regional distribution of δ13C of soil carbonates in deserts, sandy lands, and steppe areas. The predictions show the mean δ13C of -0.4 ± 0.7‰ in soil carbonates in Taklimakan Desert and Gobi Deserts, and the isotope values decrease to -3.3 ± 1.1‰ in sandy lands. The increase in vegetation coverage depletes 13C in soil carbonates, thus the steppe areas are predicted by the lowest δ13C levels (-8.1 ± 1.7‰). The measurements of atmospheric dust samples at eight sites showed that the Asian dust sources were well assigned by the 13C mapping in surface soils. Predicting 13C in large geographical areas with fine resolution offers a cost-effective tracer to monitor dust emissions from sandy lands and steppe areas which show an increasing role in Asian dust loading driven by climate change and human activities.

  5. Seasonal variation in stable carbon and nitrogen isotope values of bats reflect environmental baselines.

    Directory of Open Access Journals (Sweden)

    Ana G Popa-Lisseanu

    Full Text Available The stable carbon and nitrogen isotope composition of animal tissues is commonly used to trace wildlife diets and analyze food chains. Changes in an animal's isotopic values over time are generally assumed to indicate diet shifts or, less frequently, physiological changes. Although plant isotopic values are known to correlate with climatic seasonality, only a few studies restricted to aquatic environments have investigated whether temporal isotopic variation in consumers may also reflect environmental baselines through trophic propagation. We modeled the monthly variation in carbon and nitrogen isotope values in whole blood of four insectivorous bat species occupying different foraging niches in southern Spain. We found a common pattern of isotopic variation independent of feeding habits, with an overall change as large as or larger than one trophic step. Physiological changes related to reproduction or to fat deposition prior to hibernation had no effect on isotopic variation, but juvenile bats had higher δ13C and δ15N values than adults. Aridity was the factor that best explained isotopic variation: bat blood became enriched in both 13C and 15N after hotter and/or drier periods. Our study is the first to show that consumers in terrestrial ecosystems reflect seasonal environmental dynamics in their isotope values. We highlight the danger of misinterpreting stable isotope data when not accounting for seasonal isotopic baselines in food web studies. Understanding how environmental seasonality is integrated in animals' isotope values will be crucial for developing reliable methods to use stable isotopes as dietary tracers.

  6. Geochemistry and oxygen isotope composition of main-group pallasites and olivine-rich clasts in mesosiderites

    DEFF Research Database (Denmark)

    Greenwood, Richard C.; Barrat, Jean-Alix; Scott, Edward R. D.


    they are not. To investigate this "Great DuniteShortage" we have undertaken a geochemical and oxygen isotope study of main-group pallasites and dunitic rocks from mesosiderites.Oxygen isotope analysis of 24 main-group pallasites (103 replicates) yielded a mean Δ17O value of -0.187 ±0.016‰ (2σ), which is fully...... origin. Although the Dawn mission did not detect mesosiderite-like material on Vesta, evidence linking the mesosiderites and HEDs includes: (i) theirnearly identical oxygen isotope compositions; (ii) the presence in both of coarse-grained Mg-rich olivines; (iii) both have synchronous Lu-Hf and Mn-Cr ages...... asteroidsand meteorites results from a range of factors. However, evidence from pallasites and mesosiderites indicates that the most important reason for this olivine shortage lies in the early, catastrophic destruction ofplanetesimals in the terrestrial planet-forming region and the subsequent preferential...

  7. Major element, REE, and Pb, Nd and Sr isotopic geochemistry of Cenozoic volcanic rocks of eastern China: implications for their origin from suboceanic-type mantle reservoirs (United States)

    Basu, A.R.; Wang, Junwen; Huang, Wankang; Xie, Guanghong; Tatsumoto, M.


    Major- and rare-earth-element (REE) concentrations and UThPb, SmNd, and RbSr isotope systematics are reported for Cenozoic volcanic rocks from northeastern and eastern China. These volcanic rocks, characteristically lacking the calc-alkaline suite of orogenic belts, were emplaced in a rift system which formed in response to the subduction of the western Pacific plate beneath the eastern Asiatic continental margin. The rocks sampled range from basanite and alkali olivine basalt, through olivine tholeiite and quartz tholeiite, to potassic basalts, alkali trachytes, pantellerite, and limburgite. These rock suites represent the volcanic centers of Datong, Hanobar, Kuandian, Changbaishan and Wudalianchi in northeastern China, and Mingxi in the Fujian Province of eastern China. The major-element and REE geochemistry is characteristic of each volcanic suite broadly evolving through cogenetic magmatic processes. Some of the outstanding features of the isotopic correlation arrays are as follows: (1) NdSr shows an anticorrelation within the field of ocean island basalts, extending from the MORB end-member to an enriched, time-averaged high Rb Sr and Nd Sr end-member (EM1), (2) SrPb also shows an anticorrelation, similar to that of Hawaiian and walvis Ridge basalts, (3) NdPb shows a positive correlation, and (4) the 207Pb 204Pb vs 206Pb 204Pb plot shows linear arrays parallel to the general trend (NHRL) for MORB on both sides of the geochron, although in the 208Pb 204Pb vs 206Pb 204Pb plot the linear array is significantly displaced above the NHRL in a pattern similar to that of the oceanic island basalts that show the Dupal signatures. In all isotope correlation patterns, the data arrays define two different mantle components-a MORB-like component and an enriched mantle component. The isotopic data presented here clearly demonstrate the existence of Dupal compositions in the sources of the continental volcanic rocks of eastern China. We suggest that the subcontinental mantle

  8. Sulfur isotope geochemistry of ore and gangue minerals from the Silesian-Cracow Mississippi Valley-type ore district, Poland (United States)

    Leach, D.L.; Vets, J.G.; Gent, C.A.


    Studies of the sulfur isotopic composition of ore and gangue minerals from the Silesian-Cracow Zn-Pb district were conducted to gain insights into processes that controlled the location and distribution of the ore deposits. Results of this study show that minerals from the Silesian-Cracow ore district have the largest range of sulfur isotope compositions in sulfides observed from any Mississippi Valley-type ore district in the world. The ??34S values for sulfide minerals range from +38 to -32 per mil for the entire paragenetic sequence but individual stages exhibit smaller ranges. There is a well developed correlation between the sulfur isotope composition and paragenetic stage of ore deposition. The first important ore stage contains mostly positive ??34S values, around 5 per mil. The second stage of ore formation are lower, with a median value of around -5 to -15 per mil, and with some values as low as -32 per mil. Late stage barite contains isotopically heavy sulfur around +32 per mil. The range in sulfur isotope compositions can be explained by contributions of sulfur from a variety of source rocks together with sulfur isotope fractionations produced by the reaction paths for sulfate reduction. Much of the variation in sulfur isotope compositions can be explained by bacterial reduction of sedimentary sulfate and disequilibrium reactions by intermediate-valency sulfur species, especially in the late-stage pyrite and sphalerite. Organic reduction of sulfate and thermal release of sulfur from coals in the Upper Silesian Coal Basin may have been important contributors to sulfur in the ore minerals. The sulfur isotopic data, ore mineral textures, and fluid inclusion data, are consistent with the hypothesis that fluid mixing was the dominant ore forming mechanism. The rather distinct lowering of ?? 34S values in sulfides from stage 2 to stage 3 is believed to reflect some fundamental change in the source of reduced sulfur and/or hydrology of the ore

  9. Stable Isotope Studies of Crop Carbon and Water Relations: A Review

    Institute of Scientific and Technical Information of China (English)

    ZHANG Cong-zhi; ZHANG Jia-bao; ZHAO Bing-zi; ZHANG Hui; HUANG Ping


    Crop carbon and water relations research is important in the studies of water saving agriculture,breeding program,and energy and material cycles in soil plant atmosphere continuum (SPAC).The purpose of this paper is to review the current state of knowledge on stable isotopes of carbon,oxygen,and hydrogen in the research of crop carbon and water relations,such as carbon isotope discrimination (△13C) during carbon fixation process by photosynthesis,application of △13C in crop water use efficiency (WUE) and breeding programs,oxygen isotope enrichment during leaf water transpiration,CO2 fixation by photosynthesis and release by respiration,application of hydrogen isotope composition (δD) and oxygen isotope composition (δ18O) for determination of water source used by a crop,stable isotope coupling Keeling plot for investigating the carbon and water flux in ecosystem,energy and material cycle in SPAC and correlative integrative models on stable isotope.These aspects contain most of the stable isotope researches on crop carbon and water relations which have been widely explored internationally while less referred in China.Based on the reviewed literatures,some needs for future research are suggested.

  10. The magnesium isotope record of cave carbonate archives

    Directory of Open Access Journals (Sweden)

    S. Riechelmann


    Full Text Available Here we explore the potential of magnesium (δ26Mg isotope time-series data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco, the warm-temperate (Germany, the equatorial-humid (Peru and the cold-humid (Austria climate zones. Changes in the calcite magnesium isotope signature with time are compared against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a number of environmental, equilibrium and disequilibrium processes governs the δ26Mg fractionation in continental settings. These include the different sources of magnesium isotopes such as rainwater or snow as well as soil and host rock, soil zone biogenic activity, shifts in silicate versus carbonate weathering ratios and residence time of water in the soil and karst zone. Pleistocene stalagmites from Morocco show the lowest mean δ26Mg values (GDA: −4.26 ± 0.07‰ and HK3: −4.17 ± 0.15‰, and the data are well explained in terms of changes in aridity over time. The Pleistocene to Holocene stalagmites from Peru show the highest mean value of all stalagmites (NC-A and NC-B δ26Mg: −3.96 ± 0.04‰ but only minor variations in Mg-isotope composition, which is consistent with the rather stable equatorial climate at this site. Holocene stalagmites from Germany (AH-1 mean δ26Mg: −4.01 ± 0.07‰; BU 4 mean δ26Mg: −4.20 ± 0.10‰ suggest changes in outside air temperature was the principal driver rather than rainfall amount. The alpine Pleistocene flowstones from Austria (SPA 52: −3.00 ± 0.73‰; SPA 59: −3.70 ± 0.43‰ are affected by glacial versus interglacial climate change with outside air temperature

  11. The magnesium isotope record of cave carbonate archives

    Directory of Open Access Journals (Sweden)

    S. Riechelmann


    Full Text Available Here we explore the potential of time-series magnesium (δ26Mg isotope data as continental climate proxies in speleothem calcite archives. For this purpose, a total of six Pleistocene and Holocene stalagmites from caves in Germany, Morocco and Peru and two flowstones from a cave in Austria were investigated. These caves represent the semi-arid to arid (Morocco, the warm-temperate (Germany, the equatorial-humid (Peru and the cold-humid (Austria climate zones. Changes in the calcite magnesium isotope signature with time are placed against carbon and oxygen isotope records from these speleothems. Similar to other proxies, the non-trivial interaction of a number of environmental, equilibrium and non-equilibrium processes governs the δ26Mg fractionation in continental settings. These include the different sources of magnesium isotopes such as rain water or snow as well as soil and hostrock, soil zone biogenic activity, shifts in silicate versus carbonate weathering ratios and residence time of water in the soil and karst zone. Pleistocene stalagmites from Morocco show the lowest mean δ26Mg values (GDA: −4.26 ± 0.07 ‰ and HK3: −4.17 ± 0.15 ‰ and the data are well explained in terms of changes in aridity over time. The Pleistocene to Holocene stalagmites from Peru show the highest mean value (NC-A and NC-B δ26Mg: −3.96 ± 0.04 ‰ but only minor variations in Mg-isotope composition, which is in concert with the rather stable equatorial climate at this site. Holocene stalagmites from Germany (AH-1 mean δ26Mg: −4.01 ± 0.07 ‰; BU 4 mean δ26Mg: −4.20 ± 0.10 ‰ record changes in outside air temperature as driving factor rather than rainfall amount. The alpine Pleistocene flowstones from Austria (SPA 52: −3.00 ± 0.73 ‰; SPA 59: −3.70 ± 0.43 ‰ are affected by glacial versus interglacial climate change with outside air temperature affecting soil zone activity

  12. Isotope Geochemistry of the Dongchuan Copper Deposit, Yunnan, SW China:Stratigraphic Chronology and Application of Lead Isotopes in Geochemical Exploration

    Institute of Scientific and Technical Information of China (English)

    常向阳; 朱炳泉


    In this paper the Pb-Pb isochron method was used to determine the isotopic ages of the Luoxue Formation dolomites (1716 ± 56 Ma), the Heishan Formation carbonaceous slates(1607 ± 128 Ma) of the middle sub-group of the Kunyang Group and the Dayingpan Formation carbonaceous slates ( 1258 ± 70Ma) of the upper sub-group of the Kunyang Group. The age of the middle sub-group of the Kunyang Group is about 1800 - 1600 Ma, belonging to the Late Paleo-Proterozoic, and that of the Dayingpan Formation in the upper sub-group of the Kunyang Group is about 1200 - 1300 Ma, belonging to the Middle Proterozoic. In addition, the Pb isotope chemical exploration techniques were used to study systematically the Pb isotopic compositions of rocks and ores across the No. 14 vein in the middle segment of the No. 1 pit of the Tangdan copper deposit and the result showed that the Pb isotope V1 values are negatively correlated with the copper contents. It is the first trial to use the systematic section method to conduct Pb isotope chemical exploration.

  13. Isotope Geochemistry of the Dongchuan Copper Deposit,Yunnan,SW China: Stratigraphic Chronology and Application of Lead Isotopes in Geochemical Exploration

    Institute of Scientific and Technical Information of China (English)

    常向阳; 朱炳泉


    In this paper the Pb-Pb isochron method was used to determine the isotopic ages of te Luoxue Formation dolomites(1716±56Ma),th Heishan Formation carbonaceous slated (1607±128Ma) of the middle sub-group of the Kunyang Group and the Dayingpan Formation carbonaceous slates(1258±Ma) of the upper sub-group of the Kunyang Group.The age of the middle sub-group of the Kunyang Group is about 1800-1600Ma,belonging to the Late Paleo-Proterozoic,and that of the Dayingpan Formation in the upper sub-group of the Kunyang Group is about 1200-1300Ma, belonging to the Middle Poroterozoic.In addition,the Pb isotope chemical exploration techniques were used to study systematically the Pb isotopic compositions of rocks and ores across the No.14 vein in the middle segment of the No.1 pit of the Tangdan copper deposit and the result showed that the Pb isotope V1 values are neatively correlated with the copper contents.In is the first trial to use the systematic section method to conduct Pb isotope chemical exploration.

  14. The 1998-2001 submarine lava balloon eruption at the Serreta ridge (Azores archipelago): Constraints from volcanic facies architecture, isotope geochemistry and magnetic data (United States)

    Madureira, Pedro; Rosa, Carlos; Marques, Ana Filipa; Silva, Pedro; Moreira, Manuel; Hamelin, Cédric; Relvas, Jorge; Lourenço, Nuno; Conceição, Patrícia; Pinto de Abreu, Manuel; Barriga, Fernando J. A. S.


    The most recent submarine eruption observed offshore the Azores archipelago occurred between 1998 and 2001 along the submarine Serreta ridge (SSR), 4-5 nautical miles WNW of Terceira Island. This submarine eruption delivered abundant basaltic lava balloons floating at the sea surface and significantly changed the bathymetry around the eruption area. Our work combines bathymetry, volcanic facies cartography, petrography, rock magnetism and geochemistry in order to (1) track the possible vent source at seabed, (2) better constrain the Azores magma source(s) sampled through the Serreta submarine volcanic event, and (3) interpret the data within the small-scale mantle source heterogeneity framework that has been demonstrated for the Azores archipelago. Lava balloons sampled at sea surface display a radiogenic signature, which is also correlated with relatively primitive (low) 4He/3He isotopic ratios. Conversely, SSR lavas are characterized by significantly lower radiogenic 87Sr/86Sr, 206Pb/204Pb and 208Pb/204Pb ratios than the lava balloons and the onshore lavas from the Terceira Island. SSR lavas are primitive, but incompatible trace-enriched. Apparent decoupling between the enriched incompatible trace element abundances and depleted radiogenic isotope ratios is best explained by binary mixing of a depleted MORB source and a HIMU­type component into magma batches that evolved by similar shallower processes in their travel to the surface. The collected data suggest that the freshest samples collected in the SSR may correspond to volcanic products of an unnoticed and more recent eruption than the 1998-2001 episode.

  15. The Stable and Radio- Carbon Isotopic Content of Labile and Refractory Carbon in Atmospheric Particulate Matter (United States)

    McNichol, A. P.; Rosenheim, B. E.; Gerlach, D. S.; Hayes, J. M.


    Studies of the isotopic content of atmospheric particulate matter are hampered by difficulties in chemically defining the pools of carbon and analytically isolating the different pools. We are conducting studies on reference materials and atmospheric aerosol samples to develop a method to measure stable and radio- carbon isotopes on the labile and refractory carbon. We are using a flow-through combustion system that allows us to combust, collect and measure the isotopic content of the gases produced at all stages of heating/oxidizing. We compare our results to those measured using a chemothermal oxidation method (CTO) (Gustafsson et al., 2001). In this method, refractory carbon is defined as the material remaining after pre- combusting a sample at 375°C in the presence of oxygen for 24 hours. The reference materials are diesel soot, apple leaves and a hybrid of the two (DiesApple), all from NIST. These provide carbon with two well-defined fractions -- the soot provides refractory carbon that is radiocarbon dead and the apple leaves provide organic carbon that is radiocarbon modern. Radiocarbon results from DiesApple indicate that the "refractory" carbon defined by the CTO method is actually a mixture of old and modern carbon that contains over 25% modern carbon. This suggests that charred material formed from the apples leaves during the pre-combustion step is contributing to the fraction we identify as refractory carbon. We are studying this by analyzing the individual materials and the mixture using our flow-through system. First results with this system indicate that the refractory fraction trapped from the DiesApple contains much less modern carbon than the CTO method, less than 7%. We will present detailed concentration and isotopic results of the generation of carbon dioxide during programmed combustion of each of the reference materials. We studied the radiocarbon content of both the total carbon (TC) and refractory carbon in the fine particulate matter (PM

  16. Geochemistry, geology, and isotopic (Sr, S, and B) composition of evaporites in the Lake St. Martin impact structure: New constraints on the age of melt rock formation (United States)

    Leybourne, Matthew I.; Denison, Rodger E.; Cousens, Brian L.; Bezys, Ruth K.; Gregoire, D. Conrad; Boyle, Dan R.; Dobrzanski, Ed


    We report new Sr, S, and B isotopic data for evaporites (gypsum, anhydrite), carbonates, melt rocks, gneisses, and groundwaters recovered in and around the Lake St. Martin (LSM) impact structure, Interlake Region, Manitoba, Canada. The LSM meteorite impacted Devonian to Ordovician carbonates and sandstones of the eastern Williston Basin, resulting in partial melting of underlying Superior Province (~2.5 Ga) gneisses of the Canadian Shield. Overlying the LSM melt rocks are red beds and evaporites (anhydrite/gypsum/glauberite) previously inferred to have been deposited during the Jurassic. The 87Sr/86Sr (lowest values cluster at 0.70836) and δ 34SCDT (+23.7 +/- 0.9‰) of the evaporites, combined with B isotope compositions of associated groundwaters (δ 11BNBS951 = +25 to +28‰), are consistent with evaporite deposition within the impact structure near the edge of an ocean-connected salina. The establishment of a marine origin for the evaporites offers a method of age assignment using the secular variation of S and Sr isotopes in seawater. Comparison of Sr and S isotope results with the seawater curves precludes Jurassic deposition for the evaporites or correlation with Watrous and Amaranth formation evaporites, previously considered correlative with those at LSM. The lowest Sr and mean of S isotope values from the LSM evaporites are similar to seawater in the latest Devonian, consistent with conodonts recovered from carbonate breccia overlying melt rocks, and we suggest this as an alternative age of the evaporites. Data presented here preclude a Jurassic age for the evaporites and therefore for the impact event.

  17. Clumped isotope calibration data for lacustrine carbonates: A progress report (United States)

    Tripati, A.


    Our capacity to understand Earth's environmental history is highly dependent on the accuracy of reconstructions of past climates. Lake sediments provide important archives of terrestrial climate change, and represent an important tool for reconstructing paleohydrology, paleoclimate, paleoenvironment, and paleoaltimetry. Unfortunately, while multiple methods for constraining marine temperature exist, quantitative terrestrial proxies are scarcer - tree rings, speleothems, and leaf margin analyses have all been used with varying degrees of accuracy. Clumped isotope thermometry has the potential to be a useful instrument for determining terrestrial climates: multiple studies have shown the fraction of 13C—18O bonds in carbonates is inversely related to the temperature at which the rocks formed. We have been measuring the abundance of 13C18O16O in the CO2 produced by the dissolution of carbonate minerals in phosphoric acid in modern lake samples and comparing results to independently known estimates of lake water temperature. Here we discuss an extensive calibration dataset comprised of 132 analyses of 97 samples from 44 localities, including microbialites, tufas, and micrites endogenic carbonates, freshwater gastropods, bivalves, microbialites, and ooids.

  18. Trace Metals, Rare Earths, Carbon and Pb Isotopes as Proxies of Environmental Catastrophe at the Permian - Triassic Boundary in Spiti Himalayas, India (United States)

    Ghosh, N.; Basu, A. R.; Garzione, C. N.; Ghatak, A.; Bhargava, O. N.; Shukla, U. K.; Ahluwalia, A. D.


    Himalayan sediments from Spiti Valley, India preserve geochemical signatures of the Permian - Triassic (P-Tr) mass extinction in the Neo-Tethys Ocean. We integrate new sedimentological and fossil record with high-resolution geochemical-isotopic data from Spiti that reveals an ecological catastrophe of global proportions. Trace elements of U, Th, Nb, Ta, Zr, Hf, the rare earths (REE) and carbon, oxygen and lead isotopes measured across the P-Tr boundary in Spiti are used as proxies for evaluating abrupt changes in this continental shelf environment. δ13Corg excursions of 2.4‰ and 3.1‰ in Atargu and Guling P-Tr sections in Spiti Valley are associated with an abrupt fall of biological productivity while δ13Ccarb and δ18Ocarb record of these sediments shows effects of diagenesis. Here, the P-Tr boundary is compositionally distinct from the underlying Late Permian gray shales, as a partly gypsiferous ferruginous layer that allows additional geochemical-isotopic investigation of sedimentary sources. Conspicuous Ce - Eu anomalies in the light REE-enriched Late Permian shales reflect the source composition of the adjacent Panjal Trap basalts of Kashmir. An abrupt change of this source to continental crust is revealed by Nb - Ta and Zr - Hf anomalies at the P-Tr ferruginous layer and continuing through the overlying Early Triassic carbonate rocks. Pb concentration and isotope ratios of 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb identify changes in the sedimentary element flux, distinguishing the Late Permian shales from the distinct siliciclastic continental crustal signature in the Early Triassic carbonates. These geochemical-isotopic constraints on the sedimentary geochemistry of one of the most critical transitions in geological record establish the utility of multi-proxy datasets for paleoenvironmental reconstructions.

  19. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer (United States)

    Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus


    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

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

    Energy Technology Data Exchange (ETDEWEB)

    Gromov, Sergey S.


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

  1. Observation of Large Enhancement of Charge Exchange Cross Sections with Neutron-Rich Carbon Isotopes

    CERN Document Server

    Tanihata, I; Kanungo, R; Ameil, F; Atkinson, J; Ayyad, Y; Cortina-Gil, D; Dillmann, I; Estradé, A; Evdokimov, A; Farinon, F; Geissel, H; Guastalla, G; Janik, R; Knoebel, R; Kurcewicz, J; Litvinov, Yu A; Marta, M; Mostazo, M; Mukha, I; Nociforo, C; Ong, H J; Pietri, S; Prochazka, A; Scheidenberger, C; Sitar, B; Strmen, P; Takechi, M; Tanaka, J; Toki, H; Vargas, J; Winfield, J S; Weick, H


    Production cross sections of nitrogen isotopes from high-energy carbon isotopes on hydrogen and carbon targets have been measured for the first time for a wide range of isotopes. The fragment separator FRS at GSI was used to deliver C isotope beams. The cross sections of the production of N isotopes were determined by charge measurements of forward going fragments. The cross sections show a rapid increase with the number of neutrons in the projectile. Since the production of nitrogen is mostly due to charge exchange reactions below the proton separation energies, the present data suggests a concentration of Gamow-Teller and Fermi transition strength at low excitation energies for neutron-rich isotopes. It was also observed that the cross sections were enhanced much more strongly for neutron rich isotopes in the C-target data.

  2. Distribution coefficients of 60 elements on TODGA resin: application to Ca, Lu, Hf, U and Th isotope geochemistry. (United States)

    Pourmand, Ali; Dauphas, Nicolas


    Batch equilibration experiments are conducted to measure the distribution coefficients (K(d)) of a large number of elements in nitric, nitric plus hydrofluoric, and hydrochloric acids on Eichrom TODGA extraction chromatography resin. The K(d)s are used to devise a multi-element extraction scheme for high-precision elemental and isotopic analyses of Ca, Hf, Lu, Th and U in geological materials, using high-purity lithium metaborate (LiBO(2)) flux fusion that allows rapid digestion of even the most refractory materials. The fusion melt, dissolved in nitric acid, is directly loaded to a TODGA cartridge on a vacuum chamber for elemental separation. An Ln-Spec cartridge is used in tandem with TODGA for Lu purification. The entire procedure, from flux digestion to preparation for isotopic analysis, can be completed in a day. The accuracy of the proposed technique is tested by measuring the concentrations of Ca (standard bracketing), Hf, Lu, Th and U (isotope dilution), and the isotopic composition of Hf in geostandards (USNM3529, BCR-2, BHVO-1, AGV-1 and AGV-2). All measurements are in excellent agreement with recommended literature values, demonstrating the effectiveness of the proposed analytical procedure and the versatility of TODGA resin.

