Sample records for oxygen isotope evidence

  1. Scavenging of oxygen vacancies at modulation-doped oxide interfaces: Evidence from oxygen isotope tracing

    Chen, Yunzhong; Döbeli, M.; Pomjakushina, E.


    , the mechanisms underlying the extreme mobility enhancement remain elusive. Herein, we used 18O isotope exchanged SrTi18O3 as substrates to create 2DEG at room temperature with and without the LSMO buffer layer. By mapping the oxygen profile across the interface between STO18 and disordered LaAlO3 or yttria...

  2. The oxygen isotope composition of earth's oldest rocks and evidence of a terrestrial magma ocean

    Rumble, D.; Bowring, S.; Iizuka, T.


    Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce....... But other sources of heat for global melting cannot be excluded such as bolide impacts during early accretion of proto-Earth, the decay of short-lived radioactive isotopes, or the energy released during segregation of core from mantle.......Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce...... such long-lived consistency was most easily established by mixing in a terrestrial magma ocean. The measured identical oxygen isotope mass fractionation lines for Earth and Moon suggest that oxygen isotope reservoirs of both bodies were homogenized at the same time during a giant moon-forming impact...

  3. Multiple taxon multiple locality approach to providing oxygen isotope evidence for warm-blooded theropod dinosaurs

    Fricke, Henry C.; Rogers, Raymond R.


    Oxygen isotope ratios of fossil remains of coexisting taxa from several different localities can be used to help investigate dinosaur thermoregulation. Focusing on the Late Cretaceous, oxygen isotope ratios of crocodile tooth enamel from four separate localities exhibit less of a decrease with latitude than do ratios of tooth enamel from coexisting theropod dinosaurs. A shallower latitudinal gradient for crocodiles is consistent with how oxygen isotope ratios should vary for heterothermic animals having body temperatures coupled with their environments (“cold blooded”), while a steeper gradient for theropods is consistent with how these ratios should vary for homeothermic animals having constant body temperatures independent of their environments (“warm blooded”). This inferred homoethermy in theropods is likely due to higher rates of metabolic heat production relative to crocodiles and is not an artifact of body size.

  4. No oxygen isotope exchange between water and APS-sulfate at surface temperature: Evidence from quantum chemical modeling and triple-oxygen isotope experiments

    Kohl, Issaku E.; Asatryan, Rubik; Bao, Huiming


    In both laboratory experiments and natural environments where microbial dissimilatory sulfate reduction (MDSR) occurs in a closed system, the δ34S ((34S/32S)sample/(34S/32S)standard - 1) for dissolved SO42- has been found to follow a typical Rayleigh-Distillation path. In contrast, the corresponding δ18O ((18O/16O)sample/(18O/16O)standard) - 1) is seen to plateau with an apparent enrichment of between 23‰ and 29‰ relative to that of ambient water under surface conditions. This apparent steady-state in the observed difference between δ18O and δ18OO can be attributed to any of these three steps: (1) the formation of adenosine-5'-phosphosulfate (APS) from ATP and SO42-, (2) oxygen exchange between sulfite (or other downstream sulfoxy-anions) and water later in the MDSR reaction chain and its back reaction to APS and sulfate, and (3) the re-oxidation of produced H2S or precursor sulfoxy-anions to sulfate in environments containing Fe(III) or O2. This study examines the first step as a potential pathway for water oxygen incorporation into sulfate. We examined the structures and process of APS formation using B3LYP/6-31G(d,p) hybrid density functional theory, implemented in the Gaussian-03 program suite, to predict the potential for oxygen exchange. We conducted a set of in vitro, enzyme-catalyzed, APS formation experiments (with no further reduction to sulfite) to determine the degree of oxygen isotope exchange between the APS-sulfate and water. Triple-oxygen-isotope labeled water was used in the reactor solutions to monitor oxygen isotope exchange between water and APS sulfate. The formation and hydrolysis of APS were identified as potential steps for oxygen exchange with water to occur. Quantum chemical modeling indicates that the combination of sulfate with ATP has effects on bond strength and symmetry of the sulfate. However, these small effects impart little influence on the integrity of the SO42- tetrahedron due to the high activation energy required for


    Krot, A N; Chaussidon, M; Yurimoto, H; Sakamoto, N; Nagashima, K; Hutcheon, I D; MacPherson, G J


    Based on the mineralogy and petrography, coarse-grained, igneous, anorthite-rich (Type C) calcium-aluminum-rich inclusions (CAIs) in the CV3 carbonaceous chondrite Allende have been recently divided into three groups: (i) CAIs with melilite and Al,Ti-diopside of massive and lacy textures (coarse grains with numerous rounded inclusions of anorthite) in a fine-grained anorthite groundmass (6-1-72, 100, 160), (ii) CAI CG5 with massive melilite, Al,Ti-diopside and anorthite, and (iii) CAIs associated with chondrule material: either containing chondrule fragments in their peripheries (ABC, TS26) or surrounded by chondrule-like, igneous rims (93) (Krot et al., 2007a,b). Here, we report in situ oxygen isotopic measurements of primary (melilite, spinel, Al,Ti-diopside, anorthite) and secondary (grossular, monticellite, forsterite) minerals in these CAIs. Spinel ({Delta}{sup 17}O = -25{per_thousand} to -20{per_thousand}), massive and lacy Al,Ti-diopside ({Delta}{sup 17}O = -20{per_thousand} to -5{per_thousand}) and fine-grained anorthite ({Delta}{sup 17}O = -15{per_thousand} to -2{per_thousand}) in 100, 160 and 6-1-72 are {sup 16}O-enriched relative spinel and coarse-grained Al,Ti-diopside and anorthite in ABC, 93 and TS26 ({Delta}{sup 17}O ranges from -20{per_thousand} to -15{per_thousand}, from -15{per_thousand} to -5{per_thousand}, and from -5{per_thousand} to 0{per_thousand}, respectively). In 6-1-72, massive and lacy Al,Ti-diopside grains are {sup 16}O-depleted ({Delta}{sup 17}O {approx} -13{per_thousand}) relative to spinel ({Delta}{sup 17}O = -23{per_thousand}). Melilite is the most {sup 16}O-depleted mineral in all Allende Type C CAIs. In CAI 100, melilite and secondary grossular, monticellite and forsterite (minerals replacing melilite) are similarly {sup 16}O-depleted, whereas grossular in CAI 160 is {sup 16}O-enriched ({Delta}{sup 17}O = -10{per_thousand} to -6{per_thousand}) relative to melilite ({Delta}{sup 17}O = -5{per_thousand} to -3{per_thousand}). We infer

  6. Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

    Tichomirowa, Marion; Junghans, Manuela


    Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO 4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O 2 ) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O 2 ) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO 4 and water was observed over a pH range of 0-2 only at 50 deg. C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 deg. C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T ≤ 25 deg. C, pH ≥ 3) for decades. Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O 2 to pyrite surface sites. The sorption of molecular O 2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO 4 . The calculated bulk contribution of atmospheric O 2 in the dissolved SO 4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O 2 in the early-formed sulfates, chemisorption and electron transfer of molecular O 2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction

  7. Paleomagnetic and oxygen isotopic evidence for long term diagenesis in radiolarian chert, Pindos Mountains, Greece

    Baltuck, Miriam


    Paleomagnetics was used in an attempt to improve chronostratigraphy in the Middle and Upper Jurassic radiolarian chert and siliceous mudstone of the Pindos Zone, Greece. Remanent magnetism studies showed strong magnetic intensity but scattered orientation. Orientation of some pressure solution features in the radiolarities indicates their formation under horizontal pressure, a condition which in Pindos geologic history would only have occurred during early Cretaceous or Cenozoic tectonics, indicating very late diagenesis in these parts of the section. From time of deposition to later time at which diagenesis can be documented, the Earth's magnetic field would have reversed many times. Remagnetization during solution-precipitation steps of silica diagenesis could complicate the rock magnetics. Oxygen isotopic and major element analyses of radiolarite lithologies show a systematic variation of rate of silica diagenesis in different host lithologies, thus solution-precipitation would occur at widely differing times throughout the section lithologies. If the dissolution of the silica cement were physically to free magnetic material from an earlier orientation, the result could be a partial shift toward alignment with the ambient magnetic field. Alternatively, complete reorientation of particles could have occurred at varying times in different parts of the section as a function of host lithology. During the northward movement and clockwise rotation of the Apulian subplate (including Pindos) these different lithologies could completely reorient during different stages of silica diagenesis, locking the orientation of iron magnetic moments into alignment with the ambient magnetic field at time of precipitation to result in a strong intensity but scattered orientation of Pindos rock magnetics.

  8. Theory of oxygen isotope exchange

    den Otter, M.W.; Boukamp, Bernard A.; Bouwmeester, Henricus J.M.


    Transients for oxygen molecular mass numbers 32, 34 and 36 are derived which can be used for the interpretation of oxygen isotope exchange data based on measurement of concentrations of 16O2, 16O18O and 18O2 in the gas phase. Key parameters in the theory are the rate at which oxygen molecules are

  9. Past 20,000-year history of Himalayan aridity: Evidence from oxygen isotope records in the Bay of Bengal

    Chauhan, O.S.

    Late Quaternary climate history of the Himalayas is inferred from sea surface salinity (SSS) changes determined from the oxygen isotope in planktonic foraminifers, in a turbidity-free, 14C-dated core from the Bay of Bengal. The heaviest d18O...

  10. The source of phosphate in the oxidation zone of ore deposits: Evidence from oxygen isotope compositions of pyromorphite

    Burmann, Fabian; Keim, Maximilian F.; Oelmann, Yvonne; Teiber, Holger; Marks, Michael A. W.; Markl, Gregor


    Pyromorphite (Pb5[PO4]3Cl) is an abundant mineral in oxidized zones of lead-bearing ore deposits and due to its very low solubility product effectively binds Pb during supergene alteration of galena (PbS). The capacity of a soil or near-surface fluid to immobilize dissolved Pb depends critically on the availability of phosphate in this soil or fluid. Potential phosphorus sources in soil include (i) release during biological processes, i.e. leaching from litter/lysis of microbial cells (after intracellular enzyme activity) in soil and hydrolysis from soil organic matter by extracellular enzymes and (ii) inorganic phosphate from the dissolution of apatite in the adjacent basement rocks. Intracellular enzyme activity in plants/microorganisms associated with kinetic fractionation produces an oxygen isotope composition distinctly different from inorganic processes in soil. This study presents the first oxygen isotope data for phosphate (δ18OP) in pyromorphite and a comprehensive data set for apatite from crystalline rocks. We investigated 38 pyromorphites from 26 localities in the Schwarzwald (Southwest Germany) and five samples from localities outside the Schwarzwald in addition to 12 apatite separates from gneissic and granitic host rocks. Pyromorphites had δ18OP values between +10‰ and +19‰, comparable to literature data on δ18OP in the readily available P fraction in soil (resin-extractable P) from which minerals potentially precipitate in soils. δ18OP values below the range of equilibrium isotope fractionation can be attributed either to apatites that formed geochemically (δ18OP of apatites:+6‰ to +9‰) or less likely to biological processes (extracellular enzyme activity). However, for most of our samples isotopic equilibrium with ambient water was indicated, which suggests biological activity. Therefore, we conclude that the majority of pyromorphites in oxidized zones of ore bodies formed from biologically cycled phosphate. This study highlights that

  11. The parent body controls on cosmic spherule texture: Evidence from the oxygen isotopic compositions of large micrometeorites

    van Ginneken, M.; Gattacceca, J.; Rochette, P.; Sonzogni, C.; Alexandre, A.; Vidal, V.; Genge, M. J.


    High-precision oxygen isotopic compositions of eighteen large cosmic spherules (>500 μm diameter) from the Atacama Desert, Chile, were determined using IR-laser fluorination - Isotope Ratio Mass spectrometry. The four discrete isotopic groups defined in a previous study on cosmic spherules from the Transantarctic Mountains (Suavet et al., 2010) were identified, confirming their global distribution. Approximately 50% of the studied cosmic spherules are related to carbonaceous chondrites, 38% to ordinary chondrites and 12% to unknown parent bodies. Approximately 90% of barred olivine (BO) cosmic spherules show oxygen isotopic compositions suggesting they are related to carbonaceous chondrites. Similarly, ∼90% porphyritic olivine (Po) cosmic spherules are related to ordinary chondrites and none can be unambiguously related to carbonaceous chondrites. Other textures are related to all potential parent bodies. The data suggests that the textures of cosmic spherules are mainly controlled by the nature of the precursor rather than by the atmospheric entry parameters. We propose that the Po texture may essentially be formed from a coarse-grained precursor having an ordinary chondritic mineralogy and chemistry. Coarse-grained precursors related to carbonaceous chondrites (i.e. chondrules) are likely to either survive atmospheric entry heating or form V-type cosmic spherules. Due to the limited number of submicron nucleation sites after total melting, ordinary chondrite-related coarse-grained precursors that suffer higher peak temperatures will preferentially form cryptocrystalline (Cc) textures instead of BO textures. Conversely, the BO textures would be mostly related to the fine-grained matrices of carbonaceous chondrites due to the wide range of melting temperatures of their constituent mineral phases, allowing the preservation of submicron nucleation sites. Independently of the nature of the precursors, increasing peak temperatures form glassy textures.

  12. Faunal and oxygen isotopic evidence for surface water salinity changes during sapropel formation in the eastern Mediterranean

    Williams, D.F.; Thunell, R.C.


    The discovery of the widespread anaerobic deposits (sapropels) in late Cenozoic sediments of the eastern Mediteranean has prompted many workers to propose the periodic occurrence of extremely low surface salinites in the Mediterranean. Oxygen isotopic determinations and total faunal analyses were made at 1000-year intervals across two equivalent sapropels in two piston cores from the Levantine Basin. The sapropel layers were deposited approximately 9000 y.B.P. (Sapropel A) and 80, 000 y. B.P. (Sapropel B). Significant isotopic anomalies were recorded by the foraminiferal species within Sapropels A and B in both cores. The surface dwelling species record a larger 18 O depletion than the mesopelagic species suggesting that surface salinities were reduced by 2-3per 1000 during sapropel formation. The faunal changes associated with the sapropels also indicate that the oceanographic conditions which lead to anoxic conditions in the eastern Mediteranean involve the formation of a low salinity surface layer. The source of the low salinity water might be meltwater produced by disintegration of the Fennoscandian Ice Sheet which drained into the Black Sea, into the Aegean Sea and finally into the eastern Mediterranean. (Auth.)

  13. Paleoecologies and paleoclimates of late cenozoic mammals from Southwest China: Evidence from stable carbon and oxygen isotopes

    Biasatti, Dana; Wang, Yang; Gao, Feng; Xu, Yingfeng; Flynn, Lawrence


    To examine paleodiets and habitats of extinct taxa and to understand long-term regional climate change, we determined the carbon and oxygen isotopic compositions of fossil herbivore teeth and soil samples from six localities in Yunnan Province, Southwest China, ranging in age from ˜10 Ma to the present. Although limited in spatial and temporal coverage, these initial results reveal significant changes in the environments and diets of mammalian taxa over the last 10 million years. Prior to 2-3 Ma, while most mammals examined had pure or nearly pure C 3 diets, some individuals consumed a small amount of C 4 grasses (up to 20% C 4). Since then, C 4 grasses became a significant dietary component for most herbivores as indicated by higher enamel-δ 13C values in the Pleistocene Yuanmou Formation and at Shangri-La, most likely reflecting an increased C 4 biomass in the region. The carbon isotope results show that the diets of mammals of ˜2.5-1.75 Ma from Shangri-La ranged from pure C 3 to pure C 4 while 1.7 Ma horses from Yuanmou had 0-70% C 4 grasses in their diets. Mammals living at ˜8-7 Ma in the Yuanmou and Lufeng region had very similar diets and habitats, with similar climatic conditions. Increased C 4 biomass after ˜3-4 Ma suggests a significant change in certain aspects of regional climate, such as increased seasonality of rainfall or an increase in seasonal drought and fires as these factors are important to modern grasslands. The data also show that unlike the Siwalik fauna in the Indian subcontinent, mammals in Yunnan on the southeast side of the Himalayan-Tibetan Plateau lived in an environment dominated by dense forests until ˜3-4 Ma. Nonetheless, both δ 13C values of paleosol carbonates and fossil enamels indicate that C 4 grasses were present in the Yuanmou region in the latest Miocene and Pliocene (˜8-3.5 Ma), likely in greatly dispersed, small patches of open habitats where the forest canopy was broken or on flood plains, and the C 4 biomass

  14. Deposition of talc - kerolite-smectite - smectite at seafloor hydrothermal vent fields: Evidence from mineralogical, geochemical and oxygen isotope studies

    Dekov, V.M.; Cuadros, J.; Shanks, Wayne C.; Koski, R.A.


    Talc, kerolite-smectite, smectite, chlorite-smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite-smectite to smectite-rich kerolite-smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite-smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite-smectite with lower crystalline perfection as the proportion of smectite layers in kerolite-smectite increases. Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite-smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (> 250????C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200-250????C) phase forming deep within the sediment (??? 0.8??m). Chlorite and chlorite-smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150-200????C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two

  15. Evolution and variation of the Tsushima warm current during the late Quaternary: Evidence from planktonic foraminifera, oxygen and carbon isotopes


    The evolution and variation history of the Tsushima warm current during the late Quaternary was reconstructed based on the quantitative census data of planktonic foraminiferal fauna, together with oxygen and carbon isotope records of mixed layer dweller G. ruber and thermocline dweller N. dutertrei in piston core CSH1 and core DGKS9603 collected separately from the Tsushima warm current and the Kuroshio dominated area. The result showed that the Tsushima warm current vanished in the lowstand period during 40―24 cal ka BP, while the Kuroshio still flowed across the Okinawa Trough, arousing strong upwelling in the northern Trough. Meanwhile, the influence of freshwater greatly increased in the northern Okinawa Trough, as the broad East China Sea continental shelf emerged. The freshwater reached its maximum during the last glacial maximum (LGM), when the upwelling obviously weakened for the lowest sea-level and the depression of the Kuroshio. The modern Tsushima warm current began its development since 16 cal ka BP, and the impact of the Kuroshio increased in the middle and north- ern Okinawa Trough synchronously during the deglaciation and gradually evolved as the main water source of the Tsushima current. The modern Tsushima current finally formed at about 8.5 cal ka BP, since then the circulation structure has been relatively stable. The water of the modern Tsushima cur- rent primarily came from the Kuroshio axis. A short-term wiggle of the current occurred at about 3 cal ka BP, probably for the influences from the enhancement of the winter monsoon and the depression of the Kuroshio. The cold water masses greatly strengthened during the wiggle.

  16. Isotope anomalies in oxygen isotope exchange equilibrium systems

    Kotaka, M.


    The purpose of the present work is to elucidate the isotope anomalies in oxygen isotope exchange equilibrium systems, according to the calculations of the equilibrium constants for oxygen isotopic exchange reactions, and the calculations of the oxygen isotope separation factors between two phases. The equilibrium constants (K65, K67, K68 and K69) of 16 O- 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O exchange reactions between diatomic oxides were calculated in a wide temperature range on the basis of quantum statistical mechanics. Many equilibrium constants showed the anomalous mass effects, and then had the crossover temperatures and the mass independent fractionation (MIF) temperatures which held K67 = K65, K67 = K68, or K67 = K69, etc. For example, the equilibrium constants for the reactions between OH and the other diatomic oxides (MO) showed the anomalous mass effects, when M was Li, Na, Mg, K, Fe, Al, Ge, Zr, Pt, etc. The 16 O 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O oxygen isotope separation factors (S65, S67, S68 and S69) between two phases were calculated, when OH and CO were in the first phase, and SiO was in the second phase. Although the oxygen isotopic exchange equilibria in the two phases had no MIF and crossover temperatures, the separation factors showed the anomalous mass effects and had the temperatures. According to what is called the normal mass effects for the equilibrium constant of isotopic exchange reaction, the value of InK68/InK67 is 1.885. Therefore, the value of InS68/InS67 should be 1.885 too. The value calculated, however, widely changed. It can be concluded from the results obtained in the present work that some oxygen isotopic exchange equilibria cause the anomalous mass effects, the anomalous oxygen isotope separation factors, and then isotope anomalies

  17. Normalization of oxygen and hydrogen isotope data

    Coplen, T.B.


    To resolve confusion due to expression of isotopic data from different laboratories on non-corresponding scales, oxygen isotope analyses of all substances can be expressed relative to VSMOW or VPDB (Vienna Peedee belemnite) on scales normalized such that the ??18O of SLAP is -55.5% relative to VSMOW. H3+ contribution in hydrogen isotope ratio analysis can be easily determined using two gaseous reference samples that differ greatly in deuterium content. ?? 1988.

  18. Formation of chondrules in a moderately high dust enriched disk: Evidence from oxygen isotopes of chondrules from the Kaba CV3 chondrite

    Hertwig, Andreas T.; Defouilloy, Céline; Kita, Noriko T.


    Oxygen three-isotope analysis by secondary ion mass spectrometry of chondrule olivine and pyroxene in combination with electron microprobe analysis were carried out to investigate 24 FeO-poor (type I) and 2 FeO-rich (type II) chondrules from the Kaba (CV) chondrite. The Mg#'s of olivine and pyroxene in individual chondrules are uniform, which confirms that Kaba is one of the least thermally metamorphosed CV3 chondrites. The majority of chondrules in Kaba contain olivine and pyroxene that show indistinguishable Δ17O values (= δ17O - 0.52 × δ18O) within analytical uncertainties, as revealed by multiple spot analyses of individual chondrules. One third of chondrules contain olivine relict grains that are either 16O-rich or 16O-poor relative to other indistinguishable olivine and/or pyroxene analyses in the same chondrules. Excluding those isotopically recognized relicts, the mean oxygen isotope ratios (δ18O, δ17O, and Δ17O) of individual chondrules are calculated, which are interpreted to represent those of the final chondrule melt. Most of these isotope ratios plot on or slightly below the primitive chondrule mineral (PCM) line on the oxygen three-isotope diagram, except for the pyroxene-rich type II chondrule that plots above the PCM and on the terrestrial fractionation line. The Δ17O values of type I chondrules range from ∼-8‰ to ∼-4‰; the pyroxene-rich type II chondrule yields ∼0‰, the olivine-rich type II chondrule ∼-2‰. In contrast to the ungrouped carbonaceous chondrite Acfer 094, the Yamato 81020 CO3, and the Allende CV3 chondrite, type I chondrules in Kaba only possess Δ17O values below -3‰ and a pronounced bimodal distribution of Δ17O values, as evident for those other chondrites, was not observed for Kaba. Investigation of the Mg#-Δ17O relationship revealed that Δ17O values tend to increase with decreasing Mg#'s, similar to those observed for CR chondrites though data from Kaba cluster at the high Mg# (>98) and the low Δ17O

  19. Oxygen isotopic fractionation during bacterial sulfate reduction

    Balci, N.; Turchyn, A. V.; Lyons, T.; Bruchert, V.; Schrag, D. P.; Wall, J.


    Sulfur isotope fractionation during bacterial sulfate reduction (BSR) is understood to depend on a variety of environmental parameters, such as sulfate concentration, temperature, cell specific sulfate reduction rates, and the carbon substrate. What controls oxygen isotope fractionation during BSR is less well understood. Some studies have suggested that carbon substrate is important, whereas others concluded that there is a stoichiometric relationship between the fractionations of sulfur and oxygen during BSR. Studies of oxygen fractionation are complicated by isotopic equilibration between sulfur intermediates, particularly sulfite, and water. This process can modify the isotopic composition of the extracellular sulfate pool (δ18OSO4 ). Given this, the challenge is to distinguish between this isotopic equilibration and fractionations linked to the kinetic effects of the intercellular enzymes and the incorporation of sulfate into the bacterial cell. The δ18OSO4 , in concert with the sulfur isotope composition of sulfate (δ34SSO4), could be a powerful tool for understanding the pathways and environmental controls of BSR in natural systems. We will present δ18OSO4 data measured from batch culture growth of 14 different species of sulfate reducing bacteria for which sulfur isotope data were previously published. A general observation is that δ18OSO4 shows little isotopic change (kinetic effect during BSR and/or equilibration between sulfur intermediates and the isotopically light water (~-5‰) of the growth medium. Our present batch culture data do not allow us to convincingly isolate the magnitude and the controlling parameters of the kinetic isotope effect for oxygen. However, ongoing growth of mutant bacteria missing enzymes critical in the different steps of BSR may assist in this mission.

  20. Stable Oxygen-18 and Deuterium Isotopes

    Müller, Sascha

    The application of stable Oxygen-18 (18O) and Deuterium (2H) isotopes, as a tracer for fluxes between different compartments of the water cycle was subject of the present PhD-thesis. During a three year period, temporal data from a wide range of water cycle constituents was collected from...... the Skjern River catchment, Denmark. The presented applications focused on studying the isotopic 'input signal' to the hydrosphere in the form of precipitation, the isotopic 'output signal' with its related dynamic processes at a coastal saltwater-freshwater interface (groundwater isotopes) and the temporal...... development within a given lowland headwater catchment (stream water isotopes). Based on our investigations on the precipitation isotopic composition a local meteoric water line (LMWL) was constructed and expressed as: δ2H=7.4 δ18O + 5.36‰. Moreover, we showed that under maritime temperature climate influence...

  1. A latitudinal study of oxygen isotopes within horsehair

    Thompson, E.; Bronk Ramsey, C.; McConnell, J. R.


    This study aims to explore the hypothesis that 'if oxygen isotope ratios deplete with decreasing temperature then a study of oxygen isotope ratios within horsehair from Oxfordshire to Iceland will show a latitudinal depletion gradient'. By looking at oxygen isotope values at different geographical positions, we can track the relationship with latitude and with different regional climate features. This will provide a firmer understanding of how to compare climate records from different locations. Additionally, a comparison of the horse breeds from this study to those analysed within previous studies will create an even better understanding of the intra-species variation within the δ18O values of horsehair. A total of 24 horses were sampled on the 7th March from Thordale Stud in Shetland, the Icelandic Food And Veterinary Authority in Iceland, the Exmoor Pony Centre in Exmoor and the Pigeon House Equestrian Centre in Oxfordshire. By starting the sampling process from the most recent growth at the follicle, the sampling date becomes a chronological marker, temporally fixing the first sample within a sequential set of data points extending for one year or longer, depending on the length of each individual hair. The samples were analysed for oxygen isotope values using an IRMS coupled within a Sercon HTEA. Preliminary results show a latitudinal gradient is evident on comparison between the locations, consistent with the findings of Darling and Talbot's study of fresh water isotopes in the British Isles (2003). These results support the hypothesis, showing that a study of oxygen isotope ratios within horse hair from Oxfordshire to Iceland showing a latitudinal depletion gradient, consistent with a depletion of oxygen isotope ratios due to decreasing temperatures. Darling, W. and Talbot, J. (2003). The O and H stable isotope composition of freshwaters in the British Isles. 1. Rainfall. Hydrol. Earth System Science, 7(2), pp.163-181.

  2. Major events in Neogene oxygen isotopic records

    Kennett, J.P.; Hodell, D.A.


    Changes in oxygen isotopic ratios of foraminiferal calcite during the cainozoic have been one of the primary tools for investigating the history of Arctic and Antarctic glaciation, although interpretations of the oxygen isotopic record differ markedly. The ambiguity in interpretation results mainly from the partitioning of temperature from ice volume effects in delta 18 O changes. Oxygen isotopic records for the Cainozoic show an increase in delta 18 O values towards the present, reflecting gradual cooling and increased glaciation of the Earth's climate since the late Cretaceous. A variety of core material from the South Atlantic and South-west Pacific oceans are investigated. This composite data represents one of the most complete available with which to evaluate the evolution of glaciation during the Neogene. Expansion of ice shelves in Antarctica undoubtedly accompanied the increased glaciation of the northern hemisphere, since eustatic sea-level lowering would positively reinforce ice growth on Antarctica

  3. Oxygen isotopic anomalies in Allende inclusion HAL

    Lee, T.; Mayeda, T.K.; Clayton, R.N.


    The oxygen isotopic composition has been measured on the constituent phases of Allende inclusion HAL, which has unusual mineralogical, chemical, and calcium isotopic compositions. The oxygen in HAL is heterogeneous, with the rim showing more ''normal'' composition and the hibonite core showing large deviation from both the terrestrial material and the usual inclusions. The observed pattern indicates that HAL is a bona fide and more devious member of the rare ''FUN'' family, whose isotopic composition is characterized by correlated nuclear effects and extreme mass fractionation. The data imply that HAL has suffered a large oxygen mass fractionation of 25% 0 per mass unit, followed by exchange with oxygen in a second reservoir. The present experiment supports the identification of two distinct reservoirs from which all refractory inclusions in carbonaceous meteorites derived their oxygen. The required fractionation process seems to operate according to the volatility of various elements and could have been caused by evaporation during a heating event. Nuclear anomalies can be produced in the same heating event if the progenitors of the refractory inclusions were macroscopic aggregates of tiny pre-solar interstellar dust grains and if these grains were destroyed differentially during the evaporation

  4. Oxygen isotope fractionation in uranium oxides

    Zheng Yongfei


    Thermodynamic oxygen isotope factors for uranium oxides have been calculated by means of the modified increment method. The sequence of 18 O-enrichment in the uranium oxides with respect to the common rock-forming minerals is predicted as follows: spinel 3 < illite. Two sets of self-consistent fractionation factors between the uranium oxides and water and between the uranium oxides and the other minerals have been obtained for 0∼1200 degree C. The theoretical results are applicable to the isotopic geothermometry of uranium ores when pairing with other gangue minerals in hydrothermal uranium deposits

  5. Oxygen isotope exchange on palladium catalysts

    Kravchuk, L.S.; Beschetvertnaya, T.I.; Novorodskij, V.G.; Novikova, M.G.; Zaretskij, M.V.; Valieva, S.V.


    Oxygen heteromolecular isotope exchange on unreduced palladium catalysts, distingushing by metal content is studied. Content of 18 O in gaseous phase is eoual to 46%. Calculations of heteroexchange rates are conducted with decrease of the 18 O in the gaseous phase over solid sample. Method of oxygen thermodesorption has been used to establish that palladium, deposited on γ-Al 2 O 3 during exchange process is in oxidized state; in this case strength of Pd-O bond is determined by content dispersity) of the metal. It is shown that significant increase of exchange rate on the samples with Pd >> 0.5 mass.% content can be induced as by side decomposition reaction of its oxide and corresponding dilution of gaseous mixture by ''light'' oxygen so by possibility of exchange with oxygen of PdO phase

  6. Oxygen isotope ratios of the Icelandic crust

    Hattori, K.; Muehlenbachs, K.


    Oxygen isotope ratios of hydrothermally altered basalts from depth of up to approx.3 km are reported from three localities in Iceland: International Research Drilling Project (IRDP) core at Reydarfjordur, eastern Iceland (Tertiary age); drill cuttings from Reykjavik (Plio-Pleistocene age); and Halocene drill cuttings from the active Krafla central volcano. Whole rock samples from these three localities have delta 18 O values averaging +3.9 +- 1.3, +2.4 +- 1.1, and -7.7 +- 2.4%, respectively. The observed values in the deeper samples from Krafla are as low as the values for any rocks previously reported. There seems to be a slight negative gradient in delta 18 O with depth at the former two localities and a more pronounced one at Krafla. Oxygen isotope fractionations between epidote and quartz and those between calcite and fluid suggests that the basalts were altered at temperatures of 300 0 --400 0 C. Low deltaD and delta 18 O of epidote and low delta 34 S of anhydrite indicate that the altering fluids in all three areas originated as meteoric waters and have undergone varied 'oxygen shifts'. Differences in the 18 O shift of the fluids are attributed to differences in hydrothermal systems; low water/rock ratios ( 5) at Krafla. The convective hydrothermal activity, which is probably driven by silicic magma beneath the central volcanoes, has caused strong subsolidus depletion of 18 O in the rocks. The primary-magnetic delta 18 O value of the rocks in the Tertiary IRDP core was about +3.9%, which is lower than that obtained for fresh basalt from other places. Such exceptionally low delta 18 O magmas are common in Iceland and may occur as the result of oxygen isotope exchange with or assimilation of altered rocks that form a thick sequence beneath the island due to isostatic subsidence


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


    Oxygen is one of the major rock-forming elements in the solar system and the third most abundant element of the Sun. Oxygen isotopic composition of the Sun, however, is not known due to a poor resolution of astronomical spectroscopic measurements. Several Δ 17 O values have been proposed for the composition of the Sun based on (1) the oxygen isotopic measurements of the solar wind implanted into metallic particles in lunar soil ( 2 O 3 ) is thermodynamically the first condensate from a cooling gas of solar composition. Corundum-bearing CAIs, however, are exceptionally rare, suggesting either continuous reaction of the corundum condensates with a cooling nebular gas and their replacement by hibonite (CaAl 12 O 19 ) or their destruction by melting together with less refractory condensates during formation of igneous CAIs. In contrast to the corundum-bearing CAIs, isolated micrometer-sized corundum grains are common in the acid-resistant residues from unmetamorphosed chondrites. These grains could have avoided multistage reprocessing during CAI formation and, therefore, can potentially provide constraints on the initial oxygen isotopic composition of the solar nebula, and, hence, of the Sun. Here we report oxygen isotopic compositions of ∼60 micrometer-sized corundum grains in the acid-resistant residues from unequilibrated ordinary chondrites (Semarkona (LL3.0), Bishunpur (LL3.1), Roosevelt County 075 (H3.2)) and unmetamorphosed carbonaceous chondrites (Orgueil (CI1), Murray (CM2), and Alan Hills A77307 (CO3.0)) measured with a Cameca ims-1280 ion microprobe. All corundum grains, except two, are 16 O-rich (Δ 17 O = -22.7 per mille ± 8.5 per mille, 2σ), and compositionally similar to the mineralogically pristine CAIs from the CR carbonaceous chondrites (-23.3 per mille ± 1.9 per mille, 2σ), and solar wind returned by the Genesis spacecraft (-27 per mille ± 6 per mille, 2σ). One corundum grain is highly 17 O-enriched (δ 17 O ∼ +60 per mille, δ 18 O

  8. Decreasing Indian summer monsoon on the northern Indian sub-continent during the last 180 years: evidence from five tree-ring cellulose oxygen isotope chronologies

    Xu, Chenxi; Sano, Masaki; Priyadarshan Dimri, Ashok; Ramesh, Rengaswamy; Nakatsuka, Takeshi; Shi, Feng; Guo, Zhengtang


    We have constructed a regional tree-ring cellulose oxygen isotope (δ18O) record for the northern Indian sub-continent based on two new records from northern India and central Nepal and three published records from northwestern India, western Nepal and Bhutan. The record spans the common interval from 1743 to 2008 CE. Correlation analysis reveals that the record is significantly and negatively correlated with the three regional climatic indices: all India rainfall (AIR; r = -0.5, p changes in the ISM. The record exhibits significant interannual and long-term variations. Interannual changes are closely related to the El Niño-Southern Oscillation (ENSO), which indicates that the ISM was affected by ENSO in the past. However, the ISM-ENSO relationship was not consistent over time, and it may be partly modulated by Indian Ocean sea surface temperature (SST). Long-term changes in the regional tree-ring δ18O record indicate a possible trend of weakened ISM intensity since 1820. Decreasing ISM activity is also observed in various high-resolution ISM records from southwest China and Southeast Asia, and may be the result of reduced land-ocean thermal contrasts since 1820 CE.

  9. Oxygen isotopic and geochemical evidence for a short-lived, high-temperature hydrothermal event in the Chegem caldera, Caucasus Mountains, Russia

    Gazis, C.; Taylor, H.P.; Hon, K.; Tsvetkov, A.


    Within the 2.8 Ma Chegem ash-flow caldera (11 ?? 15 km), a single cooling unit of rhyolitic to dacitic welded tuff more than 2 km thick is exposed in deep valleys incised during recent rapid uplift of the Caucasus Mountains. The intracaldera tuff is mineralogically fresh and unaltered, and is overlain by andesite lavas and cut by a resurgent granodiorite intrusion. Major- and trace-element compositions for a 1405-m stratigraphic section of intracaldera tuff display trends of upwardly increasing Na2O, CaO, Al2O3, total Fe, MgO, TiO2, Sr and Zr and decreasing SiO2, K2O and Rb. This mafic-upward zoning (from 76.1 to 69.9% SiO2) reflects an inverted view of the upper part of the source magma chamber. Oxygen isotope studies of 35 samples from this 1405-m section define a striking profile with "normal" igneous ??18O values (+7.0 to +8.5) in the lower 600 m of tuff, much lower ??18O values (-4.0 to +4.3) in a 700-m zone above that and a shift to high ??18O values (+4.4 to -10.9) in the upper 100 m of caldera-fill exposure. Data from two other partial stratigraphic sections indicate that these oxygen isotope systematics are probably a caldera-wide phenomenon. Quartz and feldspar phenocrysts everywhere have "normal" igneous ??18O values of about +8.5 and +7.5, respectively, whereas groundmass and glass ??18O values range from -7.7 to +12.3. Consequently, the ??18O values of coexisting feldspar, groundmass and glass form a steep array in a plot of ??feldspar vs. ??groundmass/glass. Such pronounced disequilibrium between coexisting feldspar and groundmass or glass has never before been observed on this scale. It requires a hydrothermal event involving large amounts of low-18O H2O at sufficiently high temperatures and short enough time (tens of years or less) that glass exchanges thoroughly but feldspar does not. The most likely process responsible for the O depletions at Chegem is a very high temperature (500-600??C), short-lived, vigorous meteoric-hydrothermal event that was

  10. Triple oxygen isotope systematics of structurally bonded water in gypsum

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


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

  11. Petro-structural, geochemical and carbon and oxygen isotopic study on carbonates crosscuting the Oman Ophiolite peridotites: evidence of polygenic CO2 trapping

    Noël, J.; Godard, M.; Martinez, I.; Oliot, E.; Williams, M. J.; Rodriguez, O.; Chaduteau, C.; Gouze, P.


    Carbon trapping in ophiolitic peridotites contributes to the global carbon cycle between solid Earth and its outer envelopes (through subduction and/or modern alteration). To investigate this process, we performed petro-structural (microtomography, EBSD, EPMA) and geochemical studies (LA-ICP-MS, carbon and oxygen isotopes on bulk and minerals using SHRIMP) of harzburgites cored in the Oman Ophiolite. Studied harzburgites are highly serpentinized (> 90 %) and crosscut by 3 generations of carbonates (> 20 Vol%) with compositions from calcite to dolomite (Mg/Ca = 0-0.85). Type 1 carbonates are fine penetrative veinlets and mesh core after olivine. They have low REE (e.g., Yb = 0.08-0.23 x CI-chondrite) and negative Ce anomalies. They have δ13CPDB = -15.2 to 1.10‰ and δ18OSMOW = 17.5 to 33.7‰, suggesting precipitation temperatures up to 110°C. Type 2 carbonates are pluri-mm veins bounded by cm-thick serpentinized vein selvages, oriented dominantly parallel to mantle foliation. Dynamic recrystallization is observed, indicating polygenetic formation: well crystallized calcite with REE abundances similar to Type 1 carbonates are locally replaced by small dolomite and calcite grains with higher REE (e.g., Yb = 0.35-1.0 x CI-chondrite) and positive Gd anomaly. Type 2 carbonates have δ13CPDB = -12.6 to -4.1‰ and δ18OSMOW = 25.0 to 32.7‰, suggesting precipitation temperatures from 10 to 60°C. Type 3 carbonates are late pluri-mm to cm veins reactivating Type 2 veins. They consist of small grains of dolomite and calcite with REE abundances similar to recrystallized Type 2 carbonates. Type 3 carbonates have δ13CPDB = -8.3 to -5.8‰ and δ18OSMOW = 28.8 to 32.7‰, suggesting precipitation temperatures 100°C). Formation of carbonate veins (Type 2) indicates localization of fluid flux, while serpentinization remains the dominant alteration process. Low T carbonate veins (Type 3) remain the main flow path through ophiolitic peridotites. Our study suggests that

  12. Oxygen isotope geochemistry of The Geysers reservoir rocks, California

    Gunderson, Richard P.; Moore, Joseph N.


    Whole-rock oxygen isotopic compositions of Late Mesozoic graywacke, the dominant host rock at The Geysers, record evidence of a large liquid-dominated hydrothermal system that extended beyond the limits of the present steam reservoir. The graywackes show vertical and lateral isotopic variations that resulted from gradients in temperature, permeability, and fluid composition during this early liquid-dominated system. All of these effects are interpreted to have resulted from the emplacement of the granitic "felsite" intrusion 1-2 million years ago. The {delta}{sup 18}O values of the graywacke are strongly zoned around a northwest-southeast trending low located near the center of and similar in shape to the present steam system. Vertical isotopic gradients show a close relationship to the felsite intrusion. The {delta}{sup 18}O values of the graywacke decrease from approximately 15 per mil near the surface to 4-7 per mil 300 to 600 m above the intrusive contact. The {delta}{sup 18}O values then increase downward to 8-10 per mil at the felsite contact, thereafter remaining nearly constant within the intrusion itself. The large downward decrease in {delta}{sup 18}O values are interpreted to be controlled by variations in temperature during the intrusive event, ranging from 150{degree}C near the surface to about 425{degree}C near the intrusive contact. The upswing in {delta}{sup 18}O values near the intrusive contact appears to have been caused by lower rock permeability and/or heavier fluid isotopic composition there. Lateral variations in the isotopic distributions suggests that the effects of temperature were further modified by variations in rock permeability and/or fluid-isotopic composition. Time-integrated water:rock ratios are thought to have been highest within the central isotopic low where the greatest isotopic depletions are observed. We suggest that this region of the field was an area of high permeability within the main upflow zone of the liquid

  13. Active oxygen doctors the evidence

    Castelló, Ana; Francès, Francesc; Corella, Dolores; Verdú, Fernando


    Investigation at the scene of a crime begins with the search for clues. In the case of bloodstains, the most frequently used reagents are luminol and reduced phenolphthalein (or phenolphthalin that is also known as the Kastle-Meyer colour test). The limitations of these reagents have been studied and are well known. Household cleaning products have evolved with the times, and new products with active oxygen are currently widely used, as they are considered to be highly efficient at removing all kinds of stains on a wide range of surfaces. In this study, we investigated the possible effects of these new cleaning products on latent bloodstains that may be left at a scene of a crime. To do so, various fabrics were stained with blood and then washed using cleaning agents containing active oxygen. The results of reduced phenolphthalein, luminol and human haemoglobin tests on the washed fabrics were negative. The conclusion is that these new products alter blood to such an extent that it can no longer be detected by currently accepted methods employed in criminal investigations. This inability to locate bloodstains means that highly important evidence (e.g. a DNA profile) may be lost. Consequently, it is important that investigators are aware of this problem so as to compensate for it.

  14. The transport of oxygen isotopes in hydrothermal systems

    McKibbin, R.; Absar, A.; Blattner, P.


    As groundwater passes through porous rocks, exchange of oxygen between the fluid and the solid matrix causes a change in the oxygen isotope concentrations in both water and rock. If the rate at which the exchange takes place can be estimated (as a function of the isotope concentrations and temperature) then the time taken for a rock/water system to come to equilibrium with respect to isotope concentration might be calculated. In this paper, the equation for isotope transport is derived using conservation laws, and a simple equation to describe the rate of isotope exchange is proposed. These are combined with the equations for fluid flow in a porous medium, to produce a general set of equations describing isotope transport in a hydrothermal system. These equations are solved numerically, using typical parameters, for the one-dimensional case. Oxygen isotope data from the basement rocks underlying Kawerau geothermal field are modelled. The results indicate that the time taken for exchange of 18 O to present-day values is less than the postulated age of hydrothermal alteration in that field. This suggests that, although controlled by similar parameters, oxygen isotope exchange, in felsic rocks at least, is much faster than hydrothermal alteration. This conclusion is consistent with the petrographic observations from the Kawerau system as well as other geothermal fields

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

    Ryb, U.; Eiler, J. M.


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

  16. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    Hannah B Vander Zanden; David X Soto; Gabriel J Bowen; Keith A Hobson; Keith A Hobson


    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicat...

  17. Expanding the Isotopic Toolbox: Applications of Hydrogen and Oxygen Stable Isotope Ratios to Food Web Studies

    Vander Zanden, Hannah B.; Soto, David X.; Bowen, Gabriel J.; Hobson, Keith A.


    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicatio...

  18. Carbon and Oxygen isotopic composition in paleoenvironmental determination

    Silva, J.R.M. da.


    This work reports that the carbon and oxygen isotopic composition separate the mollusks from marine environment of the mollusks from continental environment in two groups isotopically different, making the biological control outdone by environment control, in the isotopic fragmentation mechanisms. The patterns from the continental environment are more rich in O 16 than the patterns from marine environments. The C 12 is also more frequent in the mollusks from continental environments. The carbon isotopic composition in paterns from continental environments is situated betwen - 10.31 and - 4,05% and the oxygen isotopic composition is situated between - 6,95 and - 2,41%. To the marine environment patterns the carbon isotopic composition is between - 2,08 and + 2,65% and the oxigen isotopic composition is between - 2,08 and + 0,45%. Was also analysed fossil marine mollusks shells and their isotopic composition permit the formulation of hypothesis about the environment which they lived. (C.D.G.) [pt


    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.

  20. Sulfur cycling in contaminated aquifers: What can we learn from oxygen isotopes in sulfate? (Invited)

    Knoeller, K.; Vogt, C.; Hoth, N.


    abandoned lignite mine. Due to the heterogeneous isotopic composition of the sulfate source (oxidation of sedimentary sulfide), sulfur isotopes alone are inappropriate for the recognition of BSR. Only the application of oxygen isotopes in sulfate provides clear evidence for the activity of sulfate reducing bacteria. However, the obtained small θ value indicates a significant influence of sulfide re-oxidation. In the second example we applied the dual isotope system to investigate the relevance of BSR for natural biodegradation in an aquifer contaminated with BTEX. Isotope fractionation parameters were determined in column experiments operated under near in situ conditions. The differences between field derived and experimental fractionation parameters revealed essential information on the occurrence of sulfur transformations competing with the actual biodegradation reactions. Most important of those processes is the re-oxidation of reduced sulfur species consuming electron acceptors that would be relevant for contaminant oxidation.

  1. Rate of oxygen isotope exchange between selenate and water.

    Kaneko, Masanori; Poulson, Simon R


    The rate of oxygen isotope exchange between selenate and water was investigated at conditions of 10 to 80 °C and pH -0.6 to 4.4. Oxygen isotope exchange proceeds as a first-order reaction, and the exchange rate is strongly affected by reaction temperature and pH, with increased rates of isotope exchange at higher temperature and lower pH. Selenate speciation (HSeO(4)(-) vs SeO(4)(2-)) also has a significant effect on the rate of isotope exchange. The half-life for isotope exchange at example natural conditions (25 °C and pH 7) is estimated to be significantly in excess of 10(6) years. The very slow rate of oxygen isotope exchange between selenate and water under most environmental conditions demonstrates that selenate-δ(18)O signatures produced by biogeochemical processes will be preserved and hence that it will be possible to use the value of selenate-δ(18)O to investigate the biogeochemical behavior of selenate, in an analogous fashion to the use of sulfate-δ(18)O to study the biogeochemical behavior of sulfate.

  2. Fluid inclusion and oxygen-isotope evidence for low-temperature Au-Pt-Pd (± U) mineralization at Corronation Hill, NT

    Mernagh, T.


    The fluid inclusion and isotope data have been used to constrain the ore genesis models for the Au-Pt-Pd-U mineralization at Coronation Hill. The fluid inclusions demonstrate that the ore fluid was strongly saline with an unusually high CaCl 2 content, and that the mineralisation was probably formed from a boiling fluid at around 140 deg C. Furthermore, the fluids were highly oxidised and the replacement of earlier chlorite by hematite is common throughout the deposit. It is concluded that both U-rich and U-poor Au-Pt-Pd mineralisation were formed by descending, low-temperature, highly oxidised, very saline, meteoric fluids. The segregation of U was controlled by fluid-rock interaction in the feldspathic or carbonate rocks. Interaction with carbonaceous or chloritic rocks resulted in a reduction in fO 2 , and consequent precipitation of U, Au, Pt and Pd. The other two types of metal associations can be explained by further reaction of the mineralizing fluids. 3 figs

  3. Exploring Neutron-Rich Oxygen Isotopes with MoNA

    Frank, N.; Gade, A.; Peters, W. A.; Thoennessen, M.; Baumann, T.; Bazin, D.; Lecouey, J.-L.; Scheit, H.; Schiller, A.; Brown, J.; DeYoung, P. A.; Finck, J. E.; Hinnefeld, J.; Howes, R.; Luther, B.


    The Modular Neutron Array (MoNA) was used in conjunction with a large-gap dipole magnet (Sweeper) to measure neutron-unbound states in oxygen isotopes close to the neutron dripline. While no excited states were observed in 24 O, a resonance at 45(2) keV above the neutron separation energy was observed in 23 O

  4. Carbon and oxygen isotope compositions of the carbonate facies

    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 ...

  5. Nitrogen and Oxygen Isotopic Studies of the Marine Nitrogen Cycle.

    Casciotti, Karen L


    The marine nitrogen cycle is a complex web of microbially mediated reactions that control the inventory, distribution, and speciation of nitrogen in the marine environment. Because nitrogen is a major nutrient that is required by all life, its availability can control biological productivity and ecosystem structure in both surface and deep-ocean communities. Stable isotopes of nitrogen and oxygen in nitrate and nitrite have provided new insights into the rates and distributions of marine nitrogen cycle processes, especially when analyzed in combination with numerical simulations of ocean circulation and biogeochemistry. This review highlights the insights gained from dual-isotope studies applied at regional to global scales and their incorporation into oceanic biogeochemical models. These studies represent significant new advances in the use of isotopic measurements to understand the modern nitrogen cycle, with implications for the study of past ocean productivity, oxygenation, and nutrient status.

  6. Oxygen isotope analysis of plant water without extraction procedure

    Gan, K.S.; Wong, S.C.; Farquhar, G.D.; Yong, J.W.H.


    Isotopic analyses of plant water (mainly xylem, phloem and leaf water) are gaming importance as the isotopic signals reflect plant-environment interactions, affect the oxygen isotopic composition of atmospheric O 2 and CO 2 and are eventually incorporated into plant organic matter. Conventionally, such isotopic measurements require a time-consuming process of isolating the plant water by azeotropic distillation or vacuum extraction, which would not complement the speed of isotope analysis provided by continuous-flow IRMS (Isotope-Ratio Mass Spectrometry), especially when large data sets are needed for statistical calculations in biological studies. Further, a substantial amount of plant material is needed for water extraction and leaf samples would invariably include unenriched water from the fine veins. To measure sub-microlitre amount of leaf mesophyll water, a new approach is undertaken where a small disc of fresh leaf is cut using a specially designed leaf punch, and pyrolysed directly in an IRMS. By comparing with results from pyrolysis of the dry matter of the same leaf, the 18 O content of leaf water can be determined without extraction from fresh leaves. This method is validated using a range of cellulose-water mixtures to simulate the constituents of fresh leaf. Cotton leaf water δ 18 O obtained from both methods of fresh leaf pyrolysis and azeotropic distillation will be compared. The pyrolysis technique provides a robust approach to measure the isotopic content of water or any volatile present in a homogeneous solution or solid hydrous substance

  7. Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

    Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky


    Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

  8. How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

    Price, Gregory; Grimes, Stephen


    The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

  9. Uranium Isotope Compositions of Mid-Proterozoic Organic-rich Mudrocks: Evidence for an Episode of Increased Ocean Oxygenation at ca. 1.36 Ga and Evaluation of the Effect of Post-Depositional Hydrothermal Fluid Flow

    Kendall, B.; Yang, S.; Lu, X.; Zhang, F.; Zheng, W.