  3. Strontium isotopic geochemistry of the volcanic rocks and associated megacrysts and inclusions from Ross Island and vicinity, Antarctica (United States)

    Stuckless, J.S.; Ericksen, R.L.


    Twelve whole-rock samples of volcanic rocks and a composite of 11 basanitoid samples from Ross Island and vicinity, Antarctica show a narrow range of 87Sr/86Sr ratios from 0.70305 to 0.70339. This range is consistent with a model of differentiation from a single parent magma, but the data allow a 30% variation in the 87Rb/86Sr ratio in the source region if the average ratio is less than 0.057 and if the source region has existed as a closed system for 1.5 b.y. Megacrysts of titaniferous augite, kaersutite, and anorthoclase are isotopically indistinguishable from the host volcanic rocks and therefore are probably cogenetic with the volcanic sequence. A single trachyte sample is isotopically distinct from the rest of the volcanic rocks and probably was contaminated with crustal strontium. Ultramafic and mafic nodules found in association with basanitoids and trachybasalts have 87Sr/86Sr ratios ranging from 0.70275 to 0.70575. Several of these nodules exhibit evidence of reaction with the melt and are isotopically indistinguishable from their hosts, but data for seven granulite-facies nodules show an apparent isochronal relationship. Although this isochron may be fortuitous, the resulting age of 158??22 m.y. is similar to ages reported for the voluminous Ferrar Dolerites, and suggests isotopic re-equilibration within the lower crust and upper mantle. These nodules are not genetically related to the Ferrar Dolerites, as evidenced by their lower initial 87Sr/86Sr ratios. Three ultramafic nodules are texturally and isotopically distinct from the rest of the analyzed nodules. These are friable, have larger 87Sr/86Sr ratios, and may represent a deeper sampling of mantle rock than the granulite-facies nodules. They were, however, derived at a shallower depth than the alkalic magma. Thus they are not genetically related to either the magma or the granulite-facies nodules. ?? 1976 Springer-Verlag.

  4. Stable Carbon Isotope Record in a Palau Sclerosponge (United States)

    Grottoli, A. G.


    The ratio of stable carbon isotopes (δ13C) deposited in the calcium carbonate skeleton of marine sclerosponges appears to record the carbon isotopic composition of seawater mixed-layer dissolved inorganic carbon (δ13CDIC). Thus the δ13C signature chronicled in sclerosponge skeletons offers a promising multi-century proxy record of seawater mixed-layer δ13CDIC throughout the tropics. Here, a high-resolution (0.1 mm) δ13C record for a 7.7 cm Acanthocheatetes wellsi sclerosponge from Palau (7N, 134W) is presented. At a published growth rate of 0.45 mm per year, this record spans ~s170 years beginning in July 2001 and going back to 1831. The δ13C values for a definitive 10-year A. wellsi record spanning 1989-1998 were similar to δ13C values here for the first 4.7 mm of the record providing supporting evidence for the growth rate. The sclerosponge δ13C shows a distinct Seuss Effect. At the time this abstract was submitted, the analysis of the first 16 mm of the sclerosponge revealed a significant decrease in δ13C with time [δ13C = 0.02 (distance) + 2.64, r2 = 0.73, p < 0.0001, where time is marked by distance in millimeters from the growing edge] corresponding to a decrease in δ13C of 0.076‰ per decade. For comparison, published low-frequency measurements in Australian, New Caledonian and Jamaican sclerosponges have yielded decreases in δ13C of ~s0.05 to 0.08 ‰ per decade over the past 40 years. Preliminary interpretation of the data indicates that the amount of atmospheric CO2 contributing to the seawater δ13CDIC at Palau is intermediate to Australia and Jamaica. In addition, visual examination of the δ13C record reveals regular fluctuation in δ13C that may correspond to annual variability in δ13CDIC. This research presents the first century or longer sclerosponge δ13C record from the northwester equatorial Pacific.

  5. Cold seeps in Monterey Bay, California: Geochemistry of pore waters and relationship to benthic foraminiferal calcite

    Energy Technology Data Exchange (ETDEWEB)

    Gieskes, Joris, E-mail: [Scripps Institution of Oceanography, IOD-0208, 9500 Gilman Drive, La Jolla, CA 92093-0208 (United States); Rathburn, Anthony E. [Scripps Institution of Oceanography, IOD-0208, 9500 Gilman Drive, La Jolla, CA 92093-0208 (United States)] [Indiana State University, Department of Earth and Environmental Systems, Terre Haute, IN 47809 (United States); Martin, Jonathan B. [University of Florida, Department of Geological Sciences, Gainesville, FL 32611-2120 (United States); Perez, M. Elena [Indiana State University, Department of Earth and Environmental Systems, Terre Haute, IN 47809 (United States)] [The Natural History Museum, Department of Palaeontology, Cromwell Road, London SW7 5BD (United Kingdom); Mahn, Chris [Scripps Institution of Oceanography, IOD-0208, 9500 Gilman Drive, La Jolla, CA 92093-0208 (United States); Bernhard, Joan M. [Woods Hole Oceanographic Institution, Geology and Geophysics Department, MS52, Woods Hole, MA 02543 (United States); Day, Shelley [University of Florida, Department of Geological Sciences, Gainesville, FL 32611-2120 (United States)


    Highlights: > We describe the geochemistry of pore waters in the Clam Flats area of Monterey Bay. > The geochemical data are compared with the {delta}{sup 13}C chemistry of benthic foraminifera. > Living foraminifera indicate little effects of pore water low {delta}{sup 13}C (DIC) in the clam bed. > This phenomenon and its implications are discussed in detail. > Implications with regards to paleo-methane seepage are discussed. - Abstract: An extensive geochemical and biogeochemical examination of CH{sub 4} seeps in the Clam Flats area of Monterey Bay provides insight into the character of relationships between seep geochemistry and benthic foraminiferal geochemistry. The area is characterized by sulfide-rich fluids. Sulfide increases are associated with large increases in alkalinity, as well as small decreases in dissolved Ca and Mg. In addition, only small increases in NH{sub 4} are observed, but values of {delta}{sup 13}C of dissolved inorganic C are as low as -60 per mille at shallow depths (<3 cm). These observations indicate that all these processes are related to the bacterial oxidation of CH{sub 4}, which is transported upward by slow seepage of pore fluids. The geochemistry of the pore fluids should be relevant to the geochemistry of the carbonate tests of living and dead foraminifera. However, a profound disequilibrium of approximately an order of magnitude occurs between the {delta}{sup 13}C values of stained (cytoplasm-containing) foraminiferal carbonate and the C isotope values of ambient pore water dissolved inorganic C. Reasons are unclear for this isotopic disequilibrium, but have important implications for interpretations of foraminiferal carbonate as a paleoenvironmental proxy. Much fine scale work is needed to fully understand the relationships between the biogeochemistry of benthic foraminifera and the geochemistry of the pore waters where they live.

  6. CO2-dependent carbon isotope fractionation in dinoflagellates relates to their inorganic carbon fluxes. (United States)

    Hoins, Mirja; Eberlein, Tim; Van de Waal, Dedmer B; Sluijs, Appy; Reichart, Gert-Jan; Rost, Björn


    Carbon isotope fractionation (εp) between the inorganic carbon source and organic matter has been proposed to be a function of pCO2. To understand the CO2-dependency of εp and species-specific differences therein, inorganic carbon fluxes in the four dinoflagellate species Alexandrium fundyense, Scrippsiella trochoidea, Gonyaulax spinifera and Protoceratium reticulatum have been measured by means of membrane-inlet mass spectrometry. In-vivo assays were carried out at different CO2 concentrations, representing a range of pCO2 from 180 to 1200 μatm. The relative bicarbonate contribution (i.e. the ratio of bicarbonate uptake to total inorganic carbon uptake) and leakage (i.e. the ratio of CO2 efflux to total inorganic carbon uptake) varied from 0.2 to 0.5 and 0.4 to 0.7, respectively, and differed significantly between species. These ratios were fed into a single-compartment model, and εp values were calculated and compared to carbon isotope fractionation measured under the same conditions. For all investigated species, modeled and measured εp values were comparable (A. fundyense, S. trochoidea, P. reticulatum) and/or showed similar trends with pCO2 (A. fundyense, G. spinifera, P. reticulatum). Offsets are attributed to biases in inorganic flux measurements, an overestimated fractionation factor for the CO2-fixing enzyme RubisCO, or the fact that intracellular inorganic carbon fluxes were not taken into account in the model. This study demonstrates that CO2-dependency in εp can largely be explained by the inorganic carbon fluxes of the individual dinoflagellates.

  7. Carbon isotopic studies of individual lipids in organisms from the Nansha sea area, China

    Institute of Scientific and Technical Information of China (English)

    DUAN; Yi; SONG; Jinming; ZHANG; Hui


    Carbon isotopes of individual lipids in typical organisms from the Nansha sea area were measured by the GC-IRMS analytical technique. δ13C values of saturated fatty acids in different organisms examined are from -25.6‰ to -29.7‰ with the average values ranging from -26.4‰ to -28.2‰ and the variance range of 1.8‰ between different organisms is also observed.Unsaturated fatty acids have heavy carbon isotopic compositions and the mean differences of 2.9‰-6.8‰ compared to the same carbon number saturated fatty acids. δ13C values of n-alkanes range from -27.5‰ to -29.7‰ and their mean values, ranging from -28.6‰ to -28.9‰, are very close in different organisms. The mean difference in δ13C between the saturated fatty acids and n-alkanes is only 1.5‰, indicating that they have similar biosynthetic pathways. The carbon isotopic variations between the different carbon-number lipids are mostly within ±2.0‰, reflecting that they experienced a biosynthetic process of the carbon chain elongation. At the same time, the carbon isotopic genetic relationships between the biological and sedimentary lipids are established by comparative studies of carbon isotopic compositions of individual lipids in organisms and sediments from the Nansha sea area, which provides scientific basis for carbon isotopic applied research of individual lipids.

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

    Institute of Scientific and Technical Information of China (English)

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


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

  9. Carbon isotope discrimination as a tool to explore C4 photosynthesis. (United States)

    von Caemmerer, Susanne; Ghannoum, Oula; Pengelly, Jasper J L; Cousins, Asaph B


    Photosynthetic carbon isotope discrimination is a non-destructive tool for investigating C4 metabolism. Tuneable diode laser absorption spectroscopy provides new opportunities for making rapid, concurrent measurements of carbon isotope discrimination and CO2 assimilation over a range of environmental conditions, and this has facilitated the use of carbon isotope discrimination as a probe of C4 metabolism. In spite of the significant progress made in recent years, understanding how photosynthetic carbon isotope discrimination measured concurrently with gas exchange relates to carbon isotope composition of leaf and plant dry matter remains a challenge that requires resolution if this technique is to be successfully applied as a screening tool in crop breeding and phylogenetic research. In this review, we update our understanding of the factors and assumptions that underlie variations in photosynthetic carbon isotope discrimination in C4 leaves. Closing the main gaps in our understanding of carbon isotope discrimination during C4 photosynthesis may help advance research aimed at developing higher productivity and efficiency in key C4 food, feed, and biofuel crops.

  10. Soil organic carbon assessments in cropping systems using isotopic techniques (United States)

    Martín De Dios Herrero, Juan; Cruz Colazo, Juan; Guzman, María Laura; Saenz, Claudio; Sager, Ricardo; Sakadevan, Karuppan


    Introduction of improved farming practices are important to address the challenges of agricultural production, food security, climate change and resource use efficiency. The integration of livestock with crops provides many benefits including: (1) resource conservation, (2) ecosystem services, (3) soil quality improvements, and (4) risk reduction through diversification of enterprises. Integrated crop livestock systems (ICLS) with the combination of no-tillage and pastures are useful practices to enhance soil organic carbon (SOC) compared with continuous cropping systems (CCS). In this study, the SOC and its fractions in two cropping systems namely (1) ICLS, and (2) CCS were evaluated in Southern Santa Fe Province in Argentina, and the use of delta carbon-13 technique and soil physical fractionation were evaluated to identify sources of SOC in these systems. Two farms inside the same soil cartographic unit and landscape position in the region were compared. The ICLS farm produces lucerne (Medicago sativa Merrill) and oat (Avena sativa L.) grazed by cattle alternatively with grain summer crops sequence of soybean (Glicine max L.) and corn (Zea mays L.), and the farm under continuous cropping system (CCS) produces soybean and corn in a continuous sequence. The soil in the area is predominantly a Typic Hapludoll. Soil samples from 0-5 and 0-20 cm depths (n=4) after the harvest of grain crops were collected in each system and analyzed for total organic carbon (SOC, 0-2000 μm), particulate organic carbon (POC, 50-100 μm) and mineral organic carbon (MOC, <50 μm). Delta carbon-13 was determined by isotopic ratio mass spectrometry. In addition, a site with natural vegetation (reference site, REF) was also sampled for delta carbon-13 determination. ANOVA and Tukey statistical analysis were carried out for all data. The SOC was higher in ICLS than in CCS at both depths (20.8 vs 17.7 g kg-1 for 0-5 cm and 16.1 vs 12.7 g kg-1 at 0-20 cm, respectively, P<0.05). MOC was

  11. Assessment of the origin and geothermal potential of the thermal waters by hydro-isotope geochemistry: Eskisehir province, Turkey. (United States)

    Yuce, Galip; Italiano, Francesco; Yasin, Didem; Taskiran, Lutfi; Gulbay, Ahmet Hilmi


    The thermal fluids vented over Eskisehir province have been investigated for their origin and to estimate the geothermal potential of the area. Thermal waters as well as bubbling and dissolved gases were collected and analysed for their chemical and isotopic features. Their isotopic composition varies in the range from -11.5 to -7.7 ‰ for δ(18)O, -84 and -57 ‰ for δ(2)H, and 0-7.2 TU for tritium. The gases (bubbling and dissolved) are mostly N2-dominated with a significant amount of CO2. The helium isotopic ratios are in the range of 0.2-0.66 R/Rac, indicate remarkable mantle-He contribution ranging between 2 and 10 % in the whole study area. Considering the estimated geothermal gradient about three times higher than the normal gradient, and the reservoir temperatures estimated to be between 50 and 100 °C using quartz and chalcedony geothermometers, a circulation model was built where possible mixing with shallow waters cool down the uprising geothermal fluids.

  12. Petrology and oxygen isotope geochemistry of a fossil seawater hydrothermal system within the Solea graben, northern Troodos ophiolite, Cyprus (United States)

    Schiffman, Peter; Smith, Brian M.


    Hydrothermal mineral zonations and O isotope patterns of the northern Troodos complex do not parallel the ophiolite pseudostratigraphy, but reflect the convective geometry of an Upper Cretaceous seawater hydrothermal system. Large areas of the sheeted intrusive complex (SIC), including the subaxial region of the Solea graben, are composed of 18O-rich, subgreenschist mineral assemblages and may represent regions of diffuse seawater recharge. Other areas of the SIC are recrystallized to distinctive epidosite rocks: granular, high-variance assemblages of epidote + quartz ± chlorite that are depleted in 18O, Al2O3, Na2O, K2O, Zr, Cu, and Zn and are enriched in CaO and Sr compared with other mafic volcanic and dike rocks of the Solea graben. Epidosite alteration occurred at temperatures of ˜310-370°C and involved fluids with δ18O values and salinities similar to those of Upper Cretaceous seawater. The epidosite zones are discordant with earlier, mineral/O isotope zonations and with the axis of spreading in the Solea graben, suggesting a postspreading, off-axis origin. The seawater hydrothermal system responsible for Solea graben massive sulfide deposits was probably driven by hypabyssal intrusions (not exposed), emplaced in a terminal, failed spreading episode. The geometries of O isotope surfaces within the Solea graben imply that the epidosites formed in fossil upflow and deep recharge conduits. Depletions in base metals show that epidosite alteration liberated Cu and Zn to mineralizing fluids within the fossil upflow zone.

  13. Fingerprinting fluid sources in Troodos ophiolite complex orbicular glasses using high spatial resolution isotope and trace element geochemistry (United States)

    Fonseca, Raúl O. C.; Kirchenbaur, Maria; Ballhaus, Chris; Münker, Carsten; Zirner, Aurelia; Gerdes, Axel; Heuser, Alexander; Botcharnikov, Roman; Lenting, Christoph


    The Troodos igneous complex (Cyprus) is a ca. 90 Ma old, well preserved supra-subduction zone ophiolite. Troodos is unique in that it shows evidence of fluid-saturation throughout the complex, from its base (i.e. podiform chromitites) to its uppermost units - the upper pillow lavas (UPL). However, it is unclear what the source of dissolved water in UPL tholeiites is, with possibilities including shallow seawater infiltration, assimilation of altered Troodos oceanic crust, recycled serpentinized oceanic crust, or subducted pelagic sediments. In order to identify and characterize these components we have carried out a detailed high-resolution study on tholeiitic lavas on orbicular structures and glasses from the UPL in Troodos. Basaltic orbicules were measured for their Sr-Nd-Hf-Pb isotope compositions, and in situ for their B isotopes using LA-MC-ICP-MS. UPL orbicules display a very narrow range in ɛ Nd and ɛ Hf (+7 to +8 and +13 to +15, respectively) indicating melting of a depleted mantle source. Lead isotopes, specifically 207Pb/204Pb vs. 206Pb/204Pb, form a mixing array with pelagic sediments. Furthermore, high-resolution characterization of individual orbicules revealed that UPL tholeiites display strong variability in 87Sr/86Sr (0.7039-0.7060) at the outcrop scale. Samples display δ11 B between -8.2 (± 0.5)‰ and +5.9 (± 1.1)‰ with an average B content of ca. 5 μg/g. Contrary to expectation, altered orbicules and their associated hyaloclastite matrixes display lower δ11 B (down to -10‰) and higher B contents (max. 200 μg/g) when compared to fresh glass. Furthermore, the orbicules studied here show little or no evidence of interaction with seawater, which is supported by their trace element contents and isotope compositions. When all isotope systems are taken into account, UPL lavas reflect melting of a depleted mantle source that was overprinted by hydrous sediment melts, and potentially, fluid-like subduction components that in part originate

  14. Geochemistry of Carbonates on Mars: Implications for Climate History and Nature of Aqueous Environments


    Niles, Paul B.; Catling, David C.; Berger, Gilles; Chassefière, Eric; Ehlmann, Bethany L.; Michalski, Joseph R.; Morris, Richard; Ruff, Steven W.; Sutter, Brad


    Ongoing research on martian meteorites and a new set of observations of carbonate minerals provided by an unprecedented series of robotic missions to Mars in the past 15 years help define new constraints on the history of martian climate with important crosscutting themes including: the CO_2 budget of Mars, the role of Mg-, Fe-rich fluids on Mars, and the interplay between carbonate formation and acidity. Carbonate minerals have now been identified in a wide range of localities on Mars as...

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

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


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

  16. Excursions to C4 vegetation recorded in the Upper Pleistocene loess of Surduk (Northern Serbia: an organic isotope geochemistry study

    Directory of Open Access Journals (Sweden)

    C. Hatté


    Full Text Available Loess sequences have been intensively studied to characterize past glacial climates of the 40–50° north and south latitude zones. Combining different approaches of sedimentology, magnetism, geochemistry, geochronology and malacology allows the general pattern of the climate and environment of the last interglacial–glacial cycle in Eurasia and America to be characterized. Previous studies performed in Europe have highlighted the predominance (if not the sole occurrence of C3 vegetation. The presence of C3 plants suggests a regular distribution of precipitation along the year. Therefore, even if the mean annual precipitation remained very low during the most extensive glacial times, free water was available for more than 2 months per year. Contrarily, the δ13C record of Surduk (Serbia clearly shows the occurrence and dominance of C4 plants during at least 4 episodes of the last glacial times at 28.0–26.0 kyr cal BP, 31.4–30.0 kyr cal BP, 53.4–44.5 kyr cal BP and 86.8–66.1 kyr. The C4 plant development is interpreted as a specific atmospheric circulation pattern that induces short and dry summer conditions. As possible explanation, we propose that during "C4 episodes", the Mediterranean Sea would have been under the combined influence of the following: (i a strong meridional circulation unfavorable to water evaporation that reduced the Mediterranean precipitation on the Balkans; and (ii a high positive North Atlantic Western Russian (NA/WR-like atmospheric pattern that favored northerlies over westerlies and reduced Atlantic precipitation over the Balkans. This configuration would imply very dry summers that did not allow C3 plants to grow, thus supporting C4 development. The intra-"C4 episode" periods would have occurred under less drastic oceanic and atmospheric patterns that made the influence of westerlies on the Balkans possible.

  17. Evidence from carbon isotope measurements for diverse origins of sedimentary hydrocarbons (United States)

    Freeman, K. H.; Hayes, J. M.; Trendel, J. M.; Albrecht, P.


    The organic matter found in sedimentary rocks must derive from many sources; not only from ancient primary producers but also from consumers and secondary producers. In all of these organisms, isotope effects can affect the abundance and distribution of 13C in metabolites. Here, by using an improved form of a previously described technique in which the effluent of a gas chromatograph is continuously analysed isotopically, we report evidence of the diverse origins of sedimentary organic matter. The record of 13C abundances in sedimentary carbonate and total organic carbon can be interpreted in terms of variations in the global carbon cycle. Our results demonstrate, however, that isotope variations within sedimentary organic mixtures substantially exceed those observed between samples of total organic carbon. Resolution of isotope variations at the molecular level offers a new and convenient means of refining views both of localized palaeoenvironments and of control mechanisms within the global carbon cycle.

  18. Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review

    Directory of Open Access Journals (Sweden)

    N. Brüggemann


    Full Text Available The terrestrial carbon (C cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual, including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. The last part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO

  19. Distribution and fractionation mechanism of stable carbon isotope of coalbed methane

    Institute of Scientific and Technical Information of China (English)

    QIN Shengfei; TANG Xiuyi; SONG Yan; WANG Hongyan


    The stable carbon isotope values of coalbed methane range widely,and also are generally lighter than that of gases in normal coal-formed gas fields with similar coal rank.There exists strong carbon isotope fractionation in coalbed methane and it makes the carbon isotope value lighter.The correlation between the carbon isotope value and Ro in coalbed methane is less obvious.The coaly source rock maturity cannot be judged by coalbed methane carbon isotope value.The carbon isotopes of coalbed methane become lighter in much different degree due to the hydrodynamics.The stronger the hydrodynamics is,the lighter the CBM carbon isotopic value becomes.Many previous investigations indicated that the desorption-diffusion effects make the carbon isotope value of coalbed methane lighter.However,the explanation has encountered many problems.The authors of this article suggest that the flowing groundwater dissolution to free methane in coal seams and the free methane exchange with absorbed one is the carbon isotope fractionation mechanism in coalbed methane.The flowing groundwater in coal can easily take more 13CH4 away from free gas and comparatively leave more 12CH4.This will make 12CH4 density in free gas comparatively higher than that in absorbed gas.The remaining 12CH4 in free gas then exchanges with the adsorbed methane in coal matrix.Some absorbed 13CH4 can be replaced and become free gas.Some free 12CH4 can be absorbed again into coal matrix and become absorbed gas.Part of the newly replaced 13CH4 in free gas will also be taken away by water,leaving preferentially more 12CH4.The remaining 12CH4 in free gas will exchange again with adsorbed methane in the coal matrix.These processes occur all the time.Through accumulative effect,the 12CH4 will be greatly concentrated in coal.Thus,the stable carbon isotope of coalbed methane becomes dramatically lighter.Through simulation experiment on water-dissolved methane,it had been proved that the flowing water could fractionate the

  20. Mesozoic black shales, source mixing and carbon isotopes (United States)

    Suan, Guillaume


    Over the last decades, considerable attention has been devoted to the paleoenvironmental and biogeochemical significance of Mesozoic black shales. Black shale-bearing successions indeed often display marked changes in the organic carbon isotope composition (δ13Corg), which have been commonly interpreted as evidence for dramatic perturbations of global carbon budgets and CO2 levels. Arguably the majority of these studies have discarded some more "local" explanations when interpreting δ13Corg profiles, most often because comparable profiles occur on geographically large and distant areas. Based on newly acquired data and selected examples from the literature, I will show that the changing contribution of organic components with distinct δ13C signatures exerts a major but overlooked influence of Mesozoic δ13Corg profiles. Such a bias occurs across a wide spectrum of sedimentological settings and ages, as shown by the good correlation between δ13Corg values and proxies of kerogen proportions (such as rock-eval, biomarker, palynofacies and palynological data) recorded in Mesozoic marginal to deep marine successions of Triassic, Jurassic and Cretaceous age. In most of these successions, labile, 12C-enriched amorphous organic matter of marine origin dominates strata deposited under anoxic conditions, while oxidation-resistant, 13C-rich terrestrial particles dominate strata deposited under well-oxygenated conditions. This influence is further illustrated by weathering profiles of Toarcian (Lower Jurassic) black shales from France, where weathered areas dominated by refractory organic matter show dramatic 13C-enrichment (and decreased total organic carbon and pyrite contents) compared to non-weathered portions of the same horizon. The implications of these results for chemostratigraphic correlations and pCO2 reconstructions of Mesozoic will be discussed, as well as strategies to overcome this major bias.

  1. Environmental forcing of terrestrial carbon isotope excursion amplification across five Eocene hyperthermals (United States)

    Bowen, G. J.; Abels, H.


    Abrupt changes in the isotope composition of exogenic carbon pools accompany many major episodes of global change in the geologic record. The global expression of this change in substrates that reflect multiple carbon pools provides important evidence that many events reflect persistent, global redistribution of carbon between reduced and oxidized stocks. As the diversity of records documenting any event grows, however, discrepancies in the expression of carbon isotope change among substrates are almost always revealed. These differences in magnitude, pace, and pattern of change can complicate interpretations of global carbon redistribution, but under ideal circumstances can also provide additional information on changes in specific environmental and biogeochemical systems that accompanied the global events. Here we evaluate possible environmental influences on new terrestrial records of the negative carbon isotope excursions (CIEs) associated with multiple hyperthermals of the Early Eocene, which show a common pattern of amplified carbon isotope change in terrestrial paleosol carbonate records relative to that recorded in marine substrates. Scaling relationships between climate and carbon-cycle proxies suggest that that the climatic (temperature) impact of each event scaled proportionally with the magnitude of its marine CIE, likely implying that all events involved release of reduced carbon with a similar isotopic composition. Amplification of the terrestrial CIEs, however, does not scale with event magnitude, being proportionally less for the first, largest event (the PETM). We conduct a sensitivity test of a coupled plant-soil carbon isotope model to identify conditions that could account for the observed CIE scaling. At least two possibilities consistent with independent lines of evidence emerge: first, varying effects of pCO2 change on photosynthetic carbon isotope discrimination under changing background pCO2, and second, contrasting changes in regional

  2. Rare Isotope Insights into Supereruptions: Rare Sulfur and Triple Oxygen Isotope Geochemistry of Stratospheric Sulfate Aerosols Absorbed on Volcanic Ash Particles (United States)

    Bindeman, I. N.; Eiler, J.; Wing, B.; Farquhar, J.


    We present analyses of stable isotopic ratios of 17O/16O, 18O/16O, 34S/32S, and 33S/32S, 36S/32S of sulfate leached from volcanic ash of a series of well-known volcanic eruptions. This list covers much of the diversity of sizes and the character of volcanic eruptions. Particular emphasis is paid to the Lava Creek Tuff of Yellowstone and we present wide geographic sample coverage for this unit. This global dataset spans a significant range in δ34S, δ18O, and Δ17O of sulfate (29, 30 and 3.3 permil respectively) with oxygen isotopes recording mass-independent fractionation and sulfur isotopes exhibiting mass-dependent behavior. These ranges are defined by the isotopic compositions of products of large caldera forming eruptions. Proximal ignimbrites and coarse ash typically do not contain sulfate. The presence of sulfate with Δ17O > 0.2 permil is characteristic of small distal ash particles, suggesting that sulfate aerosols were scavenged after they underwent atmospheric photochemical reactions. Additionally, sediments that embed ash layers either do not contain sulfate or contain minor sulfate with Δ17O near 0 permil, suggesting that the observed sulfate in ash is of volcanic origin. Mass-dependent sulfur isotopic compositions suggest that sulfate-forming reactions did not involve photolysis of SO2, unlike the situation inferred for some pre-2.3 Ga sulfates or hypothesized to occur during the formation of sulfate associated with plinian eruptions that pierce the ozone layer. However, sulfate in the products of caldera-forming eruptions display a large δ34S range and fractionation relationships that do not follow equilibrium slopes of 0.515 and 1.90 for 33S/32S vs. 34S/32S and 36S/32S vs. 34S/32S, respectively. This implies that the sulfur isotopic characteristics of these sulfates were not set by a single stage, high-temperature equilibrium process in the volcanic plum. The data presented here are consistent with a single stage kinetic fractionation of sulfur

  3. Stable carbon isotopes in tree rings: the failure of uniformitarianism (United States)

    McCarroll, Danny


    When tree rings are used to reconstruct past climate we rely on the uniformitarian principle that ‘the present is the key to the past'. Relationships between measured parameters and climate that can be calibrated and verified over the instrumental period are assumed to be applicable at longer timescales. In the case of δ13C, however, the uniformitarian principle fails for two reasons. (1) The instrumental calibration period is also the period of anthropogenic increase in atmospheric CO2. δ13C is a function of the ratio of internal to ambient CO2, so maintaining constant δ13C over the industrial period requires an active plastic response, either restricting stomatal conductance or increasing assimilation rate. In some areas trees may have reached the limits of their plasticity so that over the last few decades δ13C values have been declining, independent of any changes in climate. If no correction is made, the recent response to climate will be a poor indicator of behaviour in the past. (2) Tree ring δ13C is often used to reconstruct past temperatures even though temperature rarely has a strong direct control over fractionation. The link is therefore via either sunshine or humidity, which over the calibration period may be very strongly correlated with temperature. Long isotope chronologies, when compared with independent evidence of past temperatures, however, can show periods of marked divergence. The strong covariance of temperature, sunshine and humidity over the last century may not have persisted over longer timescales with larger climatic perturbations. In the case of carbon isotopes the key to the past is not statistical inference based on recent behaviour, but a clear mechanistic understanding of the influence of climate and other factors on fractionation.

  4. Trace element and isotopic geochemistry of Cretaceous magmatism in NE Asia: Spatial zonation, temporal evolution, and tectonic controls (United States)

    Tikhomirov, Petr L.; Kalinina, Elena A.; Moriguti, Takuya; Makishima, Akio; Kobayashi, Katsura; Nakamura, Eizo


    Results of a comprehensive geochemical study (major and trace elements, and isotopes of Sr, Nd, Pb, Hf) of Cretaceous volcanic rocks from the Chukotka area in northeastern Russia are presented. Synthesis of available geological and geochronological data suggests diachronous onset of activity of the Okhotsk-Chukotka volcanic belt (OCVB), the largest magmatic province in the region. The OCVB consists of ca. 106 km3 of volcanic rocks. At 106-105 Ma, subduction-related magmatism initiated in the southern and central segments of the OCVB. In the Central and Northern Chukotka areas, where the northern OCVB is exposed, onset of arc magmatism occurred ca. 10 m.y. after extension-related magmatism of the Chaun igneous province at 109-104 Ma. Mafic rocks from the OCVB yield (87Sr/86Sr)80 Ma of 0.7033 to 0.7047, εNd80 Ma of 0.0 to 7.10, εHf80 Ma of 4.12 to 12.88, (206Pb/204Pb)80 Ma of 18.11 to 18.42, and (208Pb/204Pb)80 Ma of 37.96 to 38.21. Volcanic rocks from the Chaun province, as well as OCVB rocks from Northern Chukotka, originate from a relatively enriched source and have (87Sr/86Sr)80 Ma of 0.7088 to 0.7100, εNd80 Ma of - 5.81 to - 3.42, εHf80 Ma of - 3.40 to - 0.25, (206Pb/204Pb)80 Ma of 18.69 to 18.90, and (208Pb/204Pb)80 Ma of 38.65 to 38.86. No definitive across-arc elemental or isotopic zonation of the OCVB has been revealed, probably because of wide-scale crustal melting and subsequent contamination of mantle-derived melts. However, there is a clear along-arc isotopic zonation. In our interpretation, this results from heterogeneity of the subcontinental lithospheric mantle, which likely was a major contributor to the magma source. The similar isotopic signatures of silicic (dominantly crust-derived) and mafic (mantle-derived) volcanic rocks in each OCVB segment imply that remelting of juvenile mafic underplated material was the main process responsible for the crust-derived magma generation. These data from the major Cretaceous magmatic provinces of northeast

  5. Geochronology and isotope geochemistry of the Baogutu porphyry copper deposit in the West Junggar region, Xinjiang, China (United States)

    Shen, Ping; Shen, Yuanchao; Pan, Hongdi; Li, Xian-hua; Dong, Lianhui; Wang, Jingbin; Zhu, Heping; Dai, Huawu; Guan, Weina


    The Baogutu copper deposit, a newly-discovered middle-sized porphyry copper deposit, is located in the West Junggar region of Xinjiang, NW China. Baogutu is associated with a Late Carboniferous intrusive complex that was emplaced into Lower Carboniferous volcano-sedimentary strata. The intrusive complex comprises main-stage diorites and minor late-stage diorite porphyries. Their intrusive activity occurred in 313.0 ± 2.2 Ma to 312.3 ± 2.2 Ma based on U-Pb zircon SIMS analyses. Molybdenite separated from ore-bearing quartz veins yields Re-Os model ages from 309.4 ± 4.4 Ma to 314.1 ± 4.5 Ma with a weighted mean age of 312.4 ± 1.8 Ma. Biotites, separated from fresh diorite and hydrothermal breccias in main-stage diorites, yield 40Ar/39Ar plateau ages of 308.26 ± 1.88 and 305.69 ± 1.76 Ma, respectively. These dates obtained from three independent dating techniques constrain the ore-forming age of the Baogutu deposit. Stable isotopes (H, O, S) and radiogenic isotope (Pb) have been used to discriminate the sources of the ore-forming fluid at Baogutu. The δ18O (1.14-1.74‰) and δD (-74‰ to -98‰) data indicate that the water of the ore-forming fluids was derived from magmatic water. The δ34S values (-0.24‰ to +0.4‰) show that the sulfur isotope composition of the ore fluids is characterized by magma sulfur. Lead isotope compositions (206Pb/204Pb = 17.92-18.89, 207Pb/204Pb = 15.45-15.62, 208Pb/204Pb = 37.68-38.36) indicate that the lead of the ore fluids is derived from the mantle. These data confirm the occurrence of a Cu-Au-Mo mineralizing event at Late Carboniferous in the Baogutu region and the ore-forming fluids are mainly derived from the mantle. The event is inferred to be associated with Late Carboniferous Junggar oceanic crust subduction.

  6. Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing. (United States)

    Piper, Thomas; Emery, Caroline; Thomas, Andreas; Saugy, Martial; Thevis, Mario


    Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical

  7. CO2 outburst events in relation to seismicity: Constraints from microscale geochronology, geochemistry of late Quaternary vein carbonates, SW Turkey (United States)

    Ünal-İmer, Ezgi; Uysal, I. Tonguç; Zhao, Jian-Xin; Işık, Veysel; Shulmeister, James; İmer, Ali; Feng, Yue-Xing


    Vein and breccia carbonates precipitated in a highly fractured/faulted carbonate bedrock in SW Turkey were investigated through high-resolution U-series geochronology, microstructural and geochemical studies including C-O-Sr isotope and rare-earth element and yttrium (REY) analyses. Petrographical observations and geochronological data are interpreted as evidence that the calcite veins formed through a crack-seal mechanism, mostly accompanied/initiated by intensive hydraulic fracturing of the host limestone in response to high-pressure fluids, which is manifested by multi-stage breccia deposits. Microscale U-series dates (272.6-20.5 kyr) and geochemical compositions of the vein/breccia samples provide information on the timing and mechanism of the vein formation and identify the source of CO2-bearing fluids responsible for the carbonate precipitation. δ18OVPDB and δ13CVPDB values of the calcite veins range between -5.9 and -1.7‰, and -10.6 and -4.6‰, respectively. The isotopic compositions of the veins show highly fluctuating values as calcite grew successively perpendicular to vein walls, which, in combination with microstructural and geochronological constraints, are interpreted to reflect episodic CO2 degassing events associated with seismic and aseismic deformation. Oxygen and Sr isotope compositions (δ18OVPDB: -5.9 to -1.7‰; 87Sr/86Sr: 0.7082 to 0.7085) together with REY concentrations indicate deep infiltration of meteoric waters with various degrees of interactions mostly with the host limestone and siliciclastic parts of the basement rocks. Oxygen and carbon isotope compositions suggest CO2 degassing through intensive limestone dissolution. While majority of the veins display similar Post-Archaean Australian Shale (PAAS)-normalised REY variations, some of the veins show positive EuPAAS anomalies, which could be indicative of contributions from a deeply derived, heated, and reduced fluid component, giving rise to multiple fluid sources for the

  8. Testing the sensitivity of stable carbon isotopes of sub-fossil Sphagnum cellulose to past climate variability: a two millennia high resolution stable carbon isotope time series from the peat deposit "Dürres Maar", Germany (United States)

    Moschen, Robert; Kühl, Norbert; Peters, Sabrina; Vos, Heinz; Lücke, Andreas


    CSphagnum. The close coupling of several environmental factors to air temperature, however, presumably also results in an indirect dependency of δ13CSphagnum on air temperature, since strong correlation between δ13CSphagnum of modern Sphagnum plants and local air temperature during the growing season has been observed for altitudinal transects (Skrzypek et al. 2007). We applied potential relationships between our δ13CSphagnum and climatological parameters as deducible from existing calibration data sets. Results are compared with quantitative climate reconstructions based on well established palynological methods applied to the same core from 'Dürres Maar'. Additionally, comparisons of the δ13CSphagnum record with time series of meteorological observations are presented to review the potential relationships between δ13CSphagnum and climatological parameters. References: Loader, N.L., McCarroll, D., van der Knaap, W.O., Robertson, I. and Gagen, M., (2007): Characterizing carbon isotopic variability in Sphagnum. The Holocene 17: 403-410. Skrzypek, G., Kalużny, A., Wojtuń, B. and Jędrysek, M.-O., (2007): The carbon stable isotopic composition of mosses: A record of temperature variation. Organic Geochemistry 38: 1770-1781. Moschen, R. et al. (2009): Stable carbon and oxygen isotopes in sub-fossil Sphagnum: Assessment of their applicability for palaeoclimatology. Chemical Geology 259: 262-272.

  9. Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review

    Directory of Open Access Journals (Sweden)

    N. Brüggemann


    Full Text Available The terrestrial carbon (C cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual, including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. A further part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as

  10. A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings. (United States)

    Roden, J. S.; Farquhar, G. D.


    Stable isotopes ratios of carbon and oxygen in tree ring cellulose have been used to infer environmental change. Process-based models have been developed to clarify the potential of historic tree ring records for meaningful paleoclimatic reconstructions. However, isotopic variation can be influenced by multiple environmental factors making simplistic interpretations problematic. Recently, the dual isotope approach, where the variation in one stable isotope ratio (e.g. oxygen) is used to constrain the interpretation of variation in another (e.g. carbon), has been shown to have the potential to de-convolute isotopic analysis. However, this approach requires further testing to determine its applicability for paleo-reconstructions using tree-ring time series. We present a study where the information needed to parameterize mechanistic models for both carbon and oxygen stable isotope ratios were collected in controlled environment chambers for two species (Pinus radiata and Eucalyptus globulus). The seedlings were exposed to treatments designed to modify leaf temperature, transpiration rates, stomatal conductance and photosynthetic capacity. Both species were grown for over 100 days under two humidity regimes that differed by 20%. Stomatal conductance was significantly different between species and for seedlings under drought conditions but not between other treatments or humidity regimes. The treatments produced large differences in transpiration rate and photosynthesis. Treatments that effected photosynthetic rates but not stomatal conductance influenced carbon isotope discrimination more than those that influenced primarily conductance. The various treatments produced a range in oxygen isotope ratios of 7 ‰. Process models predicted greater oxygen isotope enrichment in tree ring cellulose than observed. The oxygen isotope ratios of bulk leaf water were reasonably well predicted by current steady-state models. However, the fractional difference between models that

  11. Geochemistry of arsenic in low sulfide-high carbonate coal waste rock, Elk Valley, British Columbia, Canada. (United States)

    Biswas, Ashis; Hendry, M Jim; Essilfie-Dughan, Joseph


    This study investigated the geochemistry of arsenic (As) in low sulfide-high carbonate coal waste rock of the Elk Valley, British Columbia, Canada. Its abundance and mineralogical associations in waste rock of different placement periods were determined in addition to its mobilization into porewater and rock-drain effluent. The mean (5.34mg/kg; 95% confidence interval: 4.95-5.73mg/kg) As concentration in the waste rock was typical of sedimentary rock. Electron microprobe and As K-edge X-ray absorption near-edge spectroscopic analyses showed the As is predominantly associated with primary pyrites in both source and freshly blasted waste rock. However, in aged waste rock the As is associated with both primary pyrites and secondary Fe oxyhydroxides. Oxidation of pyrite in waste rock dumps was reflected by the presence of high concentrations of SO4(2-) in porewater and oxidation rims of Fe oxyhydroxides around pyrite grains. Acid released from pyrite oxidation to Fe oxyhydroxides is neutralized by carbonate mineral dissolution that buffers the pH in the waste rock to circumneutral values. Adsorption of As onto secondary Fe oxyhydroxides provides an internal geochemical control on As release during pyrite oxidation and porewater flushing from the dump, resulting in the low As concentrations observed in porewater (median: 9.91μg/L) and rock-drain effluent (median: 0.31μg/L). Secondary Fe oxyhydroxides act as a long-term sink for As under present day hydrologic settings in waste rock dumps in the Elk Valley.

  12. Sensitivity analysis and quantification of uncertainty for isotopic mixing relationships in carbon cycle research (United States)

    Zobitz, J. M.; Keener, J. P.; Bowling, D. R.


    Quantifying and understanding the uncertainty in isotopic mixing relationships is critical to isotopic applications in carbon cycle studies at all spatial and temporal scales. Studies associated with the North American Carbon Program will depend on stable isotope approaches and quantification of isotopic uncertainty. An important application of isotopic mixing relationships is determination of the isotopic content of large-scale respiration (δ 13CR) via an inverse relationship (a Keeling plot) between atmospheric CO2 concentrations ([CO2]) and carbon isotope ratios of CO2 (δ 13C). Alternatively, a linear relationship between [CO2] and the product of [CO2] and δ 13C (a Miller/Tans plot) can also be applied. We used an extensive dataset from the Niwot Ridge Ameriflux Site of [CO2] and δ 13C in forest air to examine contrasting approaches to determine δ 13CR and its uncertainty. These included Keeling plots, Miller/Tans plots, Model I, and Model II regressions Our analysis confirms previous observations that increasing the range of measurements ([CO2] range) reduces the uncertainty associated with δ 13CR. For carbon isotope studies, uncertainty in the isotopic measurements has a greater effect on the uncertainty of δ 13CR than the uncertainty in [CO2]. Reducing the uncertainty of isotopic measurements reduces the uncertainty of δ 13CR even when the [CO2] range of samples is small (13CR. We also find for carbon isotope studies no inherent advantage to using either a Keeling or a Miller/Tans approach to determine δ 13CR.

  13. Major, trace element and isotope geochemistry (Sr-Nd-Pb) of interplinian magmas from Mt. Somma-Vesuvius (Southern Italy) (United States)

    Somma, R.; Ayuso, R.A.; de Vivo, B.; Rolandi, G.


    Major, trace element and isotopic (Sr, Nd, Pb) data are reported for representative samples of interplinian (Protohistoric, Ancient Historic and Medieval Formations) activity of Mt. Somma-Vesuvius volcano during the last 3500 years. Tephra and lavas exhibit significant major, trace element and isotopic variations. Integration of these data with those obtained by previous studies on the older Somma suites and on the latest activity, allows to better trace a complete petrological and geochemical evolution of the Mt. Somma-Vesuvius magmatism. Three main groups of rocks are recognized. A first group is older than 12.000 yrs, and includes effusive-explosive activity of Mt. Somma. The second group (8000-2700 yrs B.P.) includes the products emitted by the Ottaviano (8000 yrs. B.P.) and Avellino (3550 yrs B.P.) plinian eruptions and the interplinian activity associated with the Protohistoric Formation. Ancient Historic Formation (79-472 A.D.), Medieval Formation (472-1139 A.D.) and Recent interplinian activity (1631-1944 A.D.) belong to the third group of activity (79-1944 A.D.). The three groups of rocks display distinct positive trends of alkalis vs. silica, which become increasingly steeper with age. In the first group there is an increase in silica and alkalis with time, whereas an opposite tendency is observed in the two younger groups. Systematic variations are also evident among the incompatible (Pb, Zr, Hf, Ta, Th, U, Nb, Rb, Cs, Ba) and compatible elements (Sr, Co, Cr). REE document variable degrees of fractionation, with recent activity displaying higher La/Yb ratios than Medieval and Ancient Historic products with the same degree of evolution. N-MORB normalized multi-element diagrams for interplinian rocks show enrichment in Rb, Th, Nb, Zr and Sm (> *10 N-MORB). Sr isotope ratios are variable, with Protohistoric rocks displaying 87Sr/86Sr= 0.70711-0.70810, Ancient Historic 87Sr/86Sr=0.70665-0.70729, and Medieval 87Sr/86Sr=0.70685-0.70803. Neodymium isotopic

  14. Evaluating the use of amber in palaeoatmospheric reconstructions: The carbon-isotope variability of modern and Cretaceous conifer resins (United States)

    Dal Corso, Jacopo; Schmidt, Alexander R.; Seyfullah, Leyla J.; Preto, Nereo; Ragazzi, Eugenio; Jenkyns, Hugh C.; Delclòs, Xavier; Néraudeau, Didier; Roghi, Guido


    Stable carbon-isotope geochemistry of fossilized tree resin (amber) potentially could be a very useful tool to infer the composition of past atmospheres. To test the reliability of amber as a proxy for the atmosphere, we studied the variability of modern resin δ13C at both local and global scales. An amber δ13C curve was then built for the Cretaceous, a period of abundant resin production, and interpreted in light of data from modern resins. Our data show that hardening changes the pristine δ13C value by causing a 13C-depletion in solid resin when compared to fresh liquid-viscous resin, probably due to the loss of 13C-enriched volatiles. Modern resin δ13C values vary as a function of physiological and environmental parameters in ways that are similar to those described for leaves and wood. Resin δ13C varies between plant species and localities, within the same tree and between different plant tissues by up to 6‰, and in general increases with increasing altitudes of the plant-growing site. We show that, as is the case with modern resin, Cretaceous amber δ13C has a high variability, generally higher than that of other fossil material. Despite the high natural variability, amber shows a negative 2.5-3‰ δ13C trend from the middle Early Cretaceous to the Maastrichtian that parallels published terrestrial δ13C records. This trend mirrors changes in the atmospheric δ13C calculated from the δ13C and δ18O of benthic foraminiferal tests, although the magnitude of the shift is larger in plant material than in the atmosphere. Increasing mean annual precipitation and pO2 could have enhanced plant carbon-isotope fractionation during the Late Cretaceous, whereas changing pCO2 levels seem to have had no effect on plant carbon-isotope fractionation. The results of this study suggest that amber is a powerful fossil plant material for palaeoenvironmental and palaeoclimatic reconstructions. Improvement of the resolution of the existing data coupled with more detailed

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

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


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

  16. Do stable carbon isotopes of brown coal woods record changes in Lower Miocene palaeoecology?

    NARCIS (Netherlands)

    Poole, I.J.; Dolezych, M.; Kool, J.; Burgh, J. van der; Bergen, P.F. van


    Stable carbon isotope ratios of fossil wood from the Miocene brown coal deposits in former East Germany are compared with palaeobotanical and sedimentological data to test the use of stable isotopes in determining palaeoenvironment. Significant differences in the chemical composition of samples from

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

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


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

  18. Fluid flow and water-rock interaction across the active Nankai Trough subduction zone forearc revealed by boron isotope geochemistry (United States)

    Hüpers, Andre; Kasemann, Simone A.; Kopf, Achim J.; Meixner, Anette; Toki, Tomohiro; Shinjo, Ryuichi; Wheat, C. Geoffrey; You, Chen-Feng


    Compositional changes, dehydration reactions and fluid flow in subducted sediments influence seismogenesis and arc magmatism in subduction zones. To identify fluid flow and water-rock interaction processes in the western Nankai Trough subduction zone (SW Japan) we analyzed boron concentration and boron isotope composition (δ11B) of pore fluids sampled across the subduction zone forearc from depths of up to ∼922 m below seafloor during four Integrated Ocean Drilling Program (IODP) Expeditions. The major structural regimes that were sampled by coring include: (1) sedimentary inputs, (2) the frontal thrust zone, (3) the megasplay fault zone, and (4) the forearc basin. From mass balance consideration we find that consumption of boron (B) by ash alteration and desorption of B from the solid phase, mediated by organic matter degradation, produces a net decrease in B concentrations with depth down to ∼120 μM and variable δ11B values in the range of ∼+20‰ and +49‰. Interstitial water in sediments on the incoming oceanic plate are influenced by more efficient mobilization of exchangeable B from the solid phase due to higher temperatures and alteration of the oceanic crust that acts as a sink for 10B. At the tip of the megasplay fault zone, elevated B concentration and B isotopic composition suggest that underthrust coarse-grained slope sediments provide a pathway for fluids out of the upper (balance considerations suggest a shallower fluid source depth compared to pore fluids sampled previously near the décollement zone along the central portion of the Nankai margin.

  19. The evolution of Carbon isotopes in calcite in the presence of cyanobacteria (United States)

    Grimm, Christian; Mavromatis, Vasileios; Pokrovsky, Oleg S.; Oelkers, Eric H.