    The U isotope system represents a relatively new paleoredox proxy that can help trace the evolution of global ocean redox chemistry, but has rarely been applied to the Mid-Proterozoic. We report U isotope data for marine black shales of the early Mesoproterozoic Velkerri Formation (Roper Group) and late Paleoproterozoic Wollogorang Formation (Tawallah Group) from the McArthur Basin, Northern Australia. An average authigenic δ238U of 0.13 ± 0.04‰ (1SD; relative to standard CRM145) was obtained for six euxinic shales from a 1 m interval that previously yielded a precise Re-Os depositional age of 1361 ± 21 Ma. After correcting for a U isotope fractionation of 0.60-0.85‰ between seawater and open-ocean euxinic sediments, we infer that coeval global seawater had a δ238U of -0.47‰ to -0.72‰, which is 0.1-0.3‰ lighter than modern seawater (-0.40 ± 0.03‰). A U isotope mass-balance model suggests that anoxic marine environments accounted for 25-50% of the global oceanic U sink at 1.36 Ga, which is 3-7 times greater than today. The model suggests that a significant proportion, potentially even a majority, of the seafloor was not covered by anoxic waters. Hence, we infer that a significant extent of the ocean floor was covered by O2-bearing waters at 1.36 Ga. The O2 concentrations of those waters were not necessarily high, and a large expanse of weakly to mildly oxygenated deep waters is consistent with the U isotope data. Uranium isotope data from a 1 m interval in the lower Velkerri Formation, deposited at 1417 ± 29 Ma based on Re-Os geochronology, yield a greater estimate for the extent of ocean anoxia. Hence, the upper Velkerri Formation may capture a transient episode of increased ocean oxygenation. Previous Re-Os isotope data from black shales of the ca. 1.73 Ga Paleoproterozoic Wollogorang Formation yielded an erroneously young date of 1359 ± 150 Ma because hydrothermal fluids percolated through the Tawallah Group rocks at ca. 1640 Ma. Higher δ238U

  10. Oxygen isotopic signature of CO2 from combustion processes

    W. A. Brand


    Full Text Available For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires, and human induced (fossil fuel combustion, biomass burning in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects on the order of up to 26%permil; became obvious in the derived CO2 from combustion of different kinds of material, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature, sample geometries (e.g. texture and surface-volume ratios and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original total 18O signature of the material appeared to have little influence, however, a contribution of specific bio

  11. Oxygen Isotopes in Chondritic Interplanetary Dust: Parent-Bodies and Nebular Oxygen Reservoirs

    Aleon, J; McKeegan, K D; Leshin, L


    Planetary objects have preserved various amounts of oxygen issued from isotopically different oxygen reservoirs reflecting their origin and physico-chemical history. An 16 O-rich component is preserved in refractory inclusions (CAIs) whereas meteorites matrices are enriched in an 16 O-poor component. The origin of these components is still unclear. The most recent models are based on isotope selective photodissociation of CO in a 16 O-rich nebula/presolr cloud resulting in a 16 O-poor gas in the outer part of the nebula. However because most meteorite components are thought to be formed in the inner 3AU of the solar nebula, the precise isotopic composition of outer solar system components is yet unknown. In that respect, the oxygen isotopic composition of cometary dust is a key to understand the origin of the solar system. The Stardust mission will bring back to the Earth dust samples from comet Wild2, a short period comet from the Jupiter family. A precise determination of the oxygen isotope composition of Wild2 dust grains is essential to decipher the oxygen reservoirs of the outer solar system. However, Stardust samples may be extremely fragmented upon impact in the collector. In addition, interplanetary dust particles (IDPs) collected in the stratosphere are likely to contain comet samples. Therefore, they started to investigate the oxygen isotopic composition of a suite of chondritic interplanetary dust particles that includes IDPs of potential cometary origin using a refined procedure to increase the lateral resolution for the analysis of Stardust grains or IDP subcomponents down to ∼ 3 (micro)m. High precision data for 4 IDPs were previously reported, here they have measured 6 additional IDPs


    Hinkle, Kenneth H. [National Optical Astronomy Observatory P.O. Box 26732, Tucson, AZ 85726 (United States); Lebzelter, Thomas [Department of Astrophysics, University of Vienna Türkenschanzstrasse 17, A-1180 Vienna (Austria); Straniero, Oscar, E-mail:, E-mail:, E-mail: [INAF, Osservatorio Astronomico di Collurania I-64100 Teramo (Italy)


    Carbon and oxygen isotopic ratios are reported for a sample of 46 Mira and SRa-type variable asymptotic giant branch (AGB) stars. Vibration–rotation first and second-overtone CO lines in 1.5–2.5 μ m spectra were measured to derive isotopic ratios for {sup 12}C/{sup 13}C, {sup 16}O/{sup 17}O, and {sup 16}O/{sup 18}O. Comparisons with previous measurements for individual stars and with various samples of evolved stars, as available in the extant literature, are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of M-stars have main sequence masses ≤2 M {sub ⊙} and have not experienced sizable third dredge-up (TDU) episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the six C-stars in the sample three have clear evidence relating their origin to the occurrence of TDU. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars, as represented by our sample of long period variables (LPVs), shows a large spread of {sup 16}O/{sup 17}O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2–2 M {sub ⊙} stars after the first dredge-up. In contrast, the {sup 16}O/{sup 18}O ratios of present-day LPVs are definitely smaller than those of group 1 grains. This is most probably a consequence of the the decrease with time of the {sup 16}O/{sup 18}O ratio in the interstellar medium due to the chemical evolution of the Milky Way. One star in our sample has an O composition similar to that of group 2 presolar grains originating in an AGB star undergoing extra-mixing. This may indicate that the extra-mixing process is hampered at high metallicity, or, equivalently, favored at low metallicity. Similarly to O

  13. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

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


    Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

  14. CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

    Lyons, J R; Young, E D


    The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

  15. Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

    Yurimoto; Ito; Nagasawa


    A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

  16. Oxygen isotope variations in phosphate of biogenic apatites. Pt.1

    Kolodny, Y.; Luz, B.; Navon, O.


    The major advantage of the oxygen in phosphate isotope paleothermometry is that it is a system which records temperatures with great sensitivity while bone (and teeth) building organisms are alive, and the record is nearly perfectly preserved after death. Fish from seven water bodies of different temperatures (3-23 0 C) and different delta 18 O (values - 16 to + 3) of the water were analysed. The delta 18 O values of the analysed PO 4 vary from 6 to 25. The system passed the following tests: (a) the temperature deduced from isotopic analyses of the sequence of fish from Lake Baikal are in good agreement with the temperatures measured in the thermally stratified lake; (b) the isotopic composition of fish bone phosphate is not influenced by the isotopic composition of the phosphate which is fed to the fish, but only by temperature and water composition. Isotopic analysis of fossil fish in combination with analysis of mammal bones should be a useful tool in deciphering continental paleoclimates. (orig.)

  17. Kinetic theory of oxygen isotopic exchange between minerals and water

    Criss, R.E.; Gregory, R.T.; Taylor, H.P.


    Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

  18. Oxygen and carbon isotopic compositions of gases respired by humans

    Epstein, S.; Zeiri, L.


    Oxygen-isotope fractionation associated with respiration in human individuals at rest is linearly related to the fraction of the O 2 utilized in the respiration process. The slope of this relationship is affected by a history of smoking, by vigorous exercise, and by the N 2 /O 2 ratio of the inhaled gas. For patients who suffer anemia-related diseases, the slope of this relationship is directly proportional to their level of hemoglobin. These results introduce a new approach for studying the mechanisms of O 2 consumption in human respiration and how they are affected by related diseases

  19. Oxygen isotopic analyses of individual planktic foraminifera species: Implications for seasonality in the western Arabian Sea

    Naidu, P.D.; Niitsuma, N.; Naik, S.S.

    The variation of stable isotopes between individual shells of planktic foraminifera of a given species and size may provide short-term seasonal insight on Paleoceanography. In this context, oxygen isotope analyses of individual Globigerinoides...

  20. Oxygen isotope fractionation between bird bone phosphate and drinking water

    Amiot, Romain; Angst, Delphine; Legendre, Serge; Buffetaut, Eric; Fourel, François; Adolfssen, Jan; André, Aurore; Bojar, Ana Voica; Canoville, Aurore; Barral, Abel; Goedert, Jean; Halas, Stanislaw; Kusuhashi, Nao; Pestchevitskaya, Ekaterina; Rey, Kevin; Royer, Aurélien; Saraiva, Antônio Álamo Feitosa; Savary-Sismondini, Bérengère; Siméon, Jean-Luc; Touzeau, Alexandra; Zhou, Zhonghe; Lécuyer, Christophe


    Oxygen isotope compositions of bone phosphate (δ18Op) were measured in broiler chickens reared in 21 farms worldwide characterized by contrasted latitudes and local climates. These sedentary birds were raised during an approximately 3 to 4-month period, and local precipitation was the ultimate source of their drinking water. This sampling strategy allowed the relationship to be determined between the bone phosphate δ18Op values (from 9.8 to 22.5‰ V-SMOW) and the local rainfall δ18Ow values estimated from nearby IAEA/WMO stations (from -16.0 to -1.0‰ V-SMOW). Linear least square fitting of data provided the following isotopic fractionation equation: δ18Ow = 1.119 (±0.040) δ18Op - 24.222 (±0.644); R 2 = 0.98. The δ18Op-δ18Ow couples of five extant mallard ducks, a common buzzard, a European herring gull, a common ostrich, and a greater rhea fall within the predicted range of the equation, indicating that the relationship established for extant chickens can also be applied to birds of various ecologies and body masses. Applied to published oxygen isotope compositions of Miocene and Pliocene penguins from Peru, this new equation computes estimates of local seawater similar to those previously calculated. Applied to the basal bird Confuciusornis from the Early Cretaceous of Northeastern China, our equation gives a slightly higher δ18Ow value compared to the previously estimated one, possibly as a result of lower body temperature. These data indicate that caution should be exercised when the relationship estimated for modern birds is applied to their basal counterparts that likely had a metabolism intermediate between that of their theropod dinosaur ancestors and that of advanced ornithurines.

  1. Sources and Contributions of Oxygen During Microbial Pyrite Oxidation: the Triple Oxygen Isotopes of Sulfate

    Ziegler, K.; Coleman, M. L.; Mielke, R. E.; Young, E. D.


    The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of complimentary chemistry data (in progress), we interpret our isotope data to indicate that the biotic fractionation factor ɛ18OSO4-O2 of at least ~ -25 to - 35‰ is augmented by microbially induced kinetic fractionation; it is larger than

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

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


    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...

  3. Evaporation Induced Oxygen Isotope Fractionation in Impact Ejecta

    Macris, C. A.; Young, E. D.; Kohl, I. E.; zur Loye, T. E.


    Tektites are natural glasses formed as quenched impact melt ejecta. Because they experienced extreme heating while entrained in a hot impact vapor plume, tektites allow insight into the nature of these ephemeral events, which play a critical role in planetary accretion and evolution. During tektite formation, the chemical and isotopic composition of parent materials may be modified by (1) vapor/liquid fractionation at high T in the plume, (2) incorporation of meteoric water at the target site, (3) isotope exchange with atmospheric oxygen (if present), or some combination of the three. Trends from O isotope studies reveal a dichotomy: some tektite δ18O values are 4.0-4.5‰ lower than their protoliths (Luft et al. 1987; Taylor & Epstein 1962), opposite in direction to a vaporization induced fractionation; increases in δ18O with decreasing SiO2 in tektites (Taylor & Epstein 1969) is consistent with vapor fractionation. Using an aerodynamic levitation laser furnace (e.g. Macris et al. 2016), we can experimentally determine the contributions of processes (1), (2) and (3) above to tektite compositions. We conducted a series of evaporation experiments to test process (1) using powdered tektite fused into 2 mm spheres and heated to 2423-2473 K for 50-90 s while levitated in Ar in the furnace. Mass losses were from 23 to 26%, reflecting evaporation of Si and O from the melt. The starting tektite had a δ18O value of 10.06‰ (±0.01 2se) and the residues ranged from 13.136‰ (±0.006) for the least evaporated residue to 14.30‰ (±0.02) for the most evaporated (measured by laser fluorination). The increase in δ18O with increasing mass loss is consistent with Rayleigh fractionation during evaporation, supporting the idea that O isotopes are fractionated due to vaporization at high T in an impact plume. Because atmospheric O2 and water each have distinctive Δ17O values, we should be able to use departures from our measured three-isotope fractionation law to evaluate

  4. Oxygen isotope studies of the Salton Sea geothermal field

    Olson, E.R.


    Interbedded shales and sandstones were drilled to a depth of 1588 metres in Sinclair Number Four Well, Salton Sea Geothermal Field. Bottom hole temperatures are approximately 290 0 C. The oxygen dels of hydrothermal and detrital calcite have a systematic relationship at any depth in the geothermal reservoir. Typical values are: vein calcite, +6 0 / 00 ; calcite in white sandstone, +10 0 / 00 ; calcite in dark gray shale, +11 0 / 00 ; calcite in light gray shale, +17 0 / 00 ; calcite in red-brown shale, +20 0 / 00 . This succession represents decreasing water-rock interaction that is also indicated by the clay mineralogy of the shales. Permeability has a marked effect on the equilibration of water and rocks at any given temperature. Original differences in permeability have resulted in partial preservation of original detrital sedimentary compositions. The fluids in the Salton Sea Geothermal Field are probabaly partially evaporated Colorado River water, and their oxygen del values vary as much as 4 0 / 00 throughout the field. Truesdell's (1974) data suggest that dissolved salts may make the water oxygen activity del as much as 6 0 / 00 greater than the concentration del in the geothermal reservoir. Such an uncertainty is a serious impediment to precise isotope geothermometry in this system.(auth.)

  5. Triple oxygen isotopes in biogenic and sedimentary carbonates

    Passey, Benjamin H.; Hu, Huanting; Ji, Haoyuan; Montanari, Shaena; Li, Shuning; Henkes, Gregory A.; Levin, Naomi E.


    The 17O anomaly (Δ17O) of natural waters has been shown to be sensitive to evaporation in a way analogous to deuterium excess, with evaporated bodies of water (e.g., leaf waters, lake waters, animal body waters) tending to have lower Δ17O than primary meteoric waters. In animal body water, Δ17O relates to the intake of evaporated waters, evaporative effluxes of water, and the Δ17O value of atmospheric O2, which itself carries signatures of global carbon cycling and photochemical reactions in the stratosphere. Carbonates have the potential to record the triple oxygen isotope compositions of parent waters, allowing reconstruction of past water compositions, but such investigations have awaited development of methods for high-precision measurement of Δ17O of carbonate. We describe optimized methods based on a sequential acid digestion/reduction/fluorination approach that yield Δ17O data with the high precision (∼0.010‰, 1σ) needed to resolve subtle environmental signals. We report the first high-precision Δ17O dataset for terrestrial carbonates, focusing on vertebrate biogenic carbonates and soil carbonates, but also including marine invertebrates and high-temperature carbonates. We determine apparent three-isotope fractionation factors between the O2 analyte derived from carbonate and the parent waters of the carbonate. These in combination with appropriate temperature estimates (from clumped isotope thermometry, or known or estimated body temperatures) are used to calculate the δ18O and Δ17O of parent waters. The clearest pattern to emerge is the strong 17O-depletion in avian, dinosaurian, and mammalian body water (from analyses of eggshell and tooth enamel) relative to meteoric waters, following expected influences of evaporated water (e.g., leaf water) and atmospheric O2 on vertebrate body water. Parent waters of the soil carbonates studied here have Δ17O values that are similar to or slightly lower than global precipitation. Our results suggest

  6. Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

    Cao, Xiaobin; Liu, Yun


    With a growing interest in small 17O-anomaly, there is a pressing need for the precise ratio, ln 17α/ln 18α, for a particular mass-dependent fractionation process (MDFP) (e.g., for an equilibrium isotope exchange reaction). This ratio (also denoted as " θ") can be determined experimentally, however, such efforts suffer from the demand of well-defined process or a set of processes in addition to high precision analytical capabilities. Here, we present a theoretical approach from which high-precision ratios for MDFPs can be obtained. This approach will complement and serve as a benchmark for experimental studies. We use oxygen isotope exchanges in equilibrium processes as an example. We propose that the ratio at equilibrium, θE ≡ ln 17α/ln 18α, can be calculated through the equation below: θa-bE=κa+(κa-κb){ln18βb}/{ln18α} where 18βb is the fractionation factor between a compound "b" and the mono-atomic ideal reference material "O", 18αa-b is the fractionation factor between a and b and it equals to 18βa/ 18βb and κ is a new concept defined in this study as κ ≡ ln 17β/ln 18β. The relationship between θ and κ is similar to that between α and β. The advantages of using κ include the convenience in documenting a large number of θ values for MDFPs and in estimating any θ values using a small data set due to the fact that κ values are similar among O-bearing compounds with similar chemical groups. Frequency scaling factor, anharmonic corrections and clumped isotope effects are found insignificant to the κ value calculation. However, the employment of the rule of geometric mean (RGM) can significantly affect the κ value. There are only small differences in κ values among carbonates and the structural effect is smaller than that of chemical compositions. We provide κ values for most O-bearing compounds, and we argue that κ values for Mg-bearing and S-bearing compounds should be close to their high temperature limitation (i.e., 0.5210 for

  7. Do oxygen isotope values in collagen reflect the ecology and physiology of neotropical mammals?

    Brooke eCrowley


    Full Text Available Stable isotope data provide insight into the foraging ecology of animals. Traditionally, carbon and nitrogen isotope values have been used to infer dietary and habitat preferences. Oxygen isotopes are used less frequently but may complement the ecological information provided by carbon and nitrogen, particularly in densely forested or arid environments. Additionally, because oxygen is preserved in both bioapatite and collagen, it is useful for paleoecological studies. To investigate the suitability of oxygen isotopes for complementing and building on ecological applications of carbon and nitrogen isotopes, we analyze all three isotopes in bone collagen for nearly identical assemblages of Costa Rican mammals in two ecologically distinct habitats - a evergreen rainforest and a seasonal dry forest. We assess the degree to which differences in habitat, activity pattern, diet, arboreality, and thermoregulation are revealed by each of the isotope systems. Our results highlight the potential of oxygen isotopes in modern and paleoecological contexts. In addition to reflecting habitat type, oxygen isotope values in collagen distinguish species on the basis of vertical habitat stratification and drinking behavior. Within a locality, individuals with low oxygen isotope values likely track meteoric water, whereas those with elevated values most likely consume evaporatively-enriched plant tissues, such as canopy leaves. These patterns will be useful in reconstructing paleoenvironments and interpreting ecological differences among taxa both extant and extinct.

  8. Kalahari groundwaters: Their hydrogen, carbon and oxygen isotopes

    Mazor, E.; Verhagen, B.T.; Sellschop, J.P.F.; Robins, N.S.; Hutton, L.G.


    Tritium and 14 C measurements have revealed several cases of post-nuclear bomb-test rain recharge of local groundwaters, along with values indicating recharge over larger, yet hydrologically active, time scales. In general, recharge seems to follow rain distribution in being more intense in the northern rather than in the southern Kalahari. Initial δ 13 C values vary over a wide range and reveal some correlation to pH and chemical composition of the water. They cannot be used to correct for fossil carbon dilution in 14 C-age calculations. Radiocarbon-deduced ages range from recent to 30,000 years. Stable hydrogen and oxygen isotopes indicate recharge from direct rain infiltration. (author)

  9. The development of a completely automated oxygen isotope mass spectrometer

    Ahern, T.K.


    A completely automated mass spectrometer system has been developed to measure the oxygen isotope ratio of carbon dioxide samples. The system has an accuracy of 0.03 percent, and is capable of analyzing more than 100 samples a day. The system uses an Interdata minicomputer as the primary controller. The intelligence of the system is contained within hardware circuits, software within the minicomputer, and firmware written for a Motorola 6802 microprocessor. A microprocessor-based inlet system controller maximizes the throughput of carbon dioxide samples within the inlet system. The inlet system normally contains four different aliquots of carbon dioxide and introduces these samples to the mass spectrometer through a single admittance leak. The system has been used in the analysis of 111 samples of ice taken from the Steele glacier

  10. Correlation and Stacking of Relative Paleointensity and Oxygen Isotope Data

    Lurcock, P. C.; Channell, J. E.; Lee, D.


    The transformation of a depth-series into a time-series is routinely implemented in the geological sciences. This transformation often involves correlation of a depth-series to an astronomically calibrated time-series. Eyeball tie-points with linear interpolation are still regularly used, although these have the disadvantages of being non-repeatable and not based on firm correlation criteria. Two automated correlation methods are compared: the simulated annealing algorithm (Huybers and Wunsch, 2004) and the Match protocol (Lisiecki and Lisiecki, 2002). Simulated annealing seeks to minimize energy (cross-correlation) as "temperature" is slowly decreased. The Match protocol divides records into intervals, applies penalty functions that constrain accumulation rates, and minimizes the sum of the squares of the differences between two series while maintaining the data sequence in each series. Paired relative paleointensity (RPI) and oxygen isotope records, such as those from IODP Site U1308 and/or reference stacks such as LR04 and PISO, are warped using known warping functions, and then the un-warped and warped time-series are correlated to evaluate the efficiency of the correlation methods. Correlations are performed in tandem to simultaneously optimize RPI and oxygen isotope data. Noise spectra are introduced at differing levels to determine correlation efficiency as noise levels change. A third potential method, known as dynamic time warping, involves minimizing the sum of distances between correlated point pairs across the whole series. A "cost matrix" between the two series is analyzed to find a least-cost path through the matrix. This least-cost path is used to nonlinearly map the time/depth of one record onto the depth/time of another. Dynamic time warping can be expanded to more than two dimensions and used to stack multiple time-series. This procedure can improve on arithmetic stacks, which often lose coherent high-frequency content during the stacking process.

  11. Bulk Oxygen Isotopic Composition of Ultracarbonaceous Antarctic Micrometeorites with the NanoSIMS

    Kakazu, Y.; Engrand, C.; Duprat, J.; Briani, G.; Bardin, N.; Mostefaoui, S.; Duhamel, R.; Remusat, L.


    We analyzed the carbon and oxygen isotope ratios of two UCAMMs with the NanoSIMS in order to understand the origin and formation of UCAMMs. One UCAMM has 16O-rich composition and a highly heterogeneous oxygen isotopic distribution.

  12. Oxygen stable isotopes variation in water precipitation in Poland – anthropological applications

    Lisowska-Gaczorek Aleksandra


    Full Text Available The main objective of oxygen isotope analysis is to determine the probable place of origin of an individual or the reconstruction of migration paths. The research are methodologically based on referencing oxygen isotope ratios of apatite phosphates (δ18Op to the range of environmental background δ18O, most frequently determined on the basis of precipitation.

  13. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    Hannah B Vander Zanden


    Full Text Available The measurement of stable carbon (δ13C and nitrogen (δ15N isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H and oxygen (δ18O isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applications using δ2H and, to a lesser extent, δ18O values have demonstrated potential for these elements to provide novel insights in modern food web studies. We explore the advantages and challenges associated with three applications of δ2H and δ18O values in food web studies. First, large δ2H differences between aquatic and terrestrial ecosystem end members can permit the quantification of energy inputs and nutrient fluxes between these two sources, with potential applications for determining allochthonous vs. autochthonous nutrient sources in freshwater systems and relative aquatic habitat utilization by terrestrial organisms. Next, some studies have identified a relationship between δ2H values and trophic position, which suggests that this marker may serve as a trophic indicator, in addition to the more commonly used δ15N values. Finally, coupled measurements of δ2H and δ18O values are increasing as a result of reduced analytical challenges to measure both simultaneously and may provide additional ecological information over single element measurements. In some organisms, the isotopic ratios of these two elements are tightly coupled, whereas the isotopic disequilibrium in other organisms may offer insight into the diet and physiology of individuals. Although a coherent framework for interpreting δ2H and δ18O data in the context of food web studies is emerging, many fundamental uncertainties remain. We highlight directions for targeted research that

  14. Oxygen isotopes in garnet and accessory minerals to constrain fluids in subducted crust

    Rubatto, Daniela; Gauthiez-Putallaz, Laure; Regis, Daniele; Rosa Scicchitano, Maria; Vho, Alice; Williams, Morgan


    Fluids are considered a fundamental agent for chemical exchanges between different rock types in the subduction system. Constraints on the sources and pathways of subduction fluids thus provide crucial information to reconstruct subduction processes. Garnet and U-Pb accessory minerals constitute some of the most robust and ubiquitous minerals in subducted crust and can preserve multiple growth zones that track the metamorphic evolution of the sample they are hosted in. Microbeam investigation of the chemical (major and trace elements) and isotopic composition (oxygen and U-Pb) of garnet and accessory minerals is used to track significant fluid-rock interaction at different stages of the subduction system. This approach requires consideration of the diffusivity of oxygen isotopes particularly in garnet, which has been investigated experimentally. The nature of the protolith and ocean floor alteration is preserved in relict accessory phases within eclogites that have been fully modified at HP conditions (e.g. Monviso and Dora Maira units in the Western Alps). Minerals in the lawsonite-blueschists of the Tavsanli zone in Turkey record pervasive fluid exchange between mafic and sedimentary blocks at the early stage of subduction. High pressure shear zones and lithological boundaries show evidence of intense fluid metasomatism at depth along discontinuities in Monviso and Corsica. In the UHP oceanic crust of the Zermatt-Saas Zone, garnet oxygen isotopes and tourmaline boron isotopes indicate multistage fluid infiltration during prograde metamorphism. Localized exchanges of aqueous fluids are also observed in the subducted continental crust of the Sesia-Lanzo Zone. In most cases analyses of distinct mineral zones enable identification of multiple pulses of fluids during the rock evolution.

  15. Growth history of cultured pearl oysters based on stable oxygen isotope analysis

    Nakashima, R.; Furuta, N.; Suzuki, A.; Kawahata, H.; Shikazono, N.


    We investigated the oxygen isotopic ratio in shells of the pearl oyster Pinctada martensii cultivated in embayments in Mie Prefecture, central Japan, to evaluate the biomineralization of shell structures of the species and its pearls in response to environmental change. Microsamples for oxygen isotope analysis were collected from the surfaces of shells (outer, middle, and inner shell layers) and pearls. Water temperature variations were estimated from the oxygen isotope values of the carbonate. Oxygen isotope profiles of the prismatic calcite of the outer shell layer reflected seasonal variations of water temperature, whereas those of nacreous aragonites of the middle and inner shell layers and pearls recorded temperatures from April to November, June to September, and July to September, respectively. Lower temperatures in autumn and winter might slow the growth of nacreous aragonites. The oxygen isotope values are controlled by both variations of water temperature and shell structures; the prismatic calcite of this species is useful for reconstructing seasonal changes of calcification temperature.

  16. Oxygen isotope fractionation between human phosphate and water revisited

    Daux, Valérie; Lécuyer, Christophe; Héran, Marie-Anne


    to investigate the impact of solid food consumption on the oxygen isotope composition of the total ingested water (drinking water+solid food water). The results, along with those from three, smaller published data sets, can be considered as random estimates of a unique delta18OW/delta18OP linear relationship...... collected at 12 sites located at latitudes ranging from 4 degrees N to 70 degrees N together with the corresponding oxygen composition of tap waters (delta18OW) from these areas. In addition, the delta18O of some raw and boiled foods were determined and simple mass balance calculations were performed......: delta18OW=1.54(+/-0.09)xdelta18OP-33.72(+/-1.51)(R2=0.87: p [H0:R2=0]=2x10(-19)). The delta18O of cooked food is higher than that of the drinking water. As a consequence, in a modern diet the delta18O of ingested water is +1.05 to 1.2 per thousand higher than that of drinking water in the area. In meat...

  17. Anatomy of the thriple oxygen isotope Terrestrial Fractionatoin Line

    Sharp, Z. D.; Pack, A.


    In the triple oxygen isotope system, it is well established that the δ17O value of nearly all terrestrial materials is approximately ½ that of the corresponding δ18O value. In triple isotope space then, all samples plot on a slope 1/2 line, termed the Terrestrial Fractionation Line (TFL). It has recently been recognized that subtle, but significant departures from the TFL exist, given by Δ'17O = δ'17O -λ× δ'18O + γ, where λ is the slope of the TFL (γ is the y-intercept and assumed to be zero in most studies). There have been many published λ values, ranging from 0.52 to 0.5305. λ values determined from a best-fit to rock and mineral samples range from 0.5244 to 0.5266. λ values from meteoric waters are 0.527 to 0.528 (γ = 0.007 to 0.034), explained by equilibrium and kinetic processes. Extreme polar glacial samples define a λ >0.53. As pointed out by Matsuhisia et al. (GCA, 1978), there is no single factor that controls the δ17O-δ18O slope, and clearly there is no `correct' TFL line. However, some generalities can be noted. 1) Meteoric waters generally plot with a λ = 0.528 with a Δ'17O = 0.033. At both high and low δ18O values, the Δ'17O values of meteoritic waters decrease. Mantle derived samples plot in a limited δ space, with δ18O values of 5-9‰ and a Δ'17O of -0.05‰. Rock and mineral samples falling outside this narrow range have undergone interaction with meteoric or ocean water at some point in their history, either by alteration or neoform mineral growth. The quartz-water triple isotope fractionation factor varies with temperatures, ranging from 0.5237 to 0.5266 at 0°C and 200°C, respective. A fit to published rock data gives an overall λ = 0.5237-0.5240. These results are most likely explained by the sum of hydrothermal and low-temperature mineral-water fractionations. Attempting to place any significance on a TFL from a set of data in unwarranted without understanding the processes controlling the isotopic compositions of

  18. Preliminary results of oxygen isotope ratio measurement with a particle-gamma coincidence method

    Borysiuk, Maciek, E-mail:; Kristiansson, Per; Ros, Linus; Abdel, Nassem S.; Elfman, Mikael; Nilsson, Charlotta; Pallon, Jan


    The possibility to study variations in the oxygen isotopic ratio with photon tagged nuclear reaction analysis (pNRA) is evaluated in the current work. The experiment described in the article was performed at Lund Ion Beam Analysis Facility (LIBAF) with a 2 MeV deuteron beam. Isotopic fractionation of light elements such as carbon, oxygen and nitrogen is the basis of many analytical tools in hydrology, geology, paleobiology and paleogeology. IBA methods provide one possible tool for measurement of isotopic content. During this experimental run we focused on measurement of the oxygen isotopic ratio. The measurement of stable isotopes of oxygen has a number of applications; the particular one driving the current investigation belongs to the field of astrogeology and specifically evaluation of fossil extraterrestrial material. There are three stable isotopes of oxygen: {sup 16}O, {sup 17}O and {sup 18}O. We procured samples highly enriched with all three isotopes. Isotopes {sup 16}O and {sup 18}O were easily detected in the enriched samples, but no significant signal from {sup 17}O was detected in the same samples. The measured yield was too low to detect {sup 18}O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with {sup 16}O was clearly visible.

  19. Validation of chlorine and oxygen isotope ratio analysis to differentiate perchlorate sources and to document perchlorate biodegradation

    Paul B. Hatzinger,; Böhlke, John Karl; Sturchio, Neil C.; Gu, Baohua


    Increased health concerns about perchlorate (ClO4-) during the past decade and subsequent regulatory considerations have generated appreciable interest in source identification. The key objective of the isotopic techniques described in this guidance manual is to provide evidence concerning the origin of ClO4- in soils and groundwater and, more specifically, whether that ClO4- is synthetic or natural. Chlorine and oxygen isotopic analyses of ClO4- provide the primary direct approach whereby different sources of ClO4- can be distinguished from each other. These techniques measure the relative abundances of the stable isotopes of chlorine (37Cl and 35Cl) and oxygen (18O, 17O, and 16O) in ClO4- using isotope-ratio mass spectrometry (IRMS). In addition, the relative abundance of the radioactive chlorine isotope 36Cl is measured using accelerator mass spectrometry (AMS). Taken together, these measurements provide four independent quantities that can be used to distinguish natural and synthetic ClO4- sources, to discriminate different types of natural ClO4-, and to detect ClO4- biodegradation in the environment. Other isotopic, chemical, and geochemical techniques that can be applied in conjunction with isotopic analyses of ClO4- to provide supporting data in forensic studies are also described.

  20. Oxygen isotope separation by isotopically selective infrared multiphoton dissociation of 2,3-dihydropyran

    Yokoyama, Atsushi; Ohba, Hironori; Akagi, Hiroshi; Yokoyama, Keiichi; Saeki, Morihisa; Katsumata, Keiichi


    Oxygen isotopic selectivity on infrared multiphoton dissociation of 2,3-dihydropyran has been studied by the examination of the effects of excitation frequency, laser fluence, and gas pressure on the dissociation probability of 2,3-dihydropyran and isotopic composition of products. Oxygen-18 was enriched in a dissociation product: 2-propenal. The enrichment factor of 18 O and the dissociation probability were measured at laser frequency between 1033.5 and 1057.3 cm -1 ; the laser fluence of 2.2 - 2.3 J/cm 2 ; and the 2,3-dihydropyran pressure of 0.27 kPa. The dissociation probability decreases as the laser frequency being detuned from the absorption peak of 2,3-dihydropyran around 1081 cm -1 . On the other hand, the enrichment factor increases with detuning the frequency. The enrichment factor of 18 O increases with increasing the 2,3-dihydropyran pressure at the laser fluence below 3 J/cm 2 and the laser frequency of 1033.5 cm -1 , whereas the yield of 2-propenal decreases with increasing the pressure. Very high enrichment factor of 751 was obtained by the irradiation of 0.53 kPa of 2,3-dihydropyran at 2.1 J/cm 2 . (author)

  1. Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

    Henkes, Gregory A.; Passey, Benjamin H.; Grossman, Ethan L.; Shenton, Brock J.; Yancey, Thomas E.; Pérez-Huerta, Alberto


    Surface temperature is among the most important parameters describing planetary climate and habitability, and yet there remains considerable debate about the temperature evolution of the Earth's oceans during the Phanerozoic Eon (541 million years ago to present), the time during which complex metazoan life radiated on Earth. Here we critically assess the emerging record of Phanerozoic ocean temperatures based on carbonate clumped isotope thermometry of fossil brachiopod and mollusk shells, and we present new data that fill important gaps in the Late Paleozoic record. We evaluate and reject the hypothesis that solid-state reordering of 13C-18O bonds has destroyed the primary clumped isotope temperature signal of most fossils during sedimentary burial at elevated temperatures. The resulting Phanerozoic record, which shows a general coupling between tropical seawater temperatures and atmospheric carbon dioxide (CO2) levels since the Paleozoic, indicates that tropical temperatures during the icehouse climate of the Carboniferous period were broadly similar to present (∼25-30 °C), and suggests that benthic metazoans were able to thrive at temperatures of 35-40 °C during intervals of the early and possibly the latest Paleozoic when CO2 levels were likely 5-10× higher than present-day values. Equally important, there is no resolvable trend in seawater oxygen isotope ratios (δ18 O) over the past ∼500 million years, indicating that the average temperature of oxygen exchange between seawater and the oceanic crust has been high (∼270 °C) since at least the early Paleozoic, which points to mid-ocean ridges as the dominant locus of water-rock interaction over the past half-billion years.

  2. Holocene climate variability revealed by oxygen isotope analysis of Sphagnum cellulose from Walton Moss, northern England

    Daley, T. J.; Barber, K. E.; Street-Perrott, F. A.; Loader, N. J.; Marshall, J. D.; Crowley, S. F.; Fisher, E. H.


    Stable isotope analyses of Sphagnum alpha-cellulose, precipitation and bog water from three sites across northwestern Europe (Raheenmore, Ireland, Walton Moss, northern England and Dosenmoor, northern Germany) over a total period of 26 months were used to investigate the nature of the climatic signal recorded by Sphagnum moss. The δ18O values of modern alpha-cellulose tracked precipitation more closely than bog water, with a mean isotopic fractionation factor αcellulose-precipitation of 1.0274 ± 0.001 (1 σ) (≈27‰). Sub-samples of isolated Sphagnum alpha-cellulose were subsequently analysed from core WLM22, Walton Moss, northern England yielding a Sphagnum-specific isotope record spanning the last 4300 years. The palaeo-record, calibrated using the modern data, provides evidence for large amplitude variations in the estimated oxygen isotope composition of precipitation during the mid- to late Holocene. Estimates of palaeotemperature change derived from statistical relationships between modern surface air temperatures and δ18O precipitation values for the British Isles give unrealistically large variation in comparison to proxies from other archives. We conclude that use of such relationships to calibrate mid-latitude palaeo-data must be undertaken with caution. The δ18O record from Sphagnum cellulose was highly correlated with a palaeoecologically-derived index of bog surface wetness (BSW), suggesting a common climatic driver.

  3. Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition

    Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.; McKenzie, J.A.; Bernasconi, S.; Paul, H.


    Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition above and below its melting temperature have been studied and compared with the primary (PKIE) and secondary kinetic isotope effects (SKIE) of 13 C and 18 O, respectively, in the decarboxylation of other heterocyclic acids. The temperature dependence of the secondary oxygen-18 isotope effects is negative in the total 221-255 deg C temperature interval investigated initially. The 13 C KIE measured above melting point of N.A. (temperature interval 235-270 deg C) are located in the range 1.007-1.009. Below melting point of nicotinic acid the 13 C KIE are larger and reveal the negative temperature dependence ( 13 C KIE decreases with decreasing the reaction temperature from 1.013/at 230 deg C to 1.0114/at 221 deg C). A discussion of the above isotopic results is presented. (author)

  4. Oxygen Isotopes Archived in Subfossil Chironomids: Advancing a Promising Proxy for Lake Water Isotopes

    Lasher, G. E.; Axford, Y.; Blair, N. E.


    Oxygen isotopes measured in subfossil chironomid head capsules (aquatic insect remains) in lake sediments are beginning to offer paleoclimate insights from previously under-studied areas of the world. Since the first published pilot study demonstrated the potential of chironomid δ18O to record lake water δ18O (Wooller et al., 2004), subsequent work has refined our understanding of this proxy: confirming via lab cultures that growth water controls head capsule δ18O (Wang et al., 2009), refining laboratory pretreatment protocols, and further validating the method by demonstrating strong agreement between carbonate and chironomid-derived paleo-isotope records (Verbruggen et al., 2009, 2010, 2011). However, outstanding questions remain, including the seasonality of chironomid growth, possible species-dependent vital effects, and diagenetic effects on the protein-chitin complex that comprise chironomid cuticles. To address some of these questions, we summarize available data from paired modern chironomid-lake water δ18O values from around the world and discuss climatic and environmental factors affecting chironomid isotopic signatures. We also present new data on the resistance of these subfossils to diagenesis and degradation throughout the late Quaternary using Fourier Transform Infrared Spectroscopy (FT-IR) and Pyrolysis Gas Chromatography Mass Spectrometry (Py-GC/MS) of chironomid remains up to >100,000 years old. As chironomids are nearly ubiquitous in lakes globally and, we argue, molecularly stable through glacial and interglacial cycles, this proxy has the potential to greatly expand the spatial and temporal resolution of Quaternary paleo-isotopes and thus climate records. In addition to reviewing and presenting new methodological advances, we also present applications of chironomid δ18O from millennial- to centennial-scale Holocene Greenland lake records.

  5. Stable isotope ratio measurements in hydrogen, nitrogen, and oxygen using Raman scattering

    Harney, R.C.; Bloom, S.D.; Milanovich, F.P.


    A method for measuring stable isotope ratios using laser Raman scattering was developed which may prove of significant utility and benefit in stable isotope tracer studies. Crude isotope ratio measurements obtained with a low-power laser indicate that with current technology it should be possible to construct an isotope ratio measurement system using laser Raman scattering that is capable of performing 0.1 percent accuracy isotope ratio measurements of 16 O/ 18 O in natural abundance oxygen gas or 14 N/ 15 N in natural abundance nitrogen gas in times less than two minutes per sample. Theory pertinent to the technique, designs of specific isotope ratio spectrometer systems, and data relating to isotope ratio measurements in hydrogen, nitrogen, and oxygen are presented. In addition, the current status of several studies utilizing this technique is discussed. (auth)

  6. Fractionation of oxygen isotopes between mammalian bone-phosphate and environmental drinking water

    Luz, B.; Kolodny, V.; Horowitz, M.


    The delta 18 O of mammalian bone-phosphate varies linearly with delta 18 O of environmental water, but is not in isotopic equilibrium with that water. This situation is explained by a model of delta 18 O in body water in which the important fluxes of exchangeable oxygen through the body are taken into account. Fractionation of oxygen isotopes between body and environmental drinking water is dependent on the rates of drinking and respiration. Isotopic fractionation can be estimated from physiological data and the estimates correlate very well with observed fractionation. Species whose water consumption is large relative to its energy expenditure is sensitive to isotopic ratio changes in environmental water. (author)

  7. Near Surface CO2 Triple Oxygen Isotope Composition

    Sasadhar Mahata


    Full Text Available The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000 - 0.516 × 1000 × ln(1 + δ18O/1000], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. Therefore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforementioned surface sources. We have analyzed Δ17O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation, in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could provide an additional tracer for constraining the carbon cycle.

  8. Oxygen and hydrogen isotope fractionation during cellulose metabolism in Lemna gibba L

    Yakir, D.; DeNiro, M.J.


    Lemna gibba L. B3 was grown under heterotrophic, photoheterotrophic, and autotrophic conditions in water having a variety of hydrogen and oxygen isotopic compositions. The slopes of the linear regression lines between the isotopic composition of water and leaf cellulose indicated that under the three growth conditions about 40, 70, and 100% of oxygens and carbon-bound hydrogens of cellulose exchanged with those of water prior to cellulose formation. Using the equations of the linear relationships, we estimated the overall fractionation factors between water and the exchanged oxygen and carbon bound-hydrogen of cellulose. At least two very different isotope effects must determine the hydrogen isotopic composition of Lemna cellulose. One reflects the photosynthetic reduction of NADP, while the second reflects exchange reactions that occur subsequent to NADP reduction. Oxygen isotopic composition of cellulose apparently is determined by a single type of exchange reaction with water. Under different growth conditions, variations in metabolic fluxes affect the hydrogen isotopic composition of cellulose by influencing the extent to which the two isotope effects mentioned above are recorded. The oxygen isotopic composition of cellulose is not affected by such changes in growth conditions

  9. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil

    National Aeronautics and Space Administration — This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest canopy...

  10. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil

    National Aeronautics and Space Administration — ABSTRACT: This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest...

  11. Ras Umm Sidd Oxygen Isotope (delta 18O) Data for 1750 to 1995

    National Oceanic and Atmospheric Administration, Department of Commerce — Ras Umm Sidd bimonthly coral oxygen isotope data (coral core RUS-95). Notes on the data: File (Ras Umm Sidd d18O.txt.) includes columns for Year AD (bimonthly...

  12. Comparison of interglacial warm events since the marine oxygen isotope stage 11

    Oba, T.; Banakar, V.K.

    Large numbers of oxygen isotopic curves of benthic foraminifcral tests from deep-sea sediment cores have been published. The curves are well-established reliable proxies for past climate and relative sea level fluctuations. In order to understand...

  13. Palmyra Island Monthly Oxygen Isotope Data (delta 18O) for 1886-1998

    National Oceanic and Atmospheric Administration, Department of Commerce — Palmyra Island Monthly Coral Oxygen Isotope Data. 112-yr, monthly-resolved coral record from Palmyra Island (5 deg 52 min N, 162 deg 8 min W). The coral was drilled...

  14. Oxygen isotope systematics of chondrules in the Allende CV3 chondrite: High precision ion microprobe studies

    Rudraswami, N.G.; Ushikubo, T.; Nakashima, D.; Kita, N.T.

    grains and some of them were derived from precursors related to refractory inclusions. However, most relict olivine grains show oxygen isotope ratios that overlap with those in homogeneous chondrules. The delta sup(17)O values of four barred olivine...




    Experiments were performed to determine the equilibrium as well as kinetic stable nitrogen and oxygen isotope fractionations between aqueous dissolved and gaseous N2O. The equilibrium fractionations, defined as the ratio of the isotopic abundance ratios (15R and 18R, respectively) of gaseous and

  16. Sulfur and Oxygen Isotope Fractionation During Bacterial Sulfur Disproportionation Under Anaerobic Haloalkaline Conditions

    Poser, Alexander; Vogt, Carsten; Knöller, Kay; Sorokin, Dimitry Y.; Finster, Kai W.; Richnow, Hans H.


    Sulfur and oxygen isotope fractionation of elemental sulfur disproportionation at anaerobic haloalkaline conditions was evaluated for the first time. Isotope enrichment factors of the strains Desulfurivibrio alkaliphilus and Dethiobacter alkaliphilus growing at pH 9 or 10 were −0.9‰ to −1‰ for

  17. Oxygen Isotope Records in Modern Oyster Shells from Chi Ku, Tainan and Their Implication of Seasonality

    Chen, Y. C.; Mii, H. S.; Li, K. T.


    To exam whether oxygen isotope records of Crassostrea gigasoysters can be used as proxies of environment, 133 cultivated oysters and 21 water samples were collected from Chi Ku area, Tainan City, southern Taiwan in December of 2012, and from March, 2013 to July, 2014. Instrumental air and water temperatures and precipitation records were obtained from a nearest Central Weather Bureau (CWB) station roughly 16 km north of Chi Ku. The oxygen and carbon isotope values of the ligamental area of the modern oyster shells are from -6.92‰ to -0.08‰ (-3.05 ± 1.17‰, N = 2280; 1σ; VPDB) and from -5.57‰ to 0.63‰ (-1.88 ± 0.81‰), respectively. Oxygen isotope values of the water samples are mainly between -0.28‰ and 0.74‰ (0.18 ± 0.29‰, N = 20; 1σ; VSMOW). However, water oxygen isotope value of -2.75‰ was observed for the water sample collected immediately after a typhoon heavy rainfall. Seasonal temperature fluctuation pattern of estimated oxygen isotope temperatures from modern shells is similar to that of CWB instrumental records. However, the oxygen isotope temperatures are respectively about 3 °C and 10°C higher than those of instrumental records for winter and summer. Higher estimated oxygen isotope temperatures are most likely caused by underestimated fraction of freshwater. We analyzed 5 archaeological oyster shells of Siraya culture (500~250B.P.) collected from Wu Chien Tuso North (WCTN) archaeological site of Tainan branch of Southern Taiwan Science Park to infer the harvest season of mollusks. Oxygen isotope values of the ligamental area of the archaeological oyster shells are between -5.98‰ and -1.26‰ (-3.34 ± 1.37‰, N = 60; 1σ), and carbon isotope values are between -3.21‰ and 0.60‰ (-2.04‰ ± 0.55‰). The oxygen isotope records of archaeological oyster shells also showed clear seasonality. Most of the oysters were collected in autumn and winter. Oxygen isotope values of archaeological oyster shells was 1‰ greater than that

  18. Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

    Sato, S.


    Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

  19. Fractionation of oxygen and hydrogen isotopes at the hydrate gas forming in the sea sediments

    Pashkina, V.I.; Esikov, A.D.


    The paper gives data on isotope composition of interstitial and near-bottom waters sampled in a region of gas-hydrate formation in the Sea of Okhotsk. The studies show that heavy isotopes of oxygen and hydrogen is used in gas-hydrate formation, with the result that isotope composition of its constitution water constitutes δ 18 O=+1.99per mille, δD=+23per mille relatively to SMOW. Formation of autogenic carbonates leads to isotope exchange with interstitial water wich, in turn, changes its primary isotope composition in the direction of increasing of O-18 content. The near-bottom waters are isotope-light relatively to the SMOW standard and to the mean isotope composition of interstitial water in the studied region of gas-hydrate spreading. (orig.) [de

  20. Sources of Holocene variability of oxygen isotopes in paleoclimate archives

    A. N. LeGrande


    Full Text Available Variability in water isotopes has been captured in numerous archives and used to infer past climate changes. Here we examine water isotope variability over the course of the Holocene using the water-isotope enabled, coupled atmosphere-ocean general circulation model, GISS ModelE-R. Eight Holocene time slices, ~1000 years apart are simulated and driven by estimated changes in orbital configuration, greenhouse gases, and ice sheet extent. We find that simulated water isotope archives match well with those seen in ice cores, ocean sediment cores, and speleothems. The climate changes associated with the water isotope changes, however, are more complex than simple modern spatial slope interpretations might suggest. In particular, water isotope variability in Asian speleothems is linked to alterations in landward water vapor transport, not local precipitation, and ice sheet changes over North America lead to the masking of temperature signals in Summit, Greenland. Salinity-seawater isotope variability is complicated by inter-ocean basin exchanges of water vapor. Water isotopes do reflect variability in the hydrology, but are better interpreted in terms of regional hydrological cycle changes rather than as indicators of local climate.

  1. Oxygen isotopic abundances in calcium- aluminum-rich inclusions from ordinary chondrites: implications for nebular heterogeneity.

    McKeegan, K D; Leshin, L A; Russell, S S; MacPherson, G J


    The oxygen isotopic compositions of two calcium-aluminum-rich inclusions (CAIs) from the unequilibrated ordinary chondrite meteorites Quinyambie and Semarkona are enriched in 16O by an amount similar to that in CAIs from carbonaceous chondrites. This may indicate that most CAIs formed in a restricted region of the solar nebula and were then unevenly distributed throughout the various chondrite accretion regions. The Semarkona CAI is isotopically homogeneous and contains highly 16O-enriched melilite, supporting the hypothesis that all CAI minerals were originally 16O-rich, but that in most carbonaceous chondrite inclusions some minerals exchanged oxygen isotopes with an external reservoir following crystallization.

  2. Application of carbon and oxygen stable isotopes to the study of Brazilian precambrian

    Torquato, J.R.F.


    Samples of carbonated rocks of precambrian age are studied. The stable carbon and oxygen isotopes are applied to the study of terrestrial materials considering the variations of some element isotopic composition in function of the environment of sedimentation. The isotopic analysis was done using mass spectrometers. The analytical results and the description of region geology of the site of each sample are presented. The isotopic data are interpreted aiming to the environment of sedimentation. New techniques for better improvement of carbon and oxygen ratios, are proposed, such as: to use the analysis of surface trend and the isotopic logging in mapping of surface and subsurface. A new method for approximated determination of the ages of precambrian carbonated rocks, considering the limitations of their new technique, is also presented. (M.C.K.) [pt

  3. Simultaneous determination of stable carbon, oxygen, and hydrogen isotopes in cellulose.

    Loader, N J; Street-Perrott, F A; Daley, T J; Hughes, P D M; Kimak, A; Levanič, T; Mallon, G; Mauquoy, D; Robertson, I; Roland, T P; van Bellen, S; Ziehmer, M M; Leuenberger, M


    A technological development is described through which the stable carbon-, oxygen-, and nonexchangeable hydrogen-isotopic ratios (δ(13)C, δ(18)O, δ(2)H) are determined on a single carbohydrate (cellulose) sample with precision equivalent to conventional techniques (δ(13)C 0.15‰, δ(18)O 0.30‰, δ(2)H 3.0‰). This triple-isotope approach offers significant new research opportunities, most notably in physiology and medicine, isotope biogeochemistry, forensic science, and palaeoclimatology, when isotopic analysis of a common sample is desirable or when sample material is limited.

  4. Oxygen and hydrogen isotope studies of plutonic granitic rocks

    Taylor, H.P. Jr.


    The primary deltaD values of the biotites and hornblendes in granitic batholiths are remarkably constant at about -50 to -85, identical to the values in regional metamorphic rocks, marine sediments and greenstones, and most weathering products in temperate climates. Therefore the primary water in these igneous rocks is probably not 'juvenile', but is ultimately derived by dehydration and/or partial melting of the lower crust or subducted lithosphere. Most granitic rocks have delta 18 O = +7.0 to +10.0, probably indicating significant involvment of high- 18 O metasedimentary or altered volcanic rocks in the melting process; such an origin is demanded for many other granodiorites and tonalites that have delta 18 O = +10 to +13. Gigantic meteoric-hydrothermal convective circulation systems were established in the epizonal portions of all batholiths, locally producing very low delta 18 O values (particularly in feldspars) during subsolidus exchange. Some granitic plutons in such environments also were emplaced as low- 18 O magmas probably formed by melting or assimilation of hydrothermally altered roof rocks. However, the water/rock ratios were typically low enough that over wide areas the only evidence for meteoric water exchange in the batholiths is given by low D/H ratios (deltaK as low as -180); for example, because of latitudinal isotopic variations in meteoric waters, as one moves north through the Cordilleran batholiths of western North America an increasingly higher proportion of the granitic rocks have deltaD values lower than -120. The lowering of deltaD values commonly corelates with re-setting of K-Ar ages. (Auth.)

  5. Stable carbon and oxygen isotope study on benthic foraminifera ...

    Ajoy K Bhaumik


    Jul 24, 2017 ... of a species for isotopic analysis has forced us to select multiple species from down-core samples. Thus ... microhabitat, climatic variability, bottom and pore ...... Trends, rhythms, and aberrations in global climate 65 Ma.

  6. Isotopic-spectral determination of hydrogen, nitrogen, oxygen and carbon in semiconductor materials

    Dudich, G.K.; Eremeev, V.A.; Li, V.N.; Nemets, V.M.


    Techniques of low-temperature isotopic-spectral determination of impurities of hydrogen, nitrogen, oxygen and carbon in semiconductor materials Bi, Ge, Pb tellurides are developed. The techniques include selection into special vessel with the known volume (exchanger) of sample analyzed, dosed introduction into exchanger of rare isotope of the element determined ( 2 H, 15 N, 18 O, 13 C) in the form of isotope-containing gas, balancing of the determined element isotopes in the system sample-isotope, containing gas, spectroscopic, determination of its isotope composition in gaseous phase of the system and calculation of the amount of the element determined in the sample. The lower boundaries of the amounts determined constitute 10 -7 , 10 -7 , 10 -6 and 10 -5 mass % respectively when sample of 20 g are used [ru

  7. The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

    von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel


    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

  8. Oxygen isotope exchange rate between dissolved sulfate and water at hydrothermal temperatures

    Chiba, H.; Sakai, H.


    Oxygen isotope exchange rate between dissolved sulfate and water was experimentally determined at 100, 200 and 300 deg C. The isotope exchange rate is strongly dependent on temperature and pH of the solution. Combining the temperature and pH dependence of the reaction rate, the exchange reaction was estimated to be first-order with respect to sulfate. The logarithm of apparent rate constant of exchange reaction at a given temperature is a function of the pH calculated at the experimental temperatures. From the pH dependence of the apparent rate constant, it was deduced that the isotope exchange reaction between dissolved sulfate and water proceeds through collision between H 2 SO 4 0 and H 2 O at low pH, and between HSO 4 - and H 2 O at intermediate pH. The isotope exchange rate obtained indicates that oxygen isotope geothermometry utilizing the studied isotope exchange is suitable for temperature estimation of geothermal reservoirs. The extrapolated half-life of this reaction to oceanic temperature is about 10 9 years, implying that exchange between oceanic sulfate and water cannot control the oxygen isotope ratio of oceanic sulfates. (author)

  9. Oxygen isotope study of the Long Valley magma system, California: isotope thermometry and convection in large silicic magma bodies

    Bindeman, Ilya; Valley, John


    Products of voluminous pyroclastic eruptions with eruptive draw-down of several kilometers provide a snap-shot view of batholith-scale magma chambers, and quench pre-eruptive isotopic fractionations (i.e., temperatures) between minerals. We report analyses of oxygen isotope ratio in individual quartz phenocrysts and concentrates of magnetite, pyroxene, and zircon from individual pumice clasts of ignimbrite and fall units of caldera-forming 0.76 Ma Bishop Tuff (BT), pre-caldera Glass Mountain (2.1-0.78 Ma), and post-caldera rhyolites (0.65-0.04 Ma) to characterize the long-lived, batholith-scale magma chamber beneath Long Valley Caldera in California. Values of δ18O show a subtle 1‰ decrease from the oldest Glass Mountain lavas to the youngest post-caldera rhyolites. Older Glass Mountain lavas exhibit larger ( 1‰) variability of δ18O(quartz). The youngest domes of Glass Mountain are similar to BT in δ18O(quartz) values and reflect convective homogenization during formation of BT magma chamber surrounded by extremely heterogeneous country rocks (ranging from 2 to +29‰). Oxygen isotope thermometry of BT confirms a temperature gradient between "Late" (815 °C) and "Early" (715 °C) BT. The δ18O(quartz) values of "Early" and "Late" BT are +8.33 and 8.21‰, consistent with a constant δ18O(melt)=7.8+/-0.1‰ and 100 °C temperature difference. Zircon-melt saturation equilibria gives a similar temperature range. Values of δ18O(quartz) for different stratigraphic units of BT, and in pumice clasts ranging in pre-eruptive depths from 6 to 11 km (based on melt inclusions), and document vertical and lateral homogeneity of δ18O(melt). Worldwide, five other large-volume rhyolites, Lava Creek, Lower Bandelier, Fish Canyon, Cerro Galan, and Toba, exhibit equal δ18O(melt) values of earlier and later erupted portions in each of the these climactic caldera-forming eruptions. We interpret the large-scale δ18O homogeneity of BT and other large magma chambers as evidence

  10. Hydrogen and oxygen isotope ratios of geothermal waters in the southern hachimantai area

    Matsubaya, Osamu; Etchu, Hiroshi; Takenaka, Teruo; Yoshida, Yutaka.