    Stable isotopic compositions in carbonates are widely used as indicators of environmental conditions prevailing during mineral formation. This reconstruction is substantially based on the assumption that there is no change in the mineral composition over geological time. However, recent experimental studies have shown that carbon and magnesium isotopes in hydrous Mg-carbonates undergo continuous re-equilibration with the ambient solution even after mineral precipitation stopped ([1] and [2], respectively). To verify whether this holds true for anhydrous Ca-bearing carbonates which readily form at earth's surface environments, a series of batch system calcite precipitation experiments were performed in the presence of actively growing cyanobacteria Synechococcus sp. The bacteria were grown at ambient temperature in a BG11 culture medium (SIGMA C3061) and continuous stirring, air-bubbling and illumination. Calcite precipitation was initiated by the addition of 8.5mM CaCl2 and 0-50 mM NaHCO3 or NaHCO3-Na2CO3 mixtures. The presence of cyanobacteria is on one hand promoting CaCO3 formation due to increasing pH resulting from photosynthesis. On the other hand, actively growing cyanobacteria drastically change carbon isotope signature of the aqueous fluid phase by preferably incorporating the lighter 12C isotope into biomass [1]. This study explores the effect of continuously changing carbon isotope compositions in dissolved inorganic carbon (DIC) on precipitated calcite which is in chemical equilibrium with the ambient fluid phase. [1] Mavromatis et al. (2015). The continuous re-equilibration of carbon isotope compositions of hydrous Mg-carbonates in the presence of cyanobacteria. Chem. Geol. 404, 41-51 [2] Mavromatis et al. (2012). Magnesium isotope fractionation during hydrous magnesium carbonate precipitation with and without cyanobacteria. Geochim. Cosmochim. Acta 76, 161-174

  20. C- and Sr-isotope stratigraphy of the São Caetano complex, Northeastern Brazil: a contribution to the study of the Meso-Neoproterozoic seawater geochemistry

    Directory of Open Access Journals (Sweden)

    Juan C. Silva


    Full Text Available C-isotope and 87Sr/86Sr values for five carbonate successions from the São Caetano Complex, northeastern Brazil, were used to constrain their depositional age and to determine large variations in the C- and Sr-isotopic composition of seawater under the framework of global tectonic events. Three C-isotope stages were identified from base to top in a composed chemostratigraphic section: (1 stage in which delta13C values vary from +2 to +3.7‰ PDB and average 3‰ PDB, (2 stage with delta13C values displaying stronger oscillations (from -2‰ to +‰ PDB, and (3 stage with an isotopic plateau with values around +3.7‰ PDB. Constant 87Sr/86Sr values (~ 0.70600 characterize C-isotope stage 1, whereas slightly fluctuating values (from 0.70600 to 0.70700 characterize C-isotope stage 2. Finally, 87Sr/86Sr values averaging 0.70600 characterize C-isotope stage 3. The C- and Sr- chemostratigraphic pathways permit to state: (a the C- and Sr-isotope secular curves registered primary fluctuations of the isotope composition of seawater during late Mesoproterozoic- early Neoproterozoic transition in the Borborema Province, and (b onset of the Cariris Velhos/Greenville cycle, widespread oceanic rifting, continental magmatic arc formation and onset of the agglutination of Rodinia supercontinent, mostly controlled the C- and Sr-isotope composition of seawater during the C-isotope stages 1, 2 and 3.Valores de isótopos de C e 87Sr/86Sr de cinco seqüências de carbonatos do Complexo São Caetano, nordeste do Brasil; foram usados para estimar a sua idade de deposição e relacionar variações da composição isotópica na água do mar com eventos tectônicos globais. Três estágios de variação de isótopos de carbono foram identificados de base para o topo numa seção quimioestratigráfica composta: (1 estágio em que delta13C varia de +2 a +3.7‰PDB (media 3‰PDB, (2 estágio no qual delta13C varia consideravelmente (de -2 a +3‰PDB e (3 est

  1. Original Mineralogy and Recognition of Upper Boundary of the Sarvak Formation Based on Geochemistry and Isotope Studies

    DEFF Research Database (Denmark)

    Asgari, M; Tahmasebi Poor, A; Barari, Amin


    Carbonate sequence of upper cretaceous (Cenomanian) of Sarvak Formation is a part of Bangestan Group with the thickness of 760m in Ahvaz oil field (well no. 63). This formation is overlain by the Kazhdumi Formation and is uncomfortably underlain by the Ilam Formation. In this study major and mino...

  2. Carbon stable isotope analysis of cereal remains as a way to reconstruct water availability: preliminary results


    Flohr, Pascal; Muldner, Gundula; Jenkins, Emma


    Reconstructing past water availability, both as rainfall and irrigation, is important to answer questions about the way society reacts to climate and its changes and the role of irrigation in the development of social complexity. Carbon stable isotope analysis of archaeobotanical remains is a potentially valuable method for reconstructing water availability. To further define the relationship between water availability and plant carbon isotope composition and to set up baseline values for the...

  3. Effects of carbonate leaching on foraminifer stable isotopes ratios (United States)

    Obrochta, S.; Yokoyama, Y.; Sakai, S.; Ishimura, T.


    Stable carbon and oxygen isotope ratios were measured on 125 individual epifaunal and infaunal benthic foraminifers from two discrete Holocene intervals in a shallow-water sediment core (~ 450 m) from the Timor Sea. Methane seeps are common in the area, resulting in significant precipitation of secondary calcite that is confirmed by SEM photomicrographs and has likely resulted in inconsistent downcore results. To assess the degree of removal of contaminants, individual Uvigerina peregrina were subjected to varying degrees of pretreatment prior to analysis. All foraminifers received standard cleaning with ethanol and brief sonication. A subset were further cleaned and sonicated in a dilute HCl solution (~ 0.003 M). Foraminifer tests were photographed using both reflected light and scanning electron microscopes during the course of treatment to monitor the changing degree of contaminant removal as increasingly aggressive cleaning methods were employed. Visible contamination remained on individuals not subjected to HCl treatment. The leached individuals exhibit a lower overall relative standard deviation and consistent results within morphotype groups. Based on these results, a 2% value is expected to be typical of the Holocene, though further downcore analyses are pending restoration of equipment adversely effected by the Eastern Japan 3/11 earthquake.

  4. Carbon isotopic record from Upper Devonian carbonates at Dongcun in Guilin, southern China, supporting the world-wide pattern of carbon isotope excursions during Frasnian-Famennian transition

    Institute of Scientific and Technical Information of China (English)


    Two positive δ13C excursions are presented in records from the Frasnian-Famennian (F-F) marine carbonate sediments in Europe, America, Africa, and Australia, having been considered as a worldwide pattern, and attributed to enhanced organic carbon burial during the F-F biological mass extinction. However, this worldwide pattern has not been revealed from the well-deposited Late Devonian sequences in southern China. In this paper, a detailed investigation has been made on the Late Devonian section at Dongcun, Guilin, southern China to constrain perturbations in δ13C of carbonates in the F-F deposited sequence. The result from this section also indicates two positive δ13C excursions during the F-F transition. The first excursion with an amplitude of 1.5‰ occurred at the bottom of linguiformis Zone, later than the early excursion existing in the Late rhenana Zone of the Late Devonian profiles in other continents, especially, in central Europe. This difference has been expected to be a result as conodont Palmatolepis linguiformis occurred earlier in southern China than other sites. The second excursion with an amplitude of 2.1‰ is located at the F-F boundary, same as the records from other continents. This result strongly supports the view that two carbon isotope positive excursions during the F-F transition are common in carbonate sediments, resulting from worldwide increases of organic carbon burial intensity.

  5. Geochemistry, water dynamics and metals: Major, trace elements, Pb and Sr isotope constraints on their origins and movements in a small anthropized catchment over a flood

    Energy Technology Data Exchange (ETDEWEB)

    Luck, J.M.; Othman, D.B. [University Montpellier II, Laboratoire Geofluides, Bassins, Eaux, Montpellier (France)


    Major, trace elements and Sr-Pb isotope data on the dissolved and particulate phases are reported for water samples taken regularly over the September flood of a Mediterranean river (S France). This river drains runoff from a small, carbonate, karstified watershed with Miocene and Jurassic lithologies, and characterized by agricultural, urban and road network activities. The objective is to combine all the data into a dynamic model for constraining the origin(s) and movements of waters and of their loads. Furthermore, for metals, it becomes then feasible to know their fate and bioavailability downstream 18 refs., 4 figs.

  6. Decoupling of carbon isotope records between organic matter and carbonate prior to the Toarcian Oceanic Anoxic Event (Early Jurassic) (United States)

    Bodin, Stephane; Kothe, Tim; Krencker, Francois-Nicolas; Suan, Guillaume; Heimhofer, Ulrich; Immenhauser, Adrian


    Across the Pliensbachian-Toarcian boundary (P-To, Early Jurassic), ca. 1 Myr before the Toarcian Oceanic Anoxic Event (T-OAE), an initial negative carbon isotope excursion has been documented in western Tethys sedimentary rocks. In carbonate, its amplitude (2-3 permil) is similar to the subsequent excursion recorded at the onset of the T-OAE. Being also associated with a rapid warming event, the significance of this first carbon isotope shift, in terms of paleoenvironmental interpretation and triggering mechanism, remains however elusive. Taking advantage of expanded and rather continuous sections in the High Atlas of Morocco, several high-resolution, paired organic-inorganic carbon isotope records have been obtained across the Upper Pliensbachian - Lower Toarcian interval. At the onset of the T-OAE, an abrupt 1-2 permil negative shift is recorded in both organic and inorganic phases, succeeded by a relatively longer term 1-2 permil negative trend and a final slow return to pre-excursion conditions. In accordance with previous interpretations, this pattern indicates a perturbation of the entire exogenic carbon isotope reservoir at the onset of the T-OAE by the sudden release of isotopically light carbon into the atmosphere. By contrast, there is no negative shift in carbon isotopes for the P-To event recorded in bulk organic matter of Morocco. Given the strong dominance of terrestrial particles in the bulk organic matter fraction, this absence indicates that massive input of 12C-rich carbon into the atmosphere is not likely to have happened during the P-To event. A pronounced (2 permil) and abrupt negative shift in carbon isotope is however recorded in the bulk carbonate phase. We suggest that this decoupling between organic and inorganic phase is due to changes in the nature of the bulk carbonate phase. Indeed, the negative shift occurs at the lithological transition between Pliensbachian-lowermost Toarcian limestone-marl alternations and the Lower Toarcian marl

  7. Model-based estimation of the global carbon budget and its uncertainty from carbon dioxide and carbon isotope records

    Energy Technology Data Exchange (ETDEWEB)

    Kheshgi, Haroon S. [Corporate Research Laboratories, Exxon Research and Engineering Company, Annandale, New Jersey (United States); Jain, Atul K. [Department of Atmospheric Sciences, University of Illinois, Urbana (United States); Wuebbles, Donald J. [Department of Atmospheric Sciences, University of Illinois, Urbana (United States)


    A global carbon cycle model is used to reconstruct the carbon budget, balancing emissions from fossil fuel and land use with carbon uptake by the oceans, and the terrestrial biosphere. We apply Bayesian statistics to estimate uncertainty of carbon uptake by the oceans and the terrestrial biosphere based on carbon dioxide and carbon isotope records, and prior information on model parameter probability distributions. This results in a quantitative reconstruction of past carbon budget and its uncertainty derived from an explicit choice of model, data-based constraints, and prior distribution of parameters. Our estimated ocean sink for the 1980s is 17{+-}7 Gt C (90% confidence interval) and is comparable to the estimate of 20{+-}8 Gt C given in the recent Intergovernmental Panel on Climate Change assessment [Schimel et al., 1996]. Constraint choice is tested to determine which records have the most influence over estimates of the past carbon budget; records individually (e.g., bomb-radiocarbon inventory) have little effect since there are other records which form similar constraints. (c) 1999 American Geophysical Union.

  8. Fractionation between inorganic and organic carbon during the Lomagundi (2.22 2.1 Ga) carbon isotope excursion (United States)

    Bekker, A.; Holmden, C.; Beukes, N. J.; Kenig, F.; Eglinton, B.; Patterson, W. P.


    The Lomagundi (2.22-2.1 Ga) positive carbon isotope excursion in shallow-marine sedimentary carbonates has been associated with the rise in atmospheric oxygen, but subsequent studies have demonstrated that the carbon isotope excursion was preceded by the rise in atmospheric oxygen. The amount of oxygen released to the exosphere during the Lomagundi excursion is constrained by the average global fractionation between inorganic and organic carbon, which is poorly characterized. Because dissolved inorganic and organic carbon reservoirs were arguably larger in the Paleoproterozoic ocean, at a time of lower solar luminosity and lower ocean redox state, decoupling between these two variables might be expected. We determined carbon isotope values of carbonate and organic matter in carbonates and shales of the Silverton Formation, South Africa and in the correlative Sengoma Argillite Formation, near the border in Botswana. These units were deposited between 2.22 and 2.06 Ga along the margin of the Kaapvaal Craton in an open-marine deltaic setting and experienced lower greenschist facies metamorphism. The prodelta to offshore marine shales are overlain by a subtidal carbonate sequence. Carbonates exhibit elevated 13C values ranging from 8.3 to 11.2‰ vs. VPDB consistent with deposition during the Lomagundi positive excursion. The total organic carbon (TOC) contents range from 0.01 to 0.6% and δ13C values range from - 24.8 to - 13.9‰. Thus, the isotopic fractionation between organic and carbonate carbon was on average 30.3 ± 2.8‰ ( n = 32) in the shallow-marine environment. The underlying Sengoma shales have highly variable TOC contents (0.14 to 21.94%) and δ13C values (- 33.7 to - 20.8‰) with an average of - 27.0 ± 3.0‰ ( n = 50). Considering that the shales were also deposited during the Lomagundi excursion, and taking δ13C values of the overlying carbonates as representative of the δ13C value of dissolved inorganic carbon during shale deposition, a carbon

  9. Sulphur isotope geochemistry of the ores and country rocks at the Almadén mercury deposit, Ciudad Real, Spain (United States)

    Saupé, Francis; Arnold, Michel


    Seventy-four new S isotope analyses of ore minerals and country rocks are given for the Hg deposit of Almadén. The spread of the cinnabar δ34S is narrow within each of the three orebodies, but the δ34S average values differ sufficiently between them (mean δ34S: San Nicolas = 0.2 ± 1.1 %., San Francisco = 8.1 ± 0.7%., San Pedro = 5.9 ± 1.0%.) to indicate three different mineralization episodes and possibly processes. The unweighted mean for all cinnabar samples is 5.6%. and the S source is considered to be the host-rocks, either the Footwall Shales ( δ34S = 5.5%.) or the spilites ( δ34 S = 5.1 ± 1.3%.). For geometric and chronologic reasons, the former seem the best potential source. However, the high δ34 S values of the San Francisco cinnabar cannot be explained without addition of heavy S from reduction of seawater sulphate. Orderly distributions of the δ34S values are observed in all three orebodies: (1) their increase from the stratigraphic bottom to the top in the San Pedro orebody is explained by a Rayleigh process, and (2) the maxima in the centres of the San Francisco and San Nicolas orebodies are explained by mixing of the S transporting hydrothermal fluids with seawater within the sediments. Associated pyrite and cinnabar were deposited under isotopic disequilibrium, probably because the low solubility of cinnabar caused rapid precipitation of cinnabar. The different morphological pyrite types have their own isotopic δ34S signatures. The spilites are notably enriched in S ( n = 3; average S content = 0.56%) compared to normal basalts (1000 ppm) and have an average δ34S = 5.1 ± 1.3%.. The linear relationship between the δ34S and the S content of the spilites is interpreted as a mixing line between mantle S and a constant S source, probably an infinite open reservoir. An incomplete basalt-seawater reaction at nearly constant temperature is the best explanation for this relation. The S (predominantly pyrite) of the black shales ( n = 3; δ34S

  10. Dual-Carbon sources fuel the OCS deep-reef Community, a stable isotope investigation (United States)

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


    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.

  11. Petrology, Geochemistry and Nd-Sr-Pb Isotopic Properties of Volcanic Rocks in Daheishan Island, Penglai, Shandong Province

    Institute of Scientific and Technical Information of China (English)

    Fu Yongtao; Li Anchun


    The major elements, trace elements, K-Ar age and Sr-Nd-Pb isotopic systems of the Cenozoic volcanic rocks in Daheishan Island and Cishan, Penglai, Shandong Province are measured. The volcanic rocks ( olivine-nephelinite and nepheline-basanite ) in Daheishan Island erupted periodically in an interval of 0.32 Ma, from 8.72 Ma, 8.39 Ma, 8.08 Ma to 7.73 Ma. The volcanic rocks are all rich in light REEs. They are similar to the OIB-type alkali basalt in the trace elements normalized model by primordial mantle: rich in high field elements such as Nb and Ta, and imcompatible elements such as Cs, Rb, Ba, Th, U. The volcanic rocks show a depletion of K and Rb elements. It is suggested by the trace elements that the olivine-nephelinite in Daheishan Island is originated from deep resources under the continental mantle. ε Nd (0) values of the volcanic rocks in Daheishan Island and Cisban are 5.31 ~ 8.51 and 7.33 respectively, suggesting that the volcanic rocks are from the depleted mantle resources, which have higher Sm/Nd ratios than the CHUR. 143Nd /144Nd ratios of Daheishan Island olivine-nephelinite and Cishan alkali basalts are 0.512 910 ~ 0.513 074 and 0.513 014 respectively. The 87Sr /86Sr of Daheishan Island volcanic rocks are lower than that of Cishan, 0.703 427 ~ 0.703 482 and 0.703 895 respectively. The Daheishan Island olivinenephelinite has the Pb isotopic values as follows: 206Pb /204pb = 18.028 9 ~ 17.972 8, 207Pb /204pb= 15.435 8 ~ 15.402 2 and 208Pb /204Pb = 38.087 6 ~ 37.997 5, lower than those of Cishan basanite. The Cishan basanite has 206Pb /204pb = 18.240 1, 207Pb /204Pb = 15.564 5 and 208Pb /204pb = 38.535. The authors suggest that the olivine-nephelinite in Daheishan Island is similar to the E-type MORB or Hawaii OIB, and the alkali basalts in Cishan similar to the Kerguelen OIB. The dominant mantle components of DM+PREMA and perhaps DM ( Dupal type ) are the dominant mantle components for volcanic rocks in Daheishan Island and Cishan. The

  12. Carbon isotopic evidence for microbial control of carbon supply to Orca Basin at the brine-seawater interface

    Directory of Open Access Journals (Sweden)

    S. R. Shah


    Full Text Available Orca Basin, an intraslope basin on the Texas–Louisiana continental slope, hosts a hypersaline, anoxic brine in its lowermost 200 m. This brine contains a large reservoir of reduced and aged carbon, and appears to be stable at decadal time scales: concentrations and the isotopic composition of dissolved inorganic (DIC and organic carbon (DOC are similar to previous reports. Both DIC and DOC are more "aged" within the brine pool than in overlying water, and the isotopic contrast between brine carbon and seawater carbon is much greater for DIC than DOC. While the stable carbon isotopic composition of brine DIC points towards a combination of methane and organic carbon re-mineralization as its source, radiocarbon and box model results point to the brine interface as the major source region for DIC with oxidation of methane diffusing upwards from sediments supplying only limited DIC to the brine. This conclusion is consistent with previous studies reporting microbial activity focused at the seawater-brine interface. Isotopic similarities between DIC and DOC suggest a different relationship between these two carbon reservoirs than is typically observed in deep ocean basins. Radiocarbon values implicate the seawater-brine interface region as the likely source region for DOC as well as DIC. Further investigations of the seawater-brine interface are needed to advance our understanding of the specific microbial processes contributing to dissolved carbon storage in the Orca Basin brine.


    We use measurements of the concentration and stable carbon isotopic ratio (D 13C) of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels and microbial carbon source. We found that intensive sugar cane cultivation leads to ...

  14. Geochemistry of calcareous sediments from the SW Carlsberg Ridge: Evidence for deeper carbonate compensation depth

    Digital Repository Service at National Institute of Oceanography (India)

    Valsangkar, A.B.; Ambre, N.V.

    trace metals and are depleted in the other. Variation with respect to depth is significant for CaCO sub(3) (8.5-79.8%) and benthic ratios (1.5-32.5) whereas P sub(2)O sub(5) (0.28-0.38%) and organic carbon (0.18-0.46%) is low and constant. Correlation...

  15. Carbon isotopic characterization of formaldehyde emitted by vehicles in Guangzhou, China (United States)

    Hu, Ping; Wen, Sheng; Liu, Yonglin; Bi, Xinhui; Chan, Lo Yin; Feng, Jialiang; Wang, Xinming; Sheng, Guoying; Fu, Jiamo


    Formaldehyde (HCHO) is the most abundant carbonyl compound in the atmosphere, and vehicle exhaust emission is one of its important anthropogenic sources. However, there is still uncertainty regarding HCHO flux from vehicle emission as well as from other sources. Herein, automobile source was characterized using HCHO carbon isotopic ratio to assess its contributions to atmospheric flux and demonstrate the complex production/consumption processes during combustion in engine cylinder and subsequent catalytic treatment of exhaust. Vehicle exhausts were sampled under different idling states and HCHO carbon isotopic ratios were measured by gas chromatograph-combustion-isotopic ratio mass spectrometry (GC-C-IRMS). The HCHO directly emitted from stand-alone engines (gasoline and diesel) running at different load was also sampled and measured. The HCHO carbon isotopic ratios were from -30.8 to -25.7‰ for gasoline engine, and from -26.2 to -20.7‰ for diesel engine, respectively. For diesel vehicle without catalytic converter, the HCHO carbon isotopic ratios were -22.1 ± 2.1‰, and for gasoline vehicle with catalytic converter, the ratios were -21.4 ± 0.7‰. Most of the HCHO carbon isotopic ratios were heavier than the fuel isotopic ratios (from -29 to -27‰). For gasoline vehicle, the isotopic fractionation (Δ13C) between HCHO and fuel isotopic ratios was 7.4 ± 0.7‰, which was higher than that of HCHO from stand-alone gasoline engine (Δ13Cmax = 2.7‰), suggesting additional consumption by the catalytic converter. For diesel vehicle without catalytic converter, Δ13C was 5.7 ± 2.0‰, similar to that of stand-alone diesel engine. In general, the carbon isotopic signatures of HCHO emitted from automobiles were not sensitive to idling states or to other vehicle parameters in our study condition. On comparing these HCHO carbon isotopic data with those of past studies, the atmospheric HCHO in a bus station in Guangzhou might mainly come from vehicle emission for

  16. Carbon mass-balance modeling and carbon isotope exchange processes in the Curonian Lagoon (United States)

    Barisevičiūtė, Rūta; Žilius, Mindaugas; Ertürk, Ali; Petkuvienė, Jolita


    The Curonian lagoon one of the largest coastal lagoons in Europe is located in the southeastern part of the Baltic Sea and lies along the Baltic coast of Lithuania and the Kaliningrad region of Russia. It is influenced by a discharge of the Nemunas and other smaller rivers and saline water of the Baltic Sea. The narrow (width 0.4 km, deep 8-14 m) Klaipėda Strait is the only way for fresh water run-off and brackish water intrusions. This research is focused on carbon isotope fractionations related with air - water exchange, primary production and organic carbon sedimentation, mineralization and uptake from both marine and terrestrial sources.

  17. Carbon and Oxygen Isotopic Ratios for Nearby Miras (United States)

    Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar


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

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


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


    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...

  19. Stable Isotope Measurements of Carbon Dioxide, Methane, and Hydrogen Sulfide Gas Using Frequency Modulation Spectroscopy (United States)

    Nowak-Lovato, K.


    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.

  20. Carbon-bearing iron phases and the carbon isotope composition of the deep Earth. (United States)

    Horita, Juske; Polyakov, Veniamin B


    The carbon budget and dynamics of the Earth's interior, including the core, are currently very poorly understood. Diamond-bearing, mantle-derived rocks show a very well defined peak at δ(13)C ≈ -5 ± 3‰ with a very broad distribution to lower values (∼-40‰). The processes that have produced the wide δ(13)C distributions to the observed low δ(13)C values in the deep Earth have been extensively debated, but few viable models have been proposed. Here, we present a model for understanding carbon isotope distributions within the deep Earth, involving Fe-C phases (Fe carbides and C dissolved in Fe-Ni metal). Our theoretical calculations show that Fe and Si carbides can be significantly depleted in (13)C relative to other C-bearing materials even at mantle temperatures. Thus, the redox freezing and melting cycles of lithosphere via subduction upwelling in the deep Earth that involve the Fe-C phases can readily produce diamond with the observed low δ(13)C values. The sharp contrast in the δ(13)C distributions of peridotitic and eclogitic diamonds may reflect differences in their carbon cycles, controlled by the evolution of geodynamical processes around 2.5-3 Ga. Our model also predicts that the core contains C with low δ(13)C values and that an average δ(13)C value of the bulk Earth could be much lower than ∼-5‰, consistent with those of chondrites and other planetary body. The heterogeneous and depleted δ(13)C values of the deep Earth have implications, not only for its accretion-differentiation history but also for carbon isotope biosignatures for early life on the Earth.

  1. A Novel Airborne Carbon Isotope Analyzer for Methane and Carbon Dioxide Source Fingerprinting (United States)

    Berman, E. S.; Huang, Y. W.; Owano, T. G.; Leifer, I.


    Recent field studies on major sources of the important greenhouse gas methane (CH4) indicate significant underestimation of methane release from fossil fuel industrial (FFI) and animal husbandry sources, among others. In addition, uncertainties still exist with respect to carbon dioxide (CO2) measurements, especially source fingerprinting. CO2 isotopic analysis provides a valuable in situ measurement approach to fingerprint CH4 and CO2as associated with combustion sources, leakage from geologic reservoirs, or biogenic sources. As a result, these measurements can characterize strong combustion source plumes, such as power plant emissions, and discriminate these emissions from other sources. As part of the COMEX (CO2 and MEthane eXperiment) campaign, a novel CO2 isotopic analyzer was installed and collected data aboard the CIRPAS Twin Otter aircraft. Developing methods to derive CH4 and CO2 budgets from remote sensing data is the goal of the summer 2014 COMEX campaign, which combines hyperspectral imaging (HSI) and non-imaging spectroscopy (NIS) with in situ airborne and surface data. COMEX leverages the synergy between high spatial resolution HSI and moderate spatial resolution NIS. The carbon dioxide isotope analyzer developed by Los Gatos Research (LGR) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology and incorporates proprietary internal thermal control for high sensitivity and optimal instrument stability. This analyzer measures CO2 concentration as well as δ13C, δ18O, and δ17O from CO2 at natural abundance (100-3000 ppm). The laboratory accuracy is ±1.2 ppm (1σ) in CO2 from 370-1000 ppm, with a long-term (1000 s) precision of ±0.012 ppm. The long-term precision for both δ13C and δ18O is 0.04 ‰, and for δ17O is 0.06 ‰. The analyzer was field-tested as part of the COWGAS campaign, a pre-cursor campaign to COMEX in March 2014, where it successfully discriminated plumes related to combustion processes associated with

  2. Oxygen isotope geochemistry of the lassen volcanic center, California: Resolving crustal and mantle contributions to continental Arc magmatism (United States)

    Feeley, T.C.; Clynne, M.A.; Winer, G.S.; Grice, W.C.


    This study reports oxygen isotope ratios determined by laser fluorination of mineral separates (mainly plagioclase) from basaltic andesitic to rhyolitic composition volcanic rocks erupted from the Lassen Volcanic Center (LVC), northern California. Plagioclase separates from nearly all rocks have ??18O values (6.1-8.4%) higher than expected for production of the magmas by partial melting of little evolved basaltic lavas erupted in the arc front and back-arc regions of the southernmost Cascades during the late Cenozoic. Most LVC magmas must therefore contain high 18O crustal material. In this regard, the ??18O values of the volcanic rocks show strong spatial patterns, particularly for young rhyodacitic rocks that best represent unmodified partial melts of the continental crust. Rhyodacitic magmas erupted from vents located within 3.5 km of the inferred center of the LVC have consistently lower ??18 O values (average 6.3% ?? 0.1%) at given SiO2 contents relative to rocks erupted from distal vents (>7.0 km; average 7.1% ?? 0.1%). Further, magmas erupted from vents situated at transitional distances have intermediate values and span a larger range (average 6.8% ?? 0.2%). Basaltic andesitic to andesitic composition rocks show similar spatial variations, although as a group the ??18O values of these rocks are more variable and extend to higher values than the rhyodacitic rocks. These features are interpreted to reflect assimilation of heterogeneous lower continental crust by mafic magmas, followed by mixing or mingling with silicic magmas formed by partial melting of initially high 18O continental crust (??? 9.0%) increasingly hybridized by lower ??18O (???6.0%) mantle-derived basaltic magmas toward the center of the system. Mixing calculations using estimated endmember source ??18O values imply that LVC magmas contain on a molar oxygen basis approximately 42 to 4% isotopically heavy continental crust, with proportions declining in a broadly regular fashion toward the

  3. Variability in carbon and nitrogen isotope fractionation associated with bacterial hydrolysis of atrazine (United States)

    Meyer, A.; Penning, H.; Elsner, M.


    Even after legislative prohibition in 1991 by the European Union, the pesticide atrazine and its metabolites are still detected in surface and ground water frequently exceeding the permitted drinking water concentration limit of 0,1 g/L. Despite much recent research on atrazine, its risk assessment in the environment is still a major challenge because of the difficulty of establishing mass balances in the subsurface. To obtain a better insight into the fate of atrazine, we developed compound-specific stable isotope analysis (CSIA) for atrazine. CSIA has proven valuable for assessing organic contaminants in subsurface environments, on the one hand for source identification and on the other hand to trace (bio)chemical degradation reactions through isotope fractionation in the compounds. Such assessment is based on the Rayleigh equation and therein on the isotope enrichment factor ɛ, which must be determined experimentally beforehand. In ongoing work, we therefore measured carbon and nitrogen isotope fractionation associated with biotic hydrolsis of atrazine. C and N isotope enrichment factors were determined in resting cell experiments for Pseudomonas sp. ADP, Chelatobacter heintzii and Arthrobacter aurescens TC1, strains that hydrolyse atrazine in the initial transformation reaction. Carbon and nitrogen isotope enrichment factors were distinctly different between the bacterial strains. However, when plotting shifts in carbon isotope ratios versus shifts in nitrogen isotope ratios the slopes of the different degradation experiments coincided well. These results give evidence that all bacterial strains were carrying out the same initial biochemical degradation reaction, but that the associated isotope fractionation, as represented by the enrichment factors, was masked to a different extent owing to different rate determining steps prior to the isotopically sensitive bond cleavage (commitment to catalysis). Our study therefore illustrates the benefit of multi

  4. Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana (United States)

    Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.


    Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

  5. Geochemistry and S, Pb isotope of the Yangla copper deposit, western Yunnan, China: Implication for ore genesis (United States)

    Yang, Xi-An; Liu, Jia-Jun; Cao, Ye; Han, Si-Yu; Gao, Bing-yu; Wang, Huan; Liu, Yue-Dong


    The Yangla copper deposit, situated in the middle section of Jinshajiang tectonic belt between Zhongza-Zhongdian block and Changdu-Simao block, is a representative and giant copper deposit that has been discovered in Jinshajiang-Lancangjiang-Nujiang region in recent years. There are coupled relationships between Yangla granodiorite and copper mineralization in the Yangla copper deposit. Five molybdenite samples yielded a well-constrained 187Re-187Os isochron age of 233.3 ± 3 Ma, the metallogenesis is therefore slightly younger than the crystallization age of the granodiorite. S, Pb isotopic compositions of the Yangla copper deposit indicate that the ore-forming materials were derived from the mixture of upper crust and mantle, also with the magmatic contributions. In the late Early Permian, the Jinshajiang Oceanic plate was subducted to the west, resulting in the formation of a series of gently dipping thrust faults in the Jinshajiang tectonic belt, meanwhile, accompanied magmatic activities. In the early Late Triassic, which was a time of transition from collision-related compression to extension in the Jinshajiang tectonic belt, the thrust faults were tensional; it would have been a favorable environment for forming ore fluids. The ascending magma provided a channel for the ore-forming fluid from the mantle wedge. After the magma arrived at the base of the early-stage Yangla granodiorite, the platy granodiorite at the base of the body would have shielded the late-stage magma from the fluid. The magma would have cooled slowly, and some of the ore-forming fluid in the magma would have entered the gently dipping thrust faults near the Yangla granodiorite, resulting in mineralization.

  6. Oxygen isotope geochemistry of phosphorite and dolomite and palaeo-ocean temperature estimation:A case study from the Neoproterozoic Doushantuo Formation,Guizhou Province,South China

    Institute of Scientific and Technical Information of China (English)

    LING Hongfei; JIANG Shaoyong; FENG Hongzhen; CHEN Yongquan; CHEN Jianhua; YANG Jinghong


    The Neoproterozoic Doushantuo Formation at Weng'an in Guizhou Province of South China consists of phosphorites and dolomites.Three types of samples are recongnized for the phosphate-bearing rocks.In Type I samples, interstitial phosphates occur within the dolomite rocks, whereas in Type III samples, interstitial dolomites occur within the phosphorites; both of them may have diagenetic origin.The Type II samples are interbedded phosphorites and dolomites.Oxygen isotopic compositions of phosphate and coeval carbonate were analyzed.Phosphates of Type I and II samples show similar low δ18Ophos (SMOW) values of 10.9‰~12.1‰ and 10.7‰~12.8‰, respectively, whereas Type III phosphates show higher δ18Ophos (SMOW) values of 13.2‰~15.0‰.Dolomites from Type I and II samples have δ18Ocarb (PDB) and δ13Ccarb (PDB) values of -6.2‰~-3.4‰ and -2.2‰~-0.7‰, respectively, whereas interstitial dolomites from Type III samples show lower δ18Ocarb (PDB) and δ13Ccarb (PDB) values of -12.9‰~-8.6‰ and -4.4‰~-2.6‰.Petrology and oxygen isotope data suggest that diagenetic alteration may have partially affected the studied rocks, but the dolomites from Type I and phosphates from Type III samples represent the most pristine isotopic compositions of primary carbonates and phosphates precipitated from seawater.Calculations of palaeocean temperatures from the most 18O enriched dolomite and phosphate indicate a temperature range of 32.2 ℃ to 34.0 ℃ for the seawater of the Doushantuo Formation period.Ce anomaly also suggests more oxic conditions and possibly shallower water depth in the upper strata of the Doushantuo Formation at Weng'an, Guizhou Province.

  7. The impact of recycling of organic carbon on the stable carbon isotopic composition of dissolved inorganic carbon in a stratified marine system (Kyllaren fjord, Norway)

    NARCIS (Netherlands)

    Breugel, Y. van; Schouten, S.; Paetzel, M.; Nordeide, R.; Sinninghe Damsté, J.S.


    A negative carbon isotope shift in sedimentary organic carbon deposited in stratified marine and lacustrine systems has often been inferred to be a consequence of the process of recycling of respired and, therefore, 13C-depleted, dissolved inorganic carbon (DIC) formed from mineralization of descend

  8. Zinc isotope evidence for a large-scale carbonated mantle beneath eastern China (United States)

    Liu, Sheng-Ao; Wang, Ze-Zhou; Li, Shu-Guang; Huang, Jian; Yang, Wei


    A large set of zinc (Zn) stable isotope data for continental basalts from eastern China were reported to investigate the application of Zn isotopes as a new tracer of deep carbonate cycling. All of the basalts with ages of 120 Ma basalts from eastern China (0.27 ± 0.06‰; 2sd). Given that Zn isotope fractionation during magmatic differentiation is limited (≤0.1‰), the elevated δ66Zn values reflect the involvement of isotopically heavy crustal materials (e.g., carbonates with an average δ66Zn of ∼0.91‰) in the mantle sources. SiO2 contents of the recycled Mg (Zn)-rich carbonates in the mantle beneath eastern China since the Late Mesozoic. Since Zn is a trace element in the mantle and Zn isotopic compositions of marine carbonates and the mantle differ markedly, we highlight Zn isotopes as a new and useful tool of tracing deep carbonate cycling in the Earth's mantle.

  9. Geochronology, geochemistry, and Sr-Nd-Hf isotopes of the early Paleozoic igneous rocks in the Duobaoshan area, NE China, and their geological significance (United States)

    Wu, Guang; Chen, Yuchuan; Sun, Fengyue; Liu, Jun; Wang, Guorui; Xu, Bei


    The Duobaoshan area of northwestern Heilongjiang Province is the most important copper resource concentration region in NE China. To date, the Duobaoshan superlarge Cu-Mo deposit and the Tongshan large Cu-Mo deposit have been discovered in the Duobaoshan area. Both the deposits are hosted by granodiorites and volcanic rocks. Zircon LA-ICP-MS U-Pb dating indicates that these granodiorites emplaced approximately 479 Ma ago and that those volcanic rocks erupted between 447 and 450 Ma. The early Ordovicain granodiorites belong to the high-K to medium-K calc-alkaline series and are characterized by high Al2O3 and Sr contents, low Yb and Y contents, and relatively low Mg# values and Na2O/K2O ratios, with positive Eu or slight negative Eu anomalies (averaging 1.18). All of these geochemical characters are similar to those of the adakites generated by partial melting of a thickened lower crust in the world. Moreover, the granodiorites have low initial 87Sr/86Sr ratios (varying from 0.703474 to 0.704436), very high zircon εHf(t) and whole-rock εNd(t) values (varying from 13.0 to 16.8 and 5.27 to 5.46, respectively), and young zircon Hf and whole-rock Nd single-stage and two-stage model ages. Taking these geochemical characteristics and Sr-Nd-Hf isotope compositions together, we suggest that the early Ordovician granodiorites in the Duobaoshan area occurred in a post-collision environment and were formed by partial melting of a juvenile thickened lower crust dominated by depleted mantle-derived material. These late Ordovician volcanic rocks, which are composed of basalt, basaltic andesite, and andesite, belong to the tholeiitic or calc-alkaline series. They are generally enriched in large ion lithophile elements (LILEs) and depleted in high field strength elements (HFSEs; e.g., Nb, Ta, Zr, Hf, P, and Ti), consistent with the geochemistry of igneous rocks from island arcs or active continental margins. Compared with the early Ordovician granodiorites, these volcanic rocks

  10. Carbon Stable Isotopes as Indicators of Coastal Eutrophication (United States)

    Coastal ecologists and managers have frequently used nitrogen stable isotopes (δ15N) to trace and monitor anthropogenic nitrogen (N) in coastal ecosystems. However, the interpretation of δ15N data can often be challenging, if not confounding, as the isotope values fractionate su...

  11. Carbon Isotope Evidence for the Stepwise Oxidation of the Proterozoic Environment (United States)

    DesMarais, David J.; Strauss, Harald; Summons, Roger E.; Hayes, J. M.


    The oxidation of the Earth's crust and the increase in atmospheric oxygen early in Earth history have been linked to the accumulation of reduced carbon in sedimentary rocks. Trends in the carbon isotope composition of sedimentary organic carbon and carbonate show that during the Proterozoic aeon (2.5-0.54 Gyr ago) the organic carbon reservoir grew in size, relative to the carbonate reservoir. This increase, and the concomitant release of oxidizing power in the environment, occurred mostly during episodes of global rifting and orogeny.

  12. Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China. (United States)

    Xie, Xianjun; Ellis, Andre; Wang, Yanxin; Xie, Zuoming; Duan, Mengyu; Su, Chunli


    High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 microg/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 microg/L in the basin and from 3.1 to 44 microg/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals. The wide range of delta(34)S([SO4

  13. Chlorine and carbon isotope measurements can help assessing the effectivenes of a zero valent iron barrier (United States)

    Cretnik, S.; Audi, C.; Bernstein, A.; Palau, J.; Soler, A.; Elsner, M.


    Chlorinated aliphatic hydrocarbons (CAH's) such as trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinylchloride (VC) are extensively used in industrial applications. One of the most promising remediation techniques for CAH's in groundwater is their removal via abiotic reductive dechlorination using Zero Valent Iron (ZVI). This is applied for the treatment of contaminated sites by installing permeable reactive barriers (PRB). In this study, isotope fractionation of chlorinated ethylenes in transformation by cast iron has been investigated, because such types of iron are commonly used in PRBs. Batch experiments have been carried out in closed flasks, containing cast iron with aqueous solutions of TCE, cDCE and VC. These substrates and their respective products have been monitored by headspace samplings for their concentration (by GC-FID) and isotope fractionation of carbon and chlorine (by GC-IRMS). A decreasing reactivity trend was observed when compounds contain less chlorine atoms, with differences in rate constants of about one order of magnitude between each of the substances TCE > cDCE > VC. This resulted in the accumulation of products with fewer chlorine atoms. Therefore a similar observation can be expected if degradation in the field is incomplete, for example in the case of aged or improperly designed PRB. Pronounced carbon and chlorine isotope fractionation was measured for each of the compounds, and characteristic dual isotope plots (C, Cl) were obtained for TCE and cDCE. These results may serve as an important reference for the interpretation of isotope data from field sites, since stable isotope fractionation is widely recognized as robust indicator for such pollutant transformations. However, carbon isotope fractionation in a given parent compound may be caused by either abiotic or biotic degradation. In the field, it can therefore be difficult to delineate the contribution of abiotic transformation by PRB in the presence of ongoing

  14. Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia (United States)

    Brookman, Tom H.; Ambrose, Stanley H.


    Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

  15. Trophic ecology of small yellow croaker (Larimichthys polyactis Bleeker): stable carbon and nitrogen isotope evidence

    Institute of Scientific and Technical Information of China (English)

    JI Weiwei; CHEN Xuezhong; JIANG Yazhou; LI Shengfa


    The trophic ecology of the small yellow croaker (Larimichthys polyactis) was studied using stable isotope analyses.Samples were collected from July to September 2009 and 34 individuals from eight sites were examined for stable carbon and nitrogen isotopes.Stable carbon isotope ratios (δ13C)ranged from -20.67 to -15.43,while stable nitrogen isotope ratios (δ15N) ranged 9.18-12.23.The relationship between δ13C and δ15N suggested high resource partitioning in the sampling area.Significant differences in stable isotope values among the eight sampling sites may be linked to environmental diversities involving various physical processes (such as ocean current,wind and tide) and different carbon sources.Furthermore,the stable isotope ratios may also explain the ontogenetic variability in diet and feeding,because δ13C and δ15N varied significantly with increasing body size.The findings are consistent with other studies on diet analyses in small yellow croaker.It was also demonstrated that stable isotope analysis could be used to estimate the trophic characters of small yellow croaker in feeding patterns and migrating habits.

  16. Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates (United States)

    Hippler, Dorothee; Buhl, Dieter; Witbaard, Rob; Richter, Detlev K.; Immenhauser, Adrian


    This study presents magnesium stable-isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species, seawater samples collected from the western Dutch Wadden Sea, and reference materials. The aim of this study is to explore the influence of mineralogy, taxonomy and environmental factors (e.g., seawater isotopic composition, temperature, salinity) on magnesium-isotopic (δ 26Mg) ratios of skeletal carbonates. Using high-precision multi-collector inductively coupled plasma mass spectrometry, we observed that the magnesium-isotopic composition of seawater from the semi-enclosed Dutch Wadden Sea is identical to that of open marine seawater. We further found that a considerable component of the observed variability in δ 26Mg values of marine skeletal carbonates can be attributed to differences in mineralogy. Furthermore, magnesium-isotope fractionation is species-dependent, with all skeletal carbonates being isotopically lighter than seawater. While δ 26Mg values of skeletal aragonite and high-magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences, the δ 26Mg values of echinoids, brachiopods and bivalves likely result from a taxon-specific level of control on Mg-isotope incorporation during biocalcification. Moreover, no resolvable salinity and temperature effect were observed for coralline red algae and echinoids. In contrast, Mg-isotope data of bivalves yield ambiguous results, which require further validation. The data presented here, point to a limited use of Mg isotopes as temperature proxy, but highlight the method's potential as tracer of seawater chemistry through Earth's history.

  17. Highly Efficient Quantum Sieving in Porous Graphene-like Carbon Nitride for Light Isotopes Separation (United States)

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


    Light isotopes separation, such as 3He/4He, H2/D2, H2/T2, etc., is crucial for various advanced technologies including isotope labeling, nuclear weapons, cryogenics and power generation. However, their nearly identical chemical properties made the separation challenging. The low productivity of the present isotopes separation approaches hinders the relevant applications. An efficient membrane with high performance for isotopes separation is quite appealing. Based on first-principles calculations, we theoretically demonstrated that highly efficient light isotopes separation, such as 3He/4He, can be reached in a porous graphene-like carbon nitride material via quantum sieving effect. Under moderate tensile strain, the quantum sieving of the carbon nitride membrane can be effectively tuned in a continuous way, leading to a temperature window with high 3He/4He selectivity and permeance acceptable for efficient isotopes harvest in industrial application. This mechanism also holds for separation of other light isotopes, such as H2/D2, H2/T2. Such tunable quantum sieving opens a promising avenue for light isotopes separation for industrial application. PMID:26813491

  18. Carbon Isotopic Values of Individual N—Alkanes in Pyrolysates of Algae

    Institute of Scientific and Technical Information of China (English)

    周文; 吴庆余; 等


    This paper presents the carbon isotopic values of individual n-alkanes in pyrolysates of algae,which are widely spread in marine and lacustrine environments.The carbon isotopic values of n-alkanes originated from different algal precursors vary greatly,and those of n-alka nes orginated from C.protothecoides,S.sp PCC 6803 and I.Galbana are even heavier than from higher plants,n-alkanes with different carbon numers derived from the sme organism may stem from different biomacromolecules.The dominant product nC31 diene yielded at 300℃ or lower temperature also is different from n-alkanes yielded at the same thermal evolution phase with respect to their origin.The catalysis of mineral components in limestone may lead to a lighter carbon isotope composition of n-alkanes.

  19. Linking carbon and water cycles using stable isotopes across scales: progress and challenges

    Directory of Open Access Journals (Sweden)

    C. Werner


    Full Text Available Stable isotope analysis is a powerful tool for tracing biogeochemical processes in the carbon and water cycles. One particularly powerful approach is to employ multiple isotopes where the simultaneous assessment of the D/H,18O/16O and/or 13C/12C in different compounds provide a unique means to investigate the coupling of water and carbon fluxes at various temporal and spatial scales. Here, we present a research update on recent advances in our process-based understanding of the utilization of carbon, oxygen and hydrogen isotopes to lend insight into carbon and water cycling. We highlight recent technological developments and approaches, their strengths and methodological precautions with examples covering scales from minutes to centuries and from the leaf to the globe.

  20. Geochemistry of groundwater in the Beaver and Camas Creek drainage basins, eastern Idaho (United States)

    Rattray, Gordon W.; Ginsbach, Michael L.


    The U.S. Geological Survey (USGS), in cooperation with the U.S. Department of Energy, is studying the fate and transport of waste solutes in the eastern Snake River Plain (ESRP) aquifer at the Idaho National Laboratory (INL) in eastern Idaho. This effort requires an understanding of the natural and anthropogenic geochemistry of groundwater at the INL and of the important physical and chemical processes controlling the geochemistry. In this study, the USGS applied geochemical modeling to investigate the geochemistry of groundwater in the Beaver and Camas Creek drainage basins, which provide groundwater recharge to the ESRP aquifer underlying the northeastern part of the INL. Data used in this study include petrology and mineralogy from 2 sediment and 3 rock samples, and water-quality analyses from 4 surface-water and 18 groundwater samples. The mineralogy of the sediment and rock samples was analyzed with X-ray diffraction, and the mineralogy and petrology of the rock samples were examined in thin sections. The water samples were analyzed for field parameters, major ions, silica, nutrients, dissolved organic carbon, trace elements, tritium, and the stable isotope ratios of hydrogen, oxygen, carbon, sulfur, and nitrogen. Groundwater geochemistry was influenced by reactions with rocks of the geologic terranes—carbonate rocks, rhyolite, basalt, evaporite deposits, and sediment comprised of all of these rocks. Agricultural practices near and south of Dubois and application of road anti-icing liquids on U.S. Interstate Highway 15 were likely sources of nitrate, chloride, calcium, and magnesium to groundwater. Groundwater geochemistry was successfully modeled in the alluvial aquifer in Camas Meadows and the ESRP fractured basalt aquifer using the geochemical modeling code PHREEQC. The primary geochemical processes appear to be precipitation or dissolution of calcite and dissolution of silicate minerals. Dissolution of evaporite minerals, associated with Pleistocene Lake

  1. Significance of Carbon Isotopes in Carbonate Sequence Stratigraphy—As Exemplified by the Permian System in Southwest China

    Institute of Scientific and Technical Information of China (English)

    覃建雄; 杨作升; 等


    Based on the research on sequence stratigraphy of the Permian in Southwest China,in conjunction with the carbon isotope data from the typical sections at Ganluo,Sichuan and Tianlin and Masan,Guangxi,the authors suggest that the genetic framework and internal architicture of different sequences possess quite different carbon isotopic characteristics.Therefore ,the following problems can be solved in terms of carbon isotopic values,evolutionary curve patterns and structures of carbonate sequences:(1) to determe the nature of sequence boundary surface and related geological events;(2) to recognize various kinds of sedimentary system tracts;(3) to discuss the internal architicture and genetic framework of the sequences and their evolution;(4) to subdivide and correlate sedimentary sequences on a regional or global scale; and (5)to enhance the resolution of sequence stratigraphic analysis.Stable carbon isotopes have proved themselves to be valid in sequence stratigraphic studies of carbonate rocks,as demonstrated by our results presented in this paper.

  2. Space Geodesy and Geochemistry Applied to the Monitoring, Verification of Carbon Capture and Storage

    Energy Technology Data Exchange (ETDEWEB)

    Swart, Peter


    This award was a training grant awarded by the U.S. Department of Energy (DOE). The purpose of this award was solely to provide training for two PhD graduate students for three years in the general area of carbon capture and storage (CCS). The training consisted of course work and conducting research in the area of CCS. Attendance at conferences was also encouraged as an activity and positive experience for students to learn the process of sharing research findings with the scientific community, and the peer review process. At the time of this report, both students have approximately two years remaining of their studies, so have not fully completed their scientific research projects.