    Geothermal waters from the Matsukawa and Kakkonda Geothermal Plants, wells at Amihari-Motoyu, and Nyuto and Tazawako areas were isotopically studied. The geothermal waters from Mutsukawa, Kakkonda and Amihari-Motoyu have hydrogen isotope ratios similar to the local meteoric waters, while have higher oxygen isotope ratios than the local meteoric waters. This relationship of hydrogen and oxygen isotope ratios, that is called ''oxygen shift'', means that these geothermal waters are meteoric waters undergone the oxygen isotope exchange with rocks at high temperature of underground. The exygen shifts are 2 -- 3 per mil in Matsukawa and Kakkonda, and 7 per mil in Amihari-Motoyu. This difference may be important to understand the processe of water-rock interaction in this area. The geothermal waters at Nyuto and Tazawako areas also show 2 -- 3 per mil oxygen shift. The steam from the Tazawako-cho well and the hot spring water form the Tsurunoyu are estimated to be vapor and liquid phases separated form a single geothermal water of NaCl type, though the hot water from the Tsurunoyu is diluted with shallow meteoric water. (author)

  11. Oxygen isotopic composition of mammal bones as a new tool for studying ratios of paleoenvironmental water and paleoclimates

    Longinelli, A.


    The purpose of this study is to try to establish quantitative relationships between the average oxygen isotopic composition of local meteoric water, the oxygen isotopic composition of mammal body water and the oxygen isotopic composition of phosphate in mammal bones. These relationships, after calibration of the method on living specimens, would allow quantitative paleoclimatological research based on the measurement of delta 18 O(PO 4 3- ) of fossil mammal bones

  12. The Largs high-latitude oxygen isotope anomaly (New Zealand) and climatic controls of oxygen isotopes in magma

    Blattner, P.; Williams, J.G.


    In northern Fiordland the Brook Street terrane of New Zealand consists of two units - the predominantly basaltic Plato and the predominantly andesitic Largs terrane. The Permian Plato terrane has normal to slightly enriched δ 18 O values, whereas the Largs terrane, which is of similar pre-early Triassic age, has not yielded a single normal δ 18 O SMOW result, with all of 17 total rocks showing less than 3.2per mille, seven less than -4per mille, and two less than -9per mille. These strongly anomalous data confirm an earlier suggested terrestrial character of Largs deposition, and demand the presence of Permo-Triassic geothermal systems running on subAntarctic to Antarctic meteoric water. The skewed data spectrum suggests a relatively immature flow system and likely values for the recharge water are -20per mille δ 18 O or less. For a climate distribution similar to the present one, inlcuding polar ice caps, this would indicate over 70deg of southern latitude. Rafts and xenoliths of Largs rocks have been entrained within Mackay Intrusives in the early Triassic. On field evidence the Mackay magmas have also intruded an early Darran Complex, but this complex has been substantially reactivated in the Cretaceous. It has δ 18 O values near 5.0per mille, which is distinctly low for island arc magmas. Since the complex is isotopically homogenous, its δ 18 O is unlikely to be a direct effect of the relatively shallow Largs terrane. More probable is a climate related slight depression of the δ 18 O of magma sources, in which other high-latitude, low-δ 18 O sediments and geothermal systems have been involved. (orig.)

  13. Could a secular increase in organic burial explain the rise of oxygen? Insights from a geological carbon cycle model constrained by the carbon isotope record

    Krissansen-Totton, J.; Kipp, M.; Catling, D. C.


    The stable isotopes of carbon in marine sedimentary rock provide a window into the evolution of the Earth system. Conventionally, a relatively constant carbon isotope ratio in marine sedimentary rocks has been interpreted as implying constant organic carbon burial relative to total carbon burial. Because organic carbon burial corresponds to net oxygen production from photosynthesis, it follows that secular changes in the oxygen source flux cannot explain the dramatic rise of oxygen over Earth history. Instead, secular declines in oxygen sink fluxes are often invoked as causes for the rise of oxygen. However, constant fractional organic burial is difficult to reconcile with tentative evidence for low phosphate concentrations in the Archean ocean, which would imply lower marine productivity and—all else being equal—less organic carbon burial than today. The conventional interpretation of the carbon isotope record rests on the untested assumption that the isotopic ratio of carbon inputs into the ocean reflect mantle isotopic values throughout Earth history. In practice, differing rates of carbonate and organic weathering will allow for changes in isotopic inputs, as suggested by [1] and [2]. However, these inputs can not vary freely because large changes in isotopic inputs would induce secular trends in carbon reservoirs, which are not observed in the isotope record. We apply a geological carbon cycle model to all Earth history, tracking carbon isotopes in crustal, mantle, and ocean reservoirs. Our model is constrained by the carbon isotope record such that we can determine the extent to which large changes in organic burial are permitted. We find both constant organic burial and 3-5 fold increases in organic burial since 4.0 Ga can be reconciled with the carbon isotope record. Changes in the oxygen source flux thus need to be reconsidered as a possible contributor to Earth's oxygenation. [1] L. A. Derry, Organic carbon cycling and the lithosphere, in Treatise on

  14. Biological fractionation of oxygen and carbon isotopes by recent benthic foraminifera

    Woodruff, F.; Douglas, R.G.


    Recent deep-sea benthic foraminifera from five East Pacific Rise box core tops have been analyzed for oxygen and carbon isotopic composition. The five equatorial stations, with water depths of between 3200 and 4600 m, yielded fourteen specific and generic taxonomic groups. Of the taxa analyzed, Uvigerina spp. most closely approaches oxygen isotopic equilibrium with ambient sea water. Pyrgo spp. was next closest to isotopic equilibrium, being on the average 0.59 per thousand depleted in 18 O relative to Uvigerina spp. Oridorsalis umbonatus also has relatively high delta 18 O values. Most other taxa were depleted in 18 O by large amounts. In no taxa was the carbon in the CaCO 3 secreted in carbon isotopic equilibrium with the dissolved HCO 3 - of ambient sea water. (Auth.)

  15. Modelling and Mapping Oxygen-18 Isotope Composition of Precipitation in Spain for Hydrologic and Climatic Applications

    Rodriguez-Arevalo, J.; Diaz-Teijeiro, M. F. [Centro de Estudios y Experimentacion de Obras Publicas (CEDEX), Madrid (Spain); Castano, S. [Geological Survey of Spain (IGME), Madrid (Spain)


    A simple multiple regression model based on two geographic factors (latitude and elevation) has been developed that reproduces reasonably well the spatial distribution of the current mean oxygen-18 isotope composition in precipitation over spain. In a preliminary analysis, additional geographic and climatic factors do not improve the performance of the model. A continuous digital map of oxygen-18 isotope composition in precipitation has been produced by combining the polynomial model with a digital elevation model using GIS tools. Application of the resulting map to several groundwater case studies in spain has shown it to be useful as a reference of the input function to recharge. Further validation of the model, and further testing of its usefulness in surface hydrology and climatic studies, is ongoing through comparison of model results with isotope data from the GNIP database and from isotope studies in hydrogeology and climate change taking place in spain. (author)

  16. Oxygen isotopic signature of CO2 from combustion processes

    Schumacher, M.; Werner, R. A.; Meijer, H. A. J.; Brand, W. A.; Geilmann, H.; Neubert, R. E. M.; Kaiser, J.; Jansen, Henk G.


    For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (C-13 and O-18) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the delta O-18

  17. Laser Spectroscopic Analysis of Liquid Water Samples for Stable Hydrogen and Oxygen Isotopes


    Stable isotope ratios of hydrogen and oxygen are tracers of choice for water cycle processes in hydrological, atmospheric and ecological studies. The use of isotopes has been limited to some extent because of the relatively high cost of isotope ratio mass spectrometers and the need for specialized operational skills. Here, the results of performance testing of a recently developed laser spectroscopic instrument for measuring stable hydrogen and oxygen isotope ratios of water samples are described, along with a procedure for instrument installation and operation. Over the last four years, the IAEA Water Resources Programme conducted prototype and production model testing of these instruments and this publication is the outcome of those efforts. One of the main missions of the IAEA is to promote the use of peaceful applications of isotope and nuclear methods in Member States and this publication is intended to facilitate the use of laser absorption based instruments for hydrogen and oxygen stable isotope analyses of liquid water samples for hydrological and other studies. The instrument uses off-axis integrated cavity output spectroscopy to measure absolute abundances of 2 HHO, HH 18 O, and HHO via laser absorption. Test results using a number of natural and synthetic water standards and samples with a large range of isotope values demonstrate adequate precision and accuracy (e.g. precisions of 1 per mille for δ 2 H and 0.2 per mille for δ 18 O). The laser instrument has much lower initial and maintenance costs than mass spectrometers and is substantially easier to operate. Thus, these instruments have the potential to bring about a paradigm shift in isotope applications by enabling researchers in all fields to measure isotope ratios by themselves. The appendix contains a detailed procedure for the installation and operation of the instrument. Using the procedure, new users should be able to install the instrument in less than two hours. It also provides step

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

    Helliker, B.


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

  19. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

    Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.


    MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

  20. Isotopes of carbon and oxygen in the carbonate impurities of coal have potential as palaeoenvironmental indicators

    Verhagen, B.T.; Falcon, R.M.


    The nature and systematics of impurities such as carbonates need to be established in order to understand their provenance in coal seams with reference to mining, beneficiation and ultimately their elimination or reduction. To this end, mineralogical and carbon-13 and oxygen-18 isotopic studies were undertaken on carbonate occurrences in coal from the eastern Transvaal highveld. Isotopic variations of considerable amplitude and individual values of extreme ''lightness'' are to be found in the carbonates in coal of the Witbank and adjacent basins. The observed isotopic ratios have a clear bearing on the nature and origins of the carbonates. 1 tab., 1 fig

  1. 99 Tc NMR determination of the oxygen isotope content in 18 O-enriched water.

    Tarasov, Valerii P; Kirakosyan, Gayana А; German, Konstantin E


    99 Tc NMR has been suggested as an original method of evaluating the content of oxygen isotopes in oxygen-18-enriched water, a precursor for the production of radioisotope fluorine-18 used in positron emission tomography. To this end, solutions of NH 4 TcO 4 or NaTcO 4 (up to 0.28 mol/L) with natural abundance of oxygen isotopes in virgin or recycled 18 O-enriched water have been studied by 99 Tc NMR. The method is based on 16 O/ 17 O/ 18 O intrinsic isotope effects in the 99 Tc NMR chemical shifts, and the statistical distribution of oxygen isotopes in the coordination sphere of TcO 4 - and makes it possible to quantify the composition of enriched water by measuring the relative intensities of the 99 Tc NMR signals of the Tc 16 O 4-n 18 O n - isotopologues. Because the oxygen exchange between TcO 4 - and enriched water in neutral and alkaline solutions is characterized by slow kinetics, gaseous HCl was bubbled through a solution for a few seconds to achieve the equilibrium distribution of oxygen isotopes in the Tc coordination sphere without distortion of the oxygen composition of the water. Pertechnetate ion was selected as a probe due to its high stability in solutions and the significant 99 Tc NMR shift induced by a single 16 O→ 18 O substitution (-0.43 ± 0.01 ppm) in TcO 4 - and spin coupling constant 1 J( 99 Tc- 17 O) (131.46 Hz) favourable for the observation of individual signals of Tc 16 O 4-n 18 O n - isotopologues. Copyright © 2017 John Wiley & Sons, Ltd.

  2. Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

    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.

  3. Evidence of chromaffin oxygen sensing in neuroblastoma.

    Hedborg, F; Franklin, G; Norrman, J; Grimelius, L; Wassberg, E; Hero, B; Schilling, F; Berthold, F; Harms, D; Sandstedt, B


    With the aid of IGF2 and VEGF in situ hybridization; tyrosine hydroxylase, chromogranin A, and Ki67 immunohistochemistry; and TUNEL staining applied to a large series of clinical neuroblastomas and to an animal model, we show here that stroma-poor neuroblastomas show evidence of chromaffin differentiation similar to that of type 1 small intensely fluorescent (SIF) cells and that this occurs in a vascular-dependent fashion, indicating a role for local tumor hypoxia in the differentiation process.

  4. Analytical techniques for determination of framework oxygen isotope ratio of wairakite

    Noto, Masami; Kusakabe, Minoru; Uchida, Tetsuo.


    Dehydration techniques were developed for the analysis of isotopic ratios of framework oxygen of wairakite, one of calcium zeolites often encountered in geothermal systems. Channel water in wairakite were separated from aluminosilicate framework by dehydration in vacuum at 300 deg, 400 deg, 450 deg, 500 deg, 550 deg, 650 deg, 750 deg, 850 deg, and 950 degC, and by stepwise heating at temperatures from 300 deg to 700 degC. The oxygen isotopic analyses of the separated channel water and the residual aluminosilicate framework of wairakite indicated that dehydration at temperatures higher than 400 degC is accompanied by isotopic exchang between the framework oxygen and dehydrating water vapor. The isotopic exchange during the high temperature dehydration makes the δ 18 O of framework oxygen lower and that of channel water higher than those obtained by dehydration at 300 degC. These results are consistent with dehydration behavior of wairakite under vacuum that the maximum rate of dehydration of channel water is attained at about 400 degC. Consequently it is recommended to dehydrate wairakite at a temperature as low as possible in order to avoid the effect of the isotopic exchange. Time required to attain complete dehydration becomes longer with lowering the temperature of dehydration. To compromise these conflicting effects, the optimum conditions of dehydration have been found that most of the channel water is dehydrated at 300 degC for 24 hours, followed by stepwise heating for additional 17 hours up to 700 degC. We obtained a better than ± 0.1 reproducibility for the framework oxygen isotopic determinations with this technique. (author)

  5. Oxygen isotopic fractionation of O₂ during adsorption and desorption processes using molecular sieve at low temperatures.

    Ahn, Insu; Kusakabe, Minoru; Lee, Jong Ik


    Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in

  6. Isotopic evidence for the past climates and vegetation of southern Africa

    J. C. Vogel


    Full Text Available The stable isotopes of hydrogen, oxygen and carbon can potentially provide evidence of past climates. The most detailed information has been obtained from variations in the oxygen-18 content of foraminifera from ocean floor cores, the analysis of which has produced a record of ocean temperature changes through the Quaternary and beyond. The use of isotope analysis of continental materials to reveal climatic change is more limited, but some advances have been made in recent years. One approach has been to utilize the variations in the isotopic composition of precipitation as recorded in ancient groundwater. Thus groundwater samples from a confined aquifer on the southern Cape coast show a marked rise in temperature since the Last Glacial maximum. The temperature changes during the Upper Pleistocene and Holocene are also reflected in the oxygen-18 content of stalagmites from the Cango caves in the same region. The widespread occurrence of C4 grasses in the warmer summer rainfall areas of southern Africa provides a novel possibility of observing temporal shifts of climatic boundaries. The distinctly high carbon-13 content of C4 plants is clearly reflected in the skeletons of grazers so that faunal material from suitably situated archaeological sites can be used to observe changes in the composition of the local grass-cover. The evidence thus far accumulated suggests only minor changes since the Upper Pleistocene. The combined evidence to date indicates that temperatures and also precipitation in southern Africa have changed since the Last Glacial maximum, about 18 000 years ago, but that shifts in the boundaries of the various veld-types were probably not very extensive.

  7. Paleoclimatic reconstruction in the Bolivian Andes from oxygen isotope analysis of lake sediment cellulose

    Wolfe, B.B.; Aravena, R.; Gibson, J.J.; Abbott, M.B.; Seltzer, G.O.


    Cellulose-inferred lake water δ 18 O (δ 18 O lw ) records from Lago Potosi, a seasonally-closed lake in a watershed that is not currently glaciated, and Lago Taypi Chaka Kkota, an overflowing lake in a glaciated watershed, provide the basis for late Pleistocene and Holocene paleoclimatic reconstruction in the Bolivian Andes. Deconvolution of the histories of changing evaporative isotopic enrichment from source water δ 18 O in the lake sediment records is constrained by comparison to the Sajama ice core oxygen isotope profile. At Lago Potosi, the δ 18 O lw record appears to be dominantly controlled by evaporative 18 O-enrichment, reflecting shifts in local effective moisture. Using an isotope-mass balance model, a preliminary quantitative reconstruction of summer relative humidity spanning the past 11,500 cal yr is derived from the Lago Potosi Π 18 O lw record. Results indicate that the late Pleistocene was moist with summer relative humidity values estimated at 10-20% greater than present. Increasing aridity developed in the early Holocene with maximum prolonged dryness spanning 7500 to 6000 cal yr BP at Lago Potosi, an interval characterized by summer relative humidity values that may have been 20% lower than present. Highly variable but dominantly arid conditions persist in the mid- to late Holocene, with average summer relative humidity values estimated at 15% below present, which then increase to about 10-20% greater than present by 2000 cal yr BP. Slightly more arid conditions characterize the last millennium with summer relative humidity values ranging from 5-10% lower than present. Similar long-term variations are evident in the Lago Taypi Chaka Kkota δ 18 O lw profile, except during the early Holocene when lake water evaporative 18 Oenrichment in response to low relative humidity appears to have been offset by enhanced inflow from 18 O-depleted snowmelt or groundwater from the large catchment. Close correspondence occurs between the isotope

  8. Preparation and use of nitrogen (2) oxide of special purity for production of oxygen and nitrogen isotopes

    Polevoj, A.S.


    Problems related with production of oxygen and nitrogen isotopes by means of low-temperature rectification of nitrogen (2) oxide are analyzed. Special attention, in particular, is payed to the techniques of synthesis and high purification of initial NO, utilization of waste flows formed during isotope separation. Ways to affect the initial isotope composition of nitrogen oxide and the rate of its homogeneous-isotope exchange, which provide for possibility of simultaneous production of oxygen and nitrogen isotopes by means of NO rectification, are considered. Description of a new technique for high purification of nitrogen oxide, prepared at decomposition of nitric acid by sulfurous anhydride, suggested by the author is presented

  9. Oxygen and hydrogen isotope ratios in tree rings: how well do models predict observed values?

    Waterhouse, JS


    Full Text Available . Cosmo- chim. Acta 46 (1982) 955^965. [35] W.M. Buhay, T.W.D. Edwards, Climate in southwestern Ontario, Canada, between AD 1610 and 1885 inferred from oxygen and hydrogen isotopic measurements of wood cellulose from trees in di?erent hydrological set...

  10. Estimating of gas transfer velocity using triple isotopes of dissolved oxygen.

    Sarma, V.V.S.S.; Abe, O.; Honda, M.; Saino, T.

    variations in oxygen isotopes are found to be higher than the direct estimations at low wind speed (<5 m s sup(-1)) and lower at high wind speeds (>13 m s sup(-1)) and showed significant spatial variability. The method presented here can be used to derive...

  11. A Quantitative, Time-Dependent Model of Oxygen Isotopes in the Solar Nebula: Step one

    Nuth, J. A.; Paquette, J. A.; Farquhar, A.; Johnson, N. M.


    The remarkable discovery that oxygen isotopes in primitive meteorites were fractionated along a line of slope I rather than along the typical slope 0,52 terrestrial fractionation line occurred almost 40 years ago, However, a satisfactory, quantitative explanation for this observation has yet to be found, though many different explanations have been proposed, The first of these explanations proposed that the observed line represented the final product produced by mixing molecular cloud dust with a nucleosynthetic component, rich in O-16, possibly resulting from a nearby supernova explosion, Donald Clayton suggested that Galactic Chemical Evolution would gradually change the oxygen isotopic composition of the interstellar grain population by steadily producing O-16 in supernovae, then producing the heavier isotopes as secondary products in lower mass stars, Thiemens and collaborators proposed a chemical mechanism that relied on the availability of additional active rotational and vibrational states in otherwise-symmetric molecules, such as CO2, O3 or SiO2, containing two different oxygen isotopes and a second, photochemical process that suggested that differential photochemical dissociation processes could fractionate oxygen , This second line of research has been pursued by several groups, though none of the current models is quantitative,

  12. A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee, Switzerland

    Teranes, J.L.; McKenzie, J.A.; Bernasconi, S.M.; Lotter, A.F.; Sturm, M.


    Abstract—In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in

  13. Oxygen and carbon isotope analyses of a Late Quaternary core in the Zaire (Congo) fan

    Olausson, E.


    Oxygen and carbon isotope analyses have been carried out on samples from a core of the Angola Basin (6 0 50'S, 10 0 45'E, depth 2100 m). The pelagic foraminifer Globigerinoides ruber, a species with a shallow water habitat, and two benthic species Uvigerina peregrina and Bulimina aculeata have been analysed. The data are given relative to PDB. (Auth.)

  14. Measurement of infiltration rates in urban sewer systems by use of oxygen isotopes.

    De Bénédittis, J; Bertrand-Krajewski, J L


    The paper presents the principle of a method to measure infiltration rates in sewer systems based on the use of oxygen isotopes and its application in Lyon (France). In the urban area of Lyon, significant differences in delta 18O that can reach 3 per thousand are observed between the oxygen isotopic compositions of groundwater originating from Rhone, Saone and from their associated alluvial aquifers. Drinking water supplying Lyon results mainly from pumping in the Rhone alluvial aquifer. Therefore, in some areas, the difference of isotopic composition between wastewater resulting from the consumption of drinking water and local groundwater can be used to measure infiltration in sewer systems. The application in the catchment of Ecully shows that the infiltration flow rate presents strong fluctuations at an hourly scale: it varies between 15 and 40 m3/h. This variability could be explained by non-constant discharges of pumping and by variations of the water level in the sewer.

  15. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream.

    Nishizawa, Manabu; Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken


    Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of

  16. Intracrystalline oxygen isotope effects in CuSO4.5H2O and their dependence on crystallization temperature

    Heinzinger, K.


    In copper sulphate pentahydrate the water molecules occupy three different sites, connected with different oxygen isotope ratios. Results of measurements of the change of these isotope ratios with crystallization temperature are reported. The temperature dependence found here provides the basis for the determination of crystallization temperatures of hydrated crystals from such intracrystalline oxygen isotope fractionation. Suppositions necessary for the application of this method are discussed. (author)

  17. Age and isotope evidence for the evolution of continental crust

    Moorbath, S.


    Irreversible chemical differentiation of the mantle's essentially infinite reservoir for at least the past 3800 Ma has produced new continental, sialic crust during several relatively short (ca. 100-300 Ma) episodes which were widely separated in time and may have been of global extent. During each episode (termed 'accretion-differentiation superevent'), juvenile sial underwent profound igneous, metamorphic and geochemical differentiation, resulting in thick (ca. 25-40 km), stable, compositionally gradational, largely indestructible, continental crust exhibiting close grouping of isotopic ages of rock formation, as well as mantle-type initial Sr and Pb isotopic ratios for all major constituents. Isotopic evidence suggests that within most accretion-differentiation superevents - and especially during the earlier ones - continental growth predominated over reworking of older sialic crust. Reworking of older sialic crust can occur in several types of geological environment and appears to have become more prevalent with the passage of geological time. It is usually clearly distinguishable from continental growth, by application of appropriate age and isotope data. (author)

  18. Ion Microprobe Measurements of Comet Dust and Implications for Models of Oxygen Isotope Heterogeneity in the Solar System

    Snead, C. J.; McKeegan, K. D.; Keller, L. P.; Messenger, S.


    The oxygen isotopic compositions of anhydrous minerals in carbonaceous chondrites reflect mixing between a O-16-rich and O-17, O18-rich reservoir. The UV photodissociation of CO (i.e. selfshielding) has been proposed as a mass-independent mechanism for producing these isotopically distinct reservoirs. Self-shielding models predict the composition for the CO gas reservoir to be O-16-rich, and that the accreting primordial dust was in isotopic equilibrium with the gaseous reservoir [1, 2]. Self-shielding also predicts that cometary water, presumed to represent the O-17, O-18-rich reservoir, should be enriched in O-17 and O-18, with compositions of 200 -1000per mille, and that the interaction with this O-17, O-18-rich H2O reservoir altered the compositions of the primordial dust toward planetary values. The bulk composition of the solar nebula, which may be an approximation to the 16O-rich gaseous reservoir, has been constrained by the Genesis results [3]. However, material representing the O-17, O-18-rich end-member is rare [4], and dust representing the original accreting primordial dust has been challenging to conclusively identify in current collections. Anhydrous dust from comets, which accreted in the distal cold regions of the nebula at temperatures below approximately 30K, may provide the best opportunity to measure the oxygen isotope composition of primordial dust. Chondritic porous interplanetary dust particles (CP-IDPs) have been suggested as having cometary origins [5]; however, until direct comparisons with dust from a known comet parent body were made, link between CP-IDPs and comets remained circumstantial. Oxygen isotope analyses of particles from comet 81P/Wild 2 collected by NASA's Stardust mission have revealed surprising similarities to minerals in carbonaceous chondrites which have been interpreted as evidence for large scale radial migration of dust components from the inner solar nebula to the accretion regions of Jupiter- family comets [6

  19. Controls of oxygen isotope ratios of nitrate formed during nitrification in soils

    Mayer, B.; Bollwerk, S.M.; Vorhoff, B.; Mansfeldt, T.; Veizer, J.


    The isotopic composition of nitrate is increasingly used to determine sources and transformations of nitrogen in terrestrial and aquatic ecosystems. Oxygen isotope ratios of nitrate appear to be particularly useful, since they allow the differentiation between nitrate from atmospheric deposition (δ 18 O nitrate between +25 and +70 per mille), nitrate from fertilizers (δ 18 O nitrate +23 per mille), and nitrate derived from nitrification processes in soils (δ 18 O nitrate 3 molecule derive from H 2 O (with negative δ 18 O values dependent upon location) and one oxygen derives from atmospheric O 2 (δ 18 O = +23.5 per mille).. The objective of this study was to experimentally determine the extent to which water oxygen controls the δ 18 O value of nitrate, which is formed during nitrification in soils

  20. Oxygen isotope exchange in La2NiO(4±δ).

    Ananyev, M V; Tropin, E S; Eremin, V A; Farlenkov, A S; Smirnov, A S; Kolchugin, A A; Porotnikova, N M; Khodimchuk, A V; Berenov, A V; Kurumchin, E Kh


    Oxygen surface exchange kinetics and diffusion have been studied by the isotope exchange method with gas phase equilibration using a static circulation experimental rig in the temperature range of 600-800 °C and oxygen pressure range of 0.13-2.5 kPa. A novel model which takes into account distributions of the dissociative adsorption and incorporation rates has been developed. The rates of the elementary stages have been calculated. The rate-determining stages for a La2NiO(4±δ) polycrystalline specimen have been discussed. The diffusion activation energies calculated using the gas phase equilibration method (1.4 eV) differ significantly from those calculated using isotope exchange depth profiling (0.5-0.8 eV), which was attributed to the influence of different oxygen diffusion pathways.

  1. The molecular physics of photolytic fractionation of sulfur and oxygen isotopes in planetary atmospheres (Invited)

    Johnson, M. S.; Schmidt, J. A.; Hattori, S.; Danielache, S.; Meusinger, C.; Schinke, R.; Ueno, Y.; Nanbu, S.; Kjaergaard, H. G.; Yoshida, N.


    Atmospheric photochemistry is able to produce large mass independent anomalies in atmospheric trace gases that can be found in geological and cryospheric records. This talk will present theoretical and experimental investigations of the molecular mechanisms producing photolytic fractionation of isotopes with special attention to sulfur and oxygen. The zero point vibrational energy (ZPE) shift and reflection principle theories are starting points for estimating isotopic fractionation, but these models ignore effects arising from isotope-dependent changes in couplings between surfaces, excited state dynamics, line densities and hot band populations. The isotope-dependent absorption spectra of the isotopologues of HCl, N2O, OCS, CO2 and SO2 have been examined in a series of papers and these results are compared with experiment and ZPE/reflection principle models. Isotopic fractionation in planetary atmospheres has many interesting applications. The UV absorption of CO2 is the basis of photochemistry in the CO2-rich atmospheres of the ancient Earth, and of Mars and Venus. For the first time we present accurate temperature and isotope dependent CO2 absorption cross sections with important implications for photolysis rates of SO2 and H2O, and the production of a mass independent anomaly in the Ox reservoir. Experimental and theoretical results for OCS have implications for the modern stratospheric sulfur budget. The absorption bands of SO2 are complex with rich structure producing isotopic fractionation in photolysis and photoexcitation.

  2. Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

    Valley, J.W.; O'Neil, J.R.


    The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO2-H2O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks. Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed. Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ??18O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences. The range of Adirondack carbonate ??18O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor 18O and 13C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their

  3. Nitrogen and oxygen isotopic constraints on the origin of atmospheric nitrate in coastal Antarctica

    J. Savarino


    Full Text Available Throughout the year 2001, aerosol samples were collected continuously for 10 to 15 days at the French Antarctic Station Dumont d'Urville (DDU (66°40' S, l40°0' E, 40 m above mean sea level. The nitrogen and oxygen isotopic ratios of particulate nitrate at DDU exhibit seasonal variations that are among the most extreme observed for nitrate on Earth. In association with concentration measurements, the isotope ratios delineate four distinct periods, broadly consistent with previous studies on Antarctic coastal areas. During austral autumn and early winter (March to mid-July, nitrate concentrations attain a minimum between 10 and 30 ng m−3 (referred to as Period 2. Two local maxima in August (55 ng m−3 and November/December (165 ng m−3 are used to assign Period 3 (mid-July to September and Period 4 (October to December. Period 1 (January to March is a transition period between the maximum concentration of Period 4 and the background concentration of Period 2. These seasonal changes are reflected in changes of the nitrogen and oxygen isotope ratios. During Period 2, which is characterized by background concentrations, the isotope ratios are in the range of previous measurements at mid-latitudes: δ18Ovsmow=(77.2±8.6‰; Δ17O=(29.8±4.4‰; δ15Nair=(−4.4±5.4‰ (mean ± one standard deviation. Period 3 is accompanied by a significant increase of the oxygen isotope ratios and a small increase of the nitrogen isotope ratio to δ18Ovsmow=(98.8±13.9‰; Δ17O=(38.8±4.7‰ and δ15Nair=(4.3±8.20‰. Period 4 is characterized by a minimum 15N/14N ratio, only matched by one prior study of Antarctic aerosols, and oxygen isotope ratios similar to Period 2: δ18Ovsmow=(77.2±7.7‰; Δ17O=(31.1±3.2‰; δ15Nair=(−32.7±8.4‰. Finally, during Period 1, isotope ratios reach minimum values for oxygen and intermediate values for nitrogen: δ18Ovsmow=63.2±2.5‰; Δ17O=24.0±1.1‰; δ15Nair=−17.9±4.0‰. Based on the measured

  4. Oxygen isotope fractionation and algal symbiosis in benthic foraminifera from the Gulf of Elat, Israel

    Buchardt, B.; Hansen, H.J.


    In order to investigate possible isotopic fractionations due to algal symbiosis the oxygen and carbon isotope compositions of shell carbonate from symbiont-free and symbiont-bearing benthic foraminifera have been compared to that of molluscs living at the same locality. The material was collected over a depth profile in the Gulf of Elat (Aqaba), Israel, covering the interval from 4 to 125 metres. After corrections variations for temperature with depth, characteristic 18 O-depletions were observed in the foraminiferal shell carbonate when compared to the molluscs. These depletions are interpreted as 1) a constant vital effect seen in all the foraminifera studied and 2) an additional, light-dependent vital effect observed in the symbiont-bearing forms only, caused by incorporation of photosynthetic oxygen formed by the symbiotic algae. This additional vital effect emphasizes the difficulties in applying foraminifera to oxygen isotope palaeotemperature analyses. No well-defined differences in carbon isotope compositions are observed between symbiont-bearing and symbiont-free foraminifera. (author)

  5. Oxygen isotope fractionation and algal symbiosis in benthic foraminifera from the Gulf of Elat, Israel

    Buchardt, B; Hansen, H J [Copenhagen Univ. (Denmark)


    In order to investigate possible isotopic fractionations due to algal symbiosis the oxygen and carbon isotope compositions of shell carbonate from symbiont-free and symbiont-bearing benthic foraminifera have been compared to that of molluscs living at the same locality. The material was collected over a depth profile in the Gulf of Elat (Aqaba), Israel, covering the interval from 4 to 125 metres. After correcting for variations of temperature with depth, characteristic /sup 18/O-depletions were observed in the foraminiferal shell carbonate when compared to the molluscs. These depletions are interpreted as 1) a constant vital effect seen in all the foraminifera studied and 2) an additional, light-dependent vital effect observed in the symbiont-bearing forms only, caused by incorporation of photosynthetic oxygen formed by the symbiotic algae. This additional vital effect emphasizes the difficulties in applying foraminifera to oxygen isotope palaeotemperature analyses. No well-defined differences in carbon isotope compositions are observed between symbiont-bearing and symbiont-free foraminifera.

  6. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

    Frierdich, Andrew J. [Univ. of Wisconsin, Madison, WI (United States); Univ. of Iowa, Iowa City, IA (United States); Beard, Brian L. [Univ. of Wisconsin, Madison, WI (United States); Rosso, Kevin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Scherer, Michelle M. [Univ. of Iowa, Iowa City, IA (United States); Spicuzza, Michael J. [Univ. of Wisconsin, Madison, WI (United States); Valley, John W. [Univ. of Wisconsin, Madison, WI (United States); Johnson, Clark M. [Univ. of Wisconsin, Madison, WI (United States)


    The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Fe isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II)aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II)aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II)aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous

  7. Modelling and Mapping Oxygen-18 Isotope Composition of Precipitation in Spain for Hydrologic and Climatic Applications

    Rodriguez-Arevalo, J.; Diaz-Teijeiro, M.F.; Castano, S.


    A simple multiple regression model based on two geographic factors (latitude and elevation) has been developed that reproduces reasonably well the spatial distribution of the current mean oxygen-18 isotope composition in precipitation over Spain. In a preliminary analysis, additional geographic and climatic factors do not improve the performance of the model. A continuous digital map of oxygen-18 isotope composition in precipitation has been produced by combining the polynomial model with a Digital Elevation Model using GIS tools. Application of the resulting map to several case studies in Spain has shown it to be useful as a reference of the isotope input function to groundwater recharge and surface runoff. The results obtained so far show a good fit between modelled stable isotope values and those measured in surface and ground waters from different aquifers and recharge areas. The GIS tools applied to a continuous digital layer of spatial isotope are able to provide accurate information at detailed scales that are not affordable by other means. Further validation of the model, and further testing of its usefulness in surface hydrology and climatic studies, is going on.

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

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


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

  9. Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites

    Jones, R. H.; Leshin, L. A.; Guan, Y.


    Some of the biggest challenges to understanding the early history of the solar system include determining the distribution of oxygen isotopes amongst materials that existed in the solar nebula, and interpreting the processes that might have resulted in the observed isotopic distributions. Oxygen isotope ratios in any individual mineral grain from a chondritic meteorite may be the cumulative product of a variety of processes, including stellar nucleosynthetic events, gas/solid interactions in the molecular cloud, mixing of independent isotopic reservoirs in the nebula, mass-independent processing in the nebula, and mass-dependent fractionation effects in various environments. It is not possible to unravel this complex isotopic record unless the distribution of oxygen isotope ratios in chondritic materials is fully understood.

  10. 18O isotopic tracer studies of silicon oxidation in dry oxygen

    Han, C.J.


    Oxidation of silicon in dry oxygen has been an important process in the integrated circuit industry for making gate insulators on metal-oxide-semiconductory (MOS) devices. This work examines this process using isotopic tracers of oxygen to determine the transport mechanisms of oxygen through silicon dioxide. Oxides were grown sequentially using mass-16 and mass-18 oxygen gas sources to label the oxygen molecules from each step. The resulting oxides are analyzed using secondary ion mass spectrometry (SIMS). The results of these analyses suggest two oxidant species are present during the oxidation, each diffuses and oxidizes separately during the process. A model from this finding using a sum of two linear-parabolic growth rates, each representing the growth rate from one of the oxidants, describes the reported oxidation kinetics in the literature closely. A fit of this relationship reveals excellent fits to the data for oxide thicknesses ranging from 30 A to 1 μm and for temperatures ranging from 800 to 1200 0 C. The mass-18 oxygen tracers also enable a direct observation of the oxygen solubility in the silicon dioxide during a dry oxidation process. The SIMS profiles establish a maximum solubility for interstitial oxygen at 1000 0 C at 2 x 10 20 cm -3 . Furthermore, the mass-18 oxygen profiles show negligible network diffusion during an 1000 0 C oxidation

  11. Oxygen isotope signature of UV degradation of glyphosate and phosphonoacetate: Tracing sources and cycling of phosphonates

    Sandy, Edward H. [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Department of Chemistry, University of Sierra Leone, Freetown (Sierra Leone); Blake, Ruth E., E-mail: [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Chang, Sae Jung [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Jun, Yao, E-mail: [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Yu, Chan [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China)


    Highlights: • Phosphonate (phon) hydrolysis by UVR (1.2 kW) attained ≥90% completion in 84 h. • Isotope study reveals both ambient H{sub 2}O and O{sub 2} involvements in phon C-P bond cleavage. • Mechanistic models proposed for phon C-P bond cleavage based on O-isotope analysis. • Model equations used to calculate δ{sup 18}O{sub P-org} of original phon P-moiety-useful as a tracer. • Study shows relevance in tracing phon sources and cycling in the environment. -- Abstract: The degradation of phosphonates in the natural environment constitutes a major route by which orthophosphate (Pi) is regenerated from organic phosphorus and recently implicated in marine methane production, with ramifications to environmental pollution issues and global climate change concerns. This work explores the application of stable oxygen isotope analysis in elucidating the C-P bond cleavage mechanism(s) of phosphonates by UV photo-oxidation and for tracing their sources in the environment. The two model phosphonates used, glyphosate and phosphonoacetic acid were effectively degraded after exposure to UV irradiation. The isotope results indicate the involvement of both ambient water and atmospheric oxygen in the C-P bond cleavage and generally consistent with previously posited mechanisms of UV-photon excitation reactions. A model developed to calculate the oxygen isotopic composition of the original phosphonate P-moiety, shows both synthetic phosphonates having distinctly lower values compared to naturally derived organophosphorus compounds. Such mechanistic models, based on O-isotope probing, are useful for tracing the sources and reactions of phosphonates in the environment.

  12. Stable oxygen and hydrogen isotopes of brines - comparing isotope ratio mass spectrometry and isotope ratio infrared spectroscopy

    Ahrens, Christian; Koeniger, Paul; van Geldern, Robert; Stadler, Susanne


    Today's standard analytical methods for high precision stable isotope analysis of fluids are gas-water equilibration and high temperature pyrolysis coupled to isotope ratio mass spectrometers (IRMS). In recent years, relatively new laser-based analytical instruments entered the market that are said to allow high isotope precision data on nearly every media. This optical technique is referred to as isotope ratio infrared spectroscopy (IRIS). The objective of this study is to evaluate the capability of this new instrument type for highly saline solutions and a comparison of the analytical results with traditional IRMS analysis. It has been shown for the equilibration method that the presence of salts influences the measured isotope values depending on the salt concentration (see Lécuyer et al, 2009; Martineau, 2012). This so-called 'isotope salt effect' depends on the salt type and salt concentration. These factors change the activity in the fluid and therefore shift the isotope ratios measured by the equilibration method. Consequently, correction factors have to be applied to these analytical data. Direct conversion techniques like pyrolysis or the new laser instruments allow the measurement of the water molecule from the sample directly and should therefore not suffer from the salt effect, i.e. no corrections of raw values are necessary. However, due to high salt concentrations this might cause technical problems with the analytical hardware and may require labor-intensive sample preparation (e.g. vacuum distillation). This study evaluates the salt isotope effect for the IRMS equilibration technique (Thermo Gasbench II coupled to Delta Plus XP) and the laser-based IRIS instruments with liquid injection (Picarro L2120-i). Synthetic salt solutions (NaCl, KCl, CaCl2, MgCl2, MgSO4, CaSO4) and natural brines collected from the Stassfurt Salt Anticline (Germany; Stadler et al., 2012) were analysed with both techniques. Salt concentrations ranged from seawater salinity

  13. Measurement of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen

    Wiedenbeck, M.E.; Greiner, D.E.; Bieser, F.S.; Crawford, H.J.; Heckman, H.H.; Lindstrom, P.J.


    The results of an investigation of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen (E approx. 80 to 230 MeV/amu) made using the U.C. Berkeley HKH instrument aboard the ISEE-3 spacecraft are reported. The combination of high mass resolution and a large statistical sample makes possible a precise determination of the relative isotopic abundances for these elements. In local interplanetary space we find: 13 C/C = 0.067 +- 0.008, 15 N/N = 0.54 +- 0.03, 17 O/O 18 O/O = 0.019 +- 0.003

  14. Water relations link carbon and oxygen isotope discrimination to phloem sap sugar concentration in eucalyptus globulus

    Cernusak, L.A.; Farquhar, G.D.; Arthur, D.J; Pate, J.S.


    Full text: The carbon isotope ratio of phloem sap sugars has been previously observed to correlate strongly with the phloem sap sugar concentration in Eucalyptus globulus. We hypothesized that the correspondence between these two parameters results from co-linearity in their responses to variation in plant water potential. Carbon isotope discrimination is expected to decrease with decreasing plant water potential due to the influence of stomatal conductance on the ratio of intercellular to ambient CO 2 , concentrations (c 1 /c a ). Conversely, we expected the phloem sap sugar concentration to increase with decreasing plant water potential, thereby maintaining positive turgor pressure within the sieve tubes. The study comprised 40 individual Eucalyptus globulus trees growing in three plantations situated on opposing ends of a rainfall gradient in southwestern Australia. A strong correlation was observed between the carbon isotope ratio in phloem sap sugars and phloem sap sugar concentration. Carbon isotope discrimination correlated positively with shoot water potential, whereas phloem sap sugar concentration correlated negatively with shoot water potential. The relationship between carbon isotope discrimination measured in phloem sap sugars collected from the stem and c 1 /c a measured instantaneously on subtending leaves was close to that theoretically predicted. Accordingly, a strong, negative relationship was observed between instantaneous c 1 /c a and the phloem sap sugar concentration. Oxygen isotope discrimination in phloem sap sugars also correlated strongly with phloem sap sugar concentration. A theoretical model suggested that the observed variation in stomatal conductance was sufficient to account for the variation observed in oxygen isotope discrimination across the study. Results strongly support the contention that water relations form a mechanistic link between phloem sap sugar concentration and both instantaneous and integrated measures of the

  15. Oxygen isotope fractionation in the CaCO3-DIC-H2O system

    Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.


    The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

  16. Oxygen isotope variability in snow from western Dronning Maud Land, Antarctica and its relation to temperature

    Helsen, M.M.; Wal, R.S.W. van de; Broeke, M.R. van den; As, D. van; Reijmer, C.H.; Meijer, H.A.J.


    This paper presents (delta) 18 O records from snow pits from four locations in Dronning Maud Land, Antarctica that contain at least four annual cycles. The aim of the study was to analyse in detail these records as well as the prevailing temperatures during accumulation in order to infer to what extent isotopic composition in this area can be interpreted as temperature information. The original seasonal amplitudes of the isotope records were reconstructed by use of a simple back-diffusion model. Automatic weather station data were used to describe the accumulation history and the near-surface temperatures; the temperatures at the atmospheric level of snow formation were inferred from a regional climate model. The results show that the strongly intermittent nature of the accumulation in this area can result in the exclusion of entire seasons from the isotope records. The temperature records also reveal that the oxygen isotope records in these snow pits are biased towards higher temperatures, since snowfall conditions are associated with higher temperatures. This effect is greatest at low temperatures. A comparison between the seasonal extreme isotopic and temperature values points out that on timescales of seasons to several years, isotopic variability cannot be interpreted with confidence as temperature changes at the accumulation sites

  17. Radiogenic isotope evidence for transatlantic atmospheric dust transport

    Kumar, Ashwini; Abouchami, Wafa; Garrison, Virginia H.; Galer, Stephen J. G.; Andreae, Meinrat O.


    Early studies by Prospero and colleagues [1] have shown that African dust reaches all across the Atlantic and into the Caribbean. It may contribute to fertilizing the Amazon rainforest [2,3,4], in addition to enhancing the ocean biological productivity via delivery of iron, a key nutrient element[5]. Radiogenic isotope ratios (Sr, Nd, Pb) are robust tracers of dust sources and can thus provide information on provenance and pathways of dust transport. Here we report Sr, Nd and Pb isotope data on atmospheric aerosols, collected in 2008 on quartz filters, from three different locations in Mali (12.6° N, 8.0° W; 555 m a.s.l.), Tobago (11.3° N, 60.5° W; 329 m a.s.l.) and the U.S. Virgin Islands (17.7° N, 64.6° W; 27 m a.s.l.) to investigate the hypothesis of dust transport across the Atlantic. About 2 cm2 of filter were acid-leached in 0.5 N HBr for selective removal of the anthropogenic labile Pb component (leachate) and possibly the fine soluble particle fraction. The remainder of the filter was subsequently dissolved using a mixture of HF and HNO3 acids, and should be representative of the silicate fraction. Isotopic compositions were measured by TIMS on a ThermoFisher Triton at MPIC, with Pb isotope ratios determined using the triple-spike method. Significant Pb isotope differences between leachates and residues were observed. The variability in Pb isotopic composition among leachates may be attributed to variable and distinct anthropogenic local Pb sources from Africa and South America [6], however, residues are imprinted by filter blank contribution suggesting to avoid the quartz fiber filter for isotopic study of aerosols. The Nd and Sr isotope ratios of aerosol leachates show similar signatures at all three locations investigated. The nearly identical Nd and Sr isotopic compositions in the Mali, Tobago and Virgin islands leachates are comparable to those obtained on samples from the Bodélé depression, Northern Chad [7] and suggest a possible common

  18. The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

    von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.


    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported

  19. Water vapour source impacts on oxygen isotope variability in tropical precipitation during Heinrich events

    S. C. Lewis


    Full Text Available Water isotope records such as speleothems provide extensive evidence of past tropical hydrological changes. During Heinrich events, isotopic changes in monsoon regions have been interpreted as implying a widespread drying through the Northern Hemisphere tropics and an anti-phased precipitation response in the south. Here, we examine the sources of this variability using a water isotope-enabled general circulation model, Goddard Institute for Space Studies ModelE. We incorporate a new suite of vapour source distribution tracers to help constrain the impact of precipitation source region changes on the isotopic composition of precipitation and to identify nonlocal amount effects. We simulate a collapse of the North Atlantic meridional overturning circulation with a large freshwater input to the region as an idealised analogue to iceberg discharge during Heinrich events. An increase in monsoon intensity, defined by vertical wind shear, is modelled over the South American domain, with small decreases simulated over Asia. Simulated isotopic anomalies agree well with proxy climate records, with lighter isotopic values simulated over South America and enriched values across East Asia. For this particular abrupt climate event, we identify which climatic change is most likely linked to water isotope change – changes in local precipitation amount, monsoon intensity, water vapour source distributions or precipitation seasonality. We categorise individual sites according to the climate variability that water isotope changes are most closely associated with, and find that the dominant isotopic controls are not consistent across the tropics – simple local explanations, in particular, fall short of explaining water isotope variability at all sites. Instead, the best interpretations appear to be site specific and often regional in scale.

  20. Non-mass-dependent fractionation of sulfur and oxygen isotopes during UV photolysis of sulfur dioxide

    Pen, Aranh

    Since the discovery of anomalous sulfur isotope abundance in the geological record in sulfate and sulfide minerals (Farquhar et al., 2000), much effort has been put into understanding their origin to provide new insights into the environmental conditions on the early Earth (Farquhar et al., 2001; Pavlov and Kasting, 2002; Ono et al., 2003; Zahnle et al., 2006; Farquhar et al., 2007; Lyons, 2007; Lyons, 2008). This discovery gained immense interest because of its implications for both the lack of oxygen in the atmosphere during the Archean era 2.5-3.8 Gya (billion years ago), and for rise of oxygen, or the "Great Oxidation Event", that occurred 2.2-2.4 Gya (Holland, 2002). These signatures are believed to be produced in an anticorrelation to oxygen abundance in the early atmosphere, which will aid in quantifying the rate of oxygenation during the "Great Oxidation Event". According to Farquhar et al. (2000), the non-mass-dependent (NMD), or anomalous, fractionation signatures were produced by photochemical reactions of volcanic sulfur species in Earth's early atmosphere (> 2.3 Gya) due to the lack of an oxygen and ozone shield, resulting in an atmosphere transparent to solar ultraviolet (UV) radiation (Farquhar et al., 2001). Interpretation of the anomalous rock records, though, depends on the identification of (1) chemical reactions that can produce the NMD signature (Farquhar and Wing, 2003); and (2) conditions necessary for conversion of the gas-phase products into solid minerals (Pavlov and Kasting, 2002). The focus of my research addresses the first step, which is to determine whether the chemical reactions that occurred in Earth's early atmosphere, resulting in NMD fractionation of sulfur isotopes, were due to broadband UV photochemistry, and to test isotopic self-shielding as the possible underlying mechanism. In this project, our goals were to test isotopic self-shielding during UV photolysis as a possible underlying mechanism for anomalous sulfur isotopic

  1. Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

    J. Kaiser


    Full Text Available Oxygen triple isotope measurements can be used to calculate aquatic gross oxygen production rates. Past studies have emphasised the appropriate definition of the 17O excess and often used an approximation to derive production rates from the 17O excess. Here, I show that the calculation can be phrased more consistently and without any approximations using the relative 17O/16O and 18O/16O isotope ratio differences (delta values directly. I call this the "dual delta method". The 17O excess is merely a mathematical construct and the derived production rate is independent of its definition, provided all calculations are performed with a consistent definition. I focus on the mixed layer, but also show how time series of triple isotope measurements below the mixed layer can be used to derive gross production.

    In the calculation of mixed layer productivity, I explicitly include isotopic fractionation during gas invasion and evasion, which requires the oxygen supersaturation s to be measured as well. I also suggest how bubble injection could be considered in the same mathematical framework. I distinguish between concentration steady state and isotopic steady state and show that only the latter needs to be assumed in the calculation. It is even possible to derive an estimate of the net production rate in the mixed layer that is independent of the assumption of concentration steady state.

    I review measurements of the parameters required for the calculation of gross production rates and show how their systematic uncertainties as well as the use of different published calculation methods can cause large variations in the production rates for the same underlying isotope ratios. In particular, the 17O excess of dissolved O2 in equilibrium with atmospheric O2 and the 17O excess of photosynthetic O2 need to

  2. Oxygen isotope variations at the margin of a CAI records circulation within the solar nebula.

    Simon, Justin I; Hutcheon, Ian D; Simon, Steven B; Matzel, Jennifer E P; Ramon, Erick C; Weber, Peter K; Grossman, Lawrence; DePaolo, Donald J


    Micrometer-scale analyses of a calcium-, aluminum-rich inclusion (CAI) and the characteristic mineral bands mantling the CAI reveal that the outer parts of this primitive object have a large range of oxygen isotope compositions. The variations are systematic; the relative abundance of (16)O first decreases toward the CAI margin, approaching a planetary-like isotopic composition, then shifts to extremely (16)O-rich compositions through the surrounding rim. The variability implies that CAIs probably formed from several oxygen reservoirs. The observations support early and short-lived fluctuations of the environment in which CAIs formed, either because of transport of the CAIs themselves to distinct regions of the solar nebula or because of varying gas composition near the proto-Sun.

  3. Oxygen isotopic ratio of the diatom siliceous valves: development of a new method in quantitative paleoclimatology

    Labeyrie, Laurent.


    This paper describes a new method allowing the measurement of the 18 O/ 16 O ratio of the biogenic silica oxygen, which takes into account the effects due to the organic matter and hydration water associated with this type of silica. By isotopic exchange with enriched water, we have been able to fix a treatment which eliminate all contamination and memory effects. This has permitted us to study the temperature dependance of the hydrated silica-water oxygen isotopic fractionation. As application, we present a study of the variations of the delta 18 O of fossil diatoms valves along an Equatorial Pacific sediment core covering the last 20.000 years. The results demonstrate the usefulness of the delta 18 O of the diatom silica for paleoclimatic investigations [fr

  4. Oxygen isotopes in mammal bone phosphate: A new tool for paleohydrological and paleoclimatological research?

    Longinelli, Antonio


    Oxygen isotope analyses of water in blood of humans and domestic pigs indicate that the oxygen isotope fractionation effects between ingested water and body water are the same in all specimens of the same species. The δ18O of body water has been shown to vary linearly with the mean δ18O of local meteoric water. This conclusion also holds for the bone phosphate. Thus, δ18O( PO3-4) values of unaltered fossil bones from humans and domestic pigs can be used to reconstruct the δ18O values of local meteoric waters during the life-times of the mammals. Such data can be used for paleohydrological and paleoclimatological studies both on land and at sea.