  3. Stable Carbon Isotope Ratios of Phenolic Compounds in Secondary Particulate Organic Matter Formed by Photooxidation of Toluene

    CERN Document Server

    Irei, Satoshi; Huang, Lin; Auld, Janeen; Collin, Fabrice; Hastie, Donald


    Compound-specific stable carbon isotope ratios for phenolic compounds in secondary particulate organic matter (POM) formed by photooxidation of toluene were studied. Secondary POM generated by photooxidation of toluene using a continuous-flow reactor and an 8 cubic meter indoor smog chamber was collected, and then extracted with acetonitrile. Eight phenolic compounds were identified in the extracts by a gas chromatograph coupled with a mass spectrometer, and their compound-specific stable carbon isotope ratios were determined by a gas chromatograph coupled with a combustion furnace followed by an isotope ratio mass spectrometer. The majority of the products, including methylnitrophenols and methylnitrocatechols, were isotopically depleted by 5 to 6 permil compared to the initial isotope ratio for toluene, whereas the isotope ratio for 4_nitrophenol remained the same as the initial isotope ratio for toluene. Based on the reaction mechanisms postulated in literature, stable carbon isotope ratios of these produc...

  4. Climatic and palaeoceanographic changes during the Pliensbachian (Early Jurassic) inferred from clay mineralogy and stable isotope (C-O) geochemistry (NW Europe) (United States)

    Bougeault, Cédric; Pellenard, Pierre; Deconinck, Jean-François; Hesselbo, Stephen P.; Dommergues, Jean-Louis; Bruneau, Ludovic; Cocquerez, Théophile; Laffont, Rémi; Huret, Emilia; Thibault, Nicolas


    The Early Jurassic was broadly a greenhouse climate period that was punctuated by short warm and cold climatic events, positive and negative excursions of carbon isotopes, and episodes of enhanced organic matter burial. Clay minerals from Pliensbachian sediments recovered from two boreholes in the Paris Basin, are used here as proxies of detrital supplies, runoff conditions, and palaeoceanographic changes. The combined use of these minerals with stable isotope data (C-O) from bulk carbonates and organic matter allows palaeoclimatic reconstructions to be refined for the Pliensbachian. Kaolinite/illite ratio is discussed as a reliable proxy of the hydrological cycle and runoff from landmasses. Three periods of enhanced runoff are recognised within the Pliensbachian. The first one at the Sinemurian-Pliensbachian transition shows a significant increase of kaolinite concomitant with the negative carbon isotope excursion at the so-called Sinemurian Pliensbachian Boundary Event (SPBE). The Early/Late Pliensbachian transition was also characterised by more humid conditions. This warm interval is associated with a major change in oceanic circulation during the Davoei Zone, likely triggered by sea-level rise; the newly created palaeogeography, notably the flooding of the London-Brabant Massif, allowed boreal detrital supplies, including kaolinite and chlorite, to be exported to the Paris Basin. The last event of enhanced runoff occurred during the late Pliensbachian (Subnodosus Subzone of the Margaritatus Zone), which occurred also during a warm period, favouring organic matter production and preservation. Our study highlights the major role of the London Brabant Massif in influencing oceanic circulation of the NW European area, as a topographic barrier (emerged lands) during periods of lowstand sea-level and its flooding during period of high sea-level. This massif was the unique source of smectite in the Paris Basin. Two episodes of smectite-rich sedimentation ('smectite

  5. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto (United States)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.


    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all with substantial secondary formation from the photooxidation of aromatic volatile organic compounds (VOCs), was conducted in the gas phase and particulate matter (PM) together and in PM alone. Their concentrations in the atmosphere are in the low ng m-3 range and, consequently, a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33 ‰, which is well within the range predicted by mass balance. However, the observed carbon isotope ratios cover a range of nearly 9 ‰ and approximately 20 % of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban center with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This

  6. Carbon and oxygen isotope variations of the Middle-Late Triassic Al Aziziyah Formation, northwest Libya (United States)

    Moustafa, Mohamed S. H.; Pope, Michael C.; Grossman, Ethan L.; Mriheel, Ibrahim Y.


    This study presents the δ13C and δ18O records from whole rock samples of the Middle-Late Triassic (Ladinian-Carnian) Al Aziziyah Formation that were deposited on a gently sloping carbonate ramp within the Jifarah Basin of Northwest Libya. The Al Aziziyah Formation consists of gray limestone, dolomite, and dolomitic limestone interbedded with shale. The Ghryan Dome and Kaf Bates sections were sampled and analyzed for carbon and oxygen isotope chemostratigraphy to integrate high-resolution carbon isotope data with an outcrop-based stratigraphy, to provide better age control of the Al Aziziyah Formation. This study also discusses the relation between the facies architecture of the Al Aziziyah Formation and the carbon isotope values. Seven stages of relative sea level rise and fall within the Ghryan Dome were identified based on facies stacking patterns, field observations and carbon stable isotopes. The Al Aziziyah Formation δ13C chemostratigraphic curve can be partially correlated with the Triassic global δ13C curve. This correlation indicates that the Al Aziziyah Formation was deposited during the Ladinian and early Carnian. No straight-forward relationship is seen between δ13C and relative sea level probably because local influences complicated systematic environmental and diagenetic isotopic effects associated with sea level change.

  7. Carbon isotope ratios and isotopic correlations between components in fruit juices (United States)

    Wierzchnicki, Ryszard


    Nowadays food products are defined by geographical origin, method of production and by some regulations concerning terms of their authenticity. Important data for confirm the authenticity of product are providing by isotopic methods of food control. The method checks crucial criteria which characterize the authenticity of inspected product. The European Union Regulations clearly show the tendency for application of the isotopic methods for food authenticity control (wine, honey, juice). The aim of the legislation steps is the protection of European market from possibility of the commercial frauds. Method of isotope ratio mass spectrometry is very effective tool for the use distinguishably the food products of various geographical origin. The basic problem for identification of the sample origin is the lack of databases of isotopic composition of components and information about the correlations of the data. The subject of the work was study the isotopic correlations existing between components of fruits. The chemical and instrumental methods of separation: water, sugars, organic acids and pulp from fruit were implemented. IRMS technique was used to measure isotopic composition of samples. The final results for original samples of fruits (apple, strawberry etc.) will be presented and discussed. Acknowledgement: This work was supported by the Polish Ministry of Science and Higher Education under grant NR12-0043-10/2010.

  8. Experimental fractionation of stable carbon isotopes during degassing of carbon dioxide and precipitation of calcite from aqueous solutions (United States)

    Müller, K.; Winde, V.; Escher, P.; von Geldern, R.; Böttcher, M. E.


    Processes in the carbonate system of surface waters are in particular sensitive to variations of boundary conditions as, for instance, the partial pressure of carbon dioxide in the atmosphere and the aqueous solution. Examples range from streams, rivers, to coastal marine waters. The flux of carbon dioxide from continental flowing waters was recently included into calculations of the global carbon budget (Butman & Raymond, 2011, Nature Geo.). These solutions, are often supersaturated in carbon dioxide with respect to the atmosphere. The degassing of carbon dioxide is associated with a kinetically controlled fractionation of the stable carbon isotopes, which has to be considered in balancing water-air carbon dioxide fluxes. The degassing process additionally leads to the super-saturation of the aqueous solution with respect to calcium carbonate. Stable isotope fractionation is of particular value to identify and quantify processes at the water-gas phase interface and link these non-equilibrium processes to the formation mechanisms of calcite and the hydrodynamics of surface waters. Experiments were carried out with or without inert N2 gas flow to degas carbon dioxide from initially supersaturated solutions. Natural solutions used are from different stations of the Elbe estuary, the Jade Bay, the backbarrier tidal area of Spiekeroog Island, carbonate springs of Rügen Island, and the Baltic Sea coastline. Results are compared experiments using bottled mineral waters. By following the (physico) chemical changes in the solutions (pH, TA, Ca PHREEQC modeling) it was found, that two evolutionary stages can be differentiated. Reaction progress led to the preferential liberation of carbon dioxide containing the light carbon isotope, following a Rayleigh-type process. After an induction period, where only degassing of carbon dioxide took place, a second stage was observed where calcite began to form from the highly supersaturated solutions. In this stage the carbonate

  9. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry. (United States)

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre


    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰).

  10. Research progress in studies on the coalbed gas geochemistry

    Institute of Scientific and Technical Information of China (English)


    The current situation of geochemical studies on coalbed gas is reviewed in this paper. Generally, coalbed gas is compositionally dominated by methane with δ13C1 values ranging approximately from - 80‰ to - 10‰. However, few isotopic studies have been carried out on other components of coalbed gas except for hydrogen and carbon dioxide, whose δDCH4 values available for utilization vary from - 333‰ to - 117‰, and δ13CCO2 values from -29.4‰ to + 18.6‰. Two major types of coalbed gas, thermogenic gas and secondary biogenic gas, have been identified, and there are also some other classification criteria. Compared with conventional natural gases,coalbed gas has a wide distribution range of δ13C1 andδ13CCO2 values, especially possessing some extremely heavy values. Current problems that remain unsolved in the coalbed gas geochemistry include the variation mechanism, controlling factors and application of carbon and hydrogen isotopes of methane, the relation between the values of δ13C1 and Ro, the systematic classification scheme and criterion of genetic types, and the application of the coalbed gas geochemistry in evaluating target districts of the coalbed gas exploration.

  11. Marine Carbon-Sulfur Biogeochemical Cycles during the Steptoean Positive Carbon Isotope Excursion (SPICE) in the Jiangnan Basin, South China

    Institute of Scientific and Technical Information of China (English)

    Yang Peng; Yongbo Peng; Xianguo Lang; Haoran Ma; Kangjun Huang; Fangbing Li; Bing Shen


    ABSTRACT:Global occurrences of Steptoean Positive Carbon Isotope Excursion (SPICE) during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon (δ13C) and organic carbon (δ13Corg) isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate (CAS, δ34SCAS) and pyrite (δ34Spyrite), unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰increase inδ13Ccarb of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions inδ34SCAS andδ34Spyrite have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound (VOSC, such as methanethiol and dimethyl sulfide) formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of 32S from continental margins to open oceans, elevatingδ34S of seawater sulfate in continental margins. A simple box model indicates that about 35%to 75%of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.

  12. The thermal history of char as disclosed by carbon isotope ratios

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Ambus, Per; Ahrenfeldt, Jesper

    In laboratory experiments, biomass char was produced under controlled conditions using wood chips from French pinewood. Different char qualities were obtained by pyrolysing the biomass at similar heating rates with end-temperatures ranging from 250 to 1000 o C. The char was analysed by flash...... pyrolysis and isotope ratio mass spectrometry. The results demonstrate that the temperature history of the char is reflected in the fine variation of carbon isotopes. The compound classes responsible for the variation were identified. Key words: Isotope ratio, flash pyrolysis, hot gas cleaning...

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

    Institute of Scientific and Technical Information of China (English)

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


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

  14. Mesozoic magmatism and timing of epigenetic Pb-Zn-Ag mineralization in the western Fortymile mining district, east-central Alaska: Zircon U-Pb geochronology, whole-rock geochemistry, and Pb isotopes (United States)

    Dusel-Bacon, Cynthia; Aleinkoff, J.N.; Day, W.C.; Mortensen, J.K.


    The Mesozoic magmatic history of the North American margin records the evolution from a more segmented assemblage of parautochthonous and allochthonous terranes to the more cohesive northern Cordilleran orogenic belt. We characterize the setting of magmatism, tectonism, and epigenetic mineralization in the western Fortymile mining district, east-central Alaska, where parautochthonous and allochthonous Paleozoic tectonic assemblages are juxtaposed, using sensitive high-resolution ion microprobe (SHRIMP) U-Pb zircon geochronology, whole-rock geochemistry, and feldspar Pb isotopes of Mesozoic intrusions and spatially associated mineral prospects. New SHRIMP U-Pb zircon ages and published U-Pb and 40Ar/39Ar ages indicate four episodes of plutonism in the western Fortymile district: Late Triassic (216-208 Ma), Early Jurassic (199-181 Ma), mid-Cretaceous (112-94 Ma), and Late Cretaceous (70-66 Ma). All age groups have calc-alkalic arc compositions that became more evolved through time. Pb isotope compositions of feldspars from Late Triassic, Early Jurassic, and Late Cretaceous igneous rocks similarly became more radiogenic with time and are consistent with the magmas being mantle derived but extensively contaminated by upper crustal components with evolving Pb isotopic compositions. Feldspar Pb isotopes from mid-Cretaceous rocks have isotopic ratios that indicate magma derivation from upper crustal sources, probably thickened mid-Paleozoic basement. The origin of the mantle component in Late Cretaceous granitoids suggested by Pb isotopic ratios is uncertain, but we propose that it reflects asthenospheric upwelling following slab breakoff and sinking of an inactive inner subduction zone that delivered the previously accreted Wrangellia composite terrane to the North American continental margin, after the outer Farallon subduction zone was established.

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

    Institute of Scientific and Technical Information of China (English)

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


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

  16. Carbonate clumped isotope paleothermometry and stable isotope results from the Eocene Fenghuo Shan Group, Hoh Xil Basin, Central Tibet (United States)

    Snell, K. E.; Lippert, P. C.; Eiler, J. M.


    We present preliminary clumped isotope temperatures, calcite δ13C and δ18O values, and reconstructed water δ18O values from paleosol carbonates and calcite cemented siltstones and mudstones of the Fenghuo Shan Group from stratigraphic sections in the TouTou He subbasin of Hoh Xil Basin on the northern Tibetan Plateau. Models of plateau growth vary in the timing of initial plateau growth, and in their description of the spatial distribution of the plateau through time. Oxygen isotope paleoaltimetry studies have been used to estimate the elevation of the plateau in the past, but this technique requires assumptions about the temperature of mineral formation. Independent estimates of the temperature of mineral formation are potentially useful for identifying samples in which carbonate has undergone post-depositional recrystallization and/or isotopic exchange, and, when plausible primary depositional temperatures are found, for making more accurate estimates of δ18O of the waters from which the calcite precipitated. The calcite δ18O and δ13C values for the cements are relatively invariant with stratigraphic level, averaging -10.1±1.2‰ and -4.5±2.5‰ (PDB), respectively. These values are similar to lacustrine carbonates of similar age from the same region. The paleosol carbonates, in contrast, are 18O- and 13C-enriched relative to the cements, with average δ18O and δ13C values of -2.4±0.8 and -2.8±0.7‰. Carbonate clumped isotope paleotemperatures for the cements and the paleosol carbonates are also markedly different. The cement samples vary from 26 to 83°C and increase consistently with increasing depth, at a steep gradient of ~100°C/km. Paleosol carbonates from depths at which cements recorded 60°C, preserve temperatures of 35°C and 41°C. A calcite spar-filled fracture in one paleosol carbonate had a temperature of 41°C. Finally the reconstructed cement water δ18O values range from 2.8 to -7.6‰(SMOW), with a trend of 0.2‰/°C. The

  17. Forensic utility of the carbon isotope ratio of PVC tape backings (United States)

    Stern, L. A.; Thompson, A. H.; Mehltretter, A. H.; McLaskey, V.; Parish, A.; Aranda, R.


    Forensic interest in adhesive tapes with PVC-backings (polyvinyl chloride, electrical tapes) derives from their use in construction of improvised explosive devices, drug packaging and in a variety of other illicit activities. Due to the range of physical characteristics and chemical compositions of such tapes, traditional microscopic and chemical analysis of the tape backings and adhesives offer a high degree of discrimination between tapes from different manufacturers and products. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different tapes of the same product, we assessed the PVC-backings of 87 rolls of black electrical tape for their δ13C values. The adhesive on these tapes was physically removed with hexane, and plasticizers within the PVC tape backings were removed by three-20 minute extractions with chloroform. The δ13C values of the PVC tape backings ranged between -23.8 and -41.5 (‰ V-PDB). The carbon isotopic variation within a product (identical brand and product identification) is significant, based on five products with at least 3 rolls (ranges of 7.4‰ (n=3), 10.0‰ (n=6), 4.2‰ (n=16), 3.8‰ (n=6), and 11.5‰ (n=8), respectively). There was no measurable carbon isotope variation in regards to the following: a) along the length of a roll (4 samples from 1 roll); b) between the center and edge of a strip of tape (1 pair); c) between rolls assumed to be from the same lot of tape (2 pairs); d) between different rolls from the same batch of tape (same product purchased at the same time and place; 5 pairs); and e) between samples of a tape at room temperature, heated to 50° C and 80° C for 1 week. For each sample within the population of 87 tapes, carbon isotopes alone exclude 80 to 100% of the tapes as a potential match, with an average exclusion power of 92.5%, using a window of ± 0.4‰. Carbon isotope variations originate from variations in starting

  18. Determination of organic milk authenticity using carbon and nitrogen natural isotopes. (United States)

    Chung, Ill-Min; Park, Inmyoung; Yoon, Jae-Yeon; Yang, Ye-Seul; Kim, Seung-Hyun


    Natural stable isotopes of carbon and nitrogen ((12)C, (13)C, (14)N, (15)N) have abundances unique to each living creature. Therefore, measurement of the stable isotope ratio of carbon and nitrogen (δ(13)C=(13)C/(12)C, δ(15)N=(15)N/(14)N) in milk provides a reliable method to determine organic milk (OM) authenticity. In the present study, the mean δ(13)C value of OM was higher than that of conventional milk (CM), whereas the mean δ(15)N value of OM was lower than that of CM; nonetheless both δ(13)C and δ(15)N values were statistically different for the OM and CM (Pauthenticity using stable isotopes of carbon and nitrogen.

  19. Carbon Isotope Evolution of Early Proterozoic Dolomites of Wutai Mountain Area,North China

    Institute of Scientific and Technical Information of China (English)

    钟华; 马永生; 霍卫国; 姚御元


    Carbon isotope of the early Proterozoic carbonates from the Hutuo Group of the type sec-tion in Wutai Mountain area,Shanxi Province,North China,is reported.Isotopic analyses have been madefor 484 samples of dolomites.The carbon isotope results show:(i)δ13C values distinctly change with the ge-ological time,but are relatively stable in certain horizon;(ii)like that at the Cretaceous/Tertiary and Permi-an/Triassic boundaries,δ13C values also show abrupt variation across the boundaries between the JianancunFormation and the Daguandong Formation and between the Daguandong Formation and the Huaiyincun For-mation.

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

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


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

  1. Carbon-isotope stratigraphy from terrestrial organic matter through the Monterey event, Miocene, New Jersey margin (IODP Expedition 313)

    DEFF Research Database (Denmark)

    Fang, Linhao; Bjerrum, Christian J.; Hesselbo, Stephen P.


    documented from oceanic settings (i.e., lack of positive excursion of carbon-isotope values in terrestrial organic matter through the Langhian Stage). Factors that may potentially bias local terrestrial carbon-isotope records include reworking from older deposits, degradation and diagenesis, as well....../or reworking of older woody phytoclasts, but where such processes have occurred they do not readily explain the observed carbon-isotope values. It is concluded that the overall carbon-isotope signature for the exchangeable carbon reservoir is distorted, to the extent that the Monterey event excursion...... is not easily identifiable. The most likely explanation is that phytoclast reworking has indeed occurred in clinoform toe-of-slope facies, but the reason for the resulting relatively heavy carbon-isotope values in the Burdigalian remains obscure....

  2. Linking mercury, carbon, and nitrogen stable isotopes in Tibetan biota: Implications for using mercury stable isotopes as source tracers. (United States)

    Xu, Xiaoyu; Zhang, Qianggong; Wang, Wen-Xiong


    Tibetan Plateau is located at a mountain region isolated from direct anthropogenic sources. Mercury concentrations and stable isotopes of carbon, nitrogen, and mercury were analyzed in sediment and biota for Nam Co and Yamdrok Lake. Biotic mercury concentrations and high food web magnification factors suggested that Tibetan Plateau is no longer a pristine site. The primary source of methylmercury was microbial production in local sediment despite the lack of direct methylmercury input. Strong ultraviolet intensity led to extensive photochemical reactions and up to 65% of methylmercury in water was photo-demethylated before entering the food webs. Biota displayed very high Δ(199)Hg signatures, with some highest value (8.6%) ever in living organisms. The δ(202)Hg and Δ(199)Hg in sediment and biotic samples increased with trophic positions (δ(15)N) and %methylmercury. Fish total length closely correlated to δ(13)C and Δ(199)Hg values due to dissimilar carbon sources and methylmercury pools in different living waters. This is the first mercury isotope study on high altitude lake ecosystems that demonstrated specific isotope fractionations of mercury under extreme environmental conditions.

  3. Determination of the origin of dissolved inorganic carbon in groundwater around a reclaimed landfill in Otwock using stable carbon isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Porowska, Dorota, E-mail:


    Highlights: • Research showed the origin of DIC in the groundwater around a reclaimed landfill. • Carbon isotope was used to evaluate the contributions of carbon from different sources. • The leachate-contaminated water was isotopically distinct from the natural groundwater. • DIC in the natural groundwater comes from organic matter and dissolution of carbonates. • In the contaminated water, DIC comes from organic matter in the aquifer and landfill. - Abstract: Chemical and isotopic analyses of groundwater from piezometers located around a reclaimed landfill in Otwock (Poland) were performed in order to trace the origin of dissolved inorganic carbon (DIC) in the groundwater. Due to differences in the isotopic composition of carbon from different sources, an analysis of stable carbon isotopes in the groundwater, together with the Keeling plot approach and a two-component mixing model allow us to evaluate the relative contributions of carbon from these sources in the groundwater. In the natural (background) groundwater, DIC concentrations and the isotopic composition of DIC (δ{sup 13}C{sub DIC}) comes from two sources: decomposition of organic matter and carbonate dissolution within the aquifer sediments, whereas in the leachate-contaminated groundwater, DIC concentrations and δ{sup 13}C{sub DIC} values depend on the degradation of organic matter within the aquifer sediments and biodegradation of organic matter stored in the landfill. From the mixing model, about 4–54% of the DIC pool is derived from organic matter degradation and 96–46% from carbonate dissolution in natural conditions. In the leachate-contaminated groundwater, about 20–53% of the DIC is derived from organic matter degradation of natural origin and 80–47% from biodegradation of organic matter stored in the landfill. Partial pressure of CO{sub 2} (P CO{sub 2}) was generally above the atmospheric, hence atmospheric CO{sub 2} as a source of carbon in DIC pool was negligible in the

  4. Carbon isotope fractionation of chlorinated ethenes during oxidation by Fe{sup 2+} activated persulfate

    Energy Technology Data Exchange (ETDEWEB)

    Marchesi, Massimo, E-mail: [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Aravena, Ramon [Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Sra, Kanwartej S. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada); Thomson, Neil R. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Otero, Neus; Soler, Albert [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Mancini, Silvia [Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada)


    The increased use of persulfate (S{sub 2}O{sub 8}{sup 2-}) for in situ chemical oxidation to treat groundwater and soils contaminated by chlorinated hydrocarbon compounds (CHCs) requires unbiased methods to assess treatment performance. Stable carbon isotope analysis offers a potential tool for assessing the in situ treatment performance of persulfate at sites contaminated with CHCs. This study investigated the extent of C isotope fractionation during oxidation of tetrachloroethene (PCE), trichloroethene (TCE) and cis-dichloroethene (cis-DCE) by persulfate activated by ferrous ion (Fe{sup 2+}). An average carbon isotope enrichment factor {epsilon}{sub bulk} of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cis-DCE were obtained in batch experiments. Variations in the initial S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratios did not result in any significant differences in carbon isotope fractionation. The occurrence of carbon isotope fractionation during oxidation and the lack of dependence of enrichment factors upon the S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratio demonstrate that carbon isotope analysis can potentially be used at contaminated sites as an additional technique to estimate treatment efficacy during oxidation of CHCs by Fe{sup 2+} activated persulfate. Highlights: Black-Right-Pointing-Pointer The performance of in situ chemical oxidation (ISCO) is still difficult to assess. Black-Right-Pointing-Pointer We investigated the potential of carbon isotope analysis as a new assessing tool. Black-Right-Pointing-Pointer C isotope of PCE, TCE and DCE oxidized by persulfate activated by Fe{sup 2+} was measured. Black-Right-Pointing-Pointer Enrichment factors of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cisDCE were obtained. Black-Right-Pointing-Pointer Carbon isotope can potentially be used to estimate the ISCO treatment efficacy.

  5. Rare earth element geochemistry of Late Devonian reefal carbonates, Canning Basin, Western Australia: confirmation of a seawater REE proxy in ancient limestones (United States)

    Nothdurft, Luke D.; Webb, Gregory E.; Kamber, Balz S.


    Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements ( n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average Nd SN/Yb SN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement ( n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (Nd SN/Yb SN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of


    Directory of Open Access Journals (Sweden)

    Dorota Porowska


    Full Text Available Carbon isotope analyses can be used for knowledge and practical purpose. They can be used to assess the genesis of carbon in geochemical environment, and may also be used to indicate environmental contamination by carbon-containing compounds. The aim of the paper is to indicate the possibilities of using carbon isotope composition for interpretation concerning the following elements of the natural environment: atmospheric air, subsurface zone (gases in soils and aeration zone in terms of natural and anthropogenic factors influencing on their quality. This method can be applied universally, when carbon sources are different in isotopic composition.

  7. On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Schmitt, J.; Seth, B.; Bock, M; van der Veen, C.; Möller, L.; Sapart, C.J.; Prokopiou, M.; Sowers, T.; Röckmann, T.; Fischer, H


    Stable carbon isotope analysis of methane ( 13C of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentra

  8. A versatile method for stable carbon isotope analysis of carbohydrates by high-performance liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Boschker, H.T.S.; Moerdijk-Poortvliet, T.C.W.; Van Breugel, P.; Houtekamer, M.J.; Middelburg, J.J.