  5. Assessment of nitrogen and oxygen isotopic fractionation during nitrification and its expression in the marine environment.

    Casciotti, Karen L; Buchwald, Carolyn; Santoro, Alyson E; Frame, Caitlin


    Nitrification is a microbially-catalyzed process whereby ammonia (NH(3)) is oxidized to nitrite (NO(2)(-)) and subsequently to nitrate (NO(3)(-)). It is also responsible for production of nitrous oxide (N(2)O), a climatically important greenhouse gas. Because the microbes responsible for nitrification are primarily autotrophic, nitrification provides a unique link between the carbon and nitrogen cycles. Nitrogen and oxygen stable isotope ratios have provided insights into where nitrification contributes to the availability of NO(2)(-) and NO(3)(-), and where it constitutes a significant source of N(2)O. This chapter describes methods for determining kinetic isotope effects involved with ammonia oxidation and nitrite oxidation, the two independent steps in the nitrification process, and their expression in the marine environment. It also outlines some remaining questions and issues related to isotopic fractionation during nitrification. Copyright © 2011 Elsevier Inc. All rights reserved.

  6. Meteoric water in normal fault systems: Oxygen and hydrogen isotopic measurements on authigenic phases in brittle fault rocks

    Haines, S. H.; Anderson, R.; Mulch, A.; Solum, J. G.; Valley, J. W.; van der Pluijm, B. A.


    The nature of fluid circulation systems in normal fault systems is fundamental to understanding the nature of fluid movement within the upper crust, and has important implications for the on-going controversy about the strength of faults. Authigenic phases in clay gouges and fault breccias record the isotopic signature of the fluids they formed in equilibrium with, and can be used to understand the ‘plumbing system’ of brittle fault environments. We obtained paired oxygen and hydrogen isotopic measurements on authigenic illite and/or smectite in clay gouge from normal faults in two geologic environments, 1.) low-angle normal faults (Ruby Mountains detachment, NV; Badwater Turtleback, CA; Panamint range-front detachment; CA; Amargosa detachment; CA; Waterman Hills detachment, CA), and 2.) An intracratonic high-angle normal fault (Moab Fault, UT). All authigenic phases in these clay gouges are moderately light isotopically with respect to oxygen (illite δ18O -2.0 - + 11.5 ‰ SMOW, smectite δ18O +3.6 and 17.9 ‰) and very light isotopically with respect to hydrogen (illite δD -148 to -98 ‰ SMOW, smectite δD -147 to -92 ‰). Fluid compositions calculated from the authigenic clays at temperatures of 50 - 130 ○C (as indicated by clay mineralogy) indicate that both illite and smectite in normal fault clay gouge formed in the presence of near-pristine to moderately-evolved meteoric fluids and that igneous or metamorphic fluids are not involved in clay gouge formation in these normal fault settings. We also obtained paired oxygen and hydrogen isotopic measurements on chlorites derived from footwall chlorite breccias in 4 low-angle normal fault detachment systems (Badwater and Mormon Point Turtlebacks, CA, the Chemehuevi detachment, CA, and the Buckskin-Rawhide detachment, AZ). All chlorites are isotopically light to moderately light with respect to oxygen (δ18O +0.29 to +8.1 ‰ SMOW) and very light with respect to hydrogen (δD -97 to -113 ‰) and indicate

  7. Oxygen isotopic abundances in the atmospheres of seven red giant stars

    Harris, M.J.; Lambert, D.L.


    Abundances ratios of the oxygen isotopes have been measured in α Tau, β And, μ Gem, α Her, β Peg, γ Dra, and α Boo. In all the stars the 16 O/ 18 O ratios are similar; the mean value is 475, which is consistent with the solar system value 16 O/ 18 O = 490. The 16 O/ 17 O ratios range from approx.1000 for β Peg and α Boo to 16 O/ 17 O = 160 for β And

  8. A universal carbonate ion effect on stable oxygen isotope ratios in unicellular planktonic calcifying organisms

    Ziveri, P.; Thoms, S.; Probert, I.; Geisen, M.; Langer, H.


    The oxygen isotopic composition (δ18O) of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy c...

  9. Synopsis of oxygen isotopes in geothermal solids and fluids of New Zealand

    Blattner, P.


    Geothermal minerals serve as downhole probes of oxygen isotope compositions and thus of parameters of geothermal hydrology. ''Deep'' wells (2500 m) in New Zealand show no sign of Δ 18 O values ''bottoming out''. Ngawha differs from other systems both in the level and profile details of Δ 18 O values. The reservoir fluid at Ngawha hydrogeology may or may not be suited for development of a high-throughput surface recharge system

  10. Oxygen isotopic composition of relict olivine grains in cosmic spherules: Links to chondrules from carbonaceous chondrites

    Rudraswami, N.G.; ShyamPrasad, M.; Nagashima, K.; Jones, R.H.

    aluminium rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), and some porphyritic chondrules from carbonaceous chondrites. These grains appear to have recorded the initial oxygen isotopic composition of the inner solar nebula. Three olivine... to the major components of meteorites such as chondrules and calcium-aluminium-rich inclusions (CAIs). CAIs, the first solar system objects in the solar nebula, are formed by condensation of refractory minerals at high temperatures. They are 16O...

  11. Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

    Keller, L. P.; Snead, C.; Rahman, Z.; McKeegan, K. D.


    Hibonite-rich Ca- and Al-rich inclusions (CAIs) are among the earliest formed solids that condensed in the early nebula. We discovered an unusual refractory inclusion from the Allende CV3 chondrite (SHAL) containing an approx 500 micron long single crystal of hibonite and co-existing coarse-grained perovskite. The mineralogy and petrography of SHAL show strong similarities to some FUN inclusions, especially HAL. Here we report on the mineralogy, petrography, mineral chemistry and oxygen isotopic compositions in SHAL.

  12. Permafrost oxygen isotope ratios and chronology of three cores from Antarctica

    Stuiver, M.; Yang, I.C.; Denton, G.H.


    It is stated that permafrost core sediments, associated with the last intrusion of the Ross Ice Shelf in the New Harbour region, were deposited in marine (0 - 85 m deep) as well as freshwater environments (100 - 125 m). Oxygen isotope ratio measurements on these cores provide palaeoclimatic information and show that the extension of the Ross Ice Shelf predates 150,000 yr BP, whereas the radiocarbon date of its retreat is about 5,800 yr b.p. (author)

  13. Fractionation of hydrogen and oxygen isotopes between hydrated and free water molecules in aqueous urea solution

    Kakiuchi, M.; Matsuo, S.


    Ratios of D/H and 18 O/ 16 O in the vapor phase in equilibrium with aqueous urea solution with different urea molalities were measured at 15 and 25 0 C. Under the assumption that urea solutions consist of two species, i.e., the urea-water cluster and free water, the results are interpreted to give the average hydration number, i.e., the number of water molecules per urea molecule in the urea-water cluster. Good agreement was obtained for the hydration number estimated independently from hydrogen and oxygen isotopic fractions. On the basis of hydrogen isotopic data at 25 0 C, the average hydration number of urea in the cluster is 6.3 +/- 0.8 at 2.1 m and 2.75 +/- 0.08 at saturation (20.15 m). The corresponding average hydration numbers based on oxygen isotopic data were calculated to be 6.7 +/- 2.4 at 2.1 m and 2.75 +/- 0.25 at urea saturation. HD 16 O is enriched in the urea-water cluster and H 2 18 O is enriched in free water. Isotopic partitioning between the cluster and free water is markedly different from those between hydration spheres and free water in aqueous electrolyte solutions. 29 references, 6 figures, 5 tables


    Lugaro, Maria; Liffman, Kurt; Ireland, Trevor R.; Maddison, Sarah T.


    A number of objects in primitive meteorites have oxygen isotopic compositions that place them on a distinct, mass-independent fractionation line with a slope of one on a three-isotope plot. The most popular model for describing how this fractionation arose assumes that CO self-shielding produced 16 O-rich CO and 16 O-poor H 2 O, where the H 2 O subsequently combined with interstellar dust to form relatively 16 O-poor solids within the solar nebula. Another model for creating the different reservoirs of 16 O-rich gas and 16 O-poor solids suggests that these reservoirs were produced by Galactic chemical evolution (GCE) if the solar system dust component was somewhat younger than the gas component and both components were lying on the line of slope one in the O three-isotope plot. We argue that GCE is not the cause of mass-independent fractionation of the oxygen isotopes in the solar system. The GCE scenario is in contradiction with observations of the 18 O/ 17 O ratios in nearby molecular clouds and young stellar objects. It is very unlikely for GCE to produce a line of slope one when considering the effect of incomplete mixing of stellar ejecta in the interstellar medium. Furthermore, the assumption that the solar system dust was younger than the gas requires unusual timescales or the existence of an important stardust component that is not theoretically expected to occur nor has been identified to date.

  15. Fractionation of Nitrogen and Oxygen Isotopes and Roles of Bacteria during Denitrification

    Kang, J.; Buyanjargal, A.; Jeen, S. W.


    Nitrate in groundwater can cause health and environmental problems when not properly treated. The purpose of this study was to develop a treatment method for nitrate in groundwater using organic carbon-based reactive mixtures (i.e., wood chips and gravel) through column experiments and to evaluate reaction mechanisms responsible for the treatment. The column experiments were operated for a total of 19 months. The results from the geochemical analyses for the experiments suggest that cultures of denitrifying bacteria used organic carbon while utilizing nitrate as their electron acceptor via denitrification process. Proteobacteria was the most abundant phylum in all samples, accounting for 45.7% of the bacterial reads, followed by Firmicutes (22.6%) and Chlorobi (10.6%). Bacilli, Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria_c consisted of 32, 30, 23, 11, and 2% of denitrifying bacteria class. The denitrification process caused fractionation of nitrogen and oxygen isotopes of nitrate while nitrate concentration decreased. When fitted to the Rayleigh's fractionation model, enrichment factors (ɛ) were 11.5‰ and 5.6‰ for 15N and 18O isotopes, respectively. Previous studies suggested that nitrogen isotope enrichment factors of denitrification are within the range of 4.7 to 40‰ and oxygen isotopic enrichment factors are between 8 and 18.3‰. This study shows that nitrate in groundwater can be effectively treated using passive treatment systems, such as permeable reactive barriers (PRBs), and denitrificaton is the dominant process reponsible for the removal of nitrate.

  16. Oxygen isotope mapping and evaluation of paleo-hydrothermal systems associated with synvolcanic intrusion and VMS deposits

    Taylor, B.E


    . In contrast, rocks bearing evidence of isotopic enrichment (e.g., δ 18 O≥ 9.0% o ) typically may be found in hanging wall sequences, having formed subsequent to most alteration and mineralization. Recognition of isotopically enriched zones requires that hanging wall rocks were emplaced before the end of hydrothermal activity. Together, the paired low- and high- δ 18 O zones illustrate temperature gradients and delimit semi-conformable areas of hydrothermal circulation. At a regional scale, terrane between zones of high- and low-δ 18 O is prospective. At the camp or district scale, discordant up-flow zones are also clearly indicated by mapping and serve as local vectors for exploration. Oxygen isotope maps for four of the CAMIRO-GSC study areas (Noranda, Clifford-Ben Nevis, Sturgeon Lake, and Snow Lakeown). The grade of regional metamorphism varies among the areas selected for study, from prehnite-pumpellyite facies (Clifford-Ben Nevis) to lower-amphibolite facies (Snow Lake). Similarly, the style and intensity of folding also varies, from nearly undeformed (Clifford-Ben Nevis) to folded (Snow Lake). Neither the grade of regional metamorphism, nor the accompanying deformation has diminished the value of isotopic mapping. Whereas the shapes of isotopically depleted and enriched zones may reflect the strain pattern of the host rocks, regional metamorphism does not generally disturb the primary record of paleo-hydrothermal activity at the hand-specimen scale. Because greenschist regional metamorphism can produce many of the same mineral assemblages as form in large-scale submarine hydrothermal systems, it is particularly instructive to use isotopic techniques to delineate the hydrothermally altered domains. Oxygen isotope mapping offers the possibility of distinguishing ages of intrusions relative to hydrothermal activity. In the mineralized areas studied (i.e., Noranda, Sturgeon Lake, and Snow Lake), emplacement of the latest intrusions post-dated mineralizing

  17. Isotopic exchange between CO2 and H2O and labelling kinetics of photosynthetic oxygen

    Gerster, Richard


    The reaction of carbon dioxide with water has been studied by measuring the rate of oxygen exchange between C 18 O 2 and H 2 16 O. The mathematical treatment of the kinetics allows to determine with accuracy the diffusion flow between the gas and the liquid phase, in the same way as the CO 2 hydration rate. The velocity constant of this last process, whose value gives the in situ enzymatic activity of carbonic anhydrase, has been established in the case of chloroplast and Euglena suspensions and of aerial leaves. The study of the isotopic exchange between C 18 O 2 and a vegetable submitted to alternations of dark and light has allowed to calculate the isotopic abundance of the metabolized CO 2 whose value has been compared to that of the intracellular water and that of photosynthetic oxygen. In addition, a new method using 13 C 18 O 2 gives the means to measure with accuracy eventual isotopic effects. The labelling kinetics of the oxygen evolved by Euglena suspensions whose water has been enriched with 18 O have been established at different temperatures. (author) [fr

  18. Forensic applications of nitrogen and oxygen isotopes in tracing nitrate sources in urban environments

    Silva, S.R.; Ging, P.B.; Lee, R.W.; Ebbert, J.C.; Tesoriero, A.J.; Inkpen, E.L.


    Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing ??15N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

  19. Oxygen isotope analyses of ground ice from North of West Siberia, from Yakutia and from Chukotka

    Vaikmaee, R.; Vassilchuk, Y.


    The aim of the present work is to make the large amount of original factual material obtained by studying the oxygen isotope composition in different types of permafrost and ground ice available to specialists. The samples analysed were systematically collected over a period of many years from different permafrost areas of the Soviet Union with the aim of elucidating and studying the regularities of isotope composition formation in different types of ground ice and selecting the most promising objects for paleoclimatic reconstructions. Much attention was paid on methodical problems of isotopic analysis starting with the collection, transportation and storage of samples up to the interpretation of the results obtained. Besides permafrost isotope data covering a large geographical area, a good deal of data concerns the isotopic composition of precipitation and surface water in permafrost areas. This is of great consequence as regards the understanding of the regularities of isotope compositions formation in permafrost. The largest chapter gives a brief account of the isotopic composition in different types of ground ice. The conclusion has been reached that in terms of paleoclimatic research syngenetic ice wedges are most promising. Grounding on the representative data bank it may be maintained with certainty that the isotopic composition provides a reliable basis for the differentiation of ice wedges originating in different epochs , however, it also reveals regional regularities. Much more complicated is the interpretation of textural ice isotopic composition. In some cases it is possible to use the distribution of 18 O in vertical sections of textural ice for their stratigraphic division. One has to consider here different mechanisms of textural ice formation as a result of which the initial isotopic composition of the ice-forming water can be in some cases highly modified. A problem of its own is the investigation of 18 O variations in the section of massive

  20. Isotopic determinations of carbon and oxygen in the metasedimentary rocks of the Rio Pardo group-Bahia State, Brazil

    Costa Pinto, N.M.A.C.


    Determination of the carbon and oxygen isotopic compositions were made on approximately 100 samples of Late Precambrian metasedimentary rocks of the Rio Pardo Group from Southern Bahia. The results obtained show that carbon varies from δ 13 =C=5,73 per mille to δ 13 C=+9,00 per mille, and oxygen from δ 18 O=-1,87 per mille to δ 18 O=-19,67 per mille relative to PBD. The interpretations lead to some conclusions which confirm the validity the isotopic technique as auxiliary instrument in the study of geological problems. These include: 1) the evidence of a marine transgression during the Camaca sedimentation; 2) the probability that the dolomitic metalimestones of the Agua Preta formation belong to the Serra do Paraiso formation; 3) the assignment of the dolomitic metalismestones, which occur in Itiroro and which had been previously grouped with the crystalline basement rocks, to the Serra do Paraiso formation; 4) the removal of the marble from Serra do Paraiso formation and re-signment to the basement rocks, and finally; 5) the sedimentary evolution of the Rio Pardo Group from a typical fresh-water to a marine environment. (Author) [pt

  1. Carbon, hydrogen oxygen isotope studies on imbedded old tree ring and paleoclimate reconstruction

    Sun Yanrong; Mu Zhiguo; Cui Haiting


    Tree ring is a kind of natural archives, on which the isotopic analysis is important to study global climate and environmental change. The authors mainly provide a comprehensive introduction to the fractionation models of carbon, hydrogen and oxygen isotope in plants, their research technique and the extract methods from cellulose. That results show isotopic tracer can record the message of climatic variation and has become a powerful tool for paleoclimate reconstruction and for the modern environment changing research. Especially studying on PAGES. the cellulose isotopic analyses of imbedded old tree ring have become the mainly quantitative means of environmental evolvement. In addition, China is a typical monsoon country, research in tree ring stable isotope seasonal variation can give a lot of important information on that. Up to now, the research techniques and works on tree ring in China are still in its earlier stage, and remain many limitations. It needs further accumulate basic research materials, intensity regional contrast and intercross studies on relative subjects

  2. Analysis of Atmospheric Nitrate Deposition in Lake Tahoe Using Multiple Oxygen Isotopes

    McCabe, J. R.; Michalski, G. M.; Hernandez, L. P.; Thiemens, M. H.; Taylor, K.; Kendall, C.; Wankel, S. D.


    Lake Tahoe in the Sierra Nevada Mountain Range is world renown for its depth and water clarity bringing 2.2 million visitors per year resulting in annual revenue of \\1.6 billion from tourism. In past decades the lake has suffered from decreased water clarity (from 32 m plate depth to less than 20), which is believed to be largely the result of algae growth initiated by increased nutrient loading. Lake nutrients have also seen a shift from a nitrogen limited to a phosphorous limited system indicating a large increase in the flux of fixed nitrogen. Several sources of fixed nitrogen of have been suggested including surface runoff, septic tank seepage from ground water and deposition from the atmosphere. Bio-available nitrogen in the form of nitrate (NO_{3}$-) is a main component of this system. Recent studies have estimated that approximately 50% of the nitrogen input into the lake is of atmospheric origin (Allison et al. 2000). However, the impact and magnitude of atmospheric deposition is still one of the least understood aspects of the relationship between air and water quality in the Basin (TRPA Threshold Assessment 2002). The utility of stable isotopes as tracers of nitrate reservoirs has been shown in several studies (Bohlke et al. 1997, Kendall and McDonnell 1998, Durka et al. 1994). Stable nitrogen (δ15N) and oxygen (δ18O) isotopes have been implemented in a dual isotope approach to characterize the various nitrate sources to an ecosystem. While δ18O distinguishes between atmospheric and soil sources of nitrate, processes such as denitrification can enrich the residual nitrate in δ18O leaving a misleading atmospheric signature. The benefit of δ15N as a tracer for NO3- sources is the ability to differentiate natural soil, fertilizer, and animal or septic waste, which contain equivalent δ18O values. The recent implementation of multiple oxygen isotopes to measure Δ17O in nitrate has proven to be a more sensitive tracer of atmospheric deposition. The

  3. The mechanism of oxygen isotopic fractionation during fungal denitrification - A pure culture study

    Wrage-Moennig, Nicole; Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Annette; Lewicka-Szczebak, Dominika; Well, Reinhard


    Nitrous oxide (N2O) from soil denitrification originates from bacteria and - to an unknown extent - also from fungi. During fungal denitrification, oxygen (O) exchange takes place between H2O and intermediates of the denitrification process as in bacterial exchange[1,2]. However, information about enzymes involved in fungal O exchanges and the associated fractionation effects is lacking. The objectives of this study were to estimate the O fractionation and O exchange during the fungal denitrifying steps using a conceptual model[2] adapted from concepts for bacterial denitrification[3], implementing controls of O exchange proposed by Aerssens, et al.[4] and using fractionation models by Snider et al.[5] Six different pure fungal cultures (five Hypocreales, one Sordariales) known to be capable of denitrification were incubated under anaerobic conditions, either with nitrite or nitrate. Gas samples were analyzed for N2O concentration and its isotopic signatures (SP, average δ15N, δ18O). To investigate O exchange, both treatments were also established with 18O-labelled water as a tracer in the medium. The Hypocreales strains showed O exchange mainly at NO2- reductase (Nir) with NO2- as electron acceptor and no additional O exchange at NO3- reductase (Nar) with NO3- as electron acceptor. The only Hypocreales species having higher O exchange with NO3- than with NO2- also showed O exchange at Nar. The Sordariales species tested seems capable of O exchange at NO reductase (Nor) additionally to O exchange at Nir with NO2-. The data will help to better interpret stable isotope values of N2O from soils. .[1] D. M. Kool, N. Wrage, O. Oenema, J. Dolfing, J. W. Van Groenigen. Oxygen exchange between (de)nitrification intermediates and H2O and its implications for source determination of NO?3- and N2O: a review. Rapid Commun. Mass Spec. 2007, 21, 3569. [2] L. Rohe, T.-H. Anderson, B. Braker, H. Flessa, A. Giesemann, N. Wrage-Mönnig, R. Well. Fungal Oxygen Exchange between

  4. Mobility and diet in Neolithic, Bronze Age and Iron Age Germany : evidence from multiple isotope analysis

    Oelze, Viktoria Martha


    Prehistoric human diet can be reconstructed by the analysis of carbon (C), nitrogen (N) and sulphur (S) stable isotopes in bone, whereas ancient mobility and provenance can be studied using the isotopes of strontium (Sr) and oxygen (O) in tooth enamel, and of sulphur in bone. Although thirty years

  5. Constraints on the nature of the projectile using siderophile elements and triple-oxygen isotopes: Zhamanshin impact structure, Kazakhstan

    Jonášová, Šárka; Ackerman, Lukáš; Žák, Karel; Skála, Roman; Magna, T.; Pack, A.; Deutsch, A.


    Roč. 51, SI, Supplement 1 (2016), A358-A358 ISSN 1086-9379. [Annual Meeting of the Meteoritical Society /79./. 07.08.2016-12.08.2016, Berlin] Institutional support: RVO:67985831 Keywords : impact glass * irghizites * geochemistry * meteoritic component * siderophile elements * osmium isotopes * triple-oxygen Isotopes * Zhamanshin Subject RIV: DD - Geochemistry

  6. [Research advances in identifying nitrate pollution sources of water environment by using nitrogen and oxygen stable isotopes].

    Mao, Wei; Liang, Zhi-wei; Li, Wei; Zhu, Yao; Yanng, Mu-yi; Jia, Chao-jie


    Water body' s nitrate pollution has become a common and severe environmental problem. In order to ensure human health and water environment benign evolution, it is of great importance to effectively identify the nitrate pollution sources of water body. Because of the discrepant composition of nitrogen and oxygen stable isotopes in different sources of nitrate in water body, nitrogen and oxygen stable isotopes can be used to identify the nitrate pollution sources of water environment. This paper introduced the fractionation factors of nitrogen and oxygen stable isotopes in the main processes of nitrogen cycling and the composition of these stable isotopes in main nitrate sources, compared the advantages and disadvantages of five pre-treatment methods for analyzing the nitrogen and oxygen isotopes in nitrate, and summarized the research advances in this aspect into three stages, i. e. , using nitrogen stable isotope alone, using nitrogen and oxygen stable isotopes simultaneously, and combining with mathematical models. The future research directions regarding the nitrate pollution sources identification of water environment were also discussed.

  7. Stratigraphy on Oxygen and Carbon Isotope of Paciran Formation East Java

    Premonowati; R P Koesoemadinata; Harsono-Pringgoprawiro; Wahyoe-S-Hantoro


    Paleotemperature fluctuation in tropical zone (centennial and decad al scale) has been known. It's based on stable isotopic analysis from each of unconformity zones. Those boundaries have derived on reef units of shallows marine reef complex of Paciran Formation, Tuban area in Northeast Java Basin. From 25 samples have been choosen on undeformed calcite and analyzed by oxygen and carbon stable isotope. It used to validizing a sea level changes during the formation to Reef 1 to Reef 17 from Paciran formation with sea surface temperature (SST) since 4 Ma until now. On early forming of Reef 1 to Reef 3 (since 4 Ma - 2,88 Ma), sea level occurred marine flooding surface. Since the formation of reef 4 (2,59 Ma) to Reef 8 (1,4 Ma) occurred stagnant temperature and almost to warmer condition. Then, δ 18 O have arise up drastically to 5 0/00 and shows warmer condition to Reef 8 formation, in contrary, the sea level have been arised to Reef 10 formation (0,7 Ma). The temperature have been fluctuated between 0,5 o and 1 o C until the formation of Reef 17 (Early Holocene) and continued to Reef 17 formation at 2 o C based on the rapidity sampling of Po rites sp. Wholly, in centennial scale, since the formation of Reef 4 (2,59 Ma) to Reef 17 (1 Ma), the curve of oxygen stable isotope shows decrease or cooler condition. Those condition have conducted to sea level drop since the formation to Reef 7 and Reef 8. There are 4 periods of interglacial since the formation of Reef 4. The warmer condition indicated since the formation of Reef 9, Reef 11 and Reef 17. Recently, a curve of oxygen isotopes reveals warmer drastically or sea level have been arisen. (author)

  8. The Oxygen Isotopic Composition of Phosphate: A Tracer for Phosphate Sources and Cycling

    Mclaughlin, K. [Southern California Coastal Water Research Project, Costa Mesa, University of California, CA (United States); Young, M. B.; Paytan, A.; Kendall, C. [U.S. Geological Survey, University of California, CA (United States)


    Phosphorus (P) is a limiting macro-nutrient for primary productivity and anthropogenic P-loading to aquatic ecosystems is one of the leading causes of eutrophication in many ecosystems throughout the world. Because P has only one stable isotope, traditional isotope techniques are not possible for tracing sources and cycling of P in aquatic systems. However, much of the P in nature is bonded to four oxygen (O) atoms as orthophosphate (PO{sub 4}{sup 3-}). The P-O bonds in orthophosphate are strongly resistant to inorganic hydrolysis and do not exchange oxygen with water without biological mediation (enzyme-mediated recycling). Thus, the oxygen isotopic composition of dissolved inorganic phosphate ({delta}{sup 18}O{sub p}) may be used as a tracer for phosphate sources and cycling in aquatic ecosystems. Recently, several studies have been conducted utilizing {delta}{sup 18}O{sub p} as a tracer for phosphate sources and cycling in various aquatic environments. Specifically, work to date indicates that {delta}{sup 18}O{sub p} is useful for determining sources of phosphate to aquatic systems if these sources have unique isotopic signatures and phosphate cycling within the system is limited compared to input fluxes. In addition, because various processes imprint specific fractionation effects, the {delta}{sup 18}O{sub p} tracer can be utilized to determine the degree of phosphorous cycling and processing through the biomass. This chapter reviews several of these studies and discusses the potential to utilize the {delta}{sup 18}O{sub p} of phosphate in rivers and streams. (author)

  9. High-resolution conodont oxygen isotope record of Ordovician climate change

    Chen, J.; Chen, Z.; Algeo, T. J.


    The Ordovician Period was characterized by several major events, including a prolonged 'super greenhouse' during the Early Ordovician, the 'Great Ordovician Biodiversification Event (GOBE)' of the Middle and early Late Ordovician, and the Hirnantian ice age and mass extinction of the latest Ordovician (Webby et al., 2004, The Great Ordovician Biodiversification Event, Columbia University Press). The cause of the rapid diversification of marine invertebrates during the GOBE is not clear, however, and several scenarios have been proposed including widespread development of shallow cratonic seas, strong magmatic and tectonic activity, and climate moderation. In order to investigate relationships between climate change and marine ecosystem evolution during the Ordovician, we measured the oxygen isotopic composition of single coniform conodonts using a Cameca secondary ion mass spectrometer. Our δ18O profile shows a shift at the Early/Middle Ordovician transition that is indicative of a rapid 6 to 8 °C cooling. This cooling event marks the termination of the Early Ordovician 'super greenhouse' and may have established cooler tropical seawater temperatures that were more favorable for invertebrate animals, setting the stage for the GOBE. Additional cooling episodes occurred during the early Sandbian, early Katian, and Hirnantian, the last culminating in a short-lived (extinction. Our results differ from those of Trotter et al. (2008, 'Did cooling oceans trigger Ordovician biodiversification? Evidence from conodont thermometry,' Science 321:550-554). Instead of a slow, protracted cooling through the Early and Middle Ordovician, our high-resolution record shows that cooling occurred in several discrete steps, with the largest step being at the Early/Middle Ordovician transition.


    E. Ristin Pujiindiyati


    Full Text Available There are at least 30 high temperature systems; eleven active volcanoes, five degassing volcanoes and one caldera volcano controlled by Sumatra Fault Zone over a length of 1700 km. To understand this geothermal field system, some information about geochemistry including isotope composition in its fluid is needed. Sulphur-34 and oxygen-18 isotopes in dissolved sulphate pair have been used to determine the origin of acidic fluid of sulphate and to evaluate the process involved. The fluids from eight hot springs, two fumaroles, four deep wells and crater have been collected in along Sumatra geothermal fields. Sulphur-34 (d 34S (SO4, 0/00 CDT and oxygen-18 (d 18O (SO4, 0/00 SMOW in sulphate is analyzed according to Robinson-Kusakabe and Rafter method, respectively. The d 34S (SO4 values from Sibayak wells are more enriched of 16.8 0/00 to 18.2 0/0 that may indicate the dissolution of anhydrite minerals or isotope partitioning in hydration of SO2. The d 34S (SO4 values from two fumaroles (Pusuk Bukit - North Sumatra and Rantau Dadap - South Sumatra are at depleted value of -0.150/00 and 1.80/00, those are close to d 34S from magmatic sulphur.  In general, the d 34S (SO4 of springs spread in a wide range of 5.250/00 to14.20/00 and show a mixing process between atmospheric sulphate and sulphate from deep wells. The d 18O (SO4 from wells exhibits depleted value around -3.60/00 suggesting that 87.5% of sulphate oxygen is derived from groundwater oxygen and 12.5% is derived from atmospheric molecular oxygen in sulphide oxidation reaction. In the other hand, hot springs (except Semurup, crater and fumaroles have enriched value of d 18O (SO4. These enriched values suggest that a higher percentage of atmospherically derived oxygen compared to those from the depth.   Keywords: isotope, geothermal, Sumatra

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

    Michael, Dimitra-Ermioni; Dotsika, Elissavet


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

  12. Chemical and Oxygen Isotopic Composition of Roman and Late Antique Glass from Northern Greece

    Alberta Silvestri


    Full Text Available The present paper emphasizes the importance of measuring the oxygen isotopic and chemical compositions of ancient glass, in order to constrain some features such as age, raw materials, and production technologies and to identify the “fingerprint” of local productions. In this context, thirty-nine Roman and late Antique glass samples and eight chert samples from northern Greece were selected and analysed for their oxygen isotopic and chemical compositions. Results show that the majority of glass samples are produced using natron as flux and have δ18O values of about 15.5‰, plus or minus a few tenths of one per mil, suggesting that raw materials probably come from Levantine area. Four samples are heavily enriched in 18O, and their chemical composition clearly shows that they were made with soda plant ash as flux. Isotopic and chemical data of Greek chert samples support the hypothesis of local production of the above samples. About half of the glass samples have chemical compositions, which allow their age to be constrained to the late Antique period. For the remaining glass, similarities with literature compositional groups are reported and discussed.

  13. Quasi-free one nucleon knockout reactions on neutron-rich oxygen isotopes

    Atar, Leyla; Aumann, Thomas [TU Darmstadt, Darmstadt (Germany); GSI, Darmstadt (Germany); Bertulani, Carlos [Texas A and M University-Commerce, Commerse (United States); Paschalis, Stefanos [TU Darmstadt, Darmstadt (Germany); Nociforo, Chiara [GSI, Darmstadt (Germany); Collaboration: R3B-Collaboration


    Recent experiments have shown a reduction of spectroscopic strengths to about 60-70% for stable nuclei. When going to drip lines this tendency is changing, loosely bound nucleons have spectroscopic strengths close unity while deeply bound nucleons have a large reduction of the strength. We aim to make a systematic study of spectroscopic factors (SF) of the Oxygen isotopes using quasi-free (p,2p) and (p,pn) knockout reactions in inverse kinematics. Quasi-free knockout reactions are a direct tool to study the occupancy and the location of valance and deeply bound single particle states. The Oxygen isotopes offer a large variation of separation energies which will allow us to obtain a qualitative and quantitative understanding of SF in a large variation of isospin asymmetry. For this we performed an experiment at the R3B-LAND setup at the GSI with secondary beams containing {sup 14-24}O. The {sup 16-18}O and {sup 21-23}O isotopes have been analyzed and the preliminary results will be presented. The results include the partial cross sections, gamma ray spectra of the residual fragments in coincidence, and the SF obtained via comparison with theory.

  14. Covariance of oxygen and hydrogen isotopic composition in plant water: Species effects

    Cooper, L.W.; DeNiro, M.J. (Univ. of California, Los Angeles (United States))


    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species-specific factors on leaf water enrichment of D and {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leaf water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 18}O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes.

  15. Oxygen isotopic tracing study of the dry thermal oxidation of 6H SiC

    Vickridge, I.C.; Ganem, J.-J.; Battistig, G.; Szilagyi, E.


    The (0 0 0 1) and (0 0 0 1-bar) faces of 6H SiC have been oxidised sequentially at 1100 deg. C and 100 mbar in ultra-dry oxygen of natural isotopic concentration and in ultra-dry oxygen highly enriched in 18 O. Measurement of the 18 O isotopic concentration profiles by nuclear resonance profiling with the narrow resonance at 151 keV in 18 O(p,α) 15 N shows that on the carbon-terminated face (0 0 0 1-bar) the oxidation mechanism is rather similar to that observed on Si(1 0 0), but that on the silicon-terminated face (0 0 0 1) the surface isotopic exchange and oxide formation are superposed. The surface exchange observed during a third dry oxidation, in 16 O 2 , is very similar in magnitude and spatial extent on Si(1 0 0), and the two 6H SiC faces, suggesting that at least near the surface the nature and composition of the three oxides are very similar

  16. Oxygen isotopic tracing study of the dry thermal oxidation of 6H SiC

    Vickridge, I.C. E-mail:; Ganem, J.-J.; Battistig, G.; Szilagyi, E


    The (0 0 0 1) and (0 0 0 1-bar) faces of 6H SiC have been oxidised sequentially at 1100 deg. C and 100 mbar in ultra-dry oxygen of natural isotopic concentration and in ultra-dry oxygen highly enriched in {sup 18}O. Measurement of the {sup 18}O isotopic concentration profiles by nuclear resonance profiling with the narrow resonance at 151 keV in {sup 18}O(p,{alpha}){sup 15}N shows that on the carbon-terminated face (0 0 0 1-bar) the oxidation mechanism is rather similar to that observed on Si(1 0 0), but that on the silicon-terminated face (0 0 0 1) the surface isotopic exchange and oxide formation are superposed. The surface exchange observed during a third dry oxidation, in {sup 16}O{sub 2}, is very similar in magnitude and spatial extent on Si(1 0 0), and the two 6H SiC faces, suggesting that at least near the surface the nature and composition of the three oxides are very similar.

  17. In situ oxygen isotope compositions in olivines of different types of cosmic spherules: An assessment of relationships to chondritic particles

    Rudraswami, N.G.; ShyamPrasad, M.; Jones, R.H.; Nagashima, K.

    bearing cosmic spherules (Rudraswami et al., 2015b). In addition, some Mg-rich relict olivine grains are very 16O-rich, with 17O ranging from −21.9 to -18.7‰, similar to oxygen isotopic compositions observed in calcium aluminium rich inclusions (CAIs... isotope analyses of the olivine grains are provided in Appendix B and Table 1, respectively. 5    Four scoriaceous spherules namely, AAS62-61-P64, AAS62-9-P43, AAS62-9-P51 and AAS62-9- P54 were identified for oxygen isotope studies (Fig. 1a...

  18. Effects of diagenesis on strontium, carbon, nitrogen and oxygen concentration and isotopic composition of bone

    Nelson, Bruce K.; Deniro, Michael J.; Schoeninger, Margaret J.; De Paolo, Donald J.; Hare, P. E.


    Paleodietary analysis based on variations in the trace element and stable isotopic composition of inorganic and organic phases in fossil bone depends on the assumption that measured values reflect in vivo values. To test for postmortem alteration, we measured 87Sr /86Sr , 13C /12C , 18O /16O and 15N /14N ratios and Sr concentrations in modern and prehistoric (610 to 5470 yr old) bones of animals with marine or terrestrial diets from Greenland. Bones from modern terrestrial feeders have substantially lower Sr concentrations and more radiogenic 87Sr /86Sr ratios than those from modern marine feeders. This contrast was not preserved in the prehistoric samples, which showed almost complete overlap for both Sr concentration and isotopic composition in bones from the two types of animals. Leaching experiments, X-ray diffraction analysis and infrared spectroscopy indicate that alteration of the Sr concentration and isotopic composition in prehistoric bone probably results from nearly complete exchange with groundwater. Oxygen isotope ratios in fossil apatite carbonate also failed to preserve the original discrimination between modern terrestrial and marine feeders. The C isotope ratio of apatite carbonate did not discriminate between animals with marine or terrestrial diets in the modern samples. Even so, the ranges of apatite δ 13C values in prehistoric bone are more scattered than in modern samples for both groups, suggesting alteration had occurred. δ 13C and δ 15N values of collagen in modern bone are distinctly different for the two feeding types, and this distinction is preserved in most of the prehistoric samples. Our results suggest that postmortem alteration of dietary tracers in the inorganic phases of bone may be a problem at all archaeological sites and must be evaluated in each case. While collagen analyzed in this study was resistant to alteration, evaluation of the possibility of diagenetic alteration of its isotopic composition in bones from other

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

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


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

  20. Stable hydrogen, oxygen and sulfur isotopes composition in different tissues of cattle

    Sun Fengmei; Shi Guangyu; Wang Huiwen; Yang Shuming


    In order to research on stable hydrogen, oxygen, sulfur isotopes composition in different tissues of cattle, as well as the breed, δ 2 H and δ 34 S values of different defatted muscle, cattle tail hair, blood, liver, also δ 2h and δ 18 O values of water from muscle were determined by isotope ratio mass spectrometry. The stable sulfur isotope composition was not affected by cattle variety, meanwhile the hydrogen was uncertain; the δ 2 H and δ 34 S values between different defatted muscle, blood, liver, cattle hair were significantly different, at the same time the δ 34 S and δ 2 H values between each tissue were not significantly correlated; the δ 2 H values were strongly correlated with the δ 18 O values of muscle water. The above results indicated that stable sulfur and hydrogen isotopes fractionation in the various tissues were discrepant, thus the proper tissue should be selected according to the purpose and object in the beef traceability. (authors)

  1. Understanding the circulation of geothermal waters in the Tibetan Plateau using oxygen and hydrogen stable isotopes

    Tan, Hongbing; Zhang, Yanfei; Zhang, Wenjie; Kong, Na; Zhang, Qing; Huang, Jingzhong


    Highlights: • Unique geothermal resources in Tibetan Plateau were discussed. • Isotopes were used to trace circulation of geothermal water. • Magmatic water mixing dominates geothermal water evolution. - Abstract: With the uplift of the Tibetan Plateau, many of the world’s rarest and most unique geothermal fields have been developed. This study aims to systematically analyze the characteristics of the hydrogen and oxygen isotopic data of geothermal, river, and lake waters to understand the circulation of groundwater and to uncover the mechanism of geothermal formation in the Tibetan Plateau. Field observations and isotopic data show that geothermal water has higher temperatures and hydraulic pressures, as well as more depleted D and 18 O isotopic compositions than river and lake waters. Thus, neither lakes nor those larger river waters are the recharge source of geothermal water. Snow-melt water in high mountains can vertically infiltrate and deeply circulate along some stretching tensile active tectonic belts or sutures and recharge geothermal water. After deep circulation, cold surface water evolves into high-temperature thermal water and is then discharged as springs at the surface again in a low area, under high water-head difference and cold–hot water density difference. Therefore, the large-scale, high-temperature, high-hydraulic-pressure geothermal systems in the Tibetan Plateau are developed and maintained by rapid groundwater circulation and the heat source of upwelled residual magmatic water. Inevitably, the amount of geothermal water will increase if global warming accelerates the melting of glaciers in high mountains

  2. Hydrogen and oxygen stable isotope ratios of milk in the United States.

    Chesson, Lesley A; Valenzuela, Luciano O; O'Grady, Shannon P; Cerling, Thure E; Ehleringer, James R


    Models of hydrogen and oxygen incorporation in human tissues recognize the impact of geographic location on the isotopic composition of fluid intake, but inputs can include nonlocal beverages, such as milk. Milk and cow drinking water were collected from dairies, and commercially available milk was purchased from supermarkets and fast food restaurants. It was hypothesized that milk water delta(2)H and delta(18)O values record geographic location information. Correlations between milk water isotope ratios and purchase location tap water were significant. However, the amount of variation in milk delta(2)H and delta(18)O values explained by tap water was low, suggesting a single estimation of fluid input isotope ratios may not always be adequate in studies. The delta(2)H and delta(18)O values of paired milk and cow drinking water were related, suggesting potential for geographical origin assignment using stable isotope analysis. As an application example, milk water delta(18)O values were used to predict possible regions of origin for restaurant samples.

  3. Oxygen and hydrogen isotope studies of gold mineralization in the southern Apuseni Mountains, Romania: interpretation and problems

    Alderton, David H.M.


    Precious and base metal mineralization in the southern Apuseni Mountains of western Romania occurs in several steeply-dipping veins which are hosted by Miocene andesitic rocks. Fluid inclusion evidence suggests that the majority of the mineralization was caused by low salinity fluids at temperatures between 200 and 300 o C. Although subject to several uncertainties, the oxygen and hydrogen isotope data support a model in which main stage mineralization was formed when a metal-bearing magmatic fluid was exsolved from the crystallizing melt. In contrast to many other 'epithermal' precious metal deposits, the incorporation into the hydrothermal system of local meteoric groundwaters was minor, and mostly restricted to the latest, barren, low temperature stage of mineralization. (Author)

  4. The oxygen isotope effect on the in-plane penetration depth in cuprate superconductors

    Khasanov, R; Shengelaya, A; Morenzoni, E; Conder, K; Savic, I M; Keller, H


    Muon spin rotation (μSR) studies of the oxygen isotope ( 16 O/ 18 O) effect (OIE) on the in-plane magnetic field penetration depth λ ab in cuprate high-temperature superconductors (HTS) are presented. First, the doping dependence of the OIE on the transition temperature T c in various HTS is briefly discussed. It is observed that different cuprate families show similar doping dependences of the OIE on T c . Then, bulk μSR, low-energy μSR, and magnetization studies of the total and site-selective OIE on λ ab are described in some detail. A substantial OIE on λ ab was observed in various cuprate families at all doping levels, suggesting that cuprate HTS are non-adiabatic superconductors. The experiments clearly demonstrate that the total OIE on T c and λ ab arise from the oxygen sites within the superconducting CuO 2 planes, demonstrating that the phonon modes involving the movement of planar oxygen are dominantly coupled to the supercarriers. Finally, it is shown that the OIE on T c and λ ab exhibit a relation that appears to be generic for different families of cuprate HTS. The observation of these unusual isotope effects implies that lattice effects play an essential role in cuprate HTS and have to be considered in any realistic model of high-temperature superconductivity

  5. The oxygen isotope effect on the in-plane penetration depth in cuprate superconductors

    Khasanov, R [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland); Shengelaya, A [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland); Morenzoni, E [Laboratory for Muon Spin Spectroscopy, Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Conder, K [Laboratory for Neutron Scattering, ETH Zuerich and PSI Villigen, CH-5232 Villigen PSI (Switzerland); Savic, I M [Faculty of Physics, University of Belgrade, 11001 Belgrade (Serbia and Montenegro); Keller, H [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland)


    Muon spin rotation ({mu}SR) studies of the oxygen isotope ({sup 16}O/{sup 18}O) effect (OIE) on the in-plane magnetic field penetration depth {lambda}{sub ab} in cuprate high-temperature superconductors (HTS) are presented. First, the doping dependence of the OIE on the transition temperature T{sub c} in various HTS is briefly discussed. It is observed that different cuprate families show similar doping dependences of the OIE on T{sub c}. Then, bulk {mu}SR, low-energy {mu}SR, and magnetization studies of the total and site-selective OIE on {lambda}{sub ab} are described in some detail. A substantial OIE on {lambda}{sub ab} was observed in various cuprate families at all doping levels, suggesting that cuprate HTS are non-adiabatic superconductors. The experiments clearly demonstrate that the total OIE on T{sub c} and {lambda}{sub ab} arise from the oxygen sites within the superconducting CuO{sub 2} planes, demonstrating that the phonon modes involving the movement of planar oxygen are dominantly coupled to the supercarriers. Finally, it is shown that the OIE on T{sub c} and {lambda}{sub ab} exhibit a relation that appears to be generic for different families of cuprate HTS. The observation of these unusual isotope effects implies that lattice effects play an essential role in cuprate HTS and have to be considered in any realistic model of high-temperature superconductivity.

  6. Application of oxygen and hydrogen isotopes of waters in Tengchong hydrothermal systems of China

    Shen Minzi; Hou Fagao; Lin Ruifen; Ni Baoling


    This paper summarizes the results obtained for hydrothermal systems in Tengchong by using deuterium, oxygen-18 and tritium as natural tracers. On the basis of deuterium and oxygen-18 analyses of 69 thermal springs and some other meteoric, surface and underground water samples it has been confirmed that all geothermal waters are originally meteoric, but the δD of hot spring waters is often lighter than that of local surface and underground waters. It seems that the recharging water is from higher elevations and far from the thermal areas. The differences in oxygen-18 and deuterium contents between thermal springs and deep thermal waters have been calculated for single-stage steam separation from 276 deg. C to 96 deg. C. The oxygen isotope shift of deep thermal water produced by water-rock reactions is of 1.57 per mille and part of the observed oxygen isotope shift of thermal springs seems to have occurred due to subsurface boiling. The tritium content ( 18 O three subsurface processes would have been distinguished, they are subsurface boiling, mixing-subsurface boiling and subsurface boiling-mixing. The springs formed by subsurface boiling have tritium content of less than 5 TU. The tritium content of 5-10 TU is for springs formed by mixing-subsurface boiling and 10-20 TU is for subsurface boiling-mixing. The tritium content of geothermal water in Hot Sea, geothermal field seems higher than that of the Geysers U.S.A. and Wairakei N.Z. It would show that the circulation time of the thermal water in Hot Sea geothermal system is not so long, the reservoir is quite good with percolation and the recharging water is sufficiently enough. The most important applications of oxygen and hydrogen isotopes of water in geothermal study are in two ways, as tracers of water origins and as tracers of reservoir processes. This paper discussed these two aspects of Tengchong hydrothermal systems. 6 refs, 6 figs, 5 tabs

  7. The oxygen isotope composition of baddeleyite and a test of crystal orientation effects during SIMS analysis

    Ibanez-Mejia, M.; DesOrmeau, J. W.; Eddy, M. P.; Kitajima, K.; Valley, J. W.


    Baddeleyite, the monoclinic polymorph of ZrO2, is a relatively common accessory phase in undersaturated and alkaline igneous rocks that is rapidly developing into a widely-used tool for studying the age and initial 176Hf/177Hf composition of many terrestrial and planetary rocks that typically lack zircon. The prospect of combining U-Pb-Hf data from baddeleyite with δ18O information, as regularly done with zircon, could prove a very powerful addition to the `analytical toolbox' of the igneous petrologist and for studies of crust and mantle evolution. However, the oxygen isotope systematics of this mineral remain poorly explored, as are the potential analytical hurdles involved in obtaining accurate spatially-resolved δ18O data by SIMS. Here, we report laser fluorination δ18O measurements from two baddeleyite megacrysts from Kovdor (δ18O = 0.24 ± 0.11 ‰) and Phalaborwa (4.58 ± 0.11 ‰), which were subsequently analyzed by SIMS to explore their compositional homogeneity and potential as reference materials for correcting instrumental mass fractionation (IMF). Randomly oriented grain fragments analyzed by SIMS were subsequently mapped using high-resolution EBSD, such that the incidence angle of the Cs+ primary ion beam relative to the baddeleyite crystallographic axes could be determined for each spot. We found that: a) δ18O values for both crystals reproduce fairly well, but several apparent outliers (ca. 10% of all data) were measured with no evident correlation to orientation, cracks or inclusions, suggesting these might not be ideal standards; b) there is a systematic difference in mean measured IMFs of ca. 0.6 ‰ between the two baddeleyite crystals; c) mean 16OH/16O values for Phalaborwa (2.5x10-4) are significantly higher than those of Kovdor (2.9x10-6), suggesting that different degrees of radiation damage affect IMF; and d) there is no statistically significant correlation in our dataset (n= 96 spot analyses) between IMF and crystallographic

  8. Covariance of oxygen and hydrogen isotopic compositions in plant water: species effects

    Cooper, L.W.; DeNiro, M.J.


    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species—specific factors on leaf water enrichment of D and 18 O have not been studied for different plants growing together. Accordingly, to learn whether leaf water enrichment patterns and processes for D and 18 O are different for individual species growing under the same environmental conditions we tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show higher slopes (m in the leaf water equation °D = m ° 18 O + b) than in C 3 plants. We determined the relationships between the stable hydrogen (°D) and oxygen (° 18 O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. Slopes (m in the above leaf water equation) ranged from 1.50 to 3.21, compared to °8 for meteoric water, but differences in slope could not be attributed to carboxylation pathway (CAM vs. C 3 ) nor climate (coastal California vs. Sonoran Desert). Higher slopes were correlated with greater overall ranges of leaf water enrichment of D and 18 O. Water in plants with higher slopes also differed most from unaltered meteoric water. Leaf water isotope ratios in plants with lower slopes were better correlated with temperature and humidity. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes

  9. Growth patterns of an intertidal gastropod as revealed by oxygen isotope analysis

    Bean, J. R.; Hill, T. M.; Guerra, C.


    The size and morphology of mollusk shells are affected by environmental conditions. As a result, it is difficult to assess growth rate, population age structure, shell morphologies associated with ontogenetic stages, and to compare life history patterns across various environments. Oxygen isotope analysis is a useful tool for estimating minimum ages and growth rates of calcium carbonate secreting organisms. Calcite shell material from members of two northern California populations of the intertidal muricid gastropod Acanthinucella spirata was sampled for isotopic analysis. Individual shells were sampled from apex to margin, thus providing a sequential record of juvenile and adult growth. A. spirata were collected from a sheltered habitat in Tomales Bay and from an exposed reef in Bolinas. Abiotic factors, such as temperature, wave exposure, and substrate consistency, and biotic composition differ significantly between these sites, possibly resulting in local adaptations and variation in life history and growth patterns. Shell morphology of A. spirata changes with age as internal shell margin thickenings of denticle rows associated with external growth bands are irregularly accreted. It is not known when, either seasonally and/or ontogentically, these thickenings and bands form or whether inter or intra-populational variation exists. Preliminary results demonstrate the seasonal oxygen isotopic variability present at the two coastal sites, indicating 5-6 degC changes from winter to summertime temperatures; these data are consistent with local intertidal temperature records. Analysis of the seasonal patterns indicate that: 1) differences in growth rate and seasonal growth patterns at different ontogenetic stages within populations, and 2) differences in growth patterns and possibly age structure between the two A. spirata populations. These findings indicate that isotopic analyses, in addition to field observations and morphological measurements, are necessary to

  10. Oxygen isotope regional pattern in granitoids from the Cachoeirinha Belt, northeast Brazil

    Sial, A.N.


    Four groups of granitoids are present within the Cachoeirinha belt and in the adjacent migmatitic basement, between 37 0 and 40 0 W long. and 7 0 and 8 0 15' S lat., States of Pernambuco and Paraiba: a) K 2 O - enriched, very porphyritic; b) a calc-alkalic slightly porphyritic group; c) group with trondjemitic affinities; and d) peralkalic group. Petrology and oxygen isotope geochemistry for over 100 samples from these groups were studied. Almost all plutons for which 5 or more samples were analyzed, exhibit a total range of gamma 18 O less than 2% o. A broad range of mean oxygen isotope composition is observed, varying from 6.93 to 12.79% o. There is a systematic regional trend in which the calc-alkalic granitoids (conceicao-type) found within the Cachoeirinha space are the most 18 O - enriched rocks (10.6 to 12.9% o) while the lowest mean gamma 18 O values (4.5 to 9.7% o) are found in the K 2 O - enriched granitoids (Itaporanga-type). Intermediate gamma 18 O values were recorded in the bodies with trondhjemitic affinities (8.9 to 9.8% o) which intruded metasediments of the Salgueiro Group and in the peralkalic granitoids of Catingueira (8.1 to 9.8% o) which intruded Cachoeirinha metamorphics. Among the potassic granitoids, mean gamma 18 O increases from Bodoco to Itaporanga (from west to east). As a whole, the W.R. gamma 18 O of these plutons correlate with the type of grade of metamorphism of the host rocks and, therefore, with the tectonic framework, increasing from those which intruded the gneiss-migmatites to those which intruded the low-grade metamorphics of the Cachoeirinha Group. The possible origin of each rock group is discussed in light of the oxygen isotope geochemistry. (Author) [pt

  11. Oxygen Isotopes in Intra-Back Arc Basalts from the Andean Southern Volcanic Zone

    Parks, B. H.; Wang, Z.; Saal, A. E.; Frey, F. A.; Blusztajn, J.


    The chemical compositions of volcanic rocks from the Andean Southern Volcanic Zone (SVZ) reflect complex and dynamic interactions among the subducting oceanic lithosphere, the mantle wedge, and the overlying continental crust. Oxygen isotope ratios of olivine phenocrysts can be a useful means to identifying their relative contributions to the arc magmatism. In this study, we report high-precision oxygen-isotope ratios of olivine phenocrysts in a set of intra-back arc basalts from the SVZ. The samples were collected from monogenetic cinder cones east of the volcanic front (35-39 degrees S), and have been geochemically well-characterized with major and trace element contents, and Sr-Nd-Pb isotope compositions. Compared to lavas from the volcanic front, these intra-back arc lavas have similar radiogenic isotope, and a more alkalic and primitive (higher MgO content) chemical composition. We determined the oxygen-isotope ratios using the CO2-laser-fluorination method set up at the Department of Geology and Geophysics, Yale University following the techniques reported in Wang et al (2011). The samples were analyzed with standards of Gore Mountain Garnet (5.77×0.12‰ 1σ; Valley et al., 1995) and Kilbourne Hole Olivine (5.23×0.07‰ 1σ; Sharp, 1990) in order to account for minor changes in the vacuum line during analyses. The obtained δ18OSMOW values of olivine phenocrysts from the intra-back arc basalts vary from 4.98×0.01 to 5.34×0.01‰. This range, surprisingly, is similar to the δ18O values of olivines from mantle peridotites (5.2×0.2‰). Preliminary results indicate significant correlations of 87Sr/86Sr, 143Nd/144Nd and trace element ratios of the basaltic matrix with the δ18O values of olivine phenocrysts, indicating at least three components involved in the formation of the arc volcanism. By comparing the δ18O with the variations of major and trace element contents (e.g., MgO, TiO2 and Ni), and trace element ratios (e.g. Ba/Nb), we evaluate the effects

  12. Oxygen isotope effect on 55Mn nuclear magnetic shielding in permanganate

    Haase, A.R.; Lutz, O.; Mueller, M.; Nolle, A.


    By Fourier transform NMR spectroscopy the 55 Mn resonance lines of the different permanganate species 55 Mn 16 Osub(4-n) 18 Osub(n) - (n=0,1,2,3,4) have been resolved in aqueous solutions of potassium permanganate. An isotope effect on the Larmor frequency of 55 Mn of (0.599 +- 0.015)ppm to lower frequency was found for the substition of an 16 O atom by an 18 O atom in the permanganate ion. An oxygen exchange rate in the permanganate-water system is given. (orig.) [de

  13. Oxygen isotope ratios in the shell of Mytilus edulis: Archives of glacier meltwater in Greenland?

    Versteegh, E.A.A.; Blicher, M.E.; Mortensen, J.


    Melting of the Greenland Ice Sheet (GrIS) is accelerating and will contribute significantly to global sea level rise during the 21st century. Instrumental data on GrIS melting only cover the last few decades, and proxy data extending our knowledge into the past are vital for validating models...... these variations, because it precipitates its shell calcite in oxygen isotopic equilibrium with ambient seawater. As M. edulis shells are known to occur in raised shorelines and archaeological shell middens from previous Holocene warm periods, this species may be ideal in reconstructing past meltwater dynamics. We...

  14. Oxygen 18 isotopic analysis of sub-glacial concentrations of the Laurentide Ice Sheet

    Hillaire-Marcel, C [Quebec Univ., Montreal (Canada); Cailleux, A [Observatoire de Paris, Section de Meudon, 92 (France); Soucy, J


    Calcareous concretions occuring on Grenvillian gneiss have been discovered north of Hull, Quebec. Their structure and isotopic composition (delta/sub PDB//sup 18/O approximately equal to -26%; delta/sub PDB//sup 13/C approximately equal to 0%; /sup 14/C age > 35,000 BP) indicate subglacial conditions of precipitation. It is concluded that they were deposited at the base of the Laurentide ice sheet. Assuming equilibrium conditions with the subglacial film of water during precipitation of calcite, it is possible to define a -27.5 to -31.8% (vs. 'standard mean ocean water' (SMOW)) range for the oxygen-18 content of ice.

  15. Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign

    J. Savarino


    Full Text Available Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrogen oxides (NO + NO2 = NOx. The unique and distinctive 17O excess (Δ17O = δ17O − 0.52 × δ18O of ozone, which is transferred to NOx via oxidation, is a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O excess within the NOx cycle is critical in polar areas, where there exists the possibility of extending atmospheric investigations to the glacial–interglacial timescale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C (East Antarctic Plateau during the austral summer of 2011/2012. Nitrate isotope analysis has been here combined for the first time with key precursors involved in nitrate production (NOx, O3, OH, HO2, RO2, etc. and direct observations of the transferrable Δ17O of surface ozone, which was measured at Dome C throughout 2012 using our recently developed analytical approach. Assuming that nitrate is mainly produced in Antarctica in summer through the OH + NO2 pathway and using concurrent measurements of OH and NO2, we calculated a Δ17O signature for nitrate on the order of (21–22 ± 3 ‰. These values are lower than the measured values that ranged between 27 and 31 ‰. This discrepancy between expected and observed Δ17O(NO3− values suggests the existence of an unknown process that contributes significantly to the atmospheric nitrate budget over this East Antarctic region. However, systematic errors or false isotopic balance transfer functions are not totally excluded.

  16. Electrolytic separation factors for oxygen isotopes in light and heavy water solutions

    Gulens, J.; Olmstead, W.J.; Longhurst, T.H.; Gale, K.L.; Rolston, J.H.


    The electrolytic separation factor, α, has been measured for /sup 17/O and /sup 18/O at Pt and Ni anodes in both light and heavy water solutions of 6M KOH as a function of current density. For oxygen-17, isotopic separation effects were not observed, within the experimental uncertainty of +-2%, under all conditions studied. For oxygen-18, there is a small difference of 2% in α values between Pt and Ni in both light and heavy water solutions, but there is no significant difference in α values between light and heavy water solutions. In light waters solutions, the separation factor at Pt is small, α(/sup 18/O) ≤ 1.02 for i ≥ 0.1 A/cm/sub 2/. This value agrees reasonably well with theoretical estimates

  17. Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways

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


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

  18. Dual temperature effects on oxygen isotopic ratio of shallow-water coral skeleton: Consequences on seasonal and interannual records

    Juillet-Leclerc, A.; Reynaud, S.


    Oxygen isotopic ratio from coral skeleton is regarded for a long time as promising climate archives at seasonal scale. Although in isotopic disequilibrium relative to seawater, it is supposed to obey to the isotope thermometer. Indeed, coral oxygen isotopic records are strongly temperature dependent, but d18O-temperature calibrations derived from different corals are highly variable. The isotope thermometer assumption does not take into account vital effects due to biogenic origin of the mineral. Corals are animals living in symbiosis with algae (zooxanthellae). Interactions between symbiont photosynthesis and coral skeleton carbonation have been abundantly observed but they remain poorly understood and the effects of photosynthesis on coral growth and skeleton oxygen ratio are ignored. Coral cultured under two light conditions enabled to relate metabolic parameters and oxygen isotopic variability with photosynthetic activity. By examining responses provided by each colony they revealed that photosynthesis significantly affected d18O, by an opposite sense compared with the sole temperature influence. Since temperature and light changes are associated during seasonal variations, this complicates the interpretation of seasonal record. Additionally, this complexity is amplified because photosynthetic activity is also directly impacted by temperature variability. Thus, the annual isotopic amplitude due to the "physical" temperature influence is partly compensated through photosynthesis. Similar opposite effect is also shown by extension rate of the cultured colonies. First, we will examine and quantify consequences of photosynthesis on growth rate and oxygen isotopic signature, from cultured corals. Second, we will consider the consequences of this vital effect on data series, at seasonal and interannual time scales.

  19. Iron isotopes in ancient and modern komatiites: Evidence in support of an oxidised mantle from Archean to present

    Hibbert, K. E. J.; Williams, H. M.; Kerr, A. C.; Puchtel, I. S.


    The mantle of the modern Earth is relatively oxidised compared to the initially reducing conditions inferred for core formation. The timing of the oxidation of the mantle is not conclusively resolved but has important implications for the timing of the development of the hydrosphere and atmosphere. In order to examine the timing of this oxidation event, we present iron isotope data from three exceptionally well preserved komatiite localities, Belingwe (2.7 Ga), Vetreny (2.4 Ga) and Gorgona (0.089 Ga). Measurements of Fe isotope compositions of whole-rock samples are complemented by the analysis of olivine, spinel and pyroxene separates. Bulk-rock and olivine Fe isotope compositions (δ57Fe) define clear linear correlations with indicators of magmatic differentiation (Mg#, Cr#). The mean Fe isotope compositions of the 2.7-2.4 Ga and 0.089 Ga samples are statistically distinct and this difference can be explained by greater extent of partial melting represented by the older samples and higher mantle ambient temperatures in the Archean and early Proterozoic relative to the present day. Significantly, samples of all ages define continuous positive linear correlations between bulk rock δ57Fe and V/Sc and δ57Fe and V, and between V/Sc and V with TiO2, providing evidence for the incompatible behaviour of V (relative to Sc) and of isotopically heavy Fe. Partial melting models calculated using partition coefficients for V at oxygen fugacities (fO2s) of 0 and + 1 relative to the fayalite-magnetite-quartz buffer (FMQ) best match the data arrays, which are defined by all samples, from late Archean to Tertiary. These data, therefore, provide evidence for komatiite generation under moderately oxidising conditions since the late Archean, and argue against a change in mantle fO2 concomitant with atmospheric oxygenation at ~ 2.4 Ga.

  20. Growth of the European abalone ( Haliotis tuberculata L.) in situ: Seasonality and ageing using stable oxygen isotopes

    Roussel, Sabine; Huchette, Sylvain; Clavier, Jacques; Chauvaud, Laurent


    The ormer, Haliotis tuberculata is the only European abalone species commercially exploited. The determination of growth and age in the wild is an important tool for fisheries and aquaculture management. However, the ageing technique used in the past in the field is unreliable. The stable oxygen isotope composition ( 18O/ 16O) of the shell depends on the temperature and oxygen isotope composition of the ambient sea water. The stable oxygen isotope technique, developed to study paleoclimatological changes in shellfish, was applied to three H. tuberculata specimens collected in north-west Brittany. For the specimens collected, the oxygen isotope ratios of the shell reflected the seasonal cycle in the temperature. From winter-to-winter cycles, estimates of the age and the annual growth increment, ranging from 13 to 55 mm per year were obtained. This study shows that stable oxygen isotopes can be a reliable tool for ageing and growth studies of this abalone species in the wild, and for validating other estimates.

  1. Evaluation of perchlorate sources in the Rialto-Colton and Chino California subbasins using chlorine and oxygen isotope ratio analysis

    Hatzinger, Paul B.; Böhlke, John Karl; Izbicki, John; Teague, Nicholas F.; Sturchio, Neil C.


    Perchlorate (ClO4-) in groundwater can be from synthetic or natural sources, the latter of which include both historical application of imported nitrate fertilizers from the Atacama Desert of Chile and naturally deposited ClO4- that forms atmospherically and accumulates in arid regions such as the southwestern US. The objective of this study was to evaluate the use of isotopic data to distinguish sources of ClO4- in groundwater in a specific region of the Rialto-Colton and Chino, CA groundwater subbasins (Study Area). This region includes two groundwater ClO4- plumes emanating from known military/industrial source areas, and a larger area outside of these plumes having measurable ClO4-. Perchlorate extracted from wells in this region was analyzed for chlorine and oxygen stable isotope ratios (δ37Cl, δ18O, δ17O) and radioactive chlorine-36 (36Cl) isotopic abundance, along with other geochemical, isotopic, and hydrogeologic data. Isotope data indicate synthetic, Atacama, and indigenous natural ClO4- were present in the Study Area. Stable isotope data from nearly all sampled wells within the contours of the two characterized plumes, including those located in a perched zone and within the regional groundwater aquifer, were consistent with a dominant synthetic ClO4- source. In wells downgradient from the synthetic plumes and in the Chino subbasin to the southwest, isotopic data indicate the dominant source of ClO4- largely was Atacama, presumably from historical application of nitrate fertilizer in this region. Past agricultural land use and historical records are consistent with this source being present in groundwater. The 36Cl and δ18O data indicate that wells having predominantly synthetic or Atacama ClO4- also commonly contained small fractions of indigenous natural ClO4-. The indigenous ClO4- was most evident isotopically in wells having the lowest overall ClO4- concentrations (< 1 μg/L), consistent with its occurrence as a low-level background constituent

  2. Deuterium isotope fractionation between ortho-alkyl substituted phenols and t-butylthiol in oxygen bases

    Wawer, A.; Jelenska-Kazimierczuk, M.; Szydlowski, J.


    Equilibrium isotope effect in the exchange reaction of deuterium between phenol(P), 2-isopropyl phenol (IPP), 2,6-diisopropyl phenol (DIPP), 2,6-diterbutyl phenol (DTBP) and tertbutylthiol (TBT) has been studied in 296 K. The fractionation factors (α) have been measured in cyclohexane and carbon tetrachloride solutions and in a few oxygen bases: acetone, 1,4-dioxane, ethyl formate, ethyl ether, tetrahydrofurane, N,N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide. Using chemical shifts of phenol OH protons, the thermodynamic parameters of complex formation with the oxygen bases have been determined. The experimental data show that lnα correlates with the formation enthalpy of the phenol-oxygen base complex in DIPP-TBT-base system but there is no simple correlation in IPP-TBT-base system. Furthermore, it was found that in DTBT-TBT-base system lnα depends linearly on the basicity of the solvent (DN parameters). On the other hand, lnα correlates with acidic parameters of the solvents (AN) in IPP-TBT-base and P-TBT-base systems. All above correlations are explained by taking into account two competition processes: self association of phenol molecules and their solvation by oxygen bases. (author)

  3. Devonian climate and reef evolution: Insights from oxygen isotopes in apatite

    Joachimski, M. M.; Breisig, S.; Buggisch, W.; Talent, J. A.; Mawson, R.; Gereke, M.; Morrow, J. R.; Day, J.; Weddige, K.


    Conodonts, microfossils composed of carbonate-fluor apatite, are abundant in Palaeozoic-Triassic sediments and have a high potential to preserve primary oxygen isotope signals. In order to reconstruct the palaeotemperature history of the Devonian, the oxygen isotope composition of apatite phosphate was measured on 639 conodont samples from sequences in Europe, North America and Australia. The Early Devonian (Lochkovian; 416-411 Myr) was characterized by warm tropical temperatures of around 30 °C. A cooling trend started in the Pragian (410 Myr) with intermediate temperatures around 23 to 25 °C reconstructed for the Middle Devonian (397-385 Myr). During the Frasnian (383-375 Myr), temperatures increased again with temperatures to 30 °C calculated for the Frasnian-Famennian transition (375 Myr). During the Famennian (375-359 Myr), surface water temperatures slightly decreased. Reconstructed Devonian palaeotemperatures do not support earlier views suggesting the Middle Devonian was a supergreenhouse interval, an interpretation based partly on the development of extensive tropical coral-stromatoporoid communities during the Middle Devonian. Instead, the Devonian palaeotemperature record suggests that Middle Devonian coral-stromatoporoid reefs flourished during cooler time intervals whereas microbial reefs dominated during the warm to very warm Early and Late Devonian.

  4. Temperature measurements of Transdanubian Mesozoic rocks by the oxygen isotope method

    Cornides, I.; Csaszar, G.; Haas, J.; Jochane Edelenyi, E.


    Subjected to paleotemperature measurements with the use of oxygen and carbon isotopes were Upper Triassic, Jurassic and Cretaceous sedimentary rocks and their fossils from the Transdanubian Central Mountains, the Mecsek and the Villany Mts. In determining formation temperature, an important parameter of the environment of formation, the authors relied on the fact that the oxygen isotope composition of calcium carbonate precipitating from its aqueous solution deviates, in dependence on the temperature of the solution concerned, from that of the water. Consequently, the temperature of the water of the one-time seas must have been recorded by the 18 O/ 16 O ratio in the calcite of fossils or sediments. The results reported indicate smaller changes in temperature as compared to international results. In the Jurassic the values of temperature remain consistently below those quoted for Swiss and French territories, being around the values reported from/sroe/thern Germany. These u curves have their maxima in the Toarcian, Aalenian, sediments for which unfortunately no Hungarian results are available. The few results of Cretaceous belemnites are values higher than their international counterparts. The high temperature value obtained for the Albian correlates very well with the formation of rocks known from this stratigraphic stage (red clays, bauxites). (A.L.)

  5. Carbon 13 and oxygen 18 isotope record of the early eocene nammal formation, salt range, pakistan

    Ghazi, S.; Sajid, Z.


    The Nammal Formation is the lowermost unit of the Early Eocene succession in the Salt Range, Pakistan. It is well exposed throughout the Salt Range. The Nammal Formation having 30 to 35 meters thickness is predominantly composed of nodular limestone interbedded with marl and shale. The present study was focussed on stable carbon 13 and oxygen 18 isotopic analysis based on data from two stratigraphically important sections. The samples from the Nilawahan section provided with the delta 13C values varied between 1.34 to -1.56 (VPDB) and values of delta 18O fluctuated between -4.47 to -6.59 (VPDB). Likewise the sample analysis of BadshahPur section exhibited that the delta 13C values changes from 1.09 to -1.65 (VPDB) and delta 18O values range from -4.17 to -6.85 (VPDB). The isotopic records of carbon 13 and oxygen 18 indicated the shallow marine deposition of the Nammal Formation under tropical conditions. It highlighted the palaeo climatic and diagenetic conditions of the Nammal Formation at the time of deposition in the Salt Range region. (author)

  6. Hydrogen and oxygen isotope constraints on hydrothermal alteration of the Trinity peridotite, Klamath Mountains, California

    Liakhovitch, V.; Quick, J.E.; Gregory, R.T.


    The Trinity peridotite represents a rare opportunity to examine a relatively fertile plagioclase peridotite that was exhumed and later subjected to intrusive events in a seafloor environment, followed by its emplacement and incorporation into a continent. Over 250 stable isotopic determinations on whole rocks and minerals elucidate the hydrothermal evolution of the Trinity complex. All three serpentine polymorphs are present in the Trinity peridotite; these separate on the basis of their ??D values: antigorite, -46 serpentinization, or overprinting of earlier low-temperature seafloor serpentinization. Regionally, contours of ??D values exhibit bull's-eye patterns associated with the gabbroic plutons, with ??D maxima coinciding with the blackwall alteration at the margins on the plutons. In contrast to the hydrogen isotope behavior, oxygen isotope values of the three polymorphs are indistinguishable, spanning the range 5.3 history: (1) lithospheric emplacement and cooling of the peridotite in an oceanic environment ??? 472 Ma; (2) intrusion of gabbroic plutons into cold peridotite in an arc environment between 435 and 404 Ma; and finally (3) intrusion of felsic plutons between 171 and 127 Ma, long after the peridotite was incorporated into the continental crust. Copyright ?? 2005 by V. H. Winston & Son, Inc. All rights reserved.

  7. Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

    Young, M.B.; McLaughlin, K.; Kendall, C.; Stringfellow, W.; Rollog, M.; Elsbury, K.; Donald, E.; Paytan, A.


    The oxygen isotopic composition of dissolved inorganic phosphate (δ18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ18O p to be a useful tool for source tracking, the δ18Op of phosphate sources must be distinguishable from one another; however, the δ18Op of potential sources has not been well characterized. We measured the δ18O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ18Op values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and δ18Op can be used for identifying phosphate sources to aquatic systems.

  8. Separation of isotopes of nitrogen and oxygen by low temperature distillation of nitrogen oxide

    Isomura, Shohei; Tonooka, Yasuhiko; Kaetsu, Hayato


    In general, the distillation parameters, such as the number of theoretical plate (NTP) and the height equivalent to a theoretical plate (HETP), can be obtained from the operation at the steady state. However, it is time-consuming to achieve the steady state especially in the case of isotope separation. In this paper, with the purpose of simultaneous separation of isotopes of nitrogen and oxygen by NO distillation, we tried to determine the distillation parameters by an analytical method through the transient-state operation. It was confirmed that the results from the analysis were in good agreement with those observed for the operation at the steady state. Enrichment of the isotopes was carried out using a distillation column with a height of 1 m and inside diameter of 12 mm. The dependence of HETP on liquid flow rate was measured by the proposed method. The obtained HETP values were from 2 to 4 cm. The operation time of about 5 h was found to be long enough to determine the distillation parameters.

  9. Separation of isotopes of nitrogen and oxygen by low temperature distillation of nitrogen oxide

    Isomura, Shohei; Tonooka, Yasuhiko; Kaetsu, Hayato


    In general, the distillation parameters, such as the number of theoretical plate (NTP) and the height equivalent to a theoretical plate (HETP), can be obtained from the operation at the steady state. However, it is time-consuming to achieve the steady state especially in the case of isotope separation. In this paper, with the purpose of simultaneous separation of isotopes of nitrogen and oxygen by NO distillation, we tried to determine the distillation parameters by an analytical method through the transient-state operation. It was confirmed that the results from the analysis were in good agreement with those observed for the operation at the steady state. Enrichment of the isotopes was carried out using a distillation column with a height of 1 m and inside diameter of 12 mm. The dependence of HETP on liquid flow rate was measured by the proposed method. The obtained HETP values were from 2 to 4 cm. The operation time of about 5 h was found to be long enough to determine the distillation parameters. (author)

  10. Do oxygen stable isotopes track precipitation moisture source in vascular plant dominated peatlands?

    Charman, D.; Amesbury, M. J.; Newnham, R.; Loader, N.; Goodrich, J. P.; Gallego-Sala, A. V.; Royles, J.; Keller, E. D.; Baisden, W. T.


    Variations in the isotopic composition of precipitation are determined by fractionation processes which occur during temperature and humidity dependent phase changes associated with evaporation and condensation. Oxygen stable isotope ratios have therefore been frequently used as a source of palaeoclimate data from a variety of proxy archives. Exploitation of this record from ombrotrophic peatlands, where the source water used in cellulose synthesis is derived solely from precipitation, has been mostly limited to Northern Hemisphere Sphagnum-dominated bogs, with limited application in the Southern Hemisphere (SH) or in peatlands dominated by vascular plants. Throughout New Zealand (NZ), the preserved root matrix of the restionaceous wire rush (Empodisma spp.) forms deep peat deposits. NZ provides an ideal location to undertake empirical research into oxygen isotope fractionation in vascular peatlands because sites are ideally suited to single taxon analysis, preserve potentially high resolution full Holocene palaeoclimate records and are situated in the climatically sensitive SH mid-latitudes. Crucially, large gradients exist in the mean isotopic composition of precipitation across NZ, caused primarily by the relative influence of different climate modes. We test the capacity for δ18O analysis of Empodisma alpha cellulose from ombrotrophic restiad peatlands in NZ to provide a methodology for developing palaeoclimate records. We took surface plant, water and precipitation samples over spatial (six sites spanning >10° latitude) and temporal (monthly measurements over one year) gradients. We found a strong link between the isotopic compositions of surface root water, the most likely source water for plant growth, and precipitation in both datasets. Back-trajectory modelling of precipitation moisture source for rain days prior to sampling showed clear seasonality in the temporal data that was reflected in surface root water. The link between source water and plant

  11. Simulated oxygen isotopes in cave drip water and speleothem calcite in European caves

    A. Wackerbarth


    Full Text Available Interpreting stable oxygen isotope18O records from stalagmites is still one of the complex tasks in speleothem research. Here, we present a novel model-based approach, where we force a model describing the processes and modifications of δ18O from rain water to speleothem calcite (Oxygen isotope Drip water and Stalagmite Model – ODSM with the results of a state-of-the-art atmospheric general circulation model enhanced by explicit isotope diagnostics (ECHAM5-wiso. The approach is neither climate nor cave-specific and allows an integrated assessment of the influence of different varying climate variables, e.g. temperature and precipitation amount, on the isotopic composition of drip water and speleothem calcite.

    First, we apply and evaluate this new approach under present-day climate conditions using observational data from seven caves from different geographical regions in Europe. Each of these caves provides measured δ18O values of drip water and speleothem calcite to which we compare our simulated isotope values. For six of the seven caves modeled δ18O values of drip water and speleothem calcite are in good agreement with observed values. The mismatch of the remaining caves might be caused by the complexity of the cave system, beyond the parameterizations included in our cave model.

    We then examine the response of the cave system to mid-Holocene (6000 yr before present, 6 ka climate conditions by forcing the ODSM with ECHAM5-wiso results from 6 ka simulations. For a set of twelve European caves, we compare the modeled mid-Holocene-to-modern difference in speleothem calcite δ18O to available measurements. We show that the general European changes are simulated well. However, local discrepancies are found, and might be explained either by a too low model resolution, complex local soil-atmosphere interactions affecting evapotranspiration or by cave specific factors

  12. Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

    LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M


    Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the

  13. Strontium geochemistry and carbon and oxygen isotopic compositions of Lower Proterozoic dolomite and calcite marbles from the Marmorilik Formation, West Greenland

    Garde, A.A.


    The Marmorilik Formation, Rinkian mobile belt, West Greenland, is a large, Lower Proterozoic carbonate-rock sequence, deformed and metamorphosed under greenschist to amphibolite facies conditions. The pre-deformation thickness of the sequence is at least 2000 m, with about 1400 m of dolomite marble and 350 m of calcite marble. Strontium contents of forty-two dolomite and calcite marbles range from 30 to 100 ppm and 300 to 800 ppm, respectively, whereas samples with calcite of secondary origin have strontium contents between 80 ppm and 200 ppm. Carbon and oxygen isotope ratios were determined for forty calcite and dolomite marbles as -0.2+-1.0 per 1000 delta 13 C and -9.9+-1.5 per 1000 delta 18 O (vs. PDB) and are compatible with the isotopic compositions of unmetamorphosed carbonates of similar age. Calcite from eight calciumsilicate rocks, breccias and calcite veins is significantly more negative in delta 13 C and delta 18 O. Five 13 C analyses of graphite in marble range from -9.6 to -14 per 1000. Possible post-depositional changes in the strontium content and carbon and oxygen isotope compositions are discussed. It is concluded that (a) the calcite marbles are not dedolomites and are therefore of primary origin, (b) the delta 13 C and delta 18 O values of the marbles are primary or diagenetic (i.e., pre-metamorphic), and (c) the isotopic composition of the graphite is compatible with, though not necessarily evidence for, a biogenic origin. (Auth.)

  14. Low-temperature aqueous alteration on the CR chondrite parent body: Implications from in situ oxygen-isotope analyses

    Jilly-Rehak, Christine E.; Huss, Gary R.; Nagashima, Kazu; Schrader, Devin L.


    The presence of hydrated minerals in chondrites indicates that water played an important role in the geologic evolution of the early Solar System; however, the process of aqueous alteration is still poorly understood. Renazzo-like carbonaceous (CR) chondrites are particularly well-suited for the study of aqueous alteration. Samples range from being nearly anhydrous to fully altered, essentially representing snapshots of the alteration process through time. We studied oxygen isotopes in secondary-minerals from six CR chondrites of varying hydration states to determine how aqueous fluid conditions (including composition and temperature) evolved on the parent body. Secondary minerals analyzed included calcite, dolomite, and magnetite. The O-isotope composition of calcites ranged from δ18O ≈ 9 to 35‰, dolomites from δ18O ≈ 23 to 27‰, and magnetites from δ18O ≈ -18 to 5‰. Calcite in less-altered samples showed more evidence of fluid evolution compared to heavily altered samples, likely reflecting lower water/rock ratios. Most magnetite plotted on a single trend, with the exception of grains from the extensively hydrated chondrite MIL 090292. The MIL 090292 magnetite diverges from this trend, possibly indicating an anomalous origin for the meteorite. If magnetite and calcite formed in equilibrium, then the relative 18O fractionation between them can be used to extract the temperature of co-precipitation. Isotopic fractionation in Al Rais carbonate-magnetite assemblages revealed low precipitation temperatures (∼60 °C). Assuming that the CR parent body experienced closed-system alteration, a similar exercise for parallel calcite and magnetite O-isotope arrays yields "global" alteration temperatures of ∼55 to 88 °C. These secondary mineral arrays indicate that the O-isotopic composition of the altering fluid evolved upon progressive alteration, beginning near the Al Rais water composition of Δ17O ∼ 1‰ and δ18O ∼ 10‰, and becoming increasingly

  15. Environmental isotopes in New Zealand hydrology ; 4. Oxygen isotope variations in subsurface waters of the Waimea Plains, Nelson

    Stewart, M.K.; Dicker, M.J.I.; Johnston, M.R.


    Oxygen isotope measurements of ground and surface waters of the Waimea Plains, Nelson, have been used to identify sources of water in aquifers beneath the plains. Major rivers flowing onto the plains are from higher-altitude catchments (maximum altitude 2000 m) and have delta O 18 approximately equal to -7.2%, whereas rainfall on the plains and adjacent low-altitude catchment streams have delta O 18 approximately equal to -6.2%. The delta O 18 measurements indicate that the 3 major aquifer units, the ''Lower Confined Aquifers'' and the ''Upper Confined Aquifers'' in the Hope Gravel (Late Pleistocene) and the ''Unconfined Aquifers'' in the Appleby Gravel (Holocene) are recharged from different sources. The ''Lower Confined Aquifers'' probably receive slow recharge in the south near Brightwater. The ''Upper Confined Aquifers'' are recharged, in the south, from the Wairoa River and locally in the north are connected with the unconfined aquifers. The ''Unconfined Aquifers'' are recharged from the Waimea River and, away from the river, from rainfall. Intermixing of water, via multiple screened wells, between the various aquifers is also indicated. (author). 5 refs., 5 figs., 1 tab

  16. ENSO variability reflected in precipitation oxygen isotopes across the Asian Summer Monsoon region

    Cai, Zhongyin; Tian, Lide; Bowen, Gabriel J.


    Oxygen isotope signals (δ18O) from paleo-archives are important proxies for past Asian Summer Monsoon (ASM) climate reconstruction. However, causes of interannual variation in the δ18O values of modern precipitation across the ASM region remain in argument. We report interannual δ18O variation in southern Tibetan Plateau precipitation based on long-term observations at Lhasa. These data, together with precipitation δ18O records from five Global Network of Isotopes in Precipitation (GNIP) stations and two ice core δ18O records, were used to define a regional metric of ASM precipitation δ18O (ASMOI). Back-trajectory analyses for rainy season precipitation events indicate that moisture sources vary little between years with relatively high and low δ18O values, a result that is consistent for the south (Lhasa), southeast (Bangkok), and east ASM regions (Hong Kong). In contrast, δ18O values at these three locations are significantly correlated with convection in the estimated source regions and along transport paths. These results suggest that upstream convection, rather than moisture source change, causes interannual variation in ASM precipitation δ18O values. Contrasting values of the ASMOI in El Niño and La Niña years reveal a positive isotope-El Niño Southern Oscillation (ENSO) response (e.g., high values corresponding to warm phases), which we interpret as a response to changes in regional convection. We show that the isotope-ENSO response is amplified at high elevation sites and during La Niña years. These findings should improve interpretations of paleo-δ18O data as a proxy for past ASM variation and provide new opportunities to use data from this region to study paleo-ENSO activity.

  17. Oxygen isotope fractionations across individual leaf carbohydrates in grass and tree species.

    Lehmann, Marco M; Gamarra, Bruno; Kahmen, Ansgar; Siegwolf, Rolf T W; Saurer, Matthias


    Almost no δ 18 O data are available for leaf carbohydrates, leaving a gap in the understanding of the δ 18 O relationship between leaf water and cellulose. We measured δ 18 O values of bulk leaf water (δ 18 O LW ) and individual leaf carbohydrates (e.g. fructose, glucose and sucrose) in grass and tree species and δ 18 O of leaf cellulose in grasses. The grasses were grown under two relative humidity (rH) conditions. Sucrose was generally 18 O-enriched compared with hexoses across all species with an apparent biosynthetic fractionation factor (ε bio ) of more than 27‰ relative to δ 18 O LW , which might be explained by isotopic leaf water and sucrose synthesis gradients. δ 18 O LW and δ 18 O values of carbohydrates and cellulose in grasses were strongly related, indicating that the leaf water signal in carbohydrates was transferred to cellulose (ε bio  = 25.1‰). Interestingly, damping factor p ex p x , which reflects oxygen isotope exchange with less enriched water during cellulose synthesis, responded to rH conditions if modelled from δ 18 O LW but not if modelled directly from δ 18 O of individual carbohydrates. We conclude that δ 18 O LW is not always a good substitute for δ 18 O of synthesis water due to isotopic leaf water gradients. Thus, compound-specific δ 18 O analyses of individual carbohydrates are helpful to better constrain (post-)photosynthetic isotope fractionation processes in plants. © 2017 John Wiley & Sons Ltd.

  18. Preliminary study on the characteristics of carbon and oxygen isotopes in the Shiziping geothermal field groundwater in Emei Mountain

    Yu Xiujing; Jia Shuyuan


    Emei Mountain is a well-known scenic tourism spot in China. In order to promote the development of tourist trade, the authors have explored the hydrothermal water in Emei Mountain. At the beginning of 1998, the hydrothermal water was successfully drilled from the Shiziping geothermal field. In the process of prospecting the hydrothermal water, the authors adopted the geochemical method such as carbon and oxygen isotopes. The result indicates that the groundwater of different genetic types has different constitution characteristics of carbon and oxygen isotopes. This provides the important basis for finding out the forming conditions of underground hydrothermal water. So, it is prospective to study the growth characteristics of hydrothermal water with the carbon and oxygen isotopes of HCO 3 in groundwater

  19. Seasonal Variations in Stable Isotope Ratios of Oxygen and Hydrogen in Two Tundra Rivers in NE European Russia

    Huitu, E.; Arvola, L. [Lammi Biological Station, University of Helsinki (Finland); Sonninen, E. [Radiocarbon Dating Laboratory, University of Helsinki (Finland)


    The variability in stable isotope ratios of oxygen and hydrogen ({delta} {sup 18}O and {delta}{sup 2}H values) in river waters in northeast European Russia was studied for the period from July 2007 to october 2008. Exceptional isotope composition in precipitation obtained during the sampling period was clearly traced in the composition of river waters. Water from permafrost thawing did not make a great contribution to river flow. (author)

  20. Oxygen isotope systematics of chondrules in the Murchison CM2 chondrite and implications for the CO-CM relationship

    Chaumard, Noël; Defouilloy, Céline; Kita, Noriko T.


    High-precision oxygen three-isotope measurements of olivine and pyroxene were performed on 29 chondrules in the Murchison CM2 chondrite by secondary ion mass spectrometry (SIMS). The oxygen isotope ratios of analyzed chondrules all plot very close to the primitive chondrule minerals (PCM) line. In each of 24 chondrules, the olivine and/or pyroxene grains analyzed show indistinguishable oxygen isotope ratios. Exceptions are minor occurrences of isotopically distinguished relict olivine grains, which were found in nine chondrules. The isotope homogeneity of these phenocrysts is consistent with a co-magmatic crystallization of olivine and pyroxene from the final chondrule melts and a significant oxygen isotope exchange between the ambient gas and the melts. Homogeneous type I chondrules with Mg#'s of 98.9-99.5 have host chondrule Δ17O values ranging from -6.0‰ to -4.1‰, with one exception (Δ17O: -1.2‰; Mg#: 99.6). Homogeneous chondrules with Mg#'s poor H2O ice (∼0.3-0.4× the CI dust; Δ17O > 0‰) and at dust enrichments of ∼300-2000×. Regarding the Mg# and oxygen isotope ratios, the chondrule populations sampled by CM and CO chondrites are similar and indistinguishable. The similarity of these 16O-rich components in CO and CM chondrites is also supported by the common Fe/Mn ratio of olivine in type II chondrules. Although they accreted similar high-temperature silicates, CO chondrites are anhydrous compared to CM chondrites, suggesting they derived from different parent bodies formed inside and outside the snow line, respectively. If chondrules in CO and CM chondrites formed at the same disk locations but the CM parent body accreted later than the CO parent body, the snow line might have crossed the common chondrule-forming region towards the Sun between the time of the CO and CM parent bodies accretion.

  1. Oxygen isotopic composition of carbonate concretions from the lower Cretaceous of Victoria, Australia: Implications for the evolution of meteoric waters on the Australian continent in a paleopolar environment

    Gregory, R.T.


    Oxygen isotopic data from carbonate cements in concretions have been used to infer the isotopic composition of meteoric fluids present at the time of concretion growth in terrestrial sediments that were deposited within the early Cretaceous South Polar Circle at 75-80 0 S. Carbon and oxygen isotope compositions have been determined on over 135 samples of carbonate from 45 concretions taken from 24 localities (Aptian-Albian in age) in the terrestrial sedimentary basins associated with the Otway and Strzelecki groups, southeastern Australia. The carbonate cements include calcite having -26.4≤δ 13 C≤19.6 and 3.6≤δ 18 O≤29.6 or siderite having 17.6≤δ 18 O≤30.8. Calcite-cemented concretions are more abundant and are interpreted to represent early near-surface cementation events on the basis of textural evidence such as high (>30%) porosities at the time of cementation and mineralogical evidence such as the preferential preservation within concretions of labile detrital grains including plagioclase, pyroxene, and amphibole. The oxygen isotopic data indicate that meteoric fluids with very low δ 18 O, certainly less than -15per mille and probably on the order of -20per mille, were involved in the precipitation of the early calcites. The extremely low δ 18 O values of the fluids involved in the early diagenesis of both the Otway and Strzelecki groups suggest that the catchment area of the river system that carried sediments to these basins had a cold high-latitude climate (with mean annual temperatures less than 5 0 C and quite possibly below freezing). By analogy with the relationship between modern 18 O distribution of meteoric fluids and climate, these new data suggest that the early Cretaceous polar regions may not have been ice-free. (orig.)

  2. Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event

    Planavsky, Noah J.; Asael, Dan; Hofmann, Axel; Reinhard, Christopher T.; Lalonde, Stefan V.; Knudsen, Andrew; Wang, Xiangli; Ossa Ossa, Frantz; Pecoits, Ernesto; Smith, Albertus J. B.; Beukes, Nicolas J.; Bekker, Andrey; Johnson, Thomas M.; Konhauser, Kurt O.; Lyons, Timothy W.; Rouxel, Olivier J.


    The early Earth was characterized by the absence of oxygen in the ocean-atmosphere system, in contrast to the well-oxygenated conditions that prevail today. Atmospheric concentrations first rose to appreciable levels during the Great Oxidation Event, roughly 2.5-2.3 Gyr ago. The evolution of oxygenic photosynthesis is generally accepted to have been the ultimate cause of this rise, but it has proved difficult to constrain the timing of this evolutionary innovation. The oxidation of manganese in the water column requires substantial free oxygen concentrations, and thus any indication that Mn oxides were present in ancient environments would imply that oxygenic photosynthesis was ongoing. Mn oxides are not commonly preserved in ancient rocks, but there is a large fractionation of molybdenum isotopes associated with the sorption of Mo onto the Mn oxides that would be retained. Here we report Mo isotopes from rocks of the Sinqeni Formation, Pongola Supergroup, South Africa. These rocks formed no less than 2.95 Gyr ago in a nearshore setting. The Mo isotopic signature is consistent with interaction with Mn oxides. We therefore infer that oxygen produced through oxygenic photosynthesis began to accumulate in shallow marine settings at least half a billion years before the accumulation of significant levels of atmospheric oxygen.

  3. Phosphorus cycling in forest ecosystems: insights from oxygen isotopes in phosphate

    Pistocchi, Chiara; Tamburini, Federica; Bünemann, Else; Frossard, Emmanuel


    The current view on the phosphorus (P) cycle in forest ecosystems relies mostly on measurements and correlations of pools, and to a lower extent on measurement of fluxes. We have no direct insight into the processes phosphate goes through at the ecosystem level, and into the relative importance of organic and mineral pools in sustaining P nutrition of trees. The analysis of oxygen isotopes associated to P (18Op) is expected to bring this type of information. The German Priority Program SPP 1685 aims to test the overall hypothesis that the P-depletion of soils drives forest ecosystems from P acquiring systems (efficient mobilization of P from the mineral phase) to P recycling systems (highly efficient cycling of P). Our contribution to this project will consist in studying the relative importance of biological and geochemical processes in controlling the P cycle in temperate beech forest ecosystems in Germany along a gradient of decreasing soil P availability. We will follow the fate of phosphate from litter fall to the uptake of P by plants via P release by decomposition of organic matter or after release from P-containing minerals, by using a multi-isotope approach (O in water and phosphate plus 33P). To address our research question we will rely on measurements in experimental forest sites and on laboratory incubations of the organic layer or the mineral soil. We present here the first results issued from the 2014 sampling on three study sites, where we characterized the P pools in surface soil horizons by a sequential extraction (modified after Tiessen and Moir, 2007) and we analysed the 18Op of the resin extractable- and microbial-P fractions. Contrary to what was previously found (e.g. Tamburini et al. 2012) the isotopic composition of these fractions in most of the samples does not reflect the equilibrium value (as the result of the dominance of the pyrophosphatase activity on the other enzymatic processes, Blake et al. 2005). Depending on the P availability

  4. Hf isotope evidence for a hidden mantle reservoir

    Bizzarro, Martin; Simonetti, A.; Stevenson, R.K.


    High-precision Hf isotopic analyses and U-Pb ages of carbonatites and kimberlites from Greenland and eastern North America, including Earth's oldest known carbonatite (3 Ga), indicate derivation from an enriched mantle source. This previously unidentified mantle reservoir-marked by an unradiogenic...... Hf isotopic composition and preserved in the deep mantle for at least 3 b.y.-may account for the mass imbalance in Earth's Hf-Nd budget. The Hf isotopic data presented here support a common mantle source region and genetic link between carbonatite and some oceanic-island basalt volcanoes....

  5. Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

    Keedakkadan, Habeeb Rahman; Abe, Osamu


    The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic

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

    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.

  7. Isotopic evidences of past upwelling intensity in the Arabian Sea

    Naidu, P.D.

    and understand the history of upwelling as it is recorded in deep-sea sediments. The southwest (SW) monsoon strongly influences the climatic conditions in South and Southeast Asia and biological productivity in the Arabian Sea. ability at the ODP Site 728... climatic change and ocean history (McCrea, 1950; Epstein et al., 1953; Emiliani, 1955). The isotopic role of planktic forami- nifera expanded, it was recognized that foraminifera did not secret their shells in isotopic equilibrium with ambient water (Be...

  8. Charge state distribution studies of pure and oxygen mixed krypton ECR plasma - signature of isotope anomaly and gas mixing effect.

    Kumar, Pravin; Mal, Kedar; Rodrigues, G


    We report the charge state distributions of the pure, 25% and 50% oxygen mixed krypton plasma to shed more light on the understanding of the gas mixing and the isotope anomaly [A. G. Drentje, Rev. Sci. Instrum. 63 (1992) 2875 and Y Kawai, D Meyer, A Nadzeyka, U Wolters and K Wiesemann, Plasma Sources Sci. Technol. 10 (2001) 451] in the electron cyclotron resonance (ECR) plasmas. The krypton plasma was produced using a 10 GHz all-permanent-magnet ECR ion source. The intensities of the highly abundant four isotopes, viz. 82 Kr (~11.58%), 83 Kr (~11.49%), 84 Kr (~57%) and 86 Kr (17.3%) up to ~ +14 charge state have been measured by extracting the ions from the plasma and analysing them in the mass and the energy using a large acceptance analyzer-cum-switching dipole magnet. The influence of the oxygen gas mixing on the isotopic krypton ion intensities is clearly evidenced beyond +9 charge state. With and without oxygen mixing, the charge state distribution of the krypton ECR plasma shows the isotope anomaly with unusual trends. The anomaly in the intensities of the isotopes having quite closer natural abundance, viz. 82 Kr, 86 Kr and 83 Kr, 86 Kr is prominent, whereas the intensity ratio of 86 Kr to 84 Kr shows a weak signature of it. The isotope anomaly tends to disappear with increasing oxygen mixing in the plasma. The observed trends in the intensities of the krypton isotopes do not follow the prediction of linear Landau wave damping in the plasma. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  9. Tracing the oxygen triple isotopic composition of tropospheric molecular oxygen in biogenic apatite - a new tool for palaeoclimatology

    Pack, A.; Süssenberger, A.; Gehler, A.; Wotzlaw, J.


    It has been demonstrated that tropospheric molecular oxygen posses a significant isotope anomaly [1, 2 and refs. therein]. Relative to the rocks- and minerals-defined terrestrial fractionation line (TFL), tropospheric O2 has an anomaly of -0.35‰ [2]. Because almost all oxygen on Earth is contained in rocks, we suggest that the rocks- and minerals-defined TFL [3] should be used as reference when reporting isotope anomalies with ∆17O = δ'17OSMOW - βTFL δ'18OSMOW. We have developed a new technique for the determination of δ17O and δ18O of silicates by means of laser fluorination GC-CF-irmMS. We have determined βTFL to 0.5247 (N > 100), which is identical to the value reported by other laboratories and techniques [2, 3]. The uncertainty in ∆17O is ±0.03 (1σ) for a single analysis. It was suggested that ∆17O of tropospheric O2 can be used as proxy for the global bioactivity rate [GBR, 1] as well as for past atmospheric CO2 concentrations [4]. Past ∆17O of tropospheric O2 can be determined by analyzing O2 trapped in ice [1, 5] or by analyzing sulfates from terrestrial sulphide oxidation [4]. Disadvantage of ice core data is the limitation in time back mammals of different body mass (Mb) from Northern Germany (except Indian Elephant). The ∆17O of apatite varies between -0.16‰ for a wood mouse (Apodemus sylvaticus) and +0.04‰ for a wild boar (Sus scrofa). Samples were analyzed between 5 and 7 times in order to reduce the analytical uncertainty to ±0.012-0.025‰. Our data confirm the prediction from mass balance that animals inherit a ∆17O signature from anomalous air O2. We have developed a detailed mass balance for mammals with respect to ∆17O. The mass balance considers the oxygen fluxes (drinking and food water, respired O2, metabolic water, excrements, evaporated water and exhaled CO2). The fractionation in δ18O and ∆17O (from associated β-value) was considered for each of the fluxes. The result is an allometric scaling model for ∆17

  10. Nitrogen and Triple Oxygen Isotopic Analyses of Atmospheric Particulate Nitrate over the Pacific Ocean

    Kamezaki, Kazuki; Hattori, Shohei; Iwamoto, Yoko; Ishino, Sakiko; Furutani, Hiroshi; Miki, Yusuke; Miura, Kazuhiko; Uematsu, Mitsuo; Yoshida, Naohiro


    Nitrate plays a significant role in the biogeochemical cycle. Atmospheric nitrate (NO3- and HNO3) are produced by reaction precursor as NOx (NO and NO2) emitted by combustion, biomass burning, lightning, and soil emission, with atmospheric oxidants like ozone (O3), hydroxyl radical (OH), peroxy radical and halogen oxides. Recently, industrial activity lead to increases in the concentrations of nitrogen species (NOx and NHy) throughout the environment. Because of the increase of the amount of atmospheric nitrogen deposition, the oceanic biogeochemical cycle are changed (Galloway et al., 2004; Kim et al., 2011). However, the sources and formation pathways of atmospheric nitrate are still uncertain over the Pacific Ocean because the long-term observation is limited. Stable isotope analysis is useful tool to gain information of sources, sinks and formation pathways. The nitrogen stable isotopic composition (δ15N) of atmospheric particulate NO3- can be used to posses information of its nitrogen sources (Elliott et al., 2007). Triple oxygen isotopic compositions (Δ17O = δ17O - 0.52 ×δ18O) of atmospheric particulate NO3- can be used as tracer of the relative importance of mass-independent oxygen bearing species (e.g. O3, BrO; Δ17O ≠ 0 ‰) and mass-dependent oxygen bearing species (e.g. OH radical; Δ17O ≈ 0 ‰) through the formation processes from NOx to NO3- in the atmosphere (Michalski et al., 2003; Thiemens, 2006). Here, we present the isotopic compositions of atmospheric particulate NO3- samples collected over the Pacific Ocean from 40˚ S to 68˚ N. We observed significantly low δ15N values for atmospheric particulate NO3- on equatorial Pacific Ocean during both cruises. Although the data is limited, combination analysis of δ15N and Δ17O values for atmospheric particulate NO3- showed the possibility of the main nitrogen source of atmospheric particulate NO3- on equatorial Pacific Ocean is ammonia oxidation in troposphere. Furthermore, the Δ17O values

  11. Oxygen isotope analysis of shark teeth phosphates from Bartonian (Eocene) deposits in Mangyshlak peninsula, Kazakhstan

    Pelc, Andrzej; Hałas, Stanisław; Niedźwiedzki, Robert


    We report the results of high-precision (±0.05‰) oxygen isotope analysis of phosphates in 6 teeth of fossil sharks from the Mangyshlak peninsula. This precision was achieved by the offline preparation of CO2 which was then analyzed on a dual-inlet and triple-collector IRMS. The teeth samples were separated from Middle- and Late Bartonian sediments cropping out in two locations, Usak and Kuilus. Seawater temperatures calculated from the δ18O data vary from 23-41°C. However, these temperatures are probably overestimated due to freshwater inflow. The data point at higher temperature in the Late Bartonian than in the Middle Bartonian and suggest differences in the depth habitats of the shark species studied.

  12. An oxygen isotope study on hydrothermal sources of granite-type uranium deposits in South China

    Yongfei, Z.


    The usefulness of oxygen isotope measurements in solving problems of hydrothermal sources has been demonstrated in a number of detailed studies of the granite type uranium deposits in this paper. Remarkly the granite-type uranium deposits in Southr China have been shown to have formed from magmatic water, meteoric water, of mixtures of both the above, and origin of waters in the ore-forming fluid may be different for differing uranium deposits ore differing stages of the mineralization. Consequences obtained in this study for typical uranium deposits of different age and geologic sitting agree well with that obtained by other geologic-geochemical investigation. Furthermore, not only meteoric water is of importance to origin and evolution of the ore-forming fluid, but also mixing of waters from different sources is considered to be one of the most characteristic features of many hydrothermal uranium deposits related to granitoids or volcanics. (C.D.G.) [pt

  13. Spatiotemporal variability of oxygen isotope compositions in three contrasting glacier river catchments in Greenland

    Knudsen, N. Tvis; Yde, J.C.; Steffensen, J.P.


    composition is controlled by the proportion between snowmelt and ice melt with episodic inputs of rainwater and occasional storage and release of a specific water component due to changes in the subglacial drainage system. At Kuannersuit Glacier River on the island Qeqertarsuaq, the δ18O characteristics were......Analysis of stable oxygen isotope (δ18O) characteristics is a useful tool to investigate water provenance in glacier river systems. In order to attain knowledge on the diversity of spatio-temporal δ18O variations in glacier rivers, we have examined three glacierized catchments in Greenland...... of diurnal oscillations, and in 2003 there were large diurnal fluctuations in δ18O. At Watson River, a large catchment at the western margin of the Greenland Ice Sheet, the spatial distribution of δ18O in the river system was applied to fingerprint the relative runoff contributions from sub-catchments. Spot...

  14. Interaction cross sections and matter radii of oxygen isotopes using the Glauber model

    Ahmad, Suhel; Usmani, A. A.; Ahmad, Shakeb; Khan, Z. A.


    Using the Coulomb modified correlation expansion for the Glauber model S matrix, we calculate the interaction cross sections of oxygen isotopes (O-2616) on 12C at 1.0 GeV/nucleon. The densities of O-2616 are obtained using (i) the Slater determinants consisting of the harmonic oscillator single-particle wave functions (SDHO) and (ii) the relativistic mean-field approach (RMF). Retaining up to the two-body density term in the correlation expansion, the calculations are performed employing the free as well as the in-medium nucleon-nucleon (N N ) scattering amplitude. The in-medium N N amplitude considers the effects arising due to phase variation, higher momentum transfer components, and Pauli blocking. Our main focus in this work is to reveal how could one make the best use of SDHO densities with reference to the RMF one. The results demonstrate that the SDHO densities, along with the in-medium N N amplitude, are able to provide satisfactory explanation of the experimental data. It is found that, except for O,2423, the predicted SDHO matter rms radii of oxygen isotopes closely agree with those obtained using the RMF densities. However, for O,2423, our results require reasonably larger SDHO matter rms radii than the RMF values, thereby predicting thicker neutron skins in 23O and 24O as compared to RMF ones. In conclusion, the results of the present analysis establish the utility of SDHO densities in predicting fairly reliable estimates of the matter rms radii of neutron-rich nuclei.

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

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


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

  16. Precipitation regime influence on oxygen triple-isotope distributions in Antarctic precipitation and ice cores

    Miller, Martin F.


    The relative abundance of 17O in meteoric precipitation is usually reported in terms of the 17O-excess parameter. Variations of 17O-excess in Antarctic precipitation and ice cores have hitherto been attributed to normalised relative humidity changes at the moisture source region, or to the influence of a temperature-dependent supersaturation-controlled kinetic isotope effect during in-cloud ice formation below -20 °C. Neither mechanism, however, satisfactorily explains the large range of 17O-excess values reported from measurements. A different approach, based on the regression characteristics of 103 ln (1 +δ17 O) versus 103 ln (1 +δ18 O), is applied here to previously published isotopic data sets. The analysis indicates that clear-sky precipitation ('diamond dust'), which occurs widely in inland Antarctica, is characterised by an unusual relative abundance of 17O, distinct from that associated with cloud-derived, synoptic snowfall. Furthermore, this distinction appears to be largely preserved in the ice core record. The respective mass contributions to snowfall accumulation - on both temporal and spatial scales - provides the basis of a simple, first-order explanation for the observed oxygen triple-isotope ratio variations in Antarctic precipitation, surface snow and ice cores. Using this approach, it is shown that precipitation during the last major deglaciation, both in western Antarctica at the West Antarctic Ice Sheet (WAIS) Divide and at Vostok on the eastern Antarctic plateau, consisted essentially of diamond dust only, despite a large temperature differential (and thus different water vapour supersaturation conditions) at the two locations. In contrast, synoptic snowfall events dominate the accumulation record throughout the Holocene at both sites.