    We have developed a method to analyze stable carbon isotope (13C/12C) ratios in a variety of carbohydrates using high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS). The chromatography is based on strong anion-exchange columns with low strength NaOH eluents. An eluent

  9. A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.


    RATIONALE Liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (13C/12C) in biological metabolites, at their natural abundance. However, until now this technique coul

  10. A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.


    RATIONALELiquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (C-13/C-12) in biological metabolites, at their natural abundance. However, until now this technique cou

  11. Biometrics from the carbon isotope ratio analysis of amino acids in human hair. (United States)

    Jackson, Glen P; An, Yan; Konstantynova, Kateryna I; Rashaid, Ayat H B


    This study compares and contrasts the ability to classify individuals into different grouping factors through either bulk isotope ratio analysis or amino-acid-specific isotope ratio analysis of human hair. Using LC-IRMS, we measured the isotope ratios of 14 amino acids in hair proteins independently, and leucine/isoleucine as a co-eluting pair, to provide 15 variables for classification. Multivariate analysis confirmed that the essential amino acids and non-essential amino acids were mostly independent variables in the classification rules, thereby enabling the separation of dietary factors of isotope intake from intrinsic or phenotypic factors of isotope fractionation. Multivariate analysis revealed at least two potential sources of non-dietary factors influencing the carbon isotope ratio values of the amino acids in human hair: body mass index (BMI) and age. These results provide evidence that compound-specific isotope ratio analysis has the potential to go beyond region-of-origin or geospatial movements of individuals-obtainable through bulk isotope measurements-to the provision of physical and characteristic traits about the individuals, such as age and BMI. Further development and refinement, for example to genetic, metabolic, disease and hormonal factors could ultimately be of great assistance in forensic and clinical casework.

  12. [The isotope effect in the glycine dehydrogenase reaction is the cause of the intramolecular isotope inhomogeneity of glucose carbon of starch synthesized during photorespiration]. (United States)

    Ivlev, A A


    The isotope distribution of glucose-6-phosphate in the main pathways of its biosynthesis (in the processes of CO2 assimilation and photorespiration in the Calvin cycle and during resynthesis from the degradation products of lipids and proteins) was analyzed. For reconstructing the isotope distribution of glucoso-6-phosphate synthesized in the Calvin cycle during photorespiration, the functioning of the cycle with regard to its coupling with the glycolate chain, which together constitute the photorespiration chain, was considered. In the glycine dehydrogenase reaction of the glycolate cycle, there arises an isotope effect, which determines the distribution of isotopes in the glucose-6-phosphate and other photorespiration products. The isotope effect of the glycine dehydrogenase reaction increases at the expense of the exhaustion of glucose resources feeding the photorespiration chain. As a result, atoms C-3 and C-4 of glucose become enriched with the heavy isotope, and subsequent mixing of atoms and the specificity of interactions in the photorespiration chain lead to an isotope weighting of the other atoms and an uneven distribution of carbon isotopes in glucose-6-phosphate and other photorespiration products. A comparison of the glucose-6-phosphate isotope patterns in different pathways of the synthesis with the experimental data on the distribution of carbon isotopes in starch glucose of storing plant organs led to the conclusion that the starch resources are predominantly formed at the expense of glucose-6-phosphate of photorespiration. This is consistent with the earlier observed enhancement of photorespiration at the stage of plant maturation.

  13. Carbon and nitrogen isotope variations in tree-rings as records of perturbations in regional carbon and nitrogen cycles. (United States)

    Bukata, Andrew R; Kyser, T Kurtis


    Increasing anthropogenic pollution from urban centers and fossil fuel combustion can impact the carbon and nitrogen cycles in forests. To assess the impact of twentieth century anthropogenic pollution on forested system carbon and nitrogen cycles, variations in the carbon and nitrogen isotopic compositions of tree-rings were measured. Individual annual growth rings in trees from six sites across Ontario and one in New Brunswick, Canada were used to develop site chronologies of tree-ring delta 15N and delta 13C values. Tree-ring 615N values were approximately 0.5% per hundred higher and correlated with contemporaneous foliar samples from the same tree, but not with delta 15N values of soil samples. Temporal trends in carbon and nitrogen isotopic compositions of these tree-rings are consistent with increasing anthropogenic influence on both the carbon and nitrogen cycles since 1945. Tree-ring delta 13C values and delta 15N values are correlated at both remote and urban-proximal sites, with delta 15N values decreasing since 1945 and converging on 1% per hundred at urban-proximal sites and decreasing but not converging on a single delta 15N value in remote sites. These results indicate that temporal trends in tree-ring nitrogen and carbon isotopic compositions record the regional extent of pollution.

  14. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes (United States)

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


    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  15. Separation of polybrominated diphenyl ethers in fish for compound-specific stable carbon isotope analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Yan-Hong [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Graduate University of Chinese Academy of Sciences, Beijing, 100049 (China); Luo, Xiao-Jun, E-mail: [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Chen, Hua-Shan; Wu, Jiang-Ping; Chen, She-Jun; Mai, Bi-Xian [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)


    A separation and isotopic analysis method was developed to accurately measure the stable carbon isotope ratios of polybrominated diphenyl ethers (PBDEs) with three to six substituted bromine atoms in fish samples. Sample extracts were treated with concentrated sulfuric acid to remove lipids, purified using complex silica gel column chromatography, and finally processed using alumina/silica (Al/Si) gel column chromatography. The purities of extracts were verified by gas chromatography and mass spectrometry (GC-MS) in the full-scan mode. The average recoveries of all compounds across the purification method were between 60% and 110%, with the exception of BDE-154. The stable carbon isotopic compositions of PBDEs can be measured with a standard deviation of less than 0.5 Per-Mille-Sign . No significant isotopic fraction was found during the purification of the main PBDE congeners. A significant change in the stable carbon isotope ratio of BDE-47 was observed in fish carcasses compared to the original isotopic signatures, implying that PBDE stable carbon isotopic compositions can be used to trace the biotransformation of PBDEs in biota. - Highlights: Black-Right-Pointing-Pointer A method for the purification of PBDEs for CSIA was developed. Black-Right-Pointing-Pointer The {delta}{sup 13}C of PBDE congeners can be measured with a standard deviation of less than 0.5 Per-Mille-Sign . Black-Right-Pointing-Pointer Common carp were exposed to a PBDE mixture to investigate debromination. Black-Right-Pointing-Pointer Ratios of the {delta}{sup 13}C values can be used to trace the debromination of PBDE in fish.

  16. Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts (United States)

    Socki, Richard; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K.


    The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of 20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = 13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of 35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = 34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the

  17. Molecular carbon isotopic evidence for the origin of geothermal hydrocarbons (United States)

    Des Marais, D. J.; Donchin, J. H.; Nehring, N. L.; Truesdell, A. H.


    Isotopic measurements of individual geothermal hydrocarbons that are, as a group, of higher molecular weight than methane are reported. It is believed in light of this data that the principal source of hydrocarbons in four geothermal areas in western North America is the thermal decomposition of sedimentary or groundwater organic matter.

  18. Intercontinental correlation of organic carbon and carbonate stable isotope records: evidence of climate and sea-level change during the Turonian (Cretaceous)

    NARCIS (Netherlands)

    Jarvis, I.; Trabucho-Alexandre, João; Gröcke, D.R.; Uličný, D.; Laurin, J.


    Carbon (d13Corg, d13Ccarb) and oxygen (d18Ocarb) isotope records are presented for an expanded Upper Cretaceous (Turonian–Coniacian) hemipelagic succession cored in the central Bohemian Cretaceous Basin, Czech Republic. Geophysical logs, biostratigraphy and stable carbon isotope chemostratigraphy pr

  19. Transient carbon isotope changes in complex systems: Finding the global signal, embracing the local signal (United States)

    Bowen, G. J.; Schneider-Mor, A.; Filley, T. R.


    Global, transient carbon isotope excursions (CIEs) in the geological record are increasingly invoked as evidence of short-lived changes in carbon fluxes to/from the ocean-atmosphere-biosphere (exogenic) system. Reconstructing the dynamics of carbon cycle perturbation and response during such events requires that the global extent, magnitude, and temporal pattern of carbon isotope change are well understood. Unfortunately, no simple, globally integrated measure of exogenic δ13C change exists in the geological record: during major global perturbations even the best-case candidates such as deep-ocean carbonate δ13C values likely respond to a complex of factors including ocean carbonate chemistry and circulation. Here we consider the utility of organic carbon isotope records from two complex depositional systems common in the geological record, fossil soils and continental margin sediments, which are of interest in terms of their relationship to organic carbon cycling and records of past ecological change. Within both systems changes in ecology, climate, carbon source, residence time, and molecular composition have clear potential to modulate the preserved record of global exogenic δ13C change, compromising 1st-order interpretations of bulk or compound-specific isotopic records. Process-explicit eco- geochemical models, ideally combined with multi-substrate data, provide one approach to the isolation of global δ13C change and identification of local or regional processes reflected in such records. Examples from both systems drawn from ongoing work on the Paleocene-Eocene thermal maximum illustrate the potential pitfalls, as well as opportunities, afforded by coupled data/model assessment of transient δ13C changes in complex systems.

  20. Paleoproterozoic magmatism across the Archean-Proterozoic boundary in central Fennoscandia: Geochronology, geochemistry and isotopic data (Sm-Nd, Lu-Hf, O) (United States)

    Lahtinen, Raimo; Huhma, Hannu; Lahaye, Yann; Lode, Stefanie; Heinonen, Suvi; Sayab, Mohammad; Whitehouse, Martin J.


    The central Fennoscandia is characterized by the Archean-Proterozoic (AP) boundary and the Central Finland Granitoid Complex (CFGC), a roundish area of approximately 40,000 km2 surrounded by supracrustal belts. Deep seismic reflection profile FIRE 3A runs across these units, and we have re-interpreted the profile and crustal evolution along the profile using 1.92-1.85 Ga plutonic rocks as lithospheric probes. The surface part of the profile has been divided into five subareas: Archean continent (AC) in the east, AP, CFGC, boundary zone (BZ) and the Bothnian Belt (BB) in the west. There are 12 key samples from which zircons were studied for inclusions and analyzed (core-rim) by ion probe for U-Pb dating and oxygen isotopes, followed by analyzes for Lu-Hf by LA-MC-ICP-MS. The AC plutonic rocks (1.87-1.85 Ga) form a bimodal suite, where the proposed mantle source for the mafic rocks is 2.1-2.0 Ga metasomatized lower part of the Archean subcontinental lithospheric mantle (SCLM) and the source for the felsic melts is related plume-derived underplated mafic material in the lower crust. Variable degrees of contamination of the Archean lower crust have produced "subduction-like" Nb-Ta anomalies in spidergrams and negative εNd (T) values in the mafic-intermediate rocks. The felsic AC granitoids originate from a low degree melting of eclogitic or garnet-bearing amphibolites with titanite ± rutile partly prevailing in the residue (Nb-Ta fractionation) followed by variable degree of assimilation/melting of the Archean lower crust. The AP plutonic rocks (ca. 1.88 Ga) can be divided into I-type and A-type granitoids (AP/A), where the latter follow the sediment assimilation trend in ASI diagram, have high δ18O values (up to 8‰) in zircons and exhibit negative Ba anomalies (Rb-Ba-Th in spidergram), as found in sedimentary rocks. A mixing/assimilation of enriched mantle-derived melts with melts from already migmatized sedimentary rocks ± amphibolites is proposed. The CFGC is

  1. Calcium and calcium isotope changes during carbon cycle perturbations at the end-Permian (United States)

    Komar, Nemanja; Zeebe, Richard


    Negative carbon and calcium isotope excursions, as well as climate shifts, took place during the most severe mass extinction event in Earth's history, the end-Permian (˜252 Ma). Investigating the connection between carbon and calcium cycles during transient carbon cycle perturbation events, such as the end-Permian, may help resolve the intricacies between the coupled calcium-carbon cycles, as well as provide a tool for constraining the causes of mass extinction. Here, we identify the deficiencies of a simplified calcium model employed in several previous studies and we demonstrate the importance of a fully coupled carbon-cycle model when investigating the dynamics of carbon and calcium cycling. Simulations with a modified version of the LOSCAR model, which includes a fully coupled carbon-calcium cycle, indicate that increased weathering rates and ocean acidification (potentially caused by Siberian Trap volcanism) are not capable of producing trends observed in the record, as previously claimed. Our model results suggest that combined effects of carbon input via Siberian Trap volcanism (12,000 Pg C), the cessation of biological carbon export, and variable calcium isotope fractionation (due to a change in the seawater carbonate ion concentration) represents a more plausible scenario. This scenario successfully reconciles δ13C and δ44Ca trends observed in the sediment record, as well as the proposed warming of >6oC.

  2. Zircon U-Pb geochronology, geochemistry and Sr-Nd-Pb isotopes from the metamorphic basement in the Wuhe Complex: Implications for Neoarchean active continental margin along the southeastern North China Craton and constraints on the petrogenesis of Mesozoic granitoids

    Directory of Open Access Journals (Sweden)

    Andong Wang


    Full Text Available We report zircon U-Pb geochronology, geochemistry and Sr-Nd-Pb isotope data from mafic granulites and garnet amphibolites of the Wuhe Complex in the southeastern margin of the North China Craton (NCC. In combination with previous data, our results demonstrate that these rocks represent fragments of the ancient lower crust, and have features similar to those of the granulite basement in the northern margin of the NCC. A detailed evaluation of the Pb isotope data shows that Pb isotopes cannot effectively distinguish the role of the Yangtze Craton basement from that of the NCC basement with regard to the source and generation of magmas, at least for southeastern NCC. The age data suggest that the protoliths of the granulites or amphibolites in the Wuhe Complex were most likely generated in Neoarchean and that these rocks were subjected to Paleoproterozoic (1.8–1.9 Ga high-pressure granulite facies metamorphism. This study also shows that the Precambrian metamorphic basement in the southeastern margin of the NCC might have formed in a tectonic setting characterized by a late Neoarchean active continental margin.

  3. Triassic-Jurassic organic carbon isotope stratigraphy of key sections in the western Tethys realm (Austria) (United States)

    Ruhl, Micha; Kürschner, Wolfram M.; Krystyn, Leopold


    The late Triassic period is recognized as one of the five major mass extinctions in the fossil record. All these important intervals in earth history are associated with excursions in C-isotope records thought to have been caused by perturbations in the global carbon cycle. The nature and causes of C-isotopic events across the Triassic-Jurassic (T-J) transition however, are poorly understood. We present several new high resolution organic C-isotope records from the Eiberg Basin, Austria, including the proposed Global boundary Stratotype Section and Point (GSSP) for the base of the Jurassic. The Triassic-Jurassic boundary interval in these records is characterized by the initial and main negative organic carbon isotope excursions (CIE) of up to 8‰. The initial and main CIEs are biostratigraphically constrained by first and last occurrences of boundary defining macro- and microfossils (e.g. ammonites). High resolution C-isotope records appear to be an excellent correlation proxy for this period in the Eiberg Basin. Pyrolysis analysis demonstrates increased Hydrogen Index (HI) values for organic matter coinciding with the initial CIE. Terrestrial organic matter influx and mass occurrences of green algae remains may have influenced the C-isotope composition of the sedimentary organic matter. This may have contributed to the extreme amplitude of the initial CIE in the Eiberg Basin.

  4. Beyond carbon and nitrogen: guidelines for estimating three-dimensional isotopic niche space. (United States)

    Rossman, Sam; Ostrom, Peggy H; Gordon, Forrest; Zipkin, Elise F


    Isotopic niche has typically been characterized through carbon and nitrogen ratios and most modeling approaches are limited to two dimensions. Yet, other stable isotopes can provide additional power to resolve questions associated with foraging, migration, dispersal and variations in resource use. The ellipse niche model was recently generalized to n-dimensions. We present an analogous methodology which incorporates variation across three stable dimensions to estimate the significant features of a population's isotopic niche space including: 1) niche volume (referred to as standard ellipsoid volume, SEV), 2) relative centroid location (CL), 3) shape and 4) area of overlap between multiple ellipsoids and 5) distance between two CLs. We conducted a simulation study showing the accuracy and precision of three dimensional niche models across a range of values. Importantly, the model correctly identifies differences in SEV and CL among populations, even with small sample sizes and in cases where the absolute values cannot precisely be recovered. We use these results to provide guidelines for sample size in conducting multivariate isotopic niche modeling. We demonstrate the utility of our approach with a case study of three bottlenose dolphin populations which appear to possess largely overlapping niches when analyzed with only carbon and nitrogen isotopes. Upon inclusion of sulfur, we see that the three dolphin ecotypes are in fact segregated on the basis of salinity and find the stable isotope niche of inshore bottlenose dolphins significantly larger than coastal and offshore populations.


    Directory of Open Access Journals (Sweden)

    Livia Vittori Antisari


    Full Text Available While monitoring the physico-chemical characteristics, trace elements and O-H-Sr-B isotopic data were obtained in superficial waters from a number of irrigations canals and ditches in the Ravenna coastal plain, in order to highlight the cycling of potentially toxic elements and the different sources of the solutes. Surveys were conducted during March and July 2008, and considered as representative of the waters in winter and summer, respectively. In summer, the water mass balance in the network is mostly controlled by the ingression of freshwaters from the Canale Emiliano Romagnolo (CER. The O-H isotopic data indicated that, in winter, waters are primarily recharged from Apennine catchments and undergo evaporation to different extents.The boron isotopic signature indicates the important role played by the marine component. A major seawater contribution was evidenced in canals close to the coastline; however, the process controlling the origin of dissolved boron is not solely related to direct mixing with sea water but comprises an additional source probably related to water-soil exchanges and boron of marine origin leaching, owing to the prolonged exposure of alluvial sediments to sea water. An additional boron contribution from the agricultural practice was is also evidenced. Calculation based on the conservative behaviour of chloride ions indicated that in canals and ditches not directly connected with the sea up to the 80% of the Sr budget did not originate from seawater, indicating a source from Al-silicate minerals and supporting the hypothesis of significant soil-water interactions and chemical exchanges.The positive correlation between pH and dissolved oxygen in winter waters is likely to reflect CO2 consumption during algal photosynthesis, favouring the in-situ generation of colloidal particles due to the oxidative precipitation of ferric iron oxy-hydroxides and probably small carbonate particles able to adsorb trace metals on their

  6. Extreme hydrogen, oxygen and carbon isotope anomalies in the pore waters and carbonates of the sediments and basalts from the Norwegian Sea: Methane and hydrogen from the mantle

    Energy Technology Data Exchange (ETDEWEB)

    Lawrence, J.R. (Univ. of Houston, University Park, TX (USA)); Taviani, M. (Instituto di Geologia Marina, del C.N.R., Bologna (Italy))


    D/H ratios in the pore waters of the sediments from the Norwegian Sea decrease as a function of depth to values as low as {minus}14{per thousand}. Oxygen isotope ratios in the pore waters and carbon and oxygen isotope ratios in carbonates both in the sediments and basalts are low. Extensive alteration of basalt has been given as the explanation for the low oxygen isotope ratios. Material balance calculations suggest that alteration of volcanic material and oxidation of organic matter cannot explain the hydrogen and carbon isotope anomalies. Arguments are presented suggesting that methane and hydrogen from the mantle are oxidized to carbon dioxide and water by sulfate and ferric iron in the basaltic crust to yield the low hydrogen and carbon isotope ratios.

  7. Carbon isotopic records inpaleosols over the Pliocene in Northern China: Implication on vegetation developmentand Tibetan uplift

    Institute of Scientific and Technical Information of China (English)


    Carbon isotopic composition of pedogenic carbonate can be used to estimate the proportion of C4 and C3 plants. Here we present carbon isotopic data of carbonate in a red earth section at Xifeng, central Loess Plateau. Results show that C4 vegetation increased in ~4.4 Ma B.P., stabilized between 4.0 and 3.0 Ma B.P. The character and timing of C4 expansion on the Loess Plateau are similar, but different with other localities, e.g. Pakistan and Africa, implying that regional climate changes were main factors driving the expansion of C4 plants. This event is comparable in timing with increased aridity evidenced by Xifeng grain size and North Pacific eolian dust records. Therefore we argue that the Pliocene expansion of C4 plants in northern China might have been caused by the increased aridity, which in turn might be related to rapid uplift of the Tibetan Plateau.

  8. Carbon isotope fractionation reveals distinct process of CH4 emission from different compartments of paddy ecosystem (United States)

    Zhang, Guangbin; Yu, Haiyang; Fan, Xianfang; Ma, Jing; Xu, Hua


    Carbon isotopic fractionations in the processes of CH4 emission from paddy field remain poorly understood. The δ13C-values of CH4 in association with production, oxidation and transport of CH4 in different pools of a paddy field were determined, and the stable carbon isotope fractionations were calibrated to assess relative contribution of acetate to CH4 production (fac) and fraction of CH4 oxidized (fox) by different pathways. The apparent isotope fractionation for CO2 conversion to CH4 (αapp) was 1.041-1.056 in the soil and 1.046-1.080 on the roots, indicating that fac was 10-60% and 0-50%, respectively. Isotope fractionation associated with CH4 oxidation (αox) was 1.021 ± 0.007 in the soil and 1.013 ± 0.005 on the roots, and the transport fractionation (ɛtransport) by rice plants was estimated to be -16.7‰ ~ -11.1‰. Rhizospheric fox was about 30-100%, and it was more important at the beginning but decreased fast towards the end of season. Large value of fox was also observed at the soil-water interface and soil and roots surfaces, respectively. The results demonstrate that carbon isotopic fractionations which might be different in different conditions were sensitive to the estimations of fac and fox in paddy field.

  9. Metal isotopes and carbonate proxy archives: Model-based perspectives on diagenesis (United States)

    Fantle, M. S.; Higgins, J. A.; Griffith, E. M.


    Metal isotopes are novel tools, and have expanded the geochemical toolbox for elucidating the functioning of the Earth over various time scales. Carbonate-based stable isotope proxies now extend well beyond the traditional major elements (C and O) to include Ca, as well as trace elements such as Sr, S, Mg, B, Li, Cd, and U. Such trace isotopic proxies may contain invaluable information about the Earth system in the past, but can be susceptible to diagenetic alteration over long time scales. It is therefore critical that diagenetic effects are understood and can be recognized in ancient rocks. The extent of alteration depends on reaction rate and advection velocity in the sedimentary section, and elemental partitioning and isotopic effects associated with diagenesis. Numerical approaches, such as reactive transport models, are extremely useful tools for constraining such variables, and for testing hypotheses related to alteration of proxy records. Reactive transport models allow for constraints on calcite recrystallization rates in natural systems; data from ODP Sites 807A, 1170A, 1171A, and 806B suggest rapid recrystallization in relatively young sediments, as well as a Ca isotopic fractionation factor (α) associated with calcite recrystallization close to 1 (Δ=0). While the former is critical for addressing the fidelity and accuracy of a variety of geochemical proxies, the latter is distinctly different from that associated with the formation of carbonates in the surface ocean (Δ~ -1.35‰), suggesting considerable isotopic leverage to alter Ca isotopes during diagenesis. While Ca isotopes are generally well buffered in carbonate-rich sediments, this leverage to alter may be expressed as a reduction in the amplitude of geochemical variability in the solid or as a result of reactions near the sediment-seawater interface (as seen at ODP Site 1221 associated with chemical burndown during the PETM). Further, the Ca and Mg isotopic compositions of shallow water

  10. Forensic utility of carbon isotope ratio variations in PVC tape backings. (United States)

    Dietz, Marianne E; Stern, Libby A; Mehltretter, Andria Hobbs; Parish, Ashley; McLasky, Velvet; Aranda, Roman


    Forensic interest in adhesive tapes with polyvinyl chloride (PVC) backings (electrical tape) derives from their use in a variety of illicit activities. Due to the range of physical characteristics, chemical compositions, and homogeneity within a single roll of tape, traditional microscopic and chemical analyses can offer a high degree of discrimination between tapes, permitting the assessment of potential associations between evidentiary tape samples. The carbon isotope ratios of tapes could provide additional discrimination among tape samples. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different rolls of tape of the same product, we assessed the δ(13)C values of backings from 87 rolls of PVC-based black electrical tape (~20 brands, >60 products) Prior to analysis, adhesives were removed to prevent contamination by adhering debris, and plasticizers were extracted because of concern over their potential mobility. This result is consistent with each of these tapes having approximately the same plasticizer δ(13)C value and proportion of carbon in these plasticizers. The δ(13)C values of the 87 PVC tape backings ranged between -23.5 and -41.3 (‰, V-PDB), with negligible carbon isotopic variation within single rolls of tape, yet large variations among tape brands and tape products. Within this tape population, carbon isotope ratios permitted an average exclusion power of 93.7%, using a window of +/-0.3‰; the combination of carbon isotope ratio measurement with additional chemical and physical analyses raises the discrimination power to over 98.9%, with only 41 out of a possible 3741 pairs of tape samples being indistinguishable. There was a linear relationship between the δ(13)C value of tape backings and the change in δ(13)C value with the extraction of plasticizers. Analyses of pre- and post-blast tape sample pairs show that carbon isotope signatures are within 0.3‰ of

  11. A middle Miocene benthic foraminiferal stable isotope record from extensively recrystallised carbonate sediments of IODP Site U1336 in the Equatorial Pacific (United States)

    Voigt, J.; Hathorne, E. C.; Holbourn, A. E.; Frank, M.