  17. Stable oxygen isotope variability in two contrasting glacier river catchments in Greenland

    Yde, Jacob C.; Knudsen, Niels T.; Steffensen, Jørgen P.


    the Greenland Ice Sheet (GrIS). At the Mittivakkat Gletscher river, a small river draining a local temperate glacier in southeast Greenland, diurnal oscillations in δ18O occurred with a 3 h time lag to the diurnal oscillations in run-off. The mean annual δ18O was -14.68±0.18‰ during the peak flow period...... event. Overall, a comparison of the δ18O compositions from glacial river water in Greenland shows distinct differences between water draining local glaciers and ice caps (between -23.0 and -13.7 ‰) and the GrIS (between -29.9 and -23.2 ‰). This study demonstrates that water isotope analyses can be used......Analysis of stable oxygen isotope (δ18O) characteristics is a useful tool to investigate water provenance in glacier river systems. In order to attain knowledge on the diversity of δ18O variations in Greenlandic rivers, we examined two contrasting glacierised catchments disconnected from...

  18. Study of the carbon and oxygen isotopic compositions in marine shells of Salvador-Bahia, Brazil

    Freitas, J.C.B. de.


    The carbon and oxygen isotopic composition of 68 samples of marine shells from the region of Salvador was determined. These samples are from points on the open coast and in the interior of the Todos os Santos Bay and they are composed in part by recent specimens and in part by old specimens taken from Quaternary sediments. The results for δ 18 O are in the range of -2,83per mille to + 1,21per mille (PDB) and for δ 13 C in the range of -3,10per mille to +2,63per mille (PDB). The reults for the recent shells from the interior of the Todos os Santos Bay show variations in the δ 13 C values associated to the dominance of organic matter in some regions. For the old samoles, gathered in te variations in the δ 13 C values was associated to the existence in points of that region of deposits of fluvio-lagunar sediments, originated during the last marine transgression. It was identified, for a few species with the same age and location, the effect of biological fractionations. Nevertheless, the observed dominant factor on the isotopic differentiation was the environmental fractionation. (Author) [pt

  19. Cross-continental triple oxygen isotope analysis of tropospheric CO2

    Liang, M. C.; Rangarajan, R.; Newman, S.; Laskar, A. H.


    The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, D17O (= ln(1+d17O) - 0.516´ln(1+d18O)) provides an alternative constraint on the strengths of the associated cycles involving CO2. Here, we report more than one year of data obtained from Taiwan (Taipei), South China Sea, and USA (Pasadena, CA and Palos Verdes, CA). On average, the D17O values from these locations are similar and show no significant influence from the 2014-2016 El Nino event, in contrast to what has been reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Implications for utilizing the new tracer D17O for carbon cycling studies will be made.

  20. Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Perched Water Samples

    Lee, Brady D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Moran, James J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Nims, Megan K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Saunders, Danielle L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)


    Fine-grained sediments associated with the Cold Creek Unit at Hanford have caused the formation of a perched water aquifer in the deep vadose zone at the B Complex area, which includes waste sites in the 200-DV-1 Operable Unit and the single-shell tank farms in Waste Management Area B-BX-BY. High levels of contaminants, such as uranium, technetium-99, and nitrate, make this aquifer a continuing source of contamination for the groundwater located a few meters below the perched zone. Analysis of deuterium (2H) and 18-oxygen (18O) of nine perched water samples from three different wells was performed. Samples represent time points from hydraulic tests performed on the perched aquifer using the three wells. The isotope analyses showed that the perched water had δ2H and δ18O ratios consistent with the regional meteoric water line, indicating that local precipitation events at the Hanford site likely account for recharge of the perched water aquifer. Data from the isotope analysis can be used along with pumping and recovery data to help understand the perched water dynamics related to aquifer size and hydraulic control of the aquifer in the future.

  1. Heterogenous Oxygen Isotopic Composition of a Complex Wark-Lovering Rim and the Margin of a Refractory Inclusion from Leoville

    Simon, J. I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.


    Wark-Lovering (WL) rims [1] surrounding many refractory inclusions represent marker events in the early evolution of the Solar System in which many inclusions were exposed to changes in pressure [2], temperature [3], and isotopic reservoirs [4-7]. The effects of these events can be complex, not only producing mineralogical variability of WL rims [2], but also leading to mineralogical [8-10] and isotopic [7, 11, 12] changes within inclusion interiors. Extreme oxygen isotopic heterogeneity measured in CAIs has been explained by mixing between distinct oxygen gas reservoirs in the nebula [13]. Some WL rims contain relatively simple mineral layering and/or are isotopically homogeneous [14, 15]. As part of a larger effort to document and understand the modifications observed in some CAIs, an inclusion (L6) with a complex WL rim from Leoville, a member of the reduced CV3 subgroup was studied. Initial study of the textures and mineral chemistry was presented by [16]. Here we present NanoSIMS oxygen isotopic measurements to complement these petrologic observations.

  2. Direct dating of the oxygen-isotope record of the last deglaciation by 14C accelerator mass spectrometry

    Duplessy, J.C.; Arnold, Maurice; Maurice, Pierre; Bard, Edouard; Duprat, Josette; Moyes, Jean


    The authors have measured 14 C for various species of foraminifera to produce a reliable timescale for the oxygen-isotope record. The results show that, at the end of the last ice age, continental ice sheets began to melt more than 4,000 yr before the Northern Hemisphere maximum of summer calorific radiation. (author)

  3. Oxygen stable isotopes during the Last Glacial Maximum climate: perspectives from data-model (iLOVECLIM) comparison

    Caley, T.; Roche, D.M.V.A.P.; Waelbroeck, C.; Michel, E.


    We use the fully coupled atmosphere-ocean three-dimensional model of intermediate complexity iLOVECLIM to simulate the climate and oxygen stable isotopic signal during the Last Glacial Maximum (LGM, 21 000 years). By using a model that is able to explicitly simulate the sensor (Î18O), results can be

  4. High-frequency climate linkages between the North Atlantic and the Mediterranean during marine oxygen isotope stage 100 (MIS100)

    Becker, Julia; Lourens, L.J.; Raymo, M.E.


    High-resolution records of Mediterranean and North Atlantic deep-sea sediments indicate that rapid changes in hydrology and climate occurred during marine oxygen isotope stage 100 (MIS100) (at ~2.52 Ma), which exhibits characteristics similar to late Pleistocene Dansgaard-Oeschger, Bond cycles and

  5. Oxygen-isotope wiggle maching as a tol for synchronising ice-cor and terrestrial records over Termination !

    Hoek, W.Z.; Bohncke, S.J.P.


    In NW Europe, the large number of terrestrial records that are now available from Termination 1 (15-10kcal yr BP) form the basis for a highly detailed picture of Lateglacial environmental change. Nevertheless, the Greenland oxygen-isotope records (GRIP/GISP2) are still regarded as the best

  6. Palaeotemperature reconstructions of the European permafrost zone during Oxygen Isotope Stage 3 compared with climate model results.

    van Huissteden, J.; Vandenberghe, J.; Pollard, D.


    A palaeotemperature reconstruction based on periglacial phenomena in Europe north of approximately 51 °N, is compared with high-resolution regional climate model simulations of the marine oxygen isotope Stage 3 (Stage 3) palaeoclimate. The experiments represent Stage 3 warm (interstadial), Stage 3

  7. Beyond the neutron drip line: The unbound oxygen isotopes 25O and 26O

    Caesar, C.; Simonis, J.; Adachi, T.


    The very neutron-rich oxygen isotopes 25O and 26O are investigated experimentally and theoretically. The unbound states are populated in an experiment performed at the R3B-LAND setup at GSI via proton-knockout reactions from 26F and 27F at relativistic energies around 442 and 414 MeV/nucleon, res...

  8. Isotopic evidence for multiple contributions to felsic magma chambers

    Waight, Tod Earle; Wiebe, R.A.; Krogstad, E.J.


    The Gouldsboro Granite forms part of the Coastal Maine Magmatic Province, a region characterized by granitic plutons that are intimately linked temporally and petrogenetically with abundant co-existing mafic magmas. The pluton is complex and preserves a felsic magma chamber underlain...... with identical isotopic compositions to more mafic dikes suggest that closed system fractionation may be occurring in deeper level chambers prior to injection to shallower levels. The granitic portion of the pluton has the highest Nd isotopic composition (eNd=+3.0) of plutons in the region whereas the mafic...

  9. Groundwater oxygen isotope anomaly before the M6.6 Tottori earthquake in Southwest Japan.

    Onda, Satoki; Sano, Yuji; Takahata, Naoto; Kagoshima, Takanori; Miyajima, Toshihiro; Shibata, Tomo; Pinti, Daniele L; Lan, Tefang; Kim, Nak Kyu; Kusakabe, Minoru; Nishio, Yoshiro


    Geochemical monitoring of groundwater in seismically-active regions has been carried out since 1970s. Precursors were well documented, but often criticized for anecdotal or fragmentary signals, and for lacking a clear physico-chemical explanation for these anomalies. Here we report - as potential seismic precursor - oxygen isotopic ratio anomalies of +0.24‰ relative to the local background measured in groundwater, a few months before the Tottori earthquake (M 6.6) in Southwest Japan. Samples were deep groundwater located 5 km west of the epicenter, packed in bottles and distributed as drinking water between September 2015 and July 2017, a time frame which covers the pre- and post-event. Small but substantial increase of 0.07‰ was observed soon after the earthquake. Laboratory crushing experiments of aquifer rock aimed to simulating rock deformation under strain and tensile stresses were carried out. Measured helium degassing from the rock and 18 O-shift suggest that the co-seismic oxygen anomalies are directly related to volumetric strain changes. The findings provide a plausible physico-chemical basis to explain geochemical anomalies in water and may be useful in future earthquake prediction research.

  10. Stable isotopic investigations of early development in extant and fossil chambered cephalopods I. Oxygen isotopic composition of eggwater and carbon isotopic composition of siphuncle organic matter in Nautilus

    Crocker, Kimberley C.; DeNiro, Michael J.; Ward, Peter D.


    Eggwaters from the chambered cephalopod Nautilus are depleted in both 18O and deuterium relative to ambient seawater. Eggwaters from six other species, including the related chambered cephalopod Sepia, do not show such depletion. These observations indicate that the previously observed step towards more positive δ 18O values in calcium carbonate laid down after Nautilus hatches, relative to carbonate precipitated prior to hatching, can be explained by equilibration of the carbonate with water in the egg before hatching and with seawater after hatching. The presence of an oxygen isotope difference between eggwater and seawater for Nautilus and its absence for Sepia suggest that hatching will be recorded in the δ 18O values of shell carbonates for some but not all extinct and extant chambered cephalopods. The δ 13C values of the organic fraction of the siphuncle in Nautilus do not show any consistent pattern with regard to the time of formation before or after hatching. This observation suggests that the minimum in δ 13C values previously observed for calcium carbonate precipitated after Nautilus hatches is not caused by a change in food sources once the animal becomes free-swimming, as has been suggested.

  11. Removal method of fluorescent dyes as pretreatment for measurement of major ion concentrations and hydrogen and oxygen isotopic ratios

    Nakata, Kotaro; Hasegawa, Takuma; Kashiwaya, Koki; Kodama, Hiroki; Miyajima, Tohru


    The major ion concentration and isotope ratio of hydrogen and oxygen can provide important information for migration of groundwater. Sometimes, quantitative estimation of these chemical and isotopic characteristics of solution is necessary for groundwater containing fluorescent dyes, which are used in drilling borehole and tracer experiments. However, sometimes correct estimation is disturbed by dyes and they become a cause of troubles for measurement equipments. Thus development of method to remove dyes is required so that the characteristics of groundwater can be estimated without the negative effect of dyes on measurement or equipments. In this study, removal of four representative dyes (Uranin, Eosin, Naphthalenesulfonic acid sodium(NAP) and Amino G acid potassium salt (AG)) was investigated. Uranin and Eosin were found to be removed by non-ionic synthetic resin: HP2MG. 99.99% of the dyes were removed from initial solutions containing dyes with 10 mg/L after contact with resin, while the contact had little effect on ion concentrations and oxygen and hydrogen isotope ratios. Thus the chemical and isotopic characteristics of groundwater samples containing Uranin and Eosin can be obtained by using the HP2MG resin. On the other hand, the NAP and AG were found to be difficult to remove by the HP2MG resin but they were able to be removed by anion exchange resin (Dowex 1x8). Though contact of solution with Dowex 1x8 did not affect cation concentrations and hydrogen and oxygen isotope ratios, anion concentrations were changed by the contact. Therefore the Dowex 1x8 is only applicable to estimation of the cation concentrations and isotope ratio of hydrogen and oxygen. When both anion and cation concentrations from the samples were necessary, Uranin or Eosin were recommended as a tracer in drilling or tracer experiments. (author)

  12. Isotopic evidence for induced river recharge to the Dupi Tila aquifer in the Dhaka urban area, Bangladesh

    Darling, W.G.; Burgess, W.G.; Hasan, M.K.


    The population of the greater Dhaka metropolitan area is over 8 million and growing at a rate of six percent per year. Much of the water supply for the area is obtained from the underlying Dupi Tila sand aquifer. Intensive exploitation of the aquifer has led to a progressive decline in water levels beneath the parts of the city. The resulting cone of depression is thought likely to be causing the infiltration of surface water, largely from the polluted Buriganga waterway. The use of oxygen and hydrogen stable isotopes in unravelling the subsurface hydrology of the Dhaka area is hindered by the lack of data regarding 'baseline' conditions. Nevertheless it is clear from the evidence obtained from tubewells across the city that there is leakage from the Buriganga river extending several kilometres beneath parts of the urban area, possibly as far as the centre of the city. Carbon stable isotopes and major ion chemistry confirm this general picture; though appear to indicate that polluted river water has not penetrated quite so far towards the city centre. The Dupi Tila is regarded as a multi-layer aquifer on the basis of its hydrogeology and water quality variations with depth. Since there is little stable isotopic evidence for stratification, future investigations should include sensitive recent age indicators to investigate this, and the rates of groundwater movement in general. (author)

  13. Biological Apatite Formed from Polyphosphate and Alkaline Phosphatase May Exchange Oxygen Isotopes from Water through Carbonate

    Omelon, S. J.; Stanley, S. Y.; Gorelikov, I.; Matsuura, N.


    The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

  14. Sulfur Isotope Trends in Archean Microbialite Facies Record Early Oxygen Production and Consumption

    Zerkle, A.; Meyer, N.; Izon, G.; Poulton, S.; Farquhar, J.; Claire, M.


    The major and minor sulfur isotope composition (δ34S and Δ33S) of pyrites preserved in ~2.65-2.5 billion-year-old (Ga) microbialites record localized oxygen production and consumption near the mat surface. These trends are preserved in two separate drill cores (GKF01 and BH1-Sacha) transecting the Campbellrand-Malmani carbonate platform (Ghaap Group, Transvaal Supergroup, South Africa; Zerkle et al., 2012; Izon et al., in review). Microbialite pyrites possess positive Δ33S values, plotting parallel to typical Archean trends (with a Δ33S/δ34S slope of ~0.9) but enriched in 34S by ~3 to 7‰. We propose that these 34S-enriched pyrites were formed from a residual pool of sulfide that was partially oxidized via molecular oxygen produced by surface mat-dwelling cyanobacteria. Sulfide, carrying the range of Archean Δ33S values, could have been produced deeper within the microbial mat by the reduction of sulfate and elemental sulfur, then fractionated upon reaction with O2 produced by oxygenic photosynthesis. Preservation of this positive 34S offset requires that: 1) sulfide was only partially (50­­-80%) consumed by oxidation, meaning H2S was locally more abundant (or more rapidly produced) than O2, and 2) the majority of the sulfate produced via oxidation was not immediately reduced to sulfide, implying either that the sulfate pool was much larger than the sulfide pool, or that the sulfate formed near the mat surface was transported and reduced in another part of the system. Contrastingly, older microbialite facies (> 2.7 Ga; Thomazo et al., 2013) appear to lack these observed 34S enrichments. Consequently, the onset of 34S enrichments could mark a shift in mat ecology, from communities dominated by anoxygenic photosynthesizers to cyanobacteria. Here, we test these hypotheses with new spatially resolved mm-scale trends in sulfur isotope measurements from pyritized stromatolites of the Vryburg Formation, sampled in the lower part of the BH1-Sacha core. Millimeter

  15. Diet and diversity at later medieval Fishergate: the isotopic evidence.

    Müldner, Gundula; Richards, Michael P


    We present the results of stable carbon and nitrogen isotope analysis of bone collagen for 155 individuals buried at the Later Medieval (13th to early 16th century AD) Gilbertine priory of St. Andrew, Fishergate in the city of York (UK). The data show significant variation in the consumption of marine foods between males and females as well as between individuals buried in different areas of the priory. Specifically, individuals from the crossing of the church and the cloister garth had consumed significantly less marine protein than those from other locations. Isotope data for four individuals diagnosed with diffuse idiopathic skeletal hyperostosis (DISH) are consistent with a diet rich in animal protein. We also observe that isotopic signals of individuals with perimortem sharp force trauma are unusual in the context of the Fishergate dataset. We discuss possible explanations for these patterns and suggest that there may have been a specialist hospital or a local tradition of burying victims of violent conflict at the priory. The results demonstrate how the integration of archaeological, osteological, and isotopic data can provide novel information about Medieval burial and society. (c) 2007 Wiley-Liss, Inc.

  16. Oxygen isotopes in tree rings record variation in precipitation δ18O and amount effects in the south of Mexico.

    Brienen, Roel J W; Hietz, Peter; Wanek, Wolfgang; Gloor, Manuel


    [1] Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings ( δ 18 O tr ). Interannual variation in δ 18 O tr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ 13 C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ 18 O tr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18 O-depleted rain in the region and seem to have affected the δ 18 O tr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ 18 O tr of M . acantholoba can be used as a proxy for source water δ 18 O and that interannual variation in δ 18 O prec is caused by a regional amount effect. This contrasts with δ 18 O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in

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

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


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

  18. Isotopic evidences for provenances of east asian dust

    Yang Jiedong; Chen Jun; Li Gaojun; Ji Junfeng; Rao Wenbo


    Based on systematical investigations on Nd-Sr isotopes of both the <75μm and <5μm silicate fractions of loess, sand, river and lacustrine sediment samples for ten major deserts, gobi, the Loess Plateau, and the northeast part of the Tibetan-Qinghai Plateau, the following results are obtained. (1) Three isotopic regions of Chinese deserts are identified. Region A (Aland A2), which is the deserts on the northern boundary of China with the highest ε Nd (0)>-7.0. Region B, which is the deserts on the northern margin of Tibetan Plateau with ε Nd (0) ranges form -11.9 to -7.4. Region C, which is the deserts on the Ordos Plateau with the lowest ε nd (0)<-11.5. The distribution of the three isotopic regions is controlled by the tectonic setting in North China. (2) The reliable isotope ranges of the Loess Plateau are 87 Sr/ 86 Sr from 0.71784 to 0.71944, ε Nd (0) from -9.2 to -11.3, which fall in Region B of the Qaiham Desert, Badain Jaran Desert and Tengger Desert. This indicates that the possibility of the Gurbantunggut Desert, Hunlun Buir sandy land, Onqin Daga sandy land, Horqin sandy land, the Hobq Desert and Mu Us Desert, as provenances for the loess are excluded. The isotopic range of the northeast part of the Tibetan-Qinghai Plateau coincides with those of the Badain Jaran Desert and Tengger Desert, and loess in the Loess Plateau, suggesting that the predominant source area of the Loess Plateau is most likely to be the northeast part of the Tibetan-Qinghai Plateau, and the Qaidam Desert, Badain Jaran Desert and Tengger Desert are middle transport stations of loess materials. (3) The comparison with isotopic data of dust extracted from snow deposits at Greenland and sediments of North Pacific confirms the Badain Jaran Desert, Tengger Desert and the Tibetan-Qinghai Plateau to be main source. (4) The analyzed results for dust samples in Beijing region demonstrate that aeolian dust in normal time in 2006 is mostly derived from mixing of Region B and bed rock soil

  19. Accurate and precise measurement of oxygen isotopic fractions and diffusion profiles by selective attenuation of secondary ions (SASI).

    Téllez, Helena; Druce, John; Hong, Jong-Eun; Ishihara, Tatsumi; Kilner, John A


    The accuracy and precision of isotopic analysis in Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) relies on the appropriate reduction of the dead-time and detector saturation effects, especially when analyzing species with high ion yields or present in high concentrations. Conventional approaches to avoid these problems are based on Poisson dead-time correction and/or an overall decrease of the total secondary ion intensity by reducing the target current. This ultimately leads to poor detection limits for the minor isotopes and high uncertainties of the measured isotopic ratios. An alternative strategy consists of the attenuation of those specific secondary ions that saturate the detector, providing an effective extension of the linear dynamic range. In this work, the selective attenuation of secondary ion signals (SASI) approach is applied to the study of oxygen transport properties in electroceramic materials by isotopic labeling with stable (18)O tracer and ToF-SIMS depth profiling. The better analytical performance in terms of accuracy and precision allowed a more reliable determination of the oxygen surface exchange and diffusion coefficients while maintaining good mass resolution and limits of detection for other minor secondary ion species. This improvement is especially relevant to understand the ionic transport mechanisms and properties of solid materials, such as the parallel diffusion pathways (e.g., oxygen diffusion through bulk, grain boundary, or dislocations) in electroceramic materials with relevant applications in energy storage and conversion devices.

  20. Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

    Killingsworth, Bryan A; Bao, Huiming; Kohl, Issaku E


    Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .

  1. Composition, oxygen isotope geochemistry, and origin of smectite in the metalliferous sediments of the Bauer Deep, southeast Pacific

    Cole, T G [Imperial Coll. of Science and Technology, London (UK). Geology Dept.


    The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite. Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite. Infra-red and Mossbauer spectroscopy, and wet chemical analysis (LiBO/sub 2/ fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3 deg C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth. Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed. Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO/sub 3/ accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions.)

  2. Composition, oxygen isotope geochemistry, and origin of smectite in the metalliferous sediments of the Bauer Deep, southeast Pacific

    Cole, T.G.


    The sediments of the Bauer Deep, an open ocean basin situated on the northwest Nazca Plate in the southeast Pacific, constitute a regional metalliferous deposit dominated by authigenic smectite. Two 2-metre long cores from the Bauer Deep were examined to investigate the nature and origin of the smectite. Infra-red and Mossbauer spectroscopy, and wet chemical analysis (LiBO 2 fusion) of isolated smectite, indicate the mineral is a Mg-rich, Al-rich nontronite. Oxygen isotopic compositions for isolated smectite are uniform and translate to a non-hydrothermal temperature of formation of about 3 deg C. SEM observations show an abundance of well-preserved biogenic opal in surface and near surface sediment but postburial dissolution and transformation of this phase to smectite is evident at depth. Smectite formation is the result of interaction between iron oxyhydroxide, ponded in the Bauer Deep following a hydrothermal origin at the adjacent East Pacific Rise, and biogenic opal. A reaction mechanism is proposed. Regional factors control smectite formation. In particular, formation is inhibited in areas of CaCO 3 accumulation (topographic elevations) but favoured in areas of oxyhydroxide and opal ponding (topographic depressions.) (author)

  3. Chemical and oxygen isotope zonings in garnet from subducted continental crust record mineral replacement and metasomatism

    Vho, Alice; Rubatto, Daniela; Regis, Daniele; Baumgartner, Lukas; Bouvier, Anne-Sophie


    Garnet is a key mineral in metamorphic petrology for constraining pressure, temperature and time paths. Garnet can preserve multiple growth stages due to its wide P-T stability field and the relatively slow diffusivity for major and trace elements at sub-solidus temperatures. Pressure-temperature-time-fluid paths of the host rock may be reconstructed by combining metamorphic petrology with microscale trace element and oxygen isotope measurements in garnet. Subduction zones represent relevant geological settings for geochemical investigation of element exchanges during aqueous fluid-rock interactions. The Sesia Zone consists of a complex continental sequence containing a variety of mono-metamorphic and poly-metamorphic lithologies such as metagranitoids, sediments and mafic boudins. The precursor Varisican-Permian amphibolite-facies basement (6-9 kbar 650-850°C; Lardeaux and Spalla, 1991; Robyr et al., 2013) experienced high pressure metamorphism (15-22 kbar 500-550°C; Regis, et al. 2014; Robyr et al., 2013) during Alpine subduction. In different lithologies of the Internal Complex (Eclogitic Micaschist Complex), including metabasites from the Ivozio Complex, Ti-rich metasediments from Val Malone and pre-Alpine Mn-quartzites associated to metagabbros from Cima Bonze, garnet is abundant and shows a variety of complex textures that cannot be reconciled with typical growth zoning, but indicate resorption and replacement processes and possible metasomatism. In-situ, microscale oxygen isotopes analysis of garnet zones was performed by ion microprobe with the SwissSIMS Cameca IMS 1280-HR at University of Lausanne and SHRIMP-SI at the Australian National University. Each sample has a distinct δ18O composition, and the δ18O values show different degrees of variation between domains. Homogeneously low values of < 5‰ are measured in the garnets from the Ivozio Complex metagabbro. Intragrain variations of up to 3.5‰ in the porphyroblasts from Val Malone metasediments

  4. Oxygen Isotope Speleothem record of Decadal and Multidecadal Atlantic Oscillations over the last millennium in Southwestern Morocco

    Ait Brahim, Yassine; Sha, LiJuan; Sifeddine, Abdelfettah; Cheng, Hai; Bouchaou, Lhoussaine; Da Cruz Junior, Francisco William; Khodri, Myriam; Peerbocus, Nawaaz; Mariller, Alexandre; Apaestegui, James; Guyot, Jean-Loup; Auler, Augusto; Hassane Beraaouz, El


    In this work, we present a stable oxygen isotope (δ18O) speleothem record from Ifoulki cave located South-West of Morocco (N 30°42'29'', W 09°19'39'' and 1267 meters above sea level). The age model, based on eighteen U-Th dates, reveals that the record covers the AD 790-1953 period with a data resolution of ~1.7 years. Stable oxygen isotope variations show substantial decadal to multi-decadal swings between dry and humid periods. The Medieval Climate Anomaly (MCA) is characterized by the longest period with δ18O values above the average, suggestive of pronounced drying possibly as a response to positive North Atlantic Oscillation (NAO) phases and increased volcanic activity during this period. However, at least two short wet phases are recognized during the MCA in Morocco, with peaks centered on the years AD 1040 and AD 1190 and seem to overlap with negative NAO phases as recorded in a recently published NAO reconstruction for the last millennium. During the next centuries, the NAO again depicts predominantly negative values and the δ18O drops below the average during the Little Ice Age (LIA). Furthermore, a striking resemblance is observed between our record and another recently published stalagmite record from the Piste cave in Northeastern Morocco, which is quite remarkable given the different type of tracers (δ18O vs. Mg and Sr) obtained from different environments (Western High Atlas vs. Northeastern Middle Atlas and ~634 km away). Comparison with regional paleorecords from other studies also reveals the replication of many characteristic climate features from the last millennium, first detected in Northern Morocco and the Iberian Peninsula. In particular, the evidence of generally dry conditions during the MCA and wetter conditions in the LIA, which is confirmed by all the paleorecords. These similarities indicate coherent climate variability in Northwest Africa and the Iberian Peninsula and suggest a strong regional control of the NAO during the last

  5. Carbon, nitrogen and oxygen isotope fractionation during food cooking: Implications for the interpretation of the fossil human record.

    Royer, Aurélien; Daux, Valérie; Fourel, François; Lécuyer, Christophe


    Stable isotope data provide insight into the reconstruction of ancient human diet. However, cooking may alter the original stable isotope compositions of food due to losses and modifications of biochemical and water components. To address this issue, carbon, nitrogen and oxygen isotope ratios were measured on meat aliquots sampled from various animals such as pork, beef, duck and chicken, and also from the flesh of fishes such as salmon, European seabass, European pilchard, sole, gilt-head bream, and tuna. For each specimen, three pieces were cooked according to the three most commonly-known cooking practices: boiling, frying and roasting on a barbecue. Our data show that cooking produced isotopic shifts up to 1.8‰, 3.5‰, and 5.2‰ for δ 13 C, δ 15 N, and δ 18 O values, respectively. Such variations between raw and cooked food are much greater than previously estimated in the literature; they are more sensitive to the type of food rather than to the cooking process itself, except in the case of boiling. Reconstructions of paleodietary may thus suffer slight bias in cases of populations with undiversified diets that are restrained toward a specific raw or cooked product, or using a specific cooking mode. In cases of oxygen isotope compositions from skeletal remains (bones, teeth), they not only constitute a valuable proxy for reconstructing past climatic conditions, but they could also be used to improve our knowledge of past human diet. © 2017 Wiley Periodicals, Inc.

  6. Carbon and oxygen isotope signatures in conifers from the Swiss National Park

    Churakova (Sidorova), Olga; Saurer, Matthias; Siegwolf, Rolf; Bryukhanova, Marina; Bigler, Christof


    Our study investigates the physiological response and plasticity of trees under climatic changes for larch (Larix decidua) and mountain pine (Pinus mugo var. uncinata) in the Swiss National Park.This research was done in the context of investigation tree mortality and their potential to survive under the harsh mountainous conditions. For the stable isotope analysis we selected four mountain pine and four larch trees from each a south- and north-facing slope. Oxygen isotope ratios can give insight into water sources and evaporative processes. To understand the differential response of mountain pine and larch to short-term climatic changes we measured 18O/16O in water extracted from twigs and needles as well as soil samples for each species at both sites. The seasonal variabilities in 18O/16O needles and twigs of mountain pine and larch trees as well as soil samples were related to changes in climate conditions from end of May until middle of October. To reveal the main climatic factors driving tree growth of pine and larch trees in the long-term, tree-ring width chronologies were built and bulk 18O/16O, 13C/12C wood chronologies were analyzed and correlated with climatic parameters over the last 100 years. The results indicate a strong influence of spring and summer temperatures for larch trees, while variation of spring and summer precipitations is more relevant for mountain pine trees. This work is supported by the Swiss National Science Foundation, Marie-Heim Vögtlin Program PMPDP-2 145507

  7. Oxygen Isotope Compositions of Meteoric Water Across an Elevation Gradient in Southern Peru

    Xu, D. R.; White, E.; Cassel, E. J.; Lynch, B.; Yanites, B.; Breecker, D.


    The Central Andes is a prime example of elevated topography generated by oceanic plate subduction. Whereas previous stable isotope studies have investigated the paleoelevation of the Andean Eastern Cordillera, little is known about the paleoelevation of the Western Cordillera, where arc volcanism now occurs. As a first step towards studying the paleoelevation of this region, we investigated the change in δ18O values of modern soil waters across an elevation gradient from sea level to about 4725 meters in southern Peru. We sampled soil profiles from 5 to 80 cm in 15-20cm increments, and we sampled water from flowing natural streams at various elevations. We used cryogenic vacuum extraction to quantitatively remove non-structural water from soil samples. The δ18O values of water extracted from soil samples varies with the depth in the soil due to the diminishing effect of seasonality and evaporation. Every high elevation (>3500m) soil profile we measured had nearly constant δ18O values below 5cm and a total range of δ18O values between -12.8‰ and -17.1‰, apart from the Cusco profile. In the Cusco profile, the δ18O values ranged from -7.2 ‰ at 5 cm to -21.8 ‰ at 60 cm, defining a strong monotonic decrease not seen in other soil profiles. The δ18O trend in the Cusco profile may be different due to the impact of evaporation, soil hydrology, and/or seasonality in the δ18O values of precipitation. Further spatial analysis must be conducted to pinpoint a specific cause. Considering only the samples collected below 40cm, which are likely the best estimate of mean annual precipitation, the δ18O values decrease with increasing elevation at a rate higher than the global mean, suggesting that oxygen isotope paleoaltimetry can work in this study region.

  8. Interplay between O2 and SnO2: oxygen ionosorption and spectroscopic evidence for adsorbed oxygen.

    Gurlo, Alexander


    Tin dioxide is the most commonly used material in commercial gas sensors based on semiconducting metal oxides. Despite intensive efforts, the mechanism responsible for gas-sensing effects on SnO(2) is not fully understood. The key step is the understanding of the electronic response of SnO(2) in the presence of background oxygen. For a long time, oxygen interaction with SnO(2) has been treated within the framework of the "ionosorption theory". The adsorbed oxygen species have been regarded as free oxygen ions electrostatically stabilized on the surface (with no local chemical bond formation). A contradiction, however, arises when connecting this scenario to spectroscopic findings. Despite trying for a long time, there has not been any convincing spectroscopic evidence for "ionosorbed" oxygen species. Neither superoxide ions O(2)(-), nor charged atomic oxygen O,(-) nor peroxide ions O(2)(2-) have been observed on SnO(2) under the real working conditions of sensors. Moreover, several findings show that the superoxide ion does not undergo transformations into charged atomic oxygen at the surface, and represents a dead-end form of low-temperature oxygen adsorption on reduced metal oxide.

  9. Hafnium isotope evidence for a transition in the dynamics of continental growth 3.2 Gyr ago.

    Næraa, T; Scherstén, A; Rosing, M T; Kemp, A I S; Hoffmann, J E; Kokfelt, T F; Whitehouse, M J


    Earth's lithosphere probably experienced an evolution towards the modern plate tectonic regime, owing to secular changes in mantle temperature. Radiogenic isotope variations are interpreted as evidence for the declining rates of continental crustal growth over time, with some estimates suggesting that over 70% of the present continental crustal reservoir was extracted by the end of the Archaean eon. Patterns of crustal growth and reworking in rocks younger than three billion years (Gyr) are thought to reflect the assembly and break-up of supercontinents by Wilson cycle processes and mark an important change in lithosphere dynamics. In southern West Greenland numerous studies have, however, argued for subduction settings and crust growth by arc accretion back to 3.8 Gyr ago, suggesting that modern-day tectonic regimes operated during the formation of the earliest crustal rock record. Here we report in situ uranium-lead, hafnium and oxygen isotope data from zircons of basement rocks in southern West Greenland across the critical time period during which modern-like tectonic regimes could have initiated. Our data show pronounced differences in the hafnium isotope-time patterns across this interval, requiring changes in the characteristics of the magmatic protolith. The observations suggest that 3.9-3.5-Gyr-old rocks differentiated from a >3.9-Gyr-old source reservoir with a chondritic to slightly depleted hafnium isotope composition. In contrast, rocks formed after 3.2 Gyr ago register the first additions of juvenile depleted material (that is, new mantle-derived crust) since 3.9 Gyr ago, and are characterized by striking shifts in hafnium isotope ratios similar to those shown by Phanerozoic subduction-related orogens. These data suggest a transitional period 3.5-3.2 Gyr ago from an ancient (3.9-3.5 Gyr old) crustal evolutionary regime unlike that of modern plate tectonics to a geodynamic setting after 3.2 Gyr ago that involved juvenile crust generation by plate

  10. Oxygen isotope geochemistry of Laurentide ice-sheet meltwater across Termination I

    Vetter, Lael; Spero, Howard J.; Eggins, Stephen M.; Williams, Carlie; Flower, Benjamin P.


    We present a new method that quantifies the oxygen isotope geochemistry of Laurentide ice-sheet (LIS) meltwater across the last deglaciation, and reconstruct decadal-scale variations in the δ18O of LIS meltwater entering the Gulf of Mexico between ∼18 and 11 ka. We employ a technique that combines laser ablation ICP-MS (LA-ICP-MS) and oxygen isotope analyses on individual shells of the planktic foraminifer Orbulina universa to quantify the instantaneous δ18Owater value of Mississippi River outflow, which was dominated by meltwater from the LIS. For each individual O. universa shell, we measure Mg/Ca (a proxy for temperature) and Ba/Ca (a proxy for salinity) with LA-ICP-MS, and then analyze the same O. universa for δ18O using the remaining material from the shell. From these proxies, we obtain δ18Owater and salinity estimates for each individual foraminifer. Regressions through data obtained from discrete core intervals yield δ18Ow vs. salinity relationships with a y-intercept that corresponds to the δ18Owater composition of the freshwater end-member. Our data suggest that from 15.5 through 14.6 ka, estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from -11‰ to -21‰ VSMOW, which is consistent with δ18O values from both regional precipitation and the low-elevation, southern margin of the LIS. During the Bølling and Allerød (14.0 through 13.3 ka), estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from -22‰ to -38‰ VSMOW. These values suggest a dynamic melting history of different parts of the LIS, with potential contributions to Mississippi River outflow from both the low-elevation, southern margin of the LIS and high-elevation, high-latitude domes in the LIS interior that were transported to the ablation zone. Prior to ∼15.5 ka, the δ18Owater value of the Mississippi River was similar to that of regional precipitation or low-latitude LIS meltwater, but the Ba

  11. Oxygen and Magnesium Isotopic Compositions of Asteroidal Materials Returned from Itokawa by the Hayabusa Mission

    Yurimoto, H; Abe, M.; Ebihara, M.; Fujimura, A.; Hashizume, K.; Ireland, T. R.; Itoh, S.; Kawaguchi, K.; Kitajima, F.; Mukai, T.; hide


    The Hayabusa spacecraft made two touchdowns on the surface of Asteroid 25143 Itokawa on November 20th and 26th, 2005. The Asteroid 25143 Itokawa is classified as an S-type asteroid and inferred to consist of materials similar to ordinary chondrites or primitive achondrites [1]. Near-infrared spectroscopy by the Hayabusa spacecraft proposed that the surface of this body has an olivine-rich mineral assemblage potentially similar to that of LL5 or LL6 chondrites with different degrees of space weathering [2]. The spacecraft made the reentry into the Earth s atmosphere on June 12th, 2010 and the sample capsule was successfully recovered in Australia on June 13th, 2010. Although the sample collection processes on the Itokawa surface had not been made by the designed operations, more than 1,500 grains were identified as rocky particles in the sample curation facility of JAXA, and most of them were judged to be of extraterrestrial origin, and definitely from Asteroid Itokawa on November 17th, 2010 [3]. Although their sizes are mostly less than 10 microns, some larger grains of about 100 microns or larger were also included. The mineral assembly is olivine, pyroxene, plagioclase, iron sulfide and iron metal. The mean mineral compositions are consistent with the results of near-infrared spectroscopy from Hayabusa spacecraft [2], but the variations suggest that the petrologic type may be smaller than the spectroscopic results. Several tens of grains of relatively large sizes among the 1,500 grains will be selected by the Hayabusa sample curation team for preliminary examination [4]. Each grain will be subjected to one set of preliminary examinations, i.e., micro-tomography, XRD, XRF, TEM, SEM, EPMA and SIMS in this sequence. The preliminary examination will start from the last week of January 2011. Therefore, samples for isotope analyses in this study will start from the last week of February 2011. By the time of the LPSC meeting we will have measured the oxygen and

  12. Relationship between oxygen isotopes in rainfall, cave percolation waters and speleothem calcite at Waitomo, New Zealand

    Williams, P.W.; Fowler, A.


    The relationship between the δ 18 O values of rainfall, vadose percolation water, and speleothem calcite was investigated in a cave at Waitomo. Water samples were obtained approximately monthly for two years from a storage rain gauge on the surface and from stored seepage from three stalactites underground. Rain water δ 18 O SMOW values varied considerably throughout the observation period, with a precipitation-weighted mean of -5.3 permille. Seasonal variability was evident, with winter values being more negative than summer values. Cave seepage waters had a mean of about -5 permille and showed very little variability and no discernible annual variation. This is explained by thorough mixing in the soil and subcutaneous zone stores. Given the average cave temperature (12.8 degrees C) and the δ 18 O SMOW value determined for seepage water, the δ 18 O PDB value of calcite that is actively depositing in isotopic equilibrium on speleothems at Waitomo should fall in the range of -4.1 to -4.6 permille. Observed delta-values of modern speleothem calcites overlap the positive end of this range of theoretical values, indicating that some growing speleothems are not in isotopic equilibrium with seepage waters, but are experiencing either evaporation or kinetic fractionation. (author). 32 refs., 8 figs

  13. Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis.

    Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans-Hermann


    In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS 18 O/ 16 O monitoring for future method development is proposed.

  14. Evidence for neutral beam injected oxygen impurities in 2XIIB

    Drake, R.P.; Moos, H.W.


    A series of experiments indicates that the principal source of impurities in the 2XIIB mirror confinement plasma experiment at Lawrence Livermore Laboratory is oxygen in the neutral beams. The dependence of 0 II 539 A emissions on neutral beam current, spatial scans of oxygen emissions, impurity injection experiments, spectral scans of the 0 VI 1032 A line, and other experiments all support this conclusion

  15. Digesting the data - Effects of predator ingestion on the oxygen isotopic signature of micro-mammal teeth

    Barham, Milo; Blyth, Alison J.; Wallwork, Melinda D.; Joachimski, Michael M.; Martin, Laure; Evans, Noreen J.; Laming, Belinda; McDonald, Bradley J.


    Biogenic minerals such as dental apatite have become commonly analysed archives preserving geochemical indicators of past environmental conditions and palaeoecologies. However, post-mortem, biogenic minerals are modified due to the alteration/replacement of labile components, and recent moves to utilise micro-mammal tooth δ18O signatures for refined Cenozoic terrestrial palaeoclimate reconstructions has lacked consideration of the chemical effects of predator digestion. Here, the physical and chemical condition of laboratory-raised mouse (Mus musculus) teeth have been investigated in conjunction with their bulk phosphate and tissue-specific δ18O values prior, and subsequent, to ingestion and excretion by various predator species (owls, mammals and a reptile). Substantial variability (up to 2‰) in the δ18O values of both undigested teeth and those ingested by specific predators suggests significant natural heterogeneity of individual prey δ18O. Statistically distinct, lower δ18O values (∼0.7‰) are apparent in teeth ingested by barn owls compared to undigested controls as a result of the chemically and enzymatically active digestive and waste-pellet environments. Overall, dentine tissues preserve lower δ18O values than enamel, while the greatest modification of oxygen isotope signals is exhibited in the basal enamel of ingested teeth as a result of its incompletely mineralised state. However, recognition of 18O-depletion in chemically purified phosphate analyses demonstrates that modification of original δ18O values is not restricted to labile oxygen-bearing carbonate and organic phases. The style and magnitude of digestive-alteration varies with predator species and no correlation was identified between specific physical or minor/trace-element (patterns or concentrations) modification of ingested teeth and disruption of their primary oxygen isotope values. Therefore, there is a current lack of any screening tool for oxygen isotope disruption as a result

  16. The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

    von Sperber, C.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.


    Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (myo-inositol hexakisphosphate, IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields available Pi and less phosphorylated inositol derivates as products. The hydrolysis of organic P compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'-monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as a substrate were prepared. During the hydrolysis of IP6 by phytase, four of the six Pi were released, and one oxygen atom from water was incorporated into each Pi. This incorporation of oxygen from water into Pi was subject to an apparent inverse isotopic fractionation (ϵ ~ 6 to 10 ‰), which was similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ~ 7 ‰), where less than three Pi were released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ~ -12 ‰), similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ϵ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking

  17. Origin of the brines near WIPP from the drill holes ERDA-6 and WIPP-12 based on stable isotope concentrations of hydrogen and oxygen

    Spiegler, P.; Updegraff, D.


    Pathways which might alter the isotopic compositions of deuterium and oxygen-18 meteoric water, seawaters, and in hydration waters in gypsum to the isotopic compositions of brines encountered at ERDA-6 and WIPP-12 are discussed. Present geologic conditions do not favor the alteration of the isotopic compositions of waters that exist near the WIPP site to those of the brines by these pathways. It is concluded that the brines encountered at ERDA-6 and WIPP-12 are probably derived from ancient ocean waters that have been isotopically enriched in oxygen-18 by exchange interaction with rock. The dehydration of gypsum as a process of origin of these brines cannot be ruled out

  18. Phosphorus dynamics in soils irrigated with reclaimed waste water or fresh water - A study using oxygen isotopic composition of phosphate

    Zohar, I.; Shaviv, A.; Young, M.; Kendall, C.; Silva, S.; Paytan, A.


    Transformations of phosphate (Pi) in different soil fractions were tracked using the stable isotopic composition of oxygen in phosphate (??18Op) and Pi concentrations. Clay soil from Israel was treated with either reclaimed waste water (secondary, low grade) or with fresh water amended with a chemical fertilizer of a known isotopic signature. Changes of ??18Op and Pi within different soil fractions, during a month of incubation, elucidate biogeochemical processes in the soil, revealing the biological and the chemical transformation impacting the various P pools. P in the soil solution is affected primarily by enzymatic activity that yields isotopic equilibrium with the water molecules in the soil solution. The dissolved P interacts rapidly with the loosely bound P (extracted by bicarbonate). The oxides and mineral P fractions (extracted by NaOH and HCl, respectively), which are considered as relatively stable pools of P, also exhibited isotopic alterations in the first two weeks after P application, likely related to the activity of microbial populations associated with soil surfaces. Specifically, isotopic depletion which could result from organic P mineralization was followed by isotopic enrichment which could result from preferential biological uptake of depleted P from the mineralized pool. Similar transformations were observed in both soils although transformations related to biological activity were more pronounced in the soil treated with reclaimed waste water compared to the fertilizer treated soil. ?? 2010 Elsevier B.V.

  19. Strontium and oxygen isotopic variations in mesozoic and tertiary plutons of central Idaho

    Fleck, R.J.; Criss, R.E.


    Regional variations in initial 87 Sr/ 86 Sr ratios (rsub(i)) of Mesozoic plutons in central Idaho locate the edge of Precambrian continental crust at the boundary between the late Paleozoic-Mesozoic accreted terranes and Precambrian sialic crust in western Idaho. The rsub(i) values increase abruptly but continuously from less than 0.704 in the accreted terranes to greater than 0.708 across a narrow, 5 to 15 km zone, characterized by elongate, lens-shaped, highly deformed plutons and schistose metasedimentary and metavolcanic units. The chemical and petrologic character of the plutons changes concomitantly from ocean-arc-type units to a weakly peraluminous, calcit to calcalkalic suite. Plutons in both suites yield Late Cretaceous ages, but Permian through Early Cretaceous bodies are confined to the accreted terranes and early Tertiary intrusions are restricted to areas underlain by Precambrian crust. The two major terranes were juxtaposed between 75 and 130 m.y. ago, probably between 80 and 95 m.y. Oxygen and strontium isotopic ratios and Rb and Sr concentrations of the plutonic rocks document a significant upper-crustal contribution to the magmas that intrude Precambrian crust. Magmas intruding the arc terranes were derived from the upper mantle/subducted oceanic lithosphere and may have been modified by anatexis of earlier island-arc volcanic and sedimentary units. (orig./PW)

  20. Oxygen isotopes of marine mollusc shells record Eocene elevation change in the Pyrenees

    Huyghe, Damien; Mouthereau, Frédéric; Emmanuel, Laurent


    Constraining paleoaltimetry of collisional orogens is critical to understand the dynamics of topographic evolution and climate/tectonics retroactions. Here, we use oxygen stable-isotope record on oyster shells, preserved in marine foreland deposits, to examine the past elevation of the Pyrenees during the Eocene. Our approach is based on the comparison with the Paris basin, an intracratonic basin not influenced by orogenic growth. The finding of a shift of 1.5‰ between 49 and 41 Ma, indicating more negative δ18Oc in the south Pyrenean foreland, is interpreted to reflect the inflow of river water sourced from higher elevation in the Pyrenees. To test this and provide paleoelevation estimate, we adopt a morphologic-hydrological model accounting for the hypsometry of drainage basin. Our best fitting model shows that the Pyrenees rose up to 2000 m. This indicates that the Pyrenees reached high elevation in the Eocene, thus providing new critical constraints on their long-term orogenic development. δ18O of marine mollusc shells are proved potentially attractive for paleoelevation studies, especially for mountain belts where elevated continental surfaces have not been preserved.

  1. The use of Sphagnum cellulose oxygen isotope ratios in ombrotrophic peatlands as a proxy for paleoclimate.

    Taylor, M.; Pendall, E.; Jackson, S.; Booth, R. K.; Nichols, J. E.; Huang, Y.


    Developing proxies for discerning paleoclimate that are independent of the pollen record can provide insight into various aspects of climate variability and improve confidence in the interpretation of climate-vegetation interactions. To date, proxies including plant macrofossils, humification indices, testate amoebae, and ratios of n-alkane abundances have been used to infer past climate variability from temperate ombrotrophic peatlands in upper Midwestern North America. These proxies are used to infer past changes in surface-moisture conditions, which in ombrotrophic peatlands is primarily a function of precipitation and temperature. This study investigates the potential uses of stable oxygen isotopes to complement hydrologic proxies. δ18O of surface water and Sphagnum moss cellulose from bogs throughout North America indicates a correlation between average growing season temperatures and δ18O-values. The existence of a modern temperature signal in moss cellulose suggests that δ18O-derived records will not only complement paleohydrological records, but also help assess relative changes in precipitation and temperature. Humification and testate amoebae data from two cores taken from Minden and Irwin Smith Bogs in central and northeastern Michigan have recorded several extreme drought events during the Holocene, including one at 1000 YBP. Comparison of δ18O-values of picked Sphagnum remains to down-core humification and testate amoebae data suggest good temporal correspondence, with the δ18O-values around 1000 YBP indicating a warmer growing season.

  2. Oxygen isotopes from biogenic apatites suggest widespread endothermy in Cretaceous dinosaurs

    Amiot, Romain; Lécuyer, Christophe; Buffetaut, Eric; Escarguel, Gilles; Fluteau, Frédéric; Martineau, François


    The much debated question of dinosaur thermophysiology has not yet been conclusively solved despite numerous attempts. We used the temperature-dependent oxygen isotope fractionation between vertebrate body water (δ 18O body water) and phosphatic tissues (δ 18O p) to compare the thermophysiology of dinosaurs with that of non-dinosaurian ectothermic reptiles. Present-day δ 18O p values of vertebrate apatites show that ectotherms have higher δ 18O p values than endotherms at high latitudes due to their lower body temperature, and conversely lower δ 18O p values than endotherms at low latitudes. Using a data set of 80 new and 49 published δ 18O p values, we observed similar and systematic differences in δ 18O p values (Δ 18O) between four groups of Cretaceous dinosaurs (theropods, sauropods, ornithopods and ceratopsians) and associated fresh water crocodiles and turtles. Expressed in terms of body temperatures ( Tb), these Δ 18O values indicate that dinosaurs maintained rather constant Tb in the range of endotherms whatever ambient temperatures were. This implies that high metabolic rates were widespread among Cretaceous dinosaurs belonging to widely different taxonomic groups and suggest that endothermy may be a synapomorphy of dinosaurs, or may have been acquired convergently in the studied taxa.

  3. Meridional distribution and seasonal variation of stable oxygen isotope ratio of precipitation in the Southern Ocean

    Kayo Nakamura


    Full Text Available The stable oxygen isotope ratio(δ^O in precipitation is known to have important meridional and seasonal variations, but there are almost no measurements of δ^O in precipitation over polar oceans. The present research took advantage of 4 opportunities for in situ observations in summer and winter at high latitudes in the Southern Ocean. In addition, we analyzed samples of precipitation at Syowa Station in 2008 to obtain year-round data. Based on these data, we consider the meridional and seasonal variations of δ^O in precipitation over the Southern Ocean. In general, δ^O decreases with increasing latitude, and is lower in winter than in summer. The latitude gradient is stronger in winter. At 60°S, δ^O is -5.4‰ and -11.3‰ in summer and winter, respectively, while the corresponding figures at 66°S are -10.5‰ and -20.8‰. These results will help us understand the mechanisms of the salinity distribution and its variation in the Antarctic Ocean.

  4. Oxygen isotope fine structure and fluid throughput of the Tongonan geothermal field, Philippines

    Scott, G.L.; Blattner, P.; Department of Scientific and Industrial Research, Lower Hutt


    Oxygen isotope ratios for 40 reservoir rocks from the plutonic basement and overlying andesitic rocks, and 14 separated geothermal quartz samples from the volcanics, range from 2.5 to 9.9 per mil. The lowest δ 18 O values (average 2.9 per mil) in diorite cores from wells 401, 407 and 410 are located in the most productive northwest (Mahiao) sector of the field. In the Malitbog sector, the average δ 18 O values for basement rocks are higher (c. 4.6 per mil). Plutonic rock samples from the Mamban (well MN1) sector, located outside the present-day field margin, are only slightly altered (6 per mil) except possibly near the contact zone between the basement and overlying volcanics. The highest cumulative fluid/rock ratios are calculated for the Mahiao sector, whereas Malitbog is possibly a relatively recent extension of the field. Relatively shallow (Bao Formation) quartz has δ 18 O values suggesting past tectonic uplift

  5. Oxygen isotope variations in phosphate of biogenic apatites. Pt. 2. Phosphorite rocks

    Kolodny, Y; Luz, B; Shemesh, A [Hebrew Univ., Jerusalem (Israel). Dept. of Geology


    Phosphorites from sedimentary sequences ranging in age from Archaen to Recent were analysed for delta/sup 18/O in both the PO/sub 4/ (delta/sup 18/Osub(p)) and CO/sub 3/ (delta/sup 18/Osub(c)) in the apatite lattice. The oxygen isotope record is considerably better preserved in phosphates than in either carbonates or cherts. The use of the Longinelli and Nuti temperature equation yields temperatures for Recent phosphorites that are in good agreement with those measured in the field. The delta/sup 18/Osub(p) values of ancient phosphorites decrease with increasing age. These changes with time are not likely to be due to post-depositional exchange. Changes in delta/sup 18/O values of seawater and variations of temperatures with time can account for the delta/sup 18/Osub(p) time trend, but the latter explanation is preferred. In Ancient phosphorites delta/sup 18/Osub(c) in structurally bound carbonate in apatite is not a reliable geochemical indicator.

  6. Oxygen isotopic exchange occurring during dry thermal oxidation of 6H SiC

    Vickridge, I.C. E-mail:; Tromson, D.; Trimaille, I.; Ganem, J.-J.; Szilagyi, E.; Battistig, G


    SiC is a large band gap semiconductor, promising for high power and high frequency devices. The thermal oxide is SiO{sub 2} however the growth rates of thermal oxide on SiC are substantially slower than on Si, and different along the polar directions (<0 0 0 1-bar> and <0 0 0 1> in the hexagonal polytypes). Thorough understanding of the oxide growth mechanisms may give us new insights into the nature of the SiO{sub 2}/SiC interface, crucial for device applications. We have determined growth kinetics for ultra-dry thermal oxidation of 6H SiC at 1100 deg. C for pressures from 3 to 200 mbar. At 3 mbar, the lowest pressure studied, the oxide growth rates along the two polar directions are virtually the same. At higher pressures growth is faster on the carbon-terminated (0 0 0 1-bar) face. After consecutive oxidations at 1100 deg. C and 100 mbar in {sup 18}O{sub 2} and {sup 16}O{sub 2} gases, {sup 18}O depth profiles show significant isotopic exchange and oxygen movement within the oxide during oxidation.

  7. Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

    Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.


    Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

  8. Raman spectral, elemental, crystallinity, and oxygen-isotope variations in conodont apatite during diagenesis

    Zhang, Lei; Cao, Ling; Zhao, Laishi; Algeo, Thomas J.; Chen, Zhong-Qiang; Li, Zhihong; Lv, Zhengyi; Wang, Xiangdong


    crystallinity and Raman spectral or elemental parameters. Oxygen isotopes show substantial variation within the conodont study specimens. Albid crown is on average 0.28-0.32‰ more depleted in 18O (equivalent to 1.2-1.4 °C higher temperatures) than hyaline crown and basal body, and the interiors of conodont elements are 1.08 ± 0.37‰ more depleted in 18O (equivalent to 3.0-6.4 °C higher temperatures) relative to their outer layers. Although albid crown is widely regarded as better preserved than other conodont tissue types, its 18O-depleted composition and greater development of secondary crystallinity suggest that, in fact, it may be the most strongly altered tissue type. We conclude that Raman spectral, LA elemental, and HXRD microstructural data can provide useful information about the extent of diagenetic alteration of conodont elements, and that such information should be taken into consideration in using conodont elemental and oxygen-isotope data in paleoenvironmental studies.

  9. Isotopic evidence for enhanced fossil fuel sources of aerosol ammonium in the urban atmosphere.

    Pan, Yuepeng; Tian, Shili; Liu, Dongwei; Fang, Yunting; Zhu, Xiaying; Gao, Meng; Gao, Jian; Michalski, Greg; Wang, Yuesi


    The sources of aerosol ammonium (NH 4 + ) are of interest because of the potential of NH 4 + to impact the Earth's radiative balance, as well as human health and biological diversity. Isotopic source apportionment of aerosol NH 4 + is challenging in the urban atmosphere, which has excess ammonia (NH 3 ) and where nitrogen isotopic fractionation commonly occurs. Based on year-round isotopic measurements in urban Beijing, we show the source dependence of the isotopic abundance of aerosol NH 4 + , with isotopically light (-33.8‰) and heavy (0 to +12.0‰) NH 4 + associated with strong northerly winds and sustained southerly winds, respectively. On an annual basis, 37-52% of the initial NH 3 concentrations in urban Beijing arises from fossil fuel emissions, which are episodically enhanced by air mass stagnation preceding the passage of cold fronts. These results provide strong evidence for the contribution of non-agricultural sources to NH 3 in urban regions and suggest that priority should be given to controlling these emissions for haze regulation. This study presents a carefully executed application of existing stable nitrogen isotope measurement and mass-balance techniques to a very important problem: understanding source contributions to atmospheric NH 3 in Beijing. This question is crucial to informing environmental policy on reducing particulate matter concentrations, which are some of the highest in the world. However, the isotopic source attribution results presented here still involve a number of uncertain assumptions and they are limited by the incomplete set of chemical and isotopic measurements of gas NH 3 and aerosol NH 4 + . Further field work and lab experiments are required to adequately characterize endmember isotopic signatures and the subsequent isotopic fractionation process under different air pollution and meteorological conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Experimental evidence for Mo isotope fractionation between metal and silicate liquids

    Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten


    Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

  11. Evaluation of Primary Production in the Lower Amazon River Based on a Dissolved Oxygen Stable Isotopic Mass Balance

    Gagne-Maynard, William C.; Ward, Nicholas D.; Keil, Richard G.; Sawakuchi, Henrique O.; Da Cunha, Alan C.; Neu, Vania; Brito, Daimio C.; Da Silva Less, Diani F.; Diniz, Joel E. M.; De Matos Valerio, Aline; Kampel, Milton; Krusche, Alex V.; Richey, Jeffrey E.


    The Amazon River outgasses nearly an equivalent amount of CO2 as the rainforest sequesters on an annual basis due to microbial decomposition of terrigenous and aquatic organic matter. Most research performed in the Amazon has been focused on unraveling the mechanisms driving CO2 production since the recognition of a persistent state of CO2 supersaturation. However, although the river system is clearly net heterotrophic, the interplay between primary production and respiration is an essential aspect to understanding the overall metabolism of the ecosystem and potential transfer of energy up trophic levels. For example, an efficient ecosystem is capable of both decomposing high amounts of organic matter at lower trophic levels, driving CO2 emissions, and accumulating energy/biomass in higher trophic levels, stimulating fisheries production. Early studies found minimal evidence for primary production in the Amazon River mainstem and it has since been assumed that photosynthesis is strongly limited by low light penetration attributed to the high sediment load. Here, we test this assumption by measuring the stable isotopic composition of O218O-O2) and O2 saturation levels in the lower Amazon River from Óbidos to the river mouth and its major tributaries, the Xingu and Tapajós rivers, during high and low water periods. An oxygen mass balance model was developed to estimate the input of photosynthetic oxygen in the discrete reach from Óbidos to Almeirim, midway to the river mouth. Based on the oxygen mass balance we estimate that primary production occurred at a rate of 0.39 ± 0.24 g O m3 d-1 at high water and 1.02 ± 0.55 g O m3 d-1 at low water. This translates to 41 ± 24% of the rate of O2 drawdown via respiration during high water and 67 ± 33% during low water. These primary production rates are 2-7 times higher than

  12. Oxygen isotope ratios in the shell of Mytilus edulis: archives of glacier meltwater in Greenland?

    Versteegh, E. A. A.; Blicher, Martin E.; Mortensen, J.


    Melting of the Greenland Ice Sheet (GrIS) is accelerating and will contribute significantly to global sea level rise during the 21st century. Instrumental data on GrIS melting only cover the last few decades, and proxy data extending our knowledge into the past are vital for validating models...... predicting the influence of ongoing climate change. We investigated a potential meltwater proxy in Godthåbsfjord (West Greenland), where glacier meltwater causes seasonal excursions with lower oxygen isotope water (δ18Ow) values and salinity. The blue mussel (Mytilus edulis) potentially records...... its potential as a palaeo-meltwater proxy. First, we confirmed that M. edulis shell calcite oxygen isotope (δ18Oc) values are in equilibrium with ambient water and generally reflect meltwater conditions. Subsequently we investigated if this species recorded the full range of δ18Ow values occurring...

  13. Oxygen isotope studies of early Precambrian granitic rocks from the Giants Range batholith, northeastern Minnesota, U.S.A.

    Viswanathan, S.


    Oxygen isotope studies of granitic rocks from the 2.7 b.y.-old composite Giants Range batholith show that: (1) ??(O18)quartz values of 9 to 10 permil characterize relatively uncontaminated Lower Precambrian, magmatic granodiorites and granites; (2) granitic rocks thought to have formed by static granitization have ??(O18)quartz values that are 1 to 2 permil higher than magmatic granitic rocks; (3) satellite leucogranite bodies have values nearly identical to those of the main intrusive phases even where they transect O18-rich metasedimentary wall rocks; (4) oxygen isotopic interaction between the granitic melts and their O18-rich wall rocks was minimal; and (5) O18/O18 ratios of quartz grains in a metasomatic granite are largely inherited from the precursor rock, but during the progression - sedimentary parent ??? partially granitized parent ??? metasomatic granite ??? there is gradual decrease in ??(O18)quartz by 1 to 2 permil. ?? 1974.

  14. Quasifree (p , 2 p ) Reactions on Oxygen Isotopes: Observation of Isospin Independence of the Reduced Single-Particle Strength

    Atar, L.; Paschalis, S.; Barbieri, C.; Bertulani, C. A.; Díaz Fernández, P.; Holl, M.; Najafi, M. A.; Panin, V.; Alvarez-Pol, H.; Aumann, T.; Avdeichikov, V.; Beceiro-Novo, S.; Bemmerer, D.; Benlliure, J.; Boillos, J. M.; Boretzky, K.; Borge, M. J. G.; Caamaño, M.; Caesar, C.; Casarejos, E.; Catford, W.; Cederkall, J.; Chartier, M.; Chulkov, L.; Cortina-Gil, D.; Cravo, E.; Crespo, R.; Dillmann, I.; Elekes, Z.; Enders, J.; Ershova, O.; Estrade, A.; Farinon, F.; Fraile, L. M.; Freer, M.; Galaviz Redondo, D.; Geissel, H.; Gernhäuser, R.; Golubev, P.; Göbel, K.; Hagdahl, J.; Heftrich, T.; Heil, M.; Heine, M.; Heinz, A.; Henriques, A.; Hufnagel, A.; Ignatov, A.; Johansson, H. T.; Jonson, B.; Kahlbow, J.; Kalantar-Nayestanaki, N.; Kanungo, R.; Kelic-Heil, A.; Knyazev, A.; Kröll, T.; Kurz, N.; Labiche, M.; Langer, C.; Le Bleis, T.; Lemmon, R.; Lindberg, S.; Machado, J.; Marganiec-Gałązka, J.; Movsesyan, A.; Nacher, E.; Nikolskii, E. Y.; Nilsson, T.; Nociforo, C.; Perea, A.; Petri, M.; Pietri, S.; Plag, R.; Reifarth, R.; Ribeiro, G.; Rigollet, C.; Rossi, D. M.; Röder, M.; Savran, D.; Scheit, H.; Simon, H.; Sorlin, O.; Syndikus, I.; Taylor, J. T.; Tengblad, O.; Thies, R.; Togano, Y.; Vandebrouck, M.; Velho, P.; Volkov, V.; Wagner, A.; Wamers, F.; Weick, H.; Wheldon, C.; Wilson, G. L.; Winfield, J. S.; Woods, P.; Yakorev, D.; Zhukov, M.; Zilges, A.; Zuber, K.; R3B Collaboration


    Quasifree one-proton knockout reactions have been employed in inverse kinematics for a systematic study of the structure of stable and exotic oxygen isotopes at the R3B /LAND setup with incident beam energies in the range of 300 - 450 MeV /u . The oxygen isotopic chain offers a large variation of separation energies that allows for a quantitative understanding of single-particle strength with changing isospin asymmetry. Quasifree knockout reactions provide a complementary approach to intermediate-energy one-nucleon removal reactions. Inclusive cross sections for quasifree knockout reactions of the type O A (p ,2 p )N-1A have been determined and compared to calculations based on the eikonal reaction theory. The reduction factors for the single-particle strength with respect to the independent-particle model were obtained and compared to state-of-the-art ab initio predictions. The results do not show any significant dependence on proton-neutron asymmetry.

  15. Trans-Atlantic slavery: isotopic evidence for forced migration to Barbados.

    Schroeder, Hannes; O'Connell, Tamsin C; Evans, Jane A; Shuler, Kristrina A; Hedges, Robert E M


    The question of the ultimate origin of African slaves is one of the most perplexing in the history of trans-Atlantic slavery. Here we present the results of a small, preliminary isotopic study that was conducted in order to determine the geographical origin of 25 enslaved Africans who were buried at the Newton plantation, Barbados, sometime between the late 17th and early 19th century. In order to gain a more nuanced understanding of the slaves' origin, we used a combination of carbon, nitrogen, oxygen, and strontium isotope analyses. Carbon and nitrogen isotope ratios were determined in bone and dentinal collagen; oxygen and strontium isotopes were measured in tooth enamel. Results suggest that the majority of individuals were born on the island, if not the estate itself. Seven individuals, however, yielded enamel oxygen and strontium ratios that are inconsistent with a Barbadian origin, which strongly suggests that we are dealing with first-generation captives who were brought to the island with the slave trade. This idea is also supported by the fact that their carbon and nitrogen stable isotope values differ markedly between their teeth and bones. These intra-skeletal shifts reflect major dietary changes that probably coincided with their enslavement and forced migration to Barbados. While it is impossible to determine their exact origins, the results clearly demonstrate that the slaves did not all grow up in the same part of Africa. Instead, the data seem to suggest that they originated from at least three different areas, possibly including the Gold Coast and the Senegambia.

  16. Using Oxygen Isotopic Values in Order to Infer Palaeoclimatic Differences between Northern and Central-Southern Greece

    Michael, Dimitra-Ermioni; Dotsika, Elissavet


    Even though isotopic analyses have been extensively implemented on human skeletal remains for the purpose of dietary reconstruction, less attention has been given to the ingested water and thus to the investigation of palaeoclimatic conditions. In particular, oxygen isotopic fingerprinting has never been applied on human skeletal remains from Greece for the abovementioned purpose before. The basic aim of the present study is to compare climatic conditions from two ancient populations, deriving from two different ecological locations; Edessa (Greek Macedonia; 2nd-4th c. AD) and Thebes (Sterea Hellas, 13th-14th c. AD). Oxygen values in Edessa are at -7.69 ±1.13 ‰ and -9.18 ±1.88 ‰ for tooth enamel and bone apatite respectively. On the other hand, oxygen signals in Thebes are at -5.8 ±2.16 ‰ and -9.23 ±1.3 % for the enamel and bone apatite respectively. The utility of oxygen isotopic signatures for the purpose of palaeoclimatic investigation lies on the fact that the ratio of 18 to 16O of meteoric precipitation, expressed as δ18O per mill (‰), relative to the international standard (vSMOW) varies geographically by temperature, humidity, evaporation, distance to the sea, altitude and latitude. Therefore, results as expected, point out that Edessa do presents more negative enamel isotopic values in relation to Thebes, however the noted difference is not observed for the bone apatite samples. The lack of bone apatite differentiation between sites could be attributed to cultural diversity (particularly in Thebes), shift in dietary habits due to migration or social status, climatic fluctuations within each site or to possible diagenetic alteration of bone apatite samples.

  17. Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands)

    Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro


    Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ18Ocalc and δ13Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ18Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in 18O relative to 16O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ18Ocalc value of eggshell calcite to the δ18Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ13Ccalc and δ18Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ13Ccalc and high δ18Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

  18. Early African Diaspora in colonial Campeche, Mexico: strontium isotopic evidence.

    Price, T Douglas; Tiesler, Vera; Burton, James H


    Construction activities around Campeche's central park led to the discovery of an early colonial church and an associated burial ground, in use from the mid-16th century AD to the late 17th century. Remains of some individuals revealed dental mutilations characteristic of West Africa. Analyses of strontium isotopes of dental enamel from these individuals yielded unusually high (87)Sr/(86)Sr ratios, inconsistent with an origin in Mesoamerica, but consistent with an origin in West Africa in terrain underlain by the West Africa Craton, perhaps near the port of Elmina, a principal source of slaves for the New World during the 16th century. These individuals likely represent some of the earliest representatives of the African Diaspora in the Americas.

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

    Szymanek, Marcin


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

  20. Chiral three-nucleon forces and the evolution of correlations along the oxygen isotopic chain

    Cipollone, A.; Barbieri, C.; Navrátil, P.


    Background: Three-nucleon forces (3NFs) have nontrivial implications on the evolution of correlations at extreme proton-neutron asymmetries. Recent ab initio calculations show that leading-order chiral interactions are crucial to obtain the correct binding energies and neutron driplines along the O, N, and F chains [A. Cipollone, C. Barbieri, and P. Navrátil, Phys. Rev. Lett. 111, 062501 (2013), 10.1103/PhysRevLett.111.062501]. Purpose: Here we discuss the impact of 3NFs along the oxygen chain for other quantities of interest, such has the spectral distribution for attachment and removal of a nucleon, spectroscopic factors, and radii. The objective is to better delineate the general effects of 3NFs on nuclear correlations. Methods: We employ self-consistent Green's function (SCGF) theory which allows a comprehensive calculation of the single-particle spectral function. For the closed subshell isotopes, 14O, 16O, 22O, 24O, and 28O, we perform calculations with the Dyson-ADC(3) method, which is fully nonperturbative and is the state of the art for both nuclear physics and quantum chemistry applications. The remaining open-shell isotopes are studied using the newly developed Gorkov-SCGF formalism up to second order. Results: We produce complete plots for the spectral distributions. The spectroscopic factors for the dominant quasiparticle peaks are found to depend very little on the leading-order (NNLO) chiral 3NFs. The latter have small impact on the calculated matter radii, which, however, are consistently obtained smaller than experiment. Similarly, single-particle spectra tend to be too spread with respect to the experiment. This effect might hinder, to some extent, the onset of correlations and screen the quenching of calculated spectroscopic factors. The most important effect of 3NFs is thus the fine tuning of the energies for the dominant quasiparticle states, which governs the shell evolution and the position of driplines. Conclusions: Although present chiral

  1. The isotopic composition of valves and organic tissue of diatoms grown in steady state cultures under varying conditions of temperature, light and nutrients. Implications for the interpretation of oxygen isotopes from sedimentary biogenic opal as proxies of environmental variations

    Kowalczyk, K


    The oxygen isotopes of diatomaceous silica from marine and freshwater sediments are frequently used as indicators of the palaeotemperature development, particularly in cases where calcareous microfossils are rare or absent. With regard to terrestrial waters it is unknown whether or not palaeotemperature scale can be used in a limnic ecosystem. Due to the fact that the seasonal variations in lakes are larger than in oceans, specific problems arise when working with freshwater sediments. Thus, an understanding of the contribution of the various factors (e.g. temperature, light nutrients, competition) influencing the formation of isotope signals in biogenic opal is a prerequisite for the accurate interpretation of environmental processes. Since it is impossible to examine the influence of a single parameter under natural ecosystem conditions due to permanent changes of the environment, laboratory experiments with single diatom species are needed. Therefore, the aim of this study was to investigate the correlation between the oxygen isotope variations in biogenic opal and different environmental parameters using steady state cultures with diatoms. It should be examined whether or not the different diatom species grown under identical conditions show equal oxygen isotope ratios (species relationship), if variations of the water temperature induce variations of the oxygen isotope ratio (relationship with temperature), variable parameters such as light intensity and nitrate concentration influence the isotope ratio, and if vital effects (e.g. growth rate) lead to variations of the oxygen isotope ratio. (orig.)

  2. The isotopic composition of valves and organic tissue of diatoms grown in steady state cultures under varying conditions of temperature, light and nutrients. Implications for the interpretation of oxygen isotopes from sedimentary biogenic opal as proxies of environmental variations

    Kowalczyk, K.


    The oxygen isotopes of diatomaceous silica from marine and freshwater sediments are frequently used as indicators of the palaeotemperature development, particularly in cases where calcareous microfossils are rare or absent. With regard to terrestrial waters it is unknown whether or not palaeotemperature scale can be used in a limnic ecosystem. Due to the fact that the seasonal variations in lakes are larger than in oceans, specific problems arise when working with freshwater sediments. Thus, an understanding of the contribution of the various factors (e.g. temperature, light nutrients, competition) influencing the formation of isotope signals in biogenic opal is a prerequisite for the accurate interpretation of environmental processes. Since it is impossible to examine the influence of a single parameter under natural ecosystem conditions due to permanent changes of the environment, laboratory experiments with single diatom species are needed. Therefore, the aim of this study was to investigate the correlation between the oxygen isotope variations in biogenic opal and different environmental parameters using steady state cultures with diatoms. It should be examined whether or not the different diatom species grown under identical conditions show equal oxygen isotope ratios (species relationship), if variations of the water temperature induce variations of the oxygen isotope ratio (relationship with temperature), variable parameters such as light intensity and nitrate concentration influence the isotope ratio, and if vital effects (e.g. growth rate) lead to variations of the oxygen isotope ratio. (orig.)

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

    Schmidt, Gavin A.


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

  4. Textural and isotopic evidence for Ca-Mg carbonate pedogenesis

    Diaz-Hernandez, J. L.; Sánchez-Navas, A.; Delgado, A.; Yepes, J.; Garcia-Casco, A.


    Models for evaluating the terrestrial carbon cycle must take into account not only soil organic carbon, represented by a mixture of plant and animal remains, but also soil inorganic carbon, contained in minerals, mainly in calcite and dolomite. Thick soil caliches derived from weathering of mafic and ultramafic rocks must be considered as sinks for carbon storage in soils. The formation of calcite and dolomite from pedogenic alteration of volcanic tephras under an aridic moisture regime is studied in an unusually thick 3-m soil profile on Gran Canaria island (Canary Islands, Spain). The biological activity of the pedogenic environment (soil respiration) releases CO2 incorporated as dissolved inorganic carbon (DIC) in waters. It drives the formation of low-magnesian calcite and calcian dolomite over basaltic substrates, with a δ13C negative signature (-8 to -6‰ vs. V-PDB). Precipitation of authigenic carbonates in the soil is accompanied by the formation of Mg-rich clay minerals and quartz after the weathering of basalts. Mineralogical, textural, compositional, and isotopic variations throughout the soil profile studied indicate that dolomite formed at greater depths and earlier than the calcite. The isotopic signatures of the surficial calcite and deeper dolomite crusts are primary and resulted from the dissolution-precipitation cycles that led to the formation of both types of caliches under different physicochemical conditions. Dolomite formed within a clay-rich matrix through diffusive transport of reactants. It is precipitated from water with more negative δ18O values (-1.5 to -3.5‰ vs. V-SMOW) in the subsoil compared to those of water in equilibrium with surficial calcite. Thus, calcite precipitated after dolomite, and directly from percolating solutions in equilibrium with vadose water enriched in δ18O (-0.5 to +1.5‰) due to the evaporation processes. The accumulation of inorganic carbon reaches 586.1 kg m-2 in the soil studied, which means that the

  5. An oxygen isotope study of quartz veins within eclogites from the Dabie terrane

    LI; Yiliang


    : 1011-1014.[23]Banerjee, S. K., Hunt, C. P., Liu, X., Separation of local signals from the regional paleomonsoon record of the Chinese loess plateau: A rock magnetic approach, Geophys. Res. Lett., 1993, 20: 843-846.[24]Vidic, N. J., TenPas, J. D., Verosub, K. L. et al., Separation of pedogenic and lithogenic components of magnetic suscepti-bility in the Chinese loess/paleosol sequence as determined by the CBD procedure and a mixing analysis, Geophys. J. Int., 2000, 142: 551-562.[25]Deng, C. L., Yuan, B. Y., Zhu, R. X. et al., Magnetic susceptibility of Holocene loess-black loam sequence from Jiaodao, Shanxi, before and after citrate-bicarbonate-dithionite extraction, Chinese Journal of Geophysics (in Chinese), 2000, 43(4): 514-520.[26]Hunt, C. P., Banerjee, S. K., Han, J. M. et al., Rock-magnetic proxies of climate change in the loess-palaeosol sequences of the western Loess Plateau of China, 1995, Geophys. J. Int., 1995, 123: 232-244.[27]Liu, X. M., Liu, T. S., Heller, F. et al., The grain size of magnetic minerals in Chinese loess and its implications for paleo-climate, Science in China (in Chinese), Ser. B, 1991, 21(6): 639-644.[28]Chen, F. H., Bloemendal, J., Feng, Z. D. et al., East Asian monsoon variations during oxygen isotope stage 5: Evidence from the northwestern margin of the Chinese Loess Plateau, Quaternary Science Reviews, 1999, 18: 1127-1135.[29]Pan, B. T., Wang, J. M., Loess record of Qinghai-Xizang Plateau monsoon variations in the eastern part of the plateau since the Last Interglacial, Quaternary Sciences (in Chinese), 1999, 19(4): 330-335.[30]Imbrie, J., Imbrie, J. Z., Modeling the climate response to orbital variation, Science, 1980, 207: 943-953.[31]Liu, T. S., Quaternary Environment (in Chinese), Beijing: Science Press, 1997, 189-239.

  6. The impact of moisture sources on the oxygen isotope composition of precipitation at a continental site in central Europe

    Krklec, Kristina; Domínguez-Villar, David; Lojen, Sonja


    The stable isotope composition of precipitation records processes taking place within the hydrological cycle. Potentially, moisture sources are important controls on the stable isotope composition of precipitation, but studies focused on this topic are still scarce. We studied the moisture sources contributing to precipitation at Postojna (Slovenia) from 2009 to 2013. Back trajectory analyses were computed for the days with precipitation at Postojna. The moisture uptake locations were identified along these trajectories using standard hydrometeorological formulation. The moisture uptake locations were integrated in eight source regions to facilitate its comparison to the monthly oxygen isotope composition (δ18O values) of precipitation. Nearly half of the precipitation originated from continental sources (recycled moisture), and >40% was from central and western Mediterranean. Results show that moisture sources do not have a significant impact on the oxygen isotope composition at this site. We suggest that the large proportion of recycled moisture originated from transpiration rather than evaporation, which produced water vapour with less negative δ18O values. Thus the difference between the oceanic and local vapour source was reduced, which prevented the distinction of the moisture sources based on their oxygen isotope signature. Nevertheless, δ18O values of precipitation are partially controlled by climate parameters, which is of major importance for paleoclimate studies. We found that the main climate control on Postojna δ18O values of precipitation is the surface temperature. Amount effect was not recorded at this site, and the winter North Atlantic Oscillation (NAO) does not impact the δ18O values of precipitation. The Western Mediterranean Oscillation (WeMO) was correlated to oxygen stable isotope composition, although this atmospheric pattern was not a control. Instead we found that the link to δ18O values results from synoptic scenarios affecting We

  7. Ocean circulation and shelf processes in the Arctic, Mediterranean traced by radiogenic neodymium isotopes, rare earth elements and stable oxygen isotopes

    Laukert, Georgi


    Disentangling the sources, distribution and mixing of water masses involved in the transport and transfer of heat and freshwater in the Arctic Mediterranean (i.e. the Arctic Ocean and the Nordic Seas, AM) is critical for the understanding of present and future hydrological changes in the high-latitude regions. This study refines the knowledge of water mass circulation in the AM and provides new insights into the processes occurring on the Arctic shelves and in high-latitude estuaries. A multi-proxy approach is used combining dissolved radiogenic Nd isotopes (ε{sub Nd}), rare earth elements (REEs) and stable oxygen isotopes (δ{sup 18}O) together with standard hydrographic tracers. The sources, distribution and mixing of water masses that circulate in the AM and pass the Fram Strait are assessed through evaluation of dissolved ε{sub Nd} and REE, and δ{sup 18}O data obtained from samples recovered in 2012, 2014 and 2015, and through a compilation and reassessment of literature Nd isotope and concentration data previously reported for other sites within the AM. The Nd isotope and REE distribution in the central Fram Strait and the open AM is shown to primarily reflect the lateral advection of water masses and their mixing, whereas seawater-particle interactions exert important control only above the shelf regions. New insights into the processes occurring in high latitude estuaries are provided by dissolved Nd isotope and REE compositions together with δ{sup 18}O data for the Laptev Sea based on filtered samples recovered in 2012, 2013 and 2014. A combination of REE removal through coagulation of nanoparticles and colloids and REE redistribution within the water column through formation and melting of sea ice and river ice is suggested to account for the distribution of all REEs, while no REE release from particles is observed. The ice-related processes contribute to the redistribution of other elements and ultimately may also affect primary productivity in high

  8. Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

    Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.


    Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5-10% in REE (Eu = 14%), 6-13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg-normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are 0.6 × CI with enriched La abundance ( 0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass-dependent isotope fractionation trend. Both groups show a slope-1/2 line on a three-isotope plot with subtle negative deviation in Δ17O associated with δ18O enrichment relative to δ17O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.

  9. Non-destructive estimates of soil carbonic anhydrase activity and associated soil water oxygen isotope composition

    Jones, Sam P.; Ogée, Jérôme; Sauze, Joana; Wohl, Steven; Saavedra, Noelia; Fernández-Prado, Noelia; Maire, Juliette; Launois, Thomas; Bosc, Alexandre; Wingate, Lisa


    The contribution of photosynthesis and soil respiration to net land-atmosphere carbon dioxide (CO2) exchange can be estimated based on the differential influence of leaves and soils on budgets of the oxygen isotope composition (δ18O) of atmospheric CO2. To do so, the activity of carbonic anhydrases (CAs), a group of enzymes that catalyse the hydration of CO2 in soils and plants, needs to be understood. Measurements of soil CA activity typically involve the inversion of models describing the δ18O of CO2 fluxes to solve for the apparent, potentially catalysed, rate of CO2 hydration. This requires information about the δ18O of CO2 in isotopic equilibrium with soil water, typically obtained from destructive, depth-resolved sampling and extraction of soil water. In doing so, an assumption is made about the soil water pool that CO2 interacts with, which may bias estimates of CA activity if incorrect. Furthermore, this can represent a significant challenge in data collection given the potential for spatial and temporal variability in the δ18O 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 inferring the rate of CO2 hydration and the δ18O of soil water from the relationship between the δ18O of CO2 fluxes and the δ18O of CO2 at the soil surface measured at different ambient CO2 conditions. This approach was tested through laboratory incubations of air-dried soils that were re-wetted with three waters of different δ18O. Gas exchange measurements were made on these soils to estimate the rate of hydration and the δ18O of soil water, followed by soil water extraction to allow for comparison. Estimated rates of CO2 hydration were 6.8-14.6 times greater than the theoretical uncatalysed rate of hydration, indicating that CA were active in these soils. Importantly, these estimates were not significantly different among water treatments, suggesting

  10. Early-Middle Pleistocene benthic turnover and oxygen isotope stratigraphy from the Central Mediterranean (Valle di Manche, Crotone Basin, Italy): Data and trends

    Michele Azzarone; Patrizia Ferretti; Veronica Rossi; Daniele Scarponi; Luca Capraro; Patrizia Macrì; John W. Huntley; Costanza Faranda


    Ostracod faunal turnover and oxygen isotope data (foraminifera) along the Valle di Manche (VdM) section are herein compiled. Specifically, the material reported in this work includes quantitative palaeoecological data and patterns of ostracod fauna framed within a high-resolution oxygen isotope stratigraphy (δ18O) from Uvigerina peregrina. In addition, the multivariate ostracod faunal stratigraphic trend (nMDS axis-1 sample score) is calibrated using bathymetric distributions of extant mollus...

  11. Isotopic evidence for the diverse origins of nitrate minerals

    Heaton, T.H.E.


    Nitrate minerals are rare and, apart from their occasional value as economic deposits of fertilizer, not of general importance in geology. The mechanisms by which they are formed, however, are still the subject of considerable debate. This brief discussion indicates that the study of the 15 N/ 14 N ratios of nitrate minerals can yield useful information on their origins. The low 15 N/ 14 N ratios for nitrate in desert environments indicate that soil or animal waste sources of nitrogen are unlikely. Derivation from atmospheric precipitation is consistent with the presently limited knowledge of the isotopic characteristics of atmospheric compounds, but can only be confirmed when data for these compounds in desert areas become available. For nitrates in wetter environments the 15 N/ 14 N ratios indicate that atmospheric sources are not important, and that the formation of nitrate from gaseous ammonia emanating from animal waste is probably not a significant mechanism. The nitrate appears to be chiefly derived either by direct solution of animal waste nitrate (Lydenburg cave and Prieskapoort) or from soil-derived nitrate brought in by groundwater (Autana and possibly Abjaterskop caves). In the case of Sveite special conditions involving bacterial processes are also implied

  12. Poster 9: Isotopic Ratios of Carbon and Oxygen in Titan's CO using ALMA

    Serigano, Joseph; Nixion, Conor A.; Cordiner, Martin A.; Irwin, Patrick G. J.; Teanby, Nick A.; Charnley, Steven B.; Lindberg, Johan E.


    The advent of the Atacama Large Millimeter/Submillimeter Array (ALMA) has provided a new and powerful facility for probing the atmospheres of solar system targets at long wavelengths (84-720 GHz) where the rotational lines of small, polar molecules are prominent. In the complex atmosphere of Titan, photochemical processes dissociate and ionize molecular nitrogen and methane in the upper atmosphere, creating a complex inventory of trace hydrocarbons and nitriles. Additionally, the existence of oxygen on Titan facilitates the synthesis of molecules of potential astrobiological importance. Utilization of ground-based submillimeter observations of Titan has proven to be a powerful tool to complement results from spacecraft observations. ALMA provides the ability to probe this region in greater detail with unprecedented spectral and spatial resolution at high sensitivity, allowing for the derivation of vertical mixing profiles, molecular detections, and observations of latitudinal and seasonal variations. Recent ALMA studies of Titan have presented spectrally and spatially-resolved maps of HNC and HC3N emission (Cordiner et al. 2014), as well as the first spectroscopic detection of ethyl cyanide (C2H5CN) in Titan's atmosphere (Cordiner et al. 2015). This poster will focus on ALMA observations of carbon monoxide (CO) and its isotopologues 13CO, C18O, and C 17O in Titan's atmosphere. Molecular abundances and the vertical atmospheric temperature profile were derived by modeling the observed emission line profiles using NEMESIS, a line-by-line radiative transfer code (Irwin et al. 2008). This study reports the first spectroscopic detection of 17O in the outer solar system with C17O detected at >8σ confidence. The abundances of these molecules and isotopic ratios of 12C/13C, 16O/18O, and 16O/17O will be presented. General implications for the history of Titan from these measurements will be discussed.

  13. Isotopic strontium, carbon and oxygen study on neoproterozoic marbles from Sierra de Umango, Andean Foreland, Argentina

    Varela, R; Valencio, S.; Ramos, A; Sato, K; Gonzalez, P; Panarello, H; Roverano, D


    The Umango Hill (La Rioja Province, 29 o 00'S-68 o 40'W) is one of the mountain blocks of Sierras Pampeanas Occidentales (Caminos, 1979), bounded by thrust faults and surrounded by Upper Devonian to Tertiary marine and continental sedimentites. The exposed crystalline basement is composed of basic igneous rocks and a siliciclastic-limestone sequence, both affected by amphibolite facies metamorphic peak. In the southern area (Juchi creek), the metamorphic complex carries relics of granitic orthogneisses, with Rb/Sr and U/Pb dates of ∼1000 Ma (Varela et al., 1996). These ancient inliers were asigned to a Mesoproterozoic Grenville Orogenic Cycle. Granitic bodies, intrusives at different ages in the Metamorphic Complex, have also been distinguished. The most ancient is El Penon Granite, with 469±9 Ma Rb/Sr age (Varela et al., 2000) and 523±26 Ma U/Pb zircon age (unpublished data). In this way it is possible to point out broadly that the siliciclastic-limestone sequence belongs to the Neoproterozoic-Early Palaeozoic times. It was a platform cover over grenvillian cratonic basement. The metamorphism and deformation, we understand, took place in the Early Palaeozoic, related to the Pampean-Famatinian Orogenic Cycle. In this work, compositional and isotopic data of Strontium ( 87 Sr/ 86 Sr), Carbon (δ 13 Cv PDB ) and Oxygen (δ 18 Ov PDB ) of the marbles derived from the siliciclastic-limestone sequence are presented. The results are interpreted and correlated with the temporal variation curves of 87 Sr/ 86 Sr and δ 13 C from Neoproterozoic marine carbonates (Jacobsen and Kaufman, 1999) (au)

  14. Oxygen isotopic ratios in quartz as an indicator of provenance of dust

    Jackson, M.L.


    Quartz was isolated in the long range aerosol size range (fine silt, 1-10 μm in diameter) from atmospheric aerosols, wind-erosive soils, soil silts, shales, and Pacific pelagic sediments of the Northern and Southern Hemispheres, to trace their provenance or origin, as part of a study of dust mineral sequestering of 137 Cs and other products of nuclear fission. The oxygen isotopic ratio ( 18 O/ 16 O) was determined by mass spectrometry. The provenance has been established for this fine silt fraction which reflects the relative proportion of two classes of quartz source: (a) weathering of igneous and metamorphic rocks (high temperature origin and low 18 O/ 16 O ratio) and (b) of quartz crystallized in cherts and overgrowths (low temperature origin and high 18 O/ 16 O ratio). This quartz mixing ratio is a basic model or paradigm. Analyses of present day atmospheric aerosols and eolian-derived soils, Pacific pelagic sediments, and now-raised Phanerozoic marine sediments show that the Northern and Southern Hemispheres have separate large-scale reservoirs of the fine grain sizes that contribute to aerosol dusts. These can be identified by distinctive values of 18 O/ 16 O ratios of the quartz therein. The difference in quartz delta 18 O value in parts per thousand per ml ( 0 / 00 of about 12 +- 2 0 / 00 in Southern Hemisphere mixed detrital sediments and about 19 +- 2 0 / 00 in those of the Northern Hemisphere (for constant size, the 1-10 μm size fraction) results from the presence of a considerably larger proportion of quartz having low-temperature origin and higher delta 18 O values (chert, silica overgrowths, etc.) in the Northern Hemisphere reservoirs. The early paleoclimatic and paleogeochemical differences remain the control of the North-South Hemisphere difference in delta 18 O values in long-range aerosol sized quartz

  15. Soil, the orphan hydrological compartment: evidence from O and H stable isotopes?

    Hissler, Christophe; Legout, Arnaud; Barnich, François; Pfister, Laurent


    of different water types in soil (weakly-, moderately- and tightly-bound). Our results show that mobile and tightly bound water may have different hydrogen isotopic signatures and that their respective isotopic signatures may vary between horizons and soil types. However, it is not yet possible to quantify the contribution of different bio-physico-chemical processes to the oxygen and hydrogen isotopic composition of the soil water because the techniques at hand for water separation are not yet reliable enough. Prior to this type of quantifications, we need to focus in a next step at the improvement of water extraction methods.

  16. Stable Isotope (delta OXYGEN-18, Delta Deuterium, Delta CARBON-13) Dendroclimatological Studies in the Waterloo Region of Southern Ontario, Canada, Between AD 1610 and 1990.

    Buhay, William Mark

    Oxygen (delta^{18} O), hydrogen (delta^2H) and carbon (delta^{13}C) isotopes were measured in wood cellulose from elm, white pine and maple trees that grew in southwestern Ontario, Canada. The measured oxygen and hydrogen isotopic data were used for model-based reconstructions of delta^{18}{O}_{meteoric water}, mean annual temperature (MAT) and relative humidity for a period, AD 1610 to 1880, that precedes instrumental records of climate. The carbon isotope measurements were compared with the Cellulose Model inferred climate data to reveal additional environmental information. Modifications made to the Cellulose Model focused on the dynamics of oxygen and hydrogen isotopic fractionation in plants during evapotranspiration and photosynthetic assimilation. For instance, kinetic fractionation of ^{18}O was found to be predictable from theoretical considerations of leaf energy balance and boundary layer dynamics. Kinetic fractionation during evapotranspiration is sensitive to the nature of the boundary layer, which is controlled by leaf size and morphology. Generally, plants with small segmented leaves have a lower component of turbidity in the leaf boundary layer, which results in higher kinetic fractionation values, than do plants having large simple leaves and more turbulent boundary layers. Kinetic ^2H enrichment in plant leaf water can also be rationalized in terms of leaf size and morphology when an apparent temperature-dependent isotope effect, acting in opposition to evaporative enrichment, is taken into account. Accounting for this temperature -dependent isotope effect helps to: (1) reconcile hydrogen kinetic fractionation inconsistencies for different leaves; (2) explain a temperature effect previously attributed to variable biochemical fractionation during cellulose synthesis, and; (3) verify hydrogen biochemical effects in plants. This improved characterization of the oxygen and hydrogen isotopic effects in plants, using the modified Cellulose Model, helped

  17. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

    Kevorkyants, Ruslan, E-mail:; Sboev, Mikhail N.; Chizhov, Yuri V.


    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  18. Ancient feeding ecology inferred from stable isotopic evidence from fossil horses in South America over the past 3 Ma

    Alberdi María T


    Full Text Available Abstract Background Stable isotope ratios (13C/12C and 18O/16O in fossil teeth and bone provide key archives for understanding the ecology of extinct horses during the Plio-Pleistocene in South America; however, what happened in areas of sympatry between Equus (Amerhippus and Hippidion is less understood. Results Here, we use stable carbon and oxygen isotopes preserved in 67 fossil tooth and bone samples for seven species of horses from 25 different localities to document the magnitude of the dietary shifts of horses and ancient floral change during the Plio-Pleistocene. Dietary reconstructions inferred from stable isotopes of both genera of horses present in South America document dietary separation and environmental changes in ancient ecosystems, including C3/C4 transitions. Stable isotope data demonstrate changes in C4 grass consumption, inter-species dietary partitioning and variation in isotopic niche breadth of mixed feeders with latitudinal gradient. Conclusions The data for Hippidion indicate a preference varying from C3 plants to mixed C3-C4 plants in their diet. Equus (Amerhippus shows three different patterns of dietary partitioning Equus (A. neogeus from the province of Buenos Aires indicate a preference for C3 plants in the diet. Equus (A. andium from Ecuador and Equus (A. insulatus from Bolivia show a preference for to a diet of mixed C3-C4 plants, while Equus (A. santaeelenae from La Carolina (sea level of Ecuador and Brazil are mostly C4 feeders. These results confirm that ancient feeding ecology cannot always be inferred from dental morphology. While the carbon isotope composition of horses skeletal material decreased as latitude increased, we found evidence of boundary between a mixed C3/C4 diet signal and a pure C4 signal around 32° S and a change from a mixed diet signal to an exclusively C3 signal around 35°S. We found that the horses living at high altitudes and at low to middle latitude still have a C4 component in their

  19. Isotopic evidence for identifying the mechanism of salinization of groundwater in Bacolod City,Negros Occidental

    Castaneda, Soledad S.; Almoneda, Rosalinda V.; Sucgang, Raymond J.; Desengano, Daisy; Lim, Fatima


    Saline water is easily identified by measurement of the conductivity of the ionic species in the water. In groundwater, it is important to identify the mechanism of salinization for proper management of the resource. Salinization may come from: a) leaching of salts by percolating water, b) intrusion of modern saltwater bodies of connate water, and c) concentration of dissolved salts due to evaporation. The salinity and isotopic concentrations of 18 O, 2 H, and 3 H of the water sources were used to assess the processes which lead to the salinization of groundwater in Bacolod City, Negros Occidental. The isotopic composition of deep groundwater, river water, and springs cluster along the LMWL with δ 18 O ranging from -7.9 ''promille'' to -6.5 ''promille'' and δ 2 H ranging from -52.6 ''promille'' to -39.1''promille''. Two isotopically distinct groups of deep groundwater were deleated; the higher elevation wells yielding isotopically depleted waters while the lowland wells yielding relatively enriched water with higher conductivity. The shallow coastal wells exhibited more enriched isotope values with δ 18 O values from 6.10 ''promille''-5.61''promille'' and δ 2 H from -43.1''promille'' to -38.8''promille'' and highest conductivity. The relative enrichment in the isotopic composition of the deep groundwater in the lowland and the shallow groundwater along the coast is attributed to saltwater intrusion. The process of salinization in these waters is differentiated based on the relationship between their isotopic compositions and the chlorine concentrations. The high salinity of the isotopically enriched and old deep groundwater inland is attributed to mixing with connate water. On the other hand , mixing with modern sea water is evident in the deep and shallow coastal wells. (author)

  20. Carbon and oxygen stable isotope and trace element studies in speleothems and across the J-K boundary, Central Italy

    Kudielka, G.


    Carbon and Oxygen stable isotope ratios of carbonates decisively depend on fractionation during physicochemical processes. Therefore, they represent a powerful tool to derive information on past conditions under which the carbonates formed. Isotope ratio mass spectrometry (IRMS) offers a large range of applications. This thesis presents two projects based upon investigation of carbon and oxygen stable isotope ratios combined with trace element abundances (determined by instrumental neutron activation analysis, INAA) in carbonates. (1) Palaeoclimatic investigation on speleothems from central Italy. Four speleothems from Grotta Grande del Vento, central Italy, were analyzed for stable isotope ratios and trace element abundances, and age dated to obtain a chronologically reliable stable isotope profile. The speleothems were sampled by means of a dental drill to gain a stable isotope profile with a 0.5 mm resolution, trace element abundances have been performed by INAA every 0.5 cm, and the samples for age dating were picked according to remarkable features in the stable isotope trends and analyzed by TIMS. The record covers the period from 93 ka until the early holocene with a hiatus lasting from 75 ka until 65.0 ka. Speleothem growth during the last glacial indicates moderate conditions in the Frasassi region back then. Comparison with speleothems from Ireland, France and northern Italy reveal a north-south slope in d18O, indicating, that the rain over central Italy mainly originates from the North Atlantic. Depletion of moisture in d18O during its continental trajectory is due to rainout, which primarily extracts the heavy isotopes. The stable isotope record is in good agreement with the high-resolution speleothem record from Soreq Cave, Israel. Distinct isotopic events coincide between 85 ka and 80 ka, between ∼ 60 ka and 50 ka and from the last glacial to the early holocene. An offset has been existing between the two records at any time. The speleothems of

  1. Uppermost Cretaceous to middle Oligocene carbon and oxygen isotope stratigraphy of Southwest Pacific : holes 1121B and 1124C, ODP Leg 181

    Wei, K.-Y.; Mii, H.-S.; Shu, I-T.; Lin, Y.-J.


    Oxygen and carbon isotopic ratios of bulk sediments from ODP Leg 181, holes 1121B and 1124C, in the Southwest Pacific were measured. The isotopic signals are mainly contributed by calcareous nannofossils with minimal diagenetic alteration. A complete section of the late Paleogene age between 60.7 and 57.5 Ma was recovered from Hole 1121B. However, the Paleogene sedimentary sequence of Hole 1124C was truncated by three major hiatuses: late Paleocene to middle Eocene (59-42 Ma), middle Eocene to early Oligocene (40-33.5 Ma), and early Oligocene to middle Oligocene (31.3-27.5 Ma). The middle Eocene shows the most negative δ 18 O values (c. -0.8 permille) compared to the early Paleocene (c. -0.2 to -0.3 permille) and Oligocene (c. 0.6-0.9 permille). The δ 18 O pattern is consistent with previous understanding of the Paleogene paleoclimate: a warmth optimum in the early-middle Eocene followed by a major glaciation in the early Oligocene at c. 34 Ma. The hiatus of 33.5-40 Ma indicates that the Tasmanian Gateway had deepened enough by 33.5 Ma, allowing the breakthrough of cold, bottom water and consequently the formation of the Deep Western Boundary Current (DWBC). With the aid of independent biochronological and magnetochronological markers, the Paleocene carbon isotopic profiles were correlated with that of DSDP 577 in the North Pacific. Both sites record the early part of the Paleocene carbon isotopic maximum event, while only Hole 1124C extends back to the early Paleocene and latest Cretaceous. A short hiatus of 60.5-62.5 Ma age may exist. Although the Cretaceous/Tertiary boundary is not directly recorded, a significant cooling trend across the boundary is evident. The surface water became warmer after 64.5 Ma, and reached a stable warmth level during 64-59 Ma. A major cooling took place during c. 59-57 Ma in the late Paleocene. The temperature gradients between the two sites (ODP 1121 and 1124, paleolatitudes 64 degrees S versus 53 degrees S) are estimated to be c

  2. Effects of Water Vapor on the Data Quality of the Stable Oxygen Isotopic Ratio of Atmospheric Carbon Dioxide

    Evans, C. U.; White, J. W.; Vaughn, B.; Tans, P. P.; Pardo, L.


    The stable oxygen isotopic ratio of carbon dioxide can potentially track fundamental indicators of environmental change such as the balance between photosynthesis and respiration on regional to global scales. The Stable Isotope Laboratory (SIL) at the Institute of Arctic and Alpine Research (INSTAAR), University of Colorado at Boulder, has measured the stable isotopes of atmospheric carbon dioxide from more than 60 NOAA/Earth System Research Laboratory (ESRL) air flask-sampling sites since the early 1990s. If air is sampled without drying, oxygen can exchange between carbon dioxide and water in the flasks, entirely masking the desired signal. An attempt to investigate how water vapor is affecting the δ18O signal is accomplished by comparing the SIL measurements with specific humidity, calculated from the National Climatic Data Center (NCDC) global integrated surface hourly temperature and dew point database, at the time of sampling. Analysis of sites where samples have been collected initially without drying, and subsequently with a drying kit, in conjunction with the humidity data, has led to several conclusions. Samples that initially appear isotopically unaltered, in that their δ18O values are within the expected range, are being subtly influenced by the water vapor in the air. At Bermuda and other tropical to semi-tropical sites, the 'wet' sampling values have a seasonal cycle that is strongly anti-correlated to the specific humidity, while the 'dry' values have a seasonal cycle that is shifted earlier than the specific humidity cycle by 1-2 months. The latter phasing is expected given the seasonal phasing between climate over the ocean and land, while the former is consistent with a small, but measurable isotope exchange in the flasks. In addition, we note that there is a strong (r > 0.96) correlation between the average specific humidity and the percent of rejected samples for 'wet' sampling. This presents an opportunity for determining a threshold of

  3. Measuring oxygen yields of a thermal conversion/elemental analyzer-isotope ratio mass spectrometer for organic and inorganic materials through injection of CO.

    Yin, Xijie; Chen, Zhigang


    The thermal conversion/elemental analyzer-isotope ratio mass spectrometer (TC/EA-IRMS) is widely used to measure the δ(18) O value of various substances. A premise for accurate δ(18) O measurement is that the oxygen in the sample can be converted into carbon monoxide (CO) quantitatively or at least proportionally. Therefore, a precise method to determine the oxygen yield of TC/EA-IRMS measurements is needed. Most studies have used the CO peak area obtained from a known amount of a solid reference material (for example, benzoic acid) to calibrate the oxygen yield of the sample. Although it was assumed that the oxygen yield of the solid reference material is 100%, no direct evidence has been provided. As CO is the analyte gas for δ(18) O measurement by IRMS, in this study, we use a six-port valve to inject CO gas into the TC/EA. The CO is carried to the IRMS by the He carrier gas and the CO peak area is measured by the IRMS. The CO peak area thus obtained from a known amount of the injected CO is used to calibrate the oxygen yield of the sample. The oxygen yields of commonly used organic and inorganic reference materials such as benzoic acid (C6 H5 COOH), silver phosphate (Ag3 PO4 ), calcium carbonate (CaCO3 ) and silicon dioxide (SiO2 ) are investigated at different reactor temperatures and sample sizes. We obtained excellent linear correlation between the peak area for the injected CO and its oxygen atom amount. C6 H5 COOH has the highest oxygen yield, followed by Ag3 PO4 , CaCO3 and SiO2 . The oxygen yields of TC/EA-IRMS are less than 100% for both organic and inorganic substances, but the yields are relatively stable at the specified reactor temperature and for a given quantity of sample. Copyright © 2014 John Wiley & Sons, Ltd.

  4. Oxygen and Hydrogen Isotopes of Precipitation in a Rocky Mountainous Area of Beijing to Distinguish and Estimate Spring Recharge

    Ziqiang Liu


    Full Text Available Stable isotopes of oxygen and hydrogen were used to estimate seasonal contributions of precipitation to natural spring recharge in Beijing’s mountainous area. Isotopic compositions were shown to be more positive in the dry season and more negative in the wet season, due to the seasonal patterns in the amount of precipitation. The local meteoric water line (LMWL was δ2H = 7.0 δ18O − 2.3 for the dry season and δ2H = 5.9 δ18O − 10.4 for the wet season. LMWL in the two seasons had a lower slope and intercept than the Global Meteoric Water Line (p < 0.01. The slope and intercept of the LMWL in the wet season were lower than that in the dry season because of the effect of precipitation amount during the wet season (p < 0.01. The mean precipitation effects of −15‰ and −2‰ per 100 mm change in the amount of precipitation for δ2H and δ18O, respectively, were obtained from the monthly total precipitation and its average isotopic value. The isotopic composition of precipitation decreased when precipitation duration increased. Little changes in the isotopic composition of the natural spring were found. By employing isotope conservation of mass, it could be derived that, on average, approximately 7.2% of the natural spring came from the dry season precipitation and the rest of 92.8% came from the wet season precipitation.

  5. A First Look at Oxygen and Silicon Isotope Variations in Diatom Silica from a Pliocene Antarctic Marine Sediment Core

    Abbott, T.; Dodd, J. P.; Hackett, H.; Scherer, R. P.


    Coupled oxygen (δ18O) and silicon (δ30Si) isotope variations in diatom silica (opal-A) are increasingly used as a proxy to reconstruct paleoenvironmental conditions (water temperatures, water mass mixing, nutrient cycling) in marine environments. Diatom silica is a particularly significant paleoenvironmental proxy in high latitude environments, such as the Southern Ocean, where diatom blooms are abundant and diatom frustules are well preserved in the sediment. The Andrill-1B (AND-1B) sediment core from the Ross Sea (Antarctica) preserves several Pliocene ( 4.5 Ma) age diatomite units. Here we present preliminary δ18O and δ30Si values for a diatomite subunit in the AND-1B sediment core. Initial isotope values for the AND-1B diatoms silica record relatively high variability (range δ18O: 36.3‰ to 39.9‰) that could be interpreted as large-scale changes in the water temperature and/or freshwater mixing in the Ross Sea; however, a significant concern with marine sediment of this age is isotope fractionation during diagenesis and the potential formation of opal-CT lepispheres. The effects of clay contamination on the diatom silica δ18O values have been addressed through sample purification and quantified through chemical and physical analyses of the diatom silica. The isotopic effects of opal-CT are not as clearly understood and more difficult to physically separate from the primary diatom silica. In order to better understand the isotope variations in the AND-1B diatoms, we also evaluated silicon and oxygen isotope fractionation during the transition from opal-A to opal-CT in a controlled laboratory experiment. Opal-A from cultured marine diatoms (Thalassiosira weissflogii) was subjected to elevated temperatures (150°C) in acid digestion vessels for 4 weeks to initiate opal-CT precipitation. Quantifying the effects of opal-CT formation on δ18O and δ30Si variations in biogenic silica improves our understanding of the use of diatom silica isotope values a

  6. Sr isotopic evidence on the spilitic degradation of the Deccan basalt

    Subbarao, K.V.