    The elemental and isotopic composition of foraminifera is widely used for reconstructing oceanic and climatic conditions in the past. However, ancient foraminiferal tests are altered after deposition through replacement of the original biogenic calcite by secondary (inorganic) calcite. Therefore, it is important to quantify changes in the elemental and isotopic composition of recrystallised tests to assess the reliability of proxy data. Here, we present benthic foraminiferal stable isotope data from IODP Site U1336 where the geochemistry of bulk carbonates and associated pore waters suggests extensive recrystallisation resulting from an enhanced thermal gradient. In sediments older than 20.3 Ma the 87Sr/86Sr ratios of bulk carbonates and associated pore waters exhibit lower values than contemporaneous seawater indicating the incorporation of Sr originating from older carbonates recrystallised deeper in the section. Furthermore, the generally lower Sr/Ca ratios of bulk carbonates from Site U1336 also suggest extensive recrystallisation. Despite the extensive recrystallisation at Site U1336, the stable isotope composition (δ13C and δ18O) of benthic foraminifera (C. wuellerstorfi and C. mundulus) from the middle Miocene (13-16 Ma) is in good agreement with existing records (e.g. Holbourn et al. 2007, Tian et al. 2013). The carbon-isotope events of the Monterey Excursion (including CM 3b, CM 4a, CM 5 and CM 6) can clearly be identified. The CM 3b event displays the highest δ13C values with a maximum of 1.78 ‰ at 15.61 Ma which is in accordance with values measured from Sites 1237 (Nazca Ridge off Peru) and U1337 (706 km southeast from U1336) of 1.72 and 1.74 ‰, respectively at 15.60 Ma. The Middle Miocene cooling at 13.91-13.84 Ma marks the onset of ice-sheet expansion over Antarctica and the drastic increase in δ18O (0.86 ‰) at Site U1336 during that cooling event (CM 6) is comparable to that at Site 1237 (0.79 ‰) (Holbourn et al. 2007) and U1337 (1.00

  12. Li isotopes in foraminifera: a new proxy for past ocean dissolved inorganic carbon (United States)

    Vigier, N.; Rollion-Bard, C.; Erez, J.


    Past ocean pH and pCO2 are critical parameters for establishing relationships between Earth climate and carbon cycle. For the Miocene-Pleistocene period, two main proxies have been used: carbon isotopes of di-unsaturated alkenones extracted from sea cores, and boron isotope signatures of marine carbonates [1, 2]. Both techniques lead to selfconsistent palaeooceanic pH or pCO2 estimates, but are associated with large uncertainties. Moreover, the paleovariations calculated from boron isotope measurements are a matter of debate. Additional proxies are therefore needed. Based on an in-situ analytical technique recently developed [3], we analysed a series of foraminifera - Amphistegina - cultured under various conditions (in pH, T and Dissolved Inorganic Carbon). We show that the lithium isotope signature of the foraminifera correlates with the DIC (r2 = 0.93). Conversely, there is no dependency of Li isotope signature on pH or T. A simple model of biomineralization in which growth rate is a key parameter can fit the whole dataset, including published values for other foraminifera species [4, 5]. This strongly suggests that the DIC-δ7Li correlation highlighted by the cultured Amphistegina can also be applied to other species. These results, combined with the published oceanic Li and B isotope paleovariations [2, 4, 5], allow us to estimate the ocean DIC and pCO2 evolution for the past 18Ma. The similarity with the pCO2 curve given by carbon isotopes measured in di-unsaturated alkenones is striking. This supports the use of Li isotopes as a new proxy and adds support to the existing data. It also suggests, in contrast with the common view, a less significant role of river input on the variation of the ocean Li isotope composition, at least for the period considered. [1] Pagani et al. (2005) Science 309, 600-603. [2] Pearson & Palmer (2000) Nature 406, 695-699. [3] Vigier et al. (2007) G-cubed 8, Q01003 [4] Hall et al. (2005) Mar. Geology 217, 255-265 [5] Hathorne

  13. Carbon and Nitrogen Isotope Systematics in a Sector-Zoned Diamond from the Mir Kimberlite, Yakutia (United States)

    Hauri, E.; Bulanova, G.; Pearson, G.; Griffin, B.


    A single Yakutian octahedral diamond, displaying striking cubic and octahedral growth sectors surrounded by an octahedral rim, has been analysed for carbon and nitrogen isotopic compositions by SIMS and for nitrogen concentration (by SIMS and FTIR) and nitrogen aggregation state (FTIR). A graphite "seed" inclusion identified within the diamond, enriched in K, Ca, Ti, Rb and Sr, provides evidence that the diamond may have grown from a carbonate melt/fluid interacting with upper mantle rocks. Carbon and nitrogen isotope compositions become progressively heavier from the core region (d13C = -7 to -5 and d15N= -3) towards the inner rim zones (d13C = -3 and d15N = +8.9 to +5) of the diamond. Nitrogen concentration and aggregation measurements show corresponding decreases that generally correlate with the isotopic variations. These systematic variations within the core and intermediate regions of the diamond are consistent with their formation during diamond growth from CO2-rich fluids as a continuous event, accompanied by slight progressive isotopic fractionation of carbon and nitrogen. However, the observed isotope and nitrogen abundance trends are not those predicted from thermodynamic modelling of fluid-solid equilibria in a C-N-O-H-bearing system due to changes in parameters such as fO2 (Deines, 1980; Deines et al 1989). Within the finely-zoned octahedral rim region, non-systematic variations in nitrogen abundance, nitrogen aggregation, and nitrogen and carbon isotope ratios were observed. Several interpretations are given for this phenomenon, including kinetic effects during growth of the diamond rim under different conditions from those of the core-intermediate regions, or rapidly changing fluid sources during the growth. No fractionation of nitrogen isotopes between cubic and octahedral growth zones was identified within the studied diamond, in contrast with the fractionation phenomena found in synthetic diamonds of mixed growth. Our results illustrate the

  14. Online stable carbon isotope ratio measurement in formic acid, acetic acid, methanol and ethanol in water by high performance liquid chromatography-isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tagami, Keiko [National Institute of Radiological Sciences, 4-9-1, Anagawa, Inage-ku, Chiba 263-8555 (Japan)], E-mail:; Uchida, Shigeo [National Institute of Radiological Sciences, 4-9-1, Anagawa, Inage-ku, Chiba 263-8555 (Japan)


    A suitable analysis condition was determined for high performance liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS) while making sequential measurements of stable carbon isotope ratios of {delta}{sup 13}C in formic acid, acetic acid, methanol and ethanol dissolved in water. For this online column separation method, organic reagents are not applicable due to carbon contamination; thus, water and KH{sub 2}PO{sub 4} at low concentrations were tested as mobile phase in combination with a HyPURITY AQUASTAR{sup TM} column. Formic acid, acetic acid, methanol and ethanol were separated when 2 mM KH{sub 2}PO{sub 4} aqueous solution was used. Under the determined analysis condition for HPLC-IRMS, carbon concentrations could be measured quantitatively as well as carbon isotope ratio when carbon concentration was higher than 0.4 mM L for each chemical.

  15. Assessing diet in savanna herbivores using stable carbon isotope ratios of faeces

    Directory of Open Access Journals (Sweden)

    D. Codron


    Full Text Available In African savannas, browse-based resources (@3 plants are isotopically distinct from grasses (@4 plants. The carbon isotopic composition of the basic plant diet is recorded in animal tissues. Mammal faeces are a readily accessible, non-invasive, sample material for temporally resolved dietary reconstructions. Faeces, however, include both undigested plant matter and waste, hence accuracy of dietary calculations could potentially be compromised by shifts in plant isotopic values related to seasonal or spatial differences, or by variability in the isotopic differences between faeces and diet. A controlled feeding study of four ungulate species showed a small, consistent difference between diet and faeces of-0.9 o, irrespective of whether the diet was @3 or C4-based. Results from faeces oftaxa known to be pure grazers, pure browsers, and mixed-feeders from the Kruger National Park were entirely consistent with their diets, but the accuracy of dietary reconstructions is enhanced with data from local plant communities.

  16. Carbon isotope fractionation by the marine ammonia-oxidizing archaeon Nitrosopumilus maritimus


    Könneke, Martin; Lipp, Julius Sebastian; Hinrichs, Kai-Uwe


    Abstract Ammonia-oxidizing archaea (AOA) are abundant and widely distributed microorganisms in aquatic and terrestrial habitats. By catalyzing the first and rate limiting step in nitrification, these chemolithoautotrophs play a significant role in the global nitrogen cycle and contribute to primary production. Here, the carbon isotopic fractionation relative to inorganic carbon source was determined for bulk biomass, biphytanes and polar lipid bound sugars of a marine AOA pure culture. Bu...

  17. Constraints on the formation and diagenesis of phosphorites using carbonate clumped isotopes (United States)

    Stolper, Daniel A.; Eiler, John M.


    The isotopic composition of apatites from sedimentary phosphorite deposits has been used previously to reconstruct ancient conditions on the surface of the Earth. However, questions remain as to whether these minerals retain their original isotopic composition or are modified during burial and lithification. To better understand how apatites in phosphorites form and are diagenetically modified, we present new isotopic measurements of δ18O values and clumped-isotope-based (Δ47) temperatures of carbonate groups in apatites from phosphorites from the past 265 million years. We compare these measurements to previously measured δ18O values of phosphate groups from the same apatites. These results indicate that the isotopic composition of many of the apatites do not record environmental conditions during formation but instead diagenetic conditions. To understand these results, we construct a model that describes the consequences of diagenetic modification of phosphorites as functions of the environmental conditions (i.e., temperature and δ18O values of the fluids) during initial precipitation and subsequent diagenesis. This model captures the basic features of the dataset and indicates that clumped-isotope-based temperatures provide additional quantitative constraints on both the formational environment of the apatites and subsequent diagenetic modification. Importantly, the combination of the model with the data indicates that the δ18O values and clumped-isotope temperatures recorded by phosphorites do not record either formation or diagenetic temperatures, but rather represent an integrated history that includes both the formation and diagenetic modification of the apatites.

  18. Chromium isotope fractionation during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

    Rodler, Alexandra; Sánchez-Pastor, Nuria; Fernández-Díaz, Lurdes

    the Archaean and Protoerozoic, needs careful assessment of the signal robustness and necessitates a thorough understanding of the Cr cycle in Earth system processes. We conducted experiments testing the incorporation and isotopic fractionation of chromate into the calcite lattice. Our experiments indicate...... et al., 2007, Water Air Soil Poll. 179, 381-390. [2] Sánchez-Pastor et al., 2011, Cryst. Growth Des. 11, 3081-3089....

  19. Determination of the geographical origin of Chinese teas based on stable carbon and nitrogen isotope ratios

    Institute of Scientific and Technical Information of China (English)

    Long ZHANG; Jia-rong PAN; Cheng ZHU


    The objective of this study was to investigate the geographical origin of Chinese teas using carbon and nitrogen stable isotope ratio technology.The results showed that inter-provincial dispersion of teas in Guangdong (GD),Guangxi (GX),Hainan (HA),Fujian (F J),Shandong (SD),Sichuan (SC),Chongqing (CQ),and Henan (HN) provinces was high,while in Zhejiang (ZJ),Hubei (HB),Yunnan (YN),and Anhui (AH) provinces,it was low.Tea samples from GD,GX,HA,and FJ provinces were clustered in one group and separated from those from AH and HB provinces.Thus,carbon and nitrogen stable isotope ratio technology could discriminate teas from among some provinces of China,but not from among others.Better separation might be obtained with a combination of isotopic ratios and other indexes,such as elemental data and organic components.

  20. Stable isotope composition of bulk and secondary carbonates from the Quaternary loess-paleosol sequence in Sutto, Hungary

    DEFF Research Database (Denmark)

    Koeniger, Paul; Barta, Gabriella; Thiel, Christine


    , and microscale secondary (authigenic) carbonates (calcified root cells, carbonate coatings, hypocoatings, and earthworm biospheroids) and concretions at 10 cm resolution were analysed to interpret stable isotope variations. Isotope values of bulk samples were in the range of 2.6 parts per thousand to -13.9 parts......, secondary carbonates showed more depleted values than bulk samples. Calcified root cells have the most depleted isotope composition with mean values of -16.0 parts per thousand and -11.8 parts per thousand for delta C-13 and 8180, respectively. Results indicate that loess and paleosol secondary carbonates...

  1. Studies of carbon--isotope fractionation. Annual progress report, December 1, 1974--November 30, 1975

    Energy Technology Data Exchange (ETDEWEB)

    Ishida, T.


    The vapor pressure isotope effect of /sup 13/C//sup 12/C-substitution in CClF/sub 3/ was measured at temperatures between 169/sup 0/ and 206/sup 0/K by means of cryogenic distillation. The /sup 13/C//sup 12/C-vapor pressure isotope effect in CHF/sub 3/ was also studied at temperatures between 161/sup 0/ and 205/sup 0/K by a similar method. The construction of a cryostat has progressed as scheduled. The investigation of carbon isotope exchange equilibria between carbon dioxide and various carbamates dissolved in various organic solvents has continued. The five-stage system of Taylor-Ghate design was improved to shorten the transient time. A single stage apparatus was designed, built, and tested. These systems are used to measure the equilibrium constants and various phase equilibria involved in the carbon dioxide--carbamate system. The investigation of the explicit method of total isotope effect has made progress. A satisfactory approximation was found for the classical partition function of a Morse oscillator. The method gives a reasonable result at rho identical with /sup 1///sub 2/..sqrt..(u/sub e//x/sub e/) greater than 1.5. The medium cluster approach was applied to isotopic methanes to investigate the effects of intermolecular distance and mutual orientations of molecules in the liquid upon vapor pressure isotope effect. It was found that all geometrical effects studied tend to vanish as the size of clusters is increased. Isotope effect in the zero-point energy shifts on condensation was calculated on the basis of London dispersion forces in liquid and a semi-empirical molecular orbital theory, and was favorably compared with experimental results. (auth)

  2. Uranium isotopes in carbonate aquifers of arid region setting

    DEFF Research Database (Denmark)

    Alshamsi, Dalal M.; Murad, Ahmed A.; Aldahan, Ala


    Groundwater in arid and semiarid regions is vital resource for many uses and therefore information about concentrations of uranium isotopes among other chemical parameters are necessary. In the study presented here, distribution of 238U and 235U in groundwater of four selected locations in the so......Groundwater in arid and semiarid regions is vital resource for many uses and therefore information about concentrations of uranium isotopes among other chemical parameters are necessary. In the study presented here, distribution of 238U and 235U in groundwater of four selected locations...... in the southern Arabian peninsula, namely at two locations within the United Arab Emirates (UAE) and two locations in Oman are discussed. The analyses of the uranium isotopes were performed using ICP-MS and the results indicated a range of concentrations for 235U and 238 U at 3–39 ng L-1 (average: 18 ng L-1......) and 429–5,293 ng L-1 (average: 2,508 ng L-1) respectively. These uranium concentrations are below the higher permissible WHO limit for drinking water and also comparable to averages found in groundwater from similar aquifers in Florida and Tunisia. Negative correlation between rainfall and uranium...

  3. Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream (United States)

    Doctor, D.H.; Kendall, C.; Sebestyen, S.D.; Shanley, J.B.; Ohte, N.; Boyer, E.W.


    The stable isotopic composition of dissolved inorganic carbon (??13C-DIC) was investigated as a potential tracer of streamflow generation processes at the Sleepers River Research Watershed, Vermont, USA. Downstream sampling showed ?? 13C-DIC increased between 3-5??? from the stream source to the outlet weir approximately 0??5 km downstream, concomitant with increasing pH and decreasing PCO2. An increase in ??13C-DIC of 2.4 ?? 0??1??? per log unit decrease of excess PCO2 (stream PCO2 normalized to atmospheric PCO2) was observed from downstream transect data collected during snowmelt. Isotopic fractionation of DIC due to CO2 outgassing rather than exchange with atmospheric CO2 may be the primary cause of increased ?? 13C-DIC values downstream when PCO2 of surface freshwater exceeds twice the atmospheric CO2 concentration. Although CO2 outgassing caused a general increase in stream ??13C-DIC values, points of localized groundwater seepage into the stream were identified by decreases in ??13C-DIC and increases in DIC concentration of the stream water superimposed upon the general downstream trend. In addition, comparison between snowmelt, early spring and summer seasons showed that DIC is flushed from shallow groundwater flowpaths during snowmelt and is replaced by a greater proportion of DIC derived from soil CO2 during the early spring growing season. Thus, in spite of effects from CO2 outgassing, ??13C of DIC can be a useful indicator of groundwater additions to headwater streams and a tracer of carbon dynamics in catchments. Copyright ?? 2007 John Wiley & Sons, Ltd.

  4. Normalization of stable isotope data for carbonate minerals: implementation of IUPAC guideline (United States)

    Kim, Sang-Tae; Coplen, Tyler B.; Horita, Juske


    Carbonate minerals provide a rich source of geochemical information because their δ13C and δ18O values provide information about surface and subsurface Earth processes. However, a significant problem is that the same δ18O value is not reported for the identical carbonate sample when analyzed in different isotope laboratories in spite of the fact that the International Union of Pure and Applied Chemistry (IUPAC) has provided reporting guidelines for two decades. This issue arises because (1) the δ18O measurements are performed on CO2 evolved by reaction of carbonates with phosphoric acid, (2) the acid-liberated CO2 is isotopically fractionated (enriched in 18O) because it contains only two-thirds of the oxygen from the solid carbonate, (3) this oxygen isotopic fractionation factor is a function of mineralogy, temperature, concentration of the phosphoric acid, and δ18O value of water in the phosphoric acid, (4) researchers may use any one of an assortment of oxygen isotopic fractionation factors that have been published for various minerals at various reaction temperatures, and (5) it sometimes is not clear how one should calculate δ18OVPDB values on a scale normalized such that the δ18O value of SLAP reference water is −55.5 ‰ relative to VSMOW reference water.

  5. Latitudinal differences in the amplitude of the OAE-2 carbon isotopic excursion:

    NARCIS (Netherlands)

    van Bentum, E.C.; Reichart, G.J.; Forster, A.; Sinninghe Damsté, J.S.S.


    A complete, well-preserved record of the Cenomanian/Turonian (C/T) Oceanic Anoxic Event 2 (OAE-2) was recovered from Demerara Rise in the southern North Atlantic Ocean (ODP site 1260). Across this interval, we determined changes in the stable carbon isotopic composition of sulfur-bound phytane (delt

  6. Analytical system for stable carbon isotope measurements of low molecular weight (C2-C6) hydrocarbons

    NARCIS (Netherlands)

    Zuiderweg, A.T.; Holzinger, R.; Roeckmann, T.


    We present setup, testing and initial results from a new automated system for stable carbon isotope ratio measurements on C2 to C6 atmospheric hydrocarbons. The inlet system allows analysis of trace gases from air samples ranging from a few liters for urban samples and samples with high mixing ratio

  7. Natural carbon isotopes used to study methane consumption and production in soil

    DEFF Research Database (Denmark)

    Ambus, Per; Andersen, Bertel Lohmann; Kemner, Marianne;


    Changes in the isotopic composition of carbon can be used to reveal simultaneous occurrence of methane production and oxidation in soil. The method is conducted in laboratory jar experiments as well as in the field by using flux chambers. Simultaneous occurrence of production and oxidation...


    Directory of Open Access Journals (Sweden)

    E. Novelli


    Full Text Available Stable isotopes of carbon, nitrogen, oxygen and hydrogen were used for analytical purposes for the discrimination of the type of production (farming vs. fishing in the case of sea bass and for geographical origin in the case of milk. These results corroborate similar experimental evidences and confirm the potential of this analytical tool to support of food traceability.

  9. Combined carbon and hydrogen isotope fractionation investigations for elucidating benzene biodegradation pathways

    NARCIS (Netherlands)

    Fischer, A.; Herklotz, I.; Herrmann, S.; Thullner, M.; Weelink, S.A.B.; Stams, A.J.M.; Richnow, H.H.; Vogt, C.


    Recently, combined carbon and hydrogen isotope fractionation investigations have emerged as a powerful tool for the characterization of reaction mechanisms relevant for the removal of organic pollutants. Here, we applied this approach in order to differentiate benzene biodegradation pathways under o

  10. The puzzle of the CNO isotope ratios in AGB carbon stars

    CERN Document Server

    Abia, Carlos; Domínguez, Inma; Straniero, Oscar


    Previous determinations of the oxygen isotopic ratios in AGB carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in LTE with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M_o) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the FDU a...

  11. Carbon, cesium and iodine isotopes in Japanese cedar leaves from Iwaki, Fukushima

    DEFF Research Database (Denmark)

    Xu, Sheng; Cook, Gordon T.; Cresswell, Alan J.;


    Japanese cedar leaves from Iwaki, Fukushima were analyzed for carbon, cesium and iodine isotopic compositions before and after the 2011 nuclear accident. The Δ14C values reflect ambient atmospheric 14C concentrations during the year the leaves were sampled/defoliated, and also previous year...

  12. Stable carbon isotope fractionation of organic cyst-forming dinoflagellates: Evaluating the potential for a CO

    NARCIS (Netherlands)

    Hoins, M.; Van de Waal, D.B.; Eberlein, T.; Reichart, G.-J.; Rost, B.; Sluijs, A.


    Over the past decades, significant progress has been made regarding the quantification and mechanistic understanding of stable carbon isotope fractionation (13C fractionation) in photosynthetic unicellular organisms in response to changes in the partial pressure of atmospheric CO2 (pCO2). However, h

  13. Variations of sulfur and carbon isotopes in seawater during the Doushantuo stage in late Neoproterozoic

    Institute of Scientific and Technical Information of China (English)

    ZHANG Tonggang; CHU Xuelei; ZHANG Qirui; FENG Lianjun; HUO Weiguo


    Successive analyses of sulfur and carbon isotopic compositions of carbonates strata in the Doushantuo Formation in the Yangtze area were accomplished through a method of extracting trace sulfate from carbonates. Sulfur and carbon isotopic compositions of coeval seawater were estimated from the samples that show the least diagenetic alteration. A high-resolution age curve of sulfur isotopes in seawater sulfates was obtained in the Doushantuo stage, which reflects thetrend of variation in seawater sulfur isotopes after the Neoproterozoic snowball Earth event. Similar characteristics of variation in carbon isotopes were observed in the coeval carbonates. A large positive δ34S excursion over +20‰ occurs in ancient seawater sulfates in the early Doushantuo stage. Simultaneously, the δ13C values in ancient seawater carbonates exhibit a positive excursion up to10‰. The maximum δ34S and δ13C values are +46.4‰ and +6.9‰, respectively. In the middle Doushantuo stage, the range of variation in δ34S values of seawater is relatively narrow, but δ13C values are quite high. Then, δ34S values of seawater become oscillating, and the same occurs in δ13C values. Negative excursions in δ34S and δ13C values occur simultaneously at the end of the Doushantuo stage, and the minimum δ34S and δ13C values dropped down to -10.1‰ and -5.7‰, respectively. The characteristics of variations in the sulfur and carbon isotopes of ancient seawater imply strong changes in oceanic environment that became beneficial to inhabitation and propagation of organism. The organic productivity and burial rate of organic carbon once reached a quite high level during the Doushantuo stage. However, the state of environment became unstable after the global glaciation. The global climate and environment possibly were fluctuating and reiterating. The negative excursions in δ34S and δ13C values occurring at the end of the Doushantuo stage may represent a global event, which might be related to

  14. The puzzle of the CNO isotope ratios in asymptotic giant branch carbon stars (United States)

    Abia, C.; Hedrosa, R. P.; Domínguez, I.; Straniero, O.


    Context. The abundance ratios of the main isotopes of carbon, nitrogen and oxygen are modified by the CNO-cycle in the stellar interiors. When the different dredge-up events mix the burning material with the envelope, valuable information on the nucleosynthesis and mixing processes can be extracted by measuring these isotope ratios. Aims: Previous determinations of the oxygen isotopic ratios in asymptotic giant branch (AGB) carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Methods: Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in local thermodynamic equillibrium (LTE) with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M⊙) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. Results: For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the first dredge-up (FDU) according to the initial stellar mass. This fact, as far as the oxygen isotopic ratios are concerned, leaves little space for the operation of any extra mixing mechanism during the AGB phase. Nevertheless, for a few stars with large 16O/17O/18O, the operation of such a mechanism might be required, although their observed 12C/13C and 14N/15N ratios would be difficult to reconcile within this scenario. Furthermore, J-type stars tend to have lower 16O/17O ratios than the normal carbon stars, as already indicated in previous studies

  15. Carbon isotopes characterize rapid changes in atmospheric carbon dioxide during the last deglaciation (United States)

    Bauska, Thomas K.; Baggenstos, Daniel; Brook, Edward J.; Mix, Alan C.; Marcott, Shaun A.; Petrenko, Vasilii V.; Schaefer, Hinrich; Lee, James E.


    An understanding of the mechanisms that control CO2 change during glacial–interglacial cycles remains elusive. Here we help to constrain changing sources with a high-precision, high-resolution deglacial record of the stable isotopic composition of carbon in CO2 (δ13C-CO2) in air extracted from ice samples from Taylor Glacier, Antarctica. During the initial rise in atmospheric CO2 from 17.6 to 15.5 ka, these data demarcate a decrease in δ13C-CO2, likely due to a weakened oceanic biological pump. From 15.5 to 11.5 ka, the continued atmospheric CO2 rise of 40 ppm is associated with small changes in δ13C-CO2, consistent with a nearly equal contribution from a further weakening of the biological pump and rising ocean tempera