    Similar Sr isotopic ratios (∼0.7055) for the tholeiite-spilite flow unit and the associated mineral phases, of Bombay (Deccan Traps) provide a direct evidence for the spilitic degradation of tholeiite. In contrast, a dramatic increase in the rare earth elements (REE) from basalt to spilite is rather puzzling as rare earths are considered to be relatively immobile. The geochemistry thus suggests that the process of spilitization is due to the reaction with a complex fluid having identical Sr-isotopic composition as that of the basaltic magma-thereby masking the details of the mixing process. (author)

  7. Isotope hydrological evidence of geomorphological changes in North-Eastern Hungary

    Hertelendi, E.; Marton, L.; Miko, L.


    Stable isotope and radiocarbon data of groundwater stored in Quaternary aquifers in North-Eastern Hungary can not be explained by climatic changes alone. More than two hundred δD, δ 18 O and radiocarbon ages of waters from 79 wells show that the recharge are changed during the time of upper pleniglacial and late glacial. Groundwaters of the studied are can be divided into three categories, which can explain their origin. The data are consistent with geomorphological results giving isotope evidence of hydrology for a geodynamical event during the mentioned periods. (R.P.) 3 refs.; 2 figs

  8. Stable carbon and oxygen isotope signatures in molluscan shells under ocean acidification

    Nishida, K.; Hayashi, M.; Suzuki, A.; Sato, M.; Nojiri, Y.


    Stable carbon and oxygen isotope compositions (δ13C, δ18O) of biogenic carbonate have been widely used for many paleoclimate, paleoecological, and biomineralization studies. δ13C of molluscan shells reflects the mixing of δ13C of dissolved inorganic carbon (DIC) of seawater and respiratory carbon. Previous studies reported physiological effects on molluscs by ocean acidification, and thus the metabolic changes could potentially appear in shell δ13C as changes in a fraction of two carbon sources. In addition, shell δ18O, a commonly used proxy of seawater temperature and seawater δ18O, is also affected by seawater carbonate chemistry. As changes in the marine carbonate system, such as pH and pCO2, have occurred in the past 300 million years, to estimate pH effect on paleotemperature reconstruction is important. Here, we experimentally examined acidification effects on shell δ13C and δ18O of two species of clams for understanding of environmental and physiological proxies. Juvenile specimens of bloody clam Scapharca broughtonii and Japanese surf clam Pseudocardium sachalinense were cultured at five (400, 600, 800, 1000, and 1200 µatm, P. sachalinense) or six (280, 400, 600, 800, 1000, and 1200 µatm, S. broughtonii) different pCO2 levels using CO2 control system of the Demonstration Laboratory, MERI, Japan. Significant negative correlations between shell δ13C and pH appeared in S. broughtonii, which showed non-significant pH effects on calcification, and the slope of the relationship of shell carbonate was lower than that of seawater DIC. On the other hand, in P. sachalinense which showed a decrease in calcification at low-pH treatment, the slopes of the relationship between shell δ13C and pH was roughly the same as that of seawater DIC. Thus, the extrapallial fluid of P. sachalinense might more strongly affected by acidified seawater than S. broughtonii. The results of two species might be attributable to differences in physiological responses to

  9. Doubly labeled water method: in vivo oxygen and hydrogen isotope fractionation

    Schoeller, D.A.; Leitch, C.A.; Brown, C.


    The accuracy and precision of the doubly labeled water method for measuring energy expenditure are influenced by isotope fractionation during evaporative water loss and CO 2 excretion. To characterize in vivo isotope fractionation, we collected and isotopically analyzed physiological fluids and gases. Breath and transcutaneous water vapor were isotopically fractionated. The degree of fractionation indicated that the former was fractionated under equilibrium control at 37 0 C, and the latter was kinetically fractionated. Sweat and urine were unfractionated. By use of isotopic balance models, the fraction of water lost via fractionating routes was estimated from the isotopic abundances of body water, local drinking water, and dietary solids. Fractionated water loss averaged 23% (SD = 10%) of water turnover, which agreed with our previous estimates based on metabolic rate, but there was a systematic difference between the results based on O 2 and hydrogen. Corrections for isotopic fractionation of water lost in breath and (nonsweat) transcutaneous loss should be made when using labeled water to measure water turnover or CO 2 production

  10. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

    Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.


    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

  11. Oxygen isotope calibration of the onset of ice-rafting and history of glaciation in the North Atlantic region

    Shackleton, N.J.; Backman, J.; Zimmerman, H.; Kent, D.V.; Hall, M.A.; Roberts, David G.; Schnitker, D.; Baldauf, J.G.; Desprairies, A.; Homrighausen, R.; Huddlestun, P.; Keene, J.B.; Kaltenback, A.J.; Krumsiek, K.A.O.; Morton, A.C.; Murray, J.W.; Westberg-Smith, J.


    We report here that DSDP Site 552A, cored with the hydraulic piston corer on the west flank of Rockall Bank, recovered an undisturbed sequence of alternating white deep-sea carbonate oozes and dark-coloured layers that are rich in glacial debris. Oxygen isotope analysis of the sequence together with detailed nannofossil and palaeomagnetic stratigraphy shows that the first major horizon of ice-rafting occurred at about 2.4 Myr, and was preceded by a minor pulse of ice-rafting at about 2.5 Myr. The carbon isotope record shows that the site has been bathed by a water mass of similar characteristics to present-day North Atlantic deep water at least since 3.5 Myr. ?? 1984 Nature Publishing Group.

  12. Oxygen isotope fluctuations in a modern North Sea oyster (Crassostrea gigas) compared with annual variations in seawater temperature

    Ullmann, Clemens Vinzenz; Wiechert, Uwe; Korte, Christoph


    A total of 181 oxygen isotope values from sequential samples of the left shell of a modern Pacific Oyster (Crassostrea gigas) that lived on a sub-tidal oyster bank in the List Basin (North Sea, Germany) shows periodically varying values between + 1.3‰ and -2.5‰. In order to test whether these d18O...... fluctuations reflect seawater temperature changes, the isotope values of the shell were compared to actual seawater temperature variations from the region. C. gigas serves as an excellent proxy for temperature of palaeoseawater and the results show that the examined oyster precipitated its shell in d18O...... equilibrium with the ambient seawater. A cessation of the oyster shell calcification starts at water temperatures below 6 °C, at lower temperatures than previously thought for Crassostrea. For palaeoclimate investigations the termination of shell production is important because the lowest temperatures might...

  13. Spontaneous Oxygen Isotope Exchange between Carbon Dioxide and Oxygen-Containing Minerals: Do the Minerals "breathe" CO2?

    Civiš, Svatopluk; Bouša, Milan; Zukal, Arnošt; Knížek, Antonín; Kubelík, Petr; Rojík, P.; Nováková, Jana; Ferus, Martin


    Roč. 120, č. 1 (2016), s. 508-516 ISSN 1932-7447 R&D Projects: GA MŠk LD14115; GA MŠk(CZ) LD13060; GA ČR(CZ) GA14-12010S Grant - others:COST(XE) CM1104 Institutional support: RVO:61388955 Keywords : Absorption spectroscopy * Infrared spectrometers * Oxygen Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.536, year: 2016

  14. Isotopic and Chemical Evidence for Primitive Aqueous Alteration in the Tagish Lake Meteorite

    Sakuma, Keisuke; Hidaka, Hiroshi; Yoneda, Shigekazu


    Aqueous alteration is one of the primitive activities that occurred on meteorite parent bodies in the early solar system. The Tagish Lake meteorite is known to show an intense parent body aqueous alteration signature. In this study, quantitative analyses of the alkaline elements and isotopic analyses of Sr and Ba from acid leachates of TL (C2-ungrouped) were performed to investigate effects of aqueous alteration. The main purpose of this study is to search for isotopic evidence of extinct 135Cs from the Ba isotopic analyses in the chemical separates from the Tagish Lake meteorite. Barium isotopic data from the leachates show variable 135Ba isotopic anomalies (ε = ‑2.6 ∼ +3.6) which correlatewith 137Ba and 138Ba suggesting a heterogeneous distribution of s- and r-rich nucleosynthetic components in the early solar system. The 87Rb–87Sr and 135Cs–135Ba decay systems on TL in this study do not provide any chronological information. The disturbance of the TL chronometers is likely a reflection of the selective dissolution of Cs and Rb given the relatively higher mobility of Cs and Rb compared to Ba and Sr, respectively, during fluid mineral interactions.

  15. Sulfur and Oxygen Isotopic Composition of Sulfate in the Fresh Water, King Sejong Station, King George Island, Antarctica

    Kim, M.; Lee, I.; Lee, J.; Park, B.; Mayer, B.; Kaufman, A. J.; Park, S.; Kim, G.; Lee, K.


    Isotopic compositions of sulfur (δ34S) and oxygen (δ18O) were measured for the sulfate of the fresh water near the King Sejong Station, King George Island, Antarctica. Sejong station is located in the Barton peninsular of the King George Island. The geology around King Sejong station mainly composed of basalt-andesite, quart monzodiorite, and granodiorite. Lapilli tuff, conglomerate, sandstone, and siltstone occur along the southern and eastern shore of the Barton peninsula. Lapilli tuff also occurs on the highland located on southeastern part of the Barton peninsula. The δ34S values of sulfate extracted from fresh water samples at King Sejong Station range from 13.7 to 16.3 per mil excluding 1 sample. These sulfur values are very narrow in their range compared with those from anthropogenic sources. These sulfur values are 5 to 7 per mil lower than those of typical present seawater. Considering the rocks occurring near the King Sejong station, these sulfur isotopic values do not seem to be related to any evaporites of certain age. In Antarctic region the natural source of sulfate dissolved in water could be originated from marine biogenic source (DMS), sea-salt, volcanic source, or other continental sources. Most of the δ34S values of sulfate at King Sejong station seems to indicate the dominance of marine biogenic origin for the source of sulfur. The δ18O values of sulfate extracted from fresh water samples at King Sejong Station range from 1.9 to 6.4 per mil excluding 1 sample. These oxygen isotope values are lower than those of the sulfate in the present seawater by 6 per mil. However, both sulfur and oxygen isotope values strongly represent the influence of the seawater sulfate. One sample have 2.6 and -1.1 per mil in its δ34S and δ18O values, respectively, that are quite different from the isotopic values of other samples. This sample was collected in the highland far from the King Sejong station. Therefore this sample might reflect the composition of

  16. Carbon and oxygen isotopes in carbonatites from Puna, Jujuy and Salta, Argentina

    Zappettini, Eduardo O.; Rubiolo, Daniel


    δ 13 and δ 18 O data from carbonatites indicate that bodies formed by crystallization of carbonate magma with subsequent formation of metasomatic and hydrothermal carbonatitic veins. The isotopic data are consistent with the available geochemical and petrologic information. (author)

  17. Study of the tensor correlation in oxygen isotopes using mean-field-type and shell model methods

    Sugimoto, Satoru


    The tensor force plays important roles in nuclear structure. Recently, we have developed a mean-field-type model which can treat the two-particle-two-hole correlation induced by the tensor force. We applied the model to sub-closed-shell oxygen isotopes and found that an sizable attractive energy comes from the tensor force. We also studied the tensor correlation in 16O using a shell model including two-particle-two-hole configurations. In this case, quite a large attractive energy is obtained for the correlation energy from the tensor force

  18. Oxygen isotope records of Globigerina bulloides across a north-south transect in the south-western Indian Ocean

    Khare, N.; Chaturvedi, S.K.; Saraswat, R

    , Washington, D.C). Lutjeharms, J.R.E., N.M. Walters and B.R. Allanson. 1985. Oceanic frontal systems and biologicalenhancement. p.11-21. In: Antarctic Nutrient Cycles and Food Webs. ed. by W.R. Siegfried et al., Springer-Verlag, NewYork. Matsumoto, K., J...: Ocean Sci. J.: 44(2); 2009; 117-123 OXYGEN ISOTOPE RECORDS OF GLOBIGERINA BULLOIDES ACROSS A NORTH-SOUTH TRANSECT IN THE SOUTH-WESTERN INDIAN OCEAN N. Khare 1* , S. K. Chaturvedi 2 and R. Saraswat 3 1. Ministry of Earth Sciences, Block...

  19. Chromatographic determination of the relative retention of isotopic species of oxygen in methanol and methan-d3-ol

    Pauls, R.E.; Mahle, N.H.; Shepard, A.T.; Gaw, J.C.; Rogers, L.B.


    A high-precision gas chromatograph was used in conjunction with a quadrupole mass filter and an on-line computer to study the fractionation of oxygen isotopes by Porapak T and glycerol in CH 3 OH and CD 3 OH as a function of temperature. Values of relative retention on the order of 1.002 compared favorably with results for the vapor pressure ratio obtained by classical means. Differences from unity were much smaller for the activity-coefficient ratio than for the vapor-pressure ratio. Differential thermodynamic data were also reported

  20. Oxygen isotope partitioning between rhyolitic glass/melt and CO2: An experimental study at 550-950 degrees C and 1 bar

    Palin, J.M.; Epstein, S.; Stolper, E.M.


    Oxygen isotope partitioning between gaseous CO 2 and a natural rhyolitic glass and melt (77.7 wt% SiO 2 , 0.16 wt% H 2 O total ) has been measured at 550-950 degrees C and approximately 1 bar. Equilibrium oxygen isotope fractionation factors (α CO2-rhyolite = ( 18 O/ 16 O) rhyolite ) determined in exchange experiments of 100-255 day duration. These values agree well with predictions based on experimentally determined oxygen isotope fractionation factors for CO 2 -silica glass and CO 2 -albitic glass/melt, if the rhyolitic glass is taken to be a simple mixture of normative silica and alkali feldspar components. The results indicate that oxygen isotope partitioning in felsic glasses and melts can be modeled by linear combinations of endmember silicate constituents. Rates of oxygen isotope exchange observed in the partitioning experiments are consistent with control by diffusion of molecular H 2 O dissolved in the glass/melt and are three orders of magnitude faster than predicted for rate control solely by diffusion of dissolved molecular CO 2 under the experimental conditions. Additional experiments using untreated and dehydrated (0.09 wt% H 2 O total ) rhyolitic glass quantatively support these interpretations. We conclude that diffusive oxygen isotope exchange in rhyolitic glass/melt, and probably other polymerized silicate materials, it controlled by the concentrations and diffusivities of dissolved oxygen-bearing volatile species rather than diffusion of network oxygen under all but the most volatile-poor conditions. 25 refs., 6 figs., 1 tab

  1. Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

    Johnson, Craig A.; Day, Warren C.; Rye, Robert O.


    Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition

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

    Warwick, Peter D.; 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. A route for oxygen isotope enrichment of α-COOH groups in amino acids

    Steinschneidner, A.; St Armour, T.; Valentine, B.; Burgar, M.I.; Fiat, D.


    Oxygen-17 was introduced into leucine, proline, phenylalanine and tyrosine. The corresponding tert-butyloxycarbonyl amino acids were first converted to their O-methyl esters. Following saponification with Na 17 OH, the tert-butyloxycarbonyl group was removed to yield free amino acid enriched with oxygen-17 by approximately 1000-fold. Oxygen-17 NMR revealed well-resolved peaks for the labelled amino acids. The chemical shifts are reported. (author)

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

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


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

  5. On the Use of Biomineral Oxygen Isotope Data to Identify Human Migrants in the Archaeological Record: Intra-Sample Variation, Statistical Methods and Geographical Considerations.

    Emma Lightfoot

    Full Text Available Oxygen isotope analysis of archaeological skeletal remains is an increasingly popular tool to study past human migrations. It is based on the assumption that human body chemistry preserves the δ18O of precipitation in such a way as to be a useful technique for identifying migrants and, potentially, their homelands. In this study, the first such global survey, we draw on published human tooth enamel and bone bioapatite data to explore the validity of using oxygen isotope analyses to identify migrants in the archaeological record. We use human δ18O results to show that there are large variations in human oxygen isotope values within a population sample. This may relate to physiological factors influencing the preservation of the primary isotope signal, or due to human activities (such as brewing, boiling, stewing, differential access to water sources and so on causing variation in ingested water and food isotope values. We compare the number of outliers identified using various statistical methods. We determine that the most appropriate method for identifying migrants is dependent on the data but is likely to be the IQR or median absolute deviation from the median under most archaeological circumstances. Finally, through a spatial assessment of the dataset, we show that the degree of overlap in human isotope values from different locations across Europe is such that identifying individuals' homelands on the basis of oxygen isotope analysis alone is not possible for the regions analysed to date. Oxygen isotope analysis is a valid method for identifying first-generation migrants from an archaeological site when used appropriately, however it is difficult to identify migrants using statistical methods for a sample size of less than c. 25 individuals. In the absence of local previous analyses, each sample should be treated as an individual dataset and statistical techniques can be used to identify migrants, but in most cases pinpointing a specific

  6. Oxygen-isotope trends and seawater temperature changes across the Late Cambrian Steptoean positive carbon-isotope excursion (SPICE event)

    Elrick, M.; Rieboldt, S.; Saltzman, M.; McKay, R.M.


    The globally recognized Late Cambrian Steptoean positive C-isotope excursion (SPICE) is characterized by a 3???-5??? positive ??13C shift spanning SPICE represents a widespread ocean anoxic event leading to enhanced burial/preservation of organic matter (Corg) and pyrite. We analyzed ??18O values of apatitic inarticulate brachiopods from three Upper Cambrian successions across Laurentia to evaluate paleotemperatures during the SPICE. ??18O values range from ~12.5??? to 16.5???. Estimated seawater temperatures associated with the SPICE are unreasonably warm, suggesting that the brachiopod ??18O values were altered during early diagenesis. Despite this, all three localities show similar trends with respect to the SPICE ??13C curve, suggesting that the brachiopod apatite preserves a record of relative ??18O and temperature changes. The trends include relatively high ??18O values at the onset of the SPICE, decreasing and lowest values during the main event, and an increase in values at the end of the event. The higher ??18O values during the global extinction at the onset of the SPICE suggests seawater cooling and supports earlier hypotheses of upwelling of cool waters onto the shallow shelf. Decreasing and low ??18O values coincident with the rising limb of the SPICE support the hypothesis that seawater warming and associated reduced thermohaline circulation rates contributed to decreased dissolved O2 concentrations, which enhanced the preservation/burial of Corg causing the positive ??13C shift. ?? 2011 Geological Society of America.

  7. Coordinated Oxygen Isotopic and Petrologic Studies of CAIS Record Varying Composition of Protosolar

    Simon, Justin I.; Matzel, J. E. P.; Simon, S. B.; Weber, P. K.; Grossman, L.; Ross, D. K.; Hutcheon, I. D.


    Ca-, Al-rich inclusions (CAIs) record the O-isotope composition of Solar nebular gas from which they grew [1]. High spatial resolution O-isotope measurements afforded by ion microprobe analysis across the rims and margin of CAIs reveal systematic variations in (Delta)O-17 and suggest formation from a diversity of nebular environments [2-4]. This heterogeneity has been explained by isotopic mixing between the O-16-rich Solar reservoir [6] and a second O-16-poor reservoir (probably nebular gas) with a "planetary-like" isotopic composition [e.g., 1, 6-7], but the mechanism and location(s) where these events occur within the protoplanetary disk remain uncertain. The orientation of large and systematic variations in (Delta)O-17 reported by [3] for a compact Type A CAI from the Efremovka reduced CV3 chondrite differs dramatically from reports by [4] of a similar CAI, A37 from the Allende oxidized CV3 chondrite. Both studies conclude that CAIs were exposed to distinct, nebular O-isotope reservoirs, implying the transfer of CAIs among different settings within the protoplanetary disk [4]. To test this hypothesis further and the extent of intra-CAI O-isotopic variation, a pristine compact Type A CAI, Ef-1 from Efremovka, and a Type B2 CAI, TS4 from Allende were studied. Our new results are equally intriguing because, collectively, O-isotopic zoning patterns in the CAIs indicate a progressive and cyclic record. The results imply that CAIs were commonly exposed to multiple environments of distinct gas during their formation. Numerical models help constrain conditions and duration of these events.

  8. New estimates of oxygen isotope fractionation by plants and soils - Implications for the isotopic composition of the atmosphere

    Angert, A.; Luz, B.


    Oxygen concentration and δ 18 O of O 2 have been monitored in light and heavy soils. Steep oxygen gradients were present at the heavy soil site (minimal O 2 concentration was 1% at 150cm depth) and δ 18 O values typically ranged from 0 per mille to -1.6 per mille relative to air O 2 . In the light-soil site, the O 2 concentration was 20.38% to 20.53% and δ 18 O values ranged from -0.06±0.015 per mille to 0.06±0.015 per mille relative to atmospheric O 2 . The fractionation in soil respiration was estimated from the observed [O 2 ] and δ 18 O profiles and their change with time by a five-box numerical model. Diffusion due to concentration and temperature gradients was taken into account. Good agreement was found between the model results and the measured values. The average discrimination against 18 O in the two study sites was 12±1 per mille. The current understanding of the composition of air O 2 attributes the magnitude of the fractionation in soil respiration to biochemical mechanisms alone. Thus the discrimination against 18 O is assumed to be 18 per mille in cyanide-sensitive dark respiration and 25 per mille to 30 per mille in cyanide-resistant respiration. The discrimination we report is significantly less than in dark respiration. This overall low discrimination is explained by slow diffusion in soil aggregates, and in root tissues that results in low O 2 concentration in the consumption site. Since about half of the terrestrial respiration occurs in soils, our new discrimination estimate lowers significantly the discrimination value for terrestrial uptake. Higher then currently assumed discrimination was found in experiments with illuminated plants. This high discrimination might compensate for the low discrimination found in soils. (author)

  9. Dual (oxygen and nitrogen) isotopic characterization of the museum archived nitrates from the United States of America, South Africa and Australia.

    Mizota, Chitoshi; Hosono, Takahiro; Matsunaga, Midori; Okumura, Azusa


    Dual (oxygen and nitrogen) isotopic composition of the museum archived nitrates from the United States of America, South Africa and Australia was studied. The analyzed specimens were collected in middle 19th to early 20th centuries, and represent world-wide acquisition of the Smithsonian Institution Natural Museum of Natural History (Washington, D. C., USA) and the Natural History Museum (London, UK). The samples consist of transparent to semi-transparent aggregates of minute nitrate, euhedral crystallites which imply precipitation from percolating fluids under ample space and dry regimes. The major nitrate chemistry is saltpetre (KNO 3 ) with minor nitratine (NaNO 3 ). A binary plot of δ 15 N vs. δ 18 O of almost all nitrates indicates a trend, reflecting microbial origin through nitrification of ammonium. The diagram excludes the contribution of meteoric origin formed by mass-independent, photochemical reaction of NO with ozone in stratosphere. Calculated paleo-ambient fluid compositions responsible for microbial nitrification imply extreme evaporative concentration of relevant fluids under dry climatic regimes in the Northern Cape Province (South Africa) and in the Northern Territory (central Australia), and even throughout the United States of America. The dual isotopic characterization provides direct evidence to the origin of the museum archived nitrates. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Isotope exchange of molecular oxygen with oxygen of La0,7Sr0,3CoO3-δ

    Vdovin, G.K.; Kuzin, B.L.; Kurumchin, Eh.Kh.


    The exchange rate of the oxygen in La 0,7 Sr 0,3 CoO 3-δ has been measured by an isotopic exchange method at temperatures 620-1250 K and pressures 1.6-10 torr. The activation energy and the dependence of the exchange rate on pressures in gas have been defined. It is suggested that the knees on the temperature dependences of the exchange rate are attributed to the appearance of Co 2+ ions on the surface of the sample at elevated temperature as new centres of the exchange reaction. The activation energies of the adsorption and desorption processes on the La 0,7 Sr 0,3 CoO 3-δ surface have been estimated

  11. Ice-free conditions in Fennoscandia during Marine Oxygen Isotope Stage 3?

    Wohlfarth, Barbara (Dept. of Geology and Geochemistry, Stockholm Univ., Stockholm (Sweden))


    One of the central aims of the climate research conducted by the Swedish Nuclear Fuel and Waste Management Company (SKB) is to investigate the extremes within which climate conditions may vary within a 100,000 year perspective. The 100,000 year time perspective corresponds to one glacial cycle during which warm interstadial and cold stadial conditions alternated, leading to ice sheet advance and retreat over Fennoscandia. To address the issue of how extreme climate conditions may impact the deep nuclear waste repository, a climate modelling study was initiated with the aim to investigate the response to different climate scenarios: glacial conditions, permafrost conditions and temperate conditions. A model set-up for the permafrost and glacial scenario required information on, for example past ice cover, vegetation, and land-sea configuration. The permafrost climate scenario focussed on a stadial event (Greenland stadial 12) during Marine Oxygen Isotope Stage (MIS) 3, because it was assumed that southern Sweden and the areas of Forsmark and Oskarshamn were not ice covered, but possibly experienced permafrost conditions. This assumption however needed to be validated by paleoenvironmental and paleoclimatic records for MIS 3. Available paleoenvironmental records for this time interval are comparably scarce and due to chronological uncertainties also partly conflicting. Most records are derived from marginal areas of the former Fennoscandian ice sheet and only little and inconsistent information exists for the central part. Geological investigations along the Norwegian coast, in Denmark, southern Sweden, northern and eastern Finland have for example shown that the Fennoscandian ice sheet margin responded distinctly to some of the warmest middle Weichselian interstadials (MIS 3). Interstadial organic sediments from the central part of the former ice sheet have been described from several localities in Sweden, but radiocarbon (14C) dates for these deposits provided ages

  12. Ice-free conditions in Fennoscandia during Marine Oxygen Isotope Stage 3?

    Wohlfarth, Barbara


    One of the central aims of the climate research conducted by the Swedish Nuclear Fuel and Waste Management Company (SKB) is to investigate the extremes within which climate conditions may vary within a 100,000 year perspective. The 100,000 year time perspective corresponds to one glacial cycle during which warm interstadial and cold stadial conditions alternated, leading to ice sheet advance and retreat over Fennoscandia. To address the issue of how extreme climate conditions may impact the deep nuclear waste repository, a climate modelling study was initiated with the aim to investigate the response to different climate scenarios: glacial conditions, permafrost conditions and temperate conditions. A model set-up for the permafrost and glacial scenario required information on, for example past ice cover, vegetation, and land-sea configuration. The permafrost climate scenario focussed on a stadial event (Greenland stadial 12) during Marine Oxygen Isotope Stage (MIS) 3, because it was assumed that southern Sweden and the areas of Forsmark and Oskarshamn were not ice covered, but possibly experienced permafrost conditions. This assumption however needed to be validated by paleoenvironmental and paleoclimatic records for MIS 3. Available paleoenvironmental records for this time interval are comparably scarce and due to chronological uncertainties also partly conflicting. Most records are derived from marginal areas of the former Fennoscandian ice sheet and only little and inconsistent information exists for the central part. Geological investigations along the Norwegian coast, in Denmark, southern Sweden, northern and eastern Finland have for example shown that the Fennoscandian ice sheet margin responded distinctly to some of the warmest middle Weichselian interstadials (MIS 3). Interstadial organic sediments from the central part of the former ice sheet have been described from several localities in Sweden, but radiocarbon ( 14 C) dates for these deposits provided

  13. Diversity of management strategies in Mesoamerican turkeys: archaeological, isotopic and genetic evidence

    Manin, Aurelie; Corona-M, Eduardo; Craig, Abigail; Thornton, Erin Kennedy; Yang, Dongya Y.; Richards, Michael


    The turkey (Meleagris gallopavo) represents one of the few domestic animals of the New World. While current research points to distinct domestication centres in the Southwest USA and Mesoamerica, several questions regarding the number of progenitor populations, and the timing and intensity of turkey husbandry remain unanswered. This study applied ancient mitochondrial DNA and stable isotope (δ13C, δ15N) analysis to 55 archaeological turkey remains from Mexico to investigate pre-contact turkey exploitation in Mesoamerica. Three different (sub)species of turkeys were identified in the archaeological record (M. g. mexicana, M. g. gallopavo and M. ocellata), indicating the exploitation of diverse local populations, as well as the trade of captively reared birds into the Maya area. No evidence of shared maternal haplotypes was observed between Mesoamerica and the Southwest USA, in contrast with archaeological evidence for trade of other domestic products. Isotopic analysis indicates a range of feeding behaviours in ancient Mesoamerican turkeys, including wild foraging, human provisioning and mixed feeding ecologies. This variability in turkey diet decreases through time, with archaeological, genetic and isotopic evidence all pointing to the intensification of domestic turkey management and husbandry, culminating in the Postclassic period. PMID:29410864

  14. Diversity of management strategies in Mesoamerican turkeys: archaeological, isotopic and genetic evidence.

    Manin, Aurelie; Corona-M, Eduardo; Alexander, Michelle; Craig, Abigail; Thornton, Erin Kennedy; Yang, Dongya Y; Richards, Michael; Speller, Camilla F


    The turkey ( Meleagris gallopavo ) represents one of the few domestic animals of the New World. While current research points to distinct domestication centres in the Southwest USA and Mesoamerica, several questions regarding the number of progenitor populations, and the timing and intensity of turkey husbandry remain unanswered. This study applied ancient mitochondrial DNA and stable isotope ( δ 13 C, δ 15 N) analysis to 55 archaeological turkey remains from Mexico to investigate pre-contact turkey exploitation in Mesoamerica. Three different (sub)species of turkeys were identified in the archaeological record ( M. g. mexicana , M. g. gallopavo and M. ocellata ), indicating the exploitation of diverse local populations, as well as the trade of captively reared birds into the Maya area. No evidence of shared maternal haplotypes was observed between Mesoamerica and the Southwest USA, in contrast with archaeological evidence for trade of other domestic products. Isotopic analysis indicates a range of feeding behaviours in ancient Mesoamerican turkeys, including wild foraging, human provisioning and mixed feeding ecologies. This variability in turkey diet decreases through time, with archaeological, genetic and isotopic evidence all pointing to the intensification of domestic turkey management and husbandry, culminating in the Postclassic period.

  15. Seasonal transfer of oxygen isotopes from precipitation and soil to the tree ring: source water versus needle water enrichment.

    Treydte, Kerstin; Boda, Sonja; Graf Pannatier, Elisabeth; Fonti, Patrick; Frank, David; Ullrich, Bastian; Saurer, Matthias; Siegwolf, Rolf; Battipaglia, Giovanna; Werner, Willy; Gessler, Arthur


    For accurate interpretation of oxygen isotopes in tree rings (δ(18) O), it is necessary to disentangle the mechanisms underlying the variations in the tree's internal water cycle and to understand the transfer of source versus leaf water δ(18) O to phloem sugars and stem wood. We studied the seasonal transfer of oxygen isotopes from precipitation and soil water through the xylem, needles and phloem to the tree rings of Larix decidua at two alpine sites in the Lötschental (Switzerland). Weekly resolved δ(18) O records of precipitation, soil water, xylem and needle water, phloem organic matter and tree rings were developed. Week-to-week variations in needle-water (18) O enrichment were strongly controlled by weather conditions during the growing season. These short-term variations were, however, not significantly fingerprinted in tree-ring δ(18) O. Instead, seasonal trends in tree-ring δ(18) O predominantly mirrored trends in the source water, including recent precipitation and soil water pools. Modelling results support these findings: seasonal tree-ring δ(18) O variations are captured best when the week-to-week variations of the leaf water signal are suppressed. Our results suggest that climate signals in tree-ring δ(18) O variations should be strongest at temperate sites with humid conditions and precipitation maxima during the growing season. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

  16. Quasifree (p, 2p) Reactions on Oxygen Isotopes: Observation of Isospin Independence of the Reduced Single-Particle Strength.

    Atar, L; Paschalis, S; Barbieri, C; Bertulani, C A; Díaz Fernández, P; Holl, M; Najafi, M A; Panin, V; Alvarez-Pol, H; Aumann, T; Avdeichikov, V; Beceiro-Novo, S; Bemmerer, D; Benlliure, J; Boillos, J M; Boretzky, K; Borge, M J G; Caamaño, M; Caesar, C; Casarejos, E; Catford, W; Cederkall, J; Chartier, M; Chulkov, L; Cortina-Gil, D; Cravo, E; Crespo, R; Dillmann, I; Elekes, Z; Enders, J; Ershova, O; Estrade, A; Farinon, F; Fraile, L M; Freer, M; Galaviz Redondo, D; Geissel, H; Gernhäuser, R; Golubev, P; Göbel, K; Hagdahl, J; Heftrich, T; Heil, M; Heine, M; Heinz, A; Henriques, A; Hufnagel, A; Ignatov, A; Johansson, H T; Jonson, B; Kahlbow, J; Kalantar-Nayestanaki, N; Kanungo, R; Kelic-Heil, A; Knyazev, A; Kröll, T; Kurz, N; Labiche, M; Langer, C; Le Bleis, T; Lemmon, R; Lindberg, S; Machado, J; Marganiec-Gałązka, J; Movsesyan, A; Nacher, E; Nikolskii, E Y; Nilsson, T; Nociforo, C; Perea, A; Petri, M; Pietri, S; Plag, R; Reifarth, R; Ribeiro, G; Rigollet, C; Rossi, D M; Röder, M; Savran, D; Scheit, H; Simon, H; Sorlin, O; Syndikus, I; Taylor, J T; Tengblad, O; Thies, R; Togano, Y; Vandebrouck, M; Velho, P; Volkov, V; Wagner, A; Wamers, F; Weick, H; Wheldon, C; Wilson, G L; Winfield, J S; Woods, P; Yakorev, D; Zhukov, M; Zilges, A; Zuber, K


    Quasifree one-proton knockout reactions have been employed in inverse kinematics for a systematic study of the structure of stable and exotic oxygen isotopes at the R^{3}B/LAND setup with incident beam energies in the range of 300-450  MeV/u. The oxygen isotopic chain offers a large variation of separation energies that allows for a quantitative understanding of single-particle strength with changing isospin asymmetry. Quasifree knockout reactions provide a complementary approach to intermediate-energy one-nucleon removal reactions. Inclusive cross sections for quasifree knockout reactions of the type ^{A}O(p,2p)^{A-1}N have been determined and compared to calculations based on the eikonal reaction theory. The reduction factors for the single-particle strength with respect to the independent-particle model were obtained and compared to state-of-the-art ab initio predictions. The results do not show any significant dependence on proton-neutron asymmetry.

  17. Mechanisms of Bond Cleavage during Manganese Oxide and UV Degradation of Glyphosate: Results from Phosphate Oxygen Isotopes and Molecular Simulations.

    Jaisi, Deb P; Li, Hui; Wallace, Adam F; Paudel, Prajwal; Sun, Mingjing; Balakrishna, Avula; Lerch, Robert N


    Degradation of glyphosate in the presence of manganese oxide and UV light was analyzed using phosphate oxygen isotope ratios and density function theory (DFT). The preference of C-P or C-N bond cleavage was found to vary with changing glyphosate/manganese oxide ratios, indicating the potential role of sorption-induced conformational changes on the composition of intermediate degradation products. Isotope data confirmed that one oxygen atom derived solely from water was incorporated into the released phosphate during glyphosate degradation, and this might suggest similar nucleophilic substitution at P centers and C-P bond cleavage both in manganese oxide- and UV light-mediated degradation. The DFT results reveal that the C-P bond could be cleaved by water, OH - or • OH, with the energy barrier opposing bond dissociation being lowest in the presence of the radical species, and that C-N bond cleavage is favored by the formation of both nitrogen- and carbon-centered radicals. Overall, these results highlight the factors controlling the dominance of C-P or C-N bond cleavage that determines the composition of intermediate/final products and ultimately the degradation pathway.

  18. Simultaneous Measurement of Nitrogen and Oxygen Isotopes of Nitrate to Evaluate Nitrate Sources and Processes in Catchments

    Ohte, Nobuhito [Graduate School of Agricultural and Life Sciences, University of Tokyo, Tokyo (Japan); Nagata, Toshi; Tayasu, Ichiro [Center for Ecological Research, Kyoto University, Ohtsu (Japan); Kyozu, Ayato; Yoshimizu, Chikage [CREST, Japan Science and Technology Agency, Center for Ecological Research, Kyoto University, Ohtsu (Japan); Osaka, Ken' ichi [Carbon and Nutrient Cycles Division, National Institute for Agro-Environmental Sciences, Tsukuba, (Japan)


    We review studies on applied isotope analytical techniques for identifying sources and transformations of river nitrate (NO{sub 3}{sup -}) to examine the influences of water pollution, excess nutrient (nitrogen) loads and ecosystem disturbances in river systems. We also discuss the current status and future perspectives of the application of NO{sub 3}{sup -} isotope measurements to the assessment of river nutrients. Our review shows that in recent years simultaneous measurements of nitrogen and oxygen isotopes ({delta}{sup 15}N and {delta}{sup 18}O) of NO{sub 3}{sup -} have been increasingly used to identify the sources and pathways of nitrogen in river systems. The {delta}{sup 15}N value of NO{sub 3}{sup -} is a useful indicator to evaluate the contributions of sewage and/or animal waste to NO{sub 3}{sup -} load, and the {delta}{sup 18}O value can be used for estimation of the contribution of NO{sub 3}{sup -} derived through atmospheric deposition. The microbial denitrification method is currently a most useful tool to measure the {delta}{sup 15}N and {delta}{sup 18}O values of NO{sub 3}{sup -} simultaneously, because of its capability for high throughput of samples. This method allows us to conduct a comprehensive investigation of spatial and temporal variations and mechanisms of nitrogen transport and transformation in rivers and catchments in more precise and effective manner. (author)

  19. Tracing the Sources of Atmospheric Phosphorus Deposition to a Tropical Rain Forest in Panama Using Stable Oxygen Isotopes.

    Gross, A; Turner, B L; Goren, T; Berry, A; Angert, A


    Atmospheric dust deposition can be a significant source of phosphorus (P) in some tropical forests, so information on the origins and solubility of atmospheric P is needed to understand and predict patterns of forest productivity under future climate scenarios. We characterized atmospheric dust P across a seasonal cycle in a tropical lowland rain forest on Barro Colorado Nature Monument (BCNM), Republic of Panama. We traced P sources by combining remote sensing imagery with the first measurements of stable oxygen isotopes in soluble inorganic phosphate (δ(18)OP) in dust. In addition, we measured soluble inorganic and organic P concentrations in fine (1 μm) aerosol fractions and used this data to estimate the contribution of P inputs from dust deposition to the forest P budget. Aerosol dry mass was greater in the dry season (December to April, 5.6-15.7 μg m(-3)) than the wet season (May to November, 3.1-7.1 μg m(-3)). In contrast, soluble P concentrations in the aerosols were lower in the dry season (980-1880 μg P g(-1)) than the wet season (1170-3380 μg P g(-1)). The δ(18)OP of dry-season aerosols resembled that of nearby forest soils (∼19.5‰), suggesting a local origin. In the wet season, when the Trans-Atlantic Saharan dust belt moves north close to Panama, the δ(18)OP of aerosols was considerably lower (∼15.5‰), suggesting a significant contribution of long-distance dust P transport. Using satellite retrieved aerosol optical depth (AOD) and the P concentrations in aerosols we sampled in periods when Saharan dust was evident we estimate that the monthly P input from long distance dust transport during the period with highest Saharan dust deposition is 88 ± 31 g P ha(-1) month(-1), equivalent to between 10 and 29% of the P in monthly litter fall in nearby forests. These findings have important implications for our understanding of modern nutrient budgets and the productivity of tropical forests in the region under future climate scenarios.

  20. Can oxygen stable isotopes be used to track precipitation moisture source in vascular plant-dominated peatlands?

    Amesbury, Matthew J.; Charman, Dan J.; Newnham, Rewi M.; Loader, Neil J.; Goodrich, Jordan; Royles, Jessica; Campbell, David I.; Keller, Elizabeth D.; Baisden, W. Troy; Roland, Thomas P.; Gallego-Sala, Angela V.


    Variations in the isotopic composition of precipitation are determined by fractionation processes which occur during temperature- and humidity-dependent phase changes associated with evaporation and condensation. Oxygen stable isotope ratios have therefore been frequently used as a source of palaeoclimate data from a variety of proxy archives, which integrate this signal over time. Applications from ombrotrophic peatlands, where the source water used in cellulose synthesis is derived solely from precipitation, have been mostly limited to Northern Hemisphere Sphagnum-dominated bogs, with few in the Southern Hemisphere or in peatlands dominated by vascular plants. New Zealand (NZ) provides an ideal location to undertake empirical research into oxygen isotope fractionation in vascular peatlands because single taxon analysis can be easily carried out, in particular using the preserved root matrix of the restionaceous wire rush (Empodisma spp.) that forms deep Holocene peat deposits throughout the country. Furthermore, large gradients are observed in the mean isotopic composition of precipitation across NZ, caused primarily by the relative influence of different climate modes. Here, we test whether δ18O of Empodisma α-cellulose from ombrotrophic restiad peatlands in NZ can provide a methodology for developing palaeoclimate records of past precipitation δ18O. Surface plant, water and precipitation samples were taken over spatial (six sites spanning >10° latitude) and temporal (monthly measurements over one year) gradients. A link between the isotopic composition of root-associated water, the most likely source water for plant growth, and precipitation in both datasets was found. Back-trajectory modelling of precipitation moisture source for rain days prior to sampling showed clear seasonality in the temporal data that was reflected in root-associated water. The link between source water and plant cellulose was less clear, although mechanistic modelling predicted mean

  1. Stable isotope hydrology. Deuterium and oxygen-18 in the water cycle

    Gat, J.R.; Gonfiantini, R.


    This monograph is mainly intended for hydrologists, hydrogeologists and geochemists who want to become acquainted, rapidly but in some detail, with the theoretical background of stable isotope fractionation in natural physico-chemical processes involving fresh water, with the isotopic differences actually encountered in natural waters and with their use for practical hydrological purposes. Throughout the monograph, and in particular in the last chapter, a series of examples are discussed, giving the results obtained with stable isotope techniques in current hydrological and hydrogeological investigations or, more generally, in water resources exploration and assessment. One chapter is also dedicated to the techniques for measuring D/H and 18 O/ 16 O ratios in water

  2. Stable carbon and oxygen isotope ratios of malachite from the patinas of ancient bronze objects

    Smith, A.W.


    13 C/ 12 C and 18 O/ 16 O ratios have been measured for 62 samples of the mineral malachite, taken from the patinas of ancient bronze objects (from Britain, Italy, Libya and China), in order to investigate any possible relationship which may exist between the isotope ratios and the burial conditions of the objects. The results indicate that the isotope ratios are controlled by complex factors related to the climate, vegetation and soil type at the burial site. It is suggested that the technique might be used, given favourable circumstances, in the characterization of patinas and as a possible aid in the detection of synthetic patination. (author)

  3. Petrologic and Oxygen-Isotopic Investigations of Eucritic and Anomalous Mafic Achondrites

    Mittlefehldt, D. W.; Greenwood, R. C.; Peng, Z. X.; Ross, D. K.; Berger, E. L.; Barrett, T. J.


    The most common asteroidal igneous meteorites are eucrite-type basalts and gabbros rocks composed of ferroan pigeonite and augite, calcic plagioclase, silica, ilmenite, troilite, Ca-phosphate, chromite and Fe-metal. These rocks are thought to have formed on a single asteroid along with howardites and diogenites (HEDs). However, Northwest Africa (NWA) 011 is mineralogically identical to eucrites, but has an O-isotopic composition distinct from them and was derived from a different asteroid. Modern analyses with higher precision have shown that some eucrites have smaller O-isotopic differences that are nevertheless well-resolved from the group mean.

  4. Tales of volcanoes and El-Nino southern oscillations with the oxygen isotope anomaly of sulfate aerosol.

    Shaheen, Robina; Abauanza, Mariana; Jackson, Teresa L; McCabe, Justin; Savarino, Joel; Thiemens, Mark H


    The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth's system are intricately linked to planetary scale processes, and precise characterization of the overall process requires a detailed understanding of the linkage between climate dynamics and the chemistry leading to the product sulfate. This paper reports a high-resolution, 22-y (1980-2002) record of the oxygen-triple isotopic composition of sulfate (SO4) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO4 aerosol is linked to the ozone variation in the tropical upper troposphere/lower stratosphere via the Ozone El-Niño Southern Oscillations (ENSO) Index (OEI). Higher (17)O values (3.3‰, 4.5‰, and 4.2‰) were observed during the three largest ENSO events of the past 2 decades. Volcanic events inject significant quantities of SO4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and (17)O = 3.3‰, OEI = 11 and (17)O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that (17)O of sulfate aerosols can record extreme phases of naturally occurring climate cycles, such as ENSOs, which couple variations in the ozone levels in the atmosphere and the hydrosphere via temperature driven changes in relative humidity levels. A longer term, higher resolution oxygen-triple isotope analysis of sulfate aerosols from ice cores, encompassing more ENSO periods, is required to reconstruct paleo-ENSO events and paleotropical ozone variations.

  5. Thallium isotope evidence for a permanent increase in marine organic carbon export in the early Eocene

    Nielsen, S.G.; Mar-Gerrison, S.; Gannoun, A.; LaRowe, D.; Klemm, V.; Halliday, A.N.; Burton, K.W.; Hein, J.R.


    The first high resolution thallium (Tl) isotope records in two ferromanganese crusts (Fe-Mn crusts), CD29 and D11 from the Pacific Ocean are presented. The crusts record pronounced but systematic changes in 205Tl/203Tl that are unlikely to reflect diagenetic overprinting or changes in isotope fractionation between seawater and Fe-Mn crusts. It appears more likely that the Fe-Mn crusts track the Tl isotope composition of seawater over time. The present-day oceanic residence time of Tl is estimated to be about 20,000??yr, such that the isotopic composition should reflect ocean-wide events. New and published Os isotope data are used to construct age models for these crusts that are consistent with each other and significantly different from previous age models. Application of these age models reveals that the Tl isotope composition of seawater changed systematically between ~ 55??Ma and ~ 45??Ma. Using a simple box model it is shown that the present day Tl isotope composition of seawater depends almost exclusively on the ratio between the two principal output fluxes of marine Tl. These fluxes are the rate of removal of Tl from seawater via scavenging by authigenic Fe-Mn oxyhydroxide precipitation and the uptake rate of Tl during low temperature alteration of oceanic crust. It is highly unlikely that the latter has changed greatly. Therefore, assuming that the marine Tl budget has also not changed significantly during the Cenozoic, the low 205Tl/203Tl during the Paleocene is best explained by a more than four-fold higher sequestration of Tl by Fe-Mn oxyhydroxides compared with at the present day. The calculated Cenozoic Tl isotopic seawater curve displays a striking similarity to that of S, providing evidence that both systems may have responded to the same change in the marine environment. A plausible explanation is a marked and permanent increase in organic carbon export from ~ 55??Ma to ~ 45??Ma, which led to higher pyrite burial rates and a significantly reduced

  6. Isotopic Evidence for Early Trade in Animals between Old Kingdom Egypt and Canaan.

    Arnold, Elizabeth R; Hartman, Gideon; Greenfield, Haskel J; Shai, Itzhaq; Babcock, Lindsay E; Maeir, Aren M


    Isotope data from a sacrificial ass and several ovicaprines (sheep/goat) from Early Bronze Age household deposits at Tell es-Safi/Gath, Israel provide direct evidence for the movement of domestic draught/draft and husbandry animals between Old Kingdom Egypt (during the time of the Pyramids) and Early Bronze Age III Canaan (ca. 2900-2500 BCE). Vacillating, bi-directional connections between Egypt and Canaan are known throughout the Early Bronze Age, but here we provide the first concrete evidence of early trade in animals from Egypt to Canaan.

  7. Isotopic Evidence for Early Trade in Animals between Old Kingdom Egypt and Canaan.

    Elizabeth R Arnold

    Full Text Available Isotope data from a sacrificial ass and several ovicaprines (sheep/goat from Early Bronze Age household deposits at Tell es-Safi/Gath, Israel provide direct evidence for the movement of domestic draught/draft and husbandry animals between Old Kingdom Egypt (during the time of the Pyramids and Early Bronze Age III Canaan (ca. 2900-2500 BCE. Vacillating, bi-directional connections between Egypt and Canaan are known throughout the Early Bronze Age, but here we provide the first concrete evidence of early trade in animals from Egypt to Canaan.

  8. Isotopic Evidence for Early Trade in Animals between Old Kingdom Egypt and Canaan

    Greenfield, Haskel J.; Shai, Itzhaq; Babcock, Lindsay E.; Maeir, Aren M.


    Isotope data from a sacrificial ass and several ovicaprines (sheep/goat) from Early Bronze Age household deposits at Tell es-Safi/Gath, Israel provide direct evidence for the movement of domestic draught/draft and husbandry animals between Old Kingdom Egypt (during the time of the Pyramids) and Early Bronze Age III Canaan (ca. 2900–2500 BCE). Vacillating, bi-directional connections between Egypt and Canaan are known throughout the Early Bronze Age, but here we provide the first concrete evidence of early trade in animals from Egypt to Canaan. PMID:27322197

  9. Keratin decomposition by trogid beetles: evidence from a feeding experiment and stable isotope analysis

    Sugiura, Shinji; Ikeda, Hiroshi


    The decomposition of vertebrate carcasses is an important ecosystem function. Soft tissues of dead vertebrates are rapidly decomposed by diverse animals. However, decomposition of hard tissues such as hairs and feathers is much slower because only a few animals can digest keratin, a protein that is concentrated in hairs and feathers. Although beetles of the family Trogidae are considered keratin feeders, their ecological function has rarely been explored. Here, we investigated the keratin-decomposition function of trogid beetles in heron-breeding colonies where keratin was frequently supplied as feathers. Three trogid species were collected from the colonies and observed feeding on heron feathers under laboratory conditions. We also measured the nitrogen (δ15N) and carbon (δ13C) stable isotope ratios of two trogid species that were maintained on a constant diet (feathers from one heron individual) during 70 days under laboratory conditions. We compared the isotopic signatures of the trogids with the feathers to investigate isotopic shifts from the feathers to the consumers for δ15N and δ13C. We used mixing models (MixSIR and SIAR) to estimate the main diets of individual field-collected trogid beetles. The analysis indicated that heron feathers were more important as food for trogid beetles than were soft tissues under field conditions. Together, the feeding experiment and stable isotope analysis provided strong evidence of keratin decomposition by trogid beetles.

  10. Copper-catalyzed oxidative desulfurization-oxygenation of thiocarbonyl compounds using molecular oxygen: an efficient method for the preparation of oxygen isotopically labeled carbonyl compounds.

    Shibahara, Fumitoshi; Suenami, Aiko; Yoshida, Atsunori; Murai, Toshiaki


    A novel copper-catalyzed oxidative desulfurization reaction of thiocarbonyl compounds, using molecular oxygen as an oxidant and leading to formation of carbonyl compounds, has been developed, and the utility of the process is demonstrated by its application to the preparation of a carbonyl-18O labeled sialic acid derivative.

  11. In vivo EPR oximetry using an isotopically-substituted nitroxide: Potential for quantitative measurement of tissue oxygen

    Weaver, John; Burks, Scott R.; Liu, Ke Jian; Kao, Joseph P.Y.; Rosen, Gerald M.


    Variations in brain oxygen (O2) concentration can have profound effects on brain physiology. Thus, the ability to quantitate local O2 concentrations noninvasively in vivo could significantly enhance understanding of several brain pathologies. However, quantitative O2 mapping in the brain has proven difficult. The electron paramagnetic resonance (EPR) spectra of nitroxides are sensitive to molecular O2 and can be used to estimate O2 concentrations in aqueous media. We recently synthesized labile-ester-containing nitroxides, such as 3-acetoxymethoxycarbonyl-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl (nitroxide 4), which accumulate in cerebral tissue after in situ hydrolysis, and thus enable spatial mapping of O2 concentrations in the mouse brain by EPR imaging. In an effort to improve O2 quantitation, we prepared 3-acetoxymethox ycarbonyl-2,2,5,5-tetra(2H3)methyl-1-(3,4,4-2H3,1-15N)pyrrolidinyloxyl (nitroxide 2), which proved to be a more sensitive probe than its normo-isotopic version for quantifying O2 in aqueous solutions of various O2 concentrations. We now demonstrate that this isotopically substituted nitroxide is ~2-fold more sensitive in vivo than the normo-isotopic nitroxide 4. Moreover, in vitro and in vivo EPR spectral-spatial imaging results with nitroxide 2 demonstrate significant improvement in resolution, reconstruction and spectral response to local O2 concentrations in cerebral tissue. Thus, isotopic-substituted nitroxides, such as 2, are excellent sensors for in vivo O2 quantitation in tissues, such as the brain. PMID:27567323

  12. Nitrogen and triple oxygen isotopes in near-road air samples using chemical conversion and thermal decomposition.

    Smirnoff, Anna; Savard, Martine M; Vet, Robert; Simard, Marie-Christine


    The determination of triple oxygen (δ(18)O and δ(17)O) and nitrogen isotopes (δ(15)N) is important when investigating the sources and atmospheric paths of nitrate and nitrite. To fully understand the atmospheric contribution into the terrestrial nitrogen cycle, it is crucial to determine the δ(15)N values of oxidised and reduced nitrogen species in precipitation and dry deposition. In an attempt to further develop non-biotic methods and avoid expensive modifications of the gas-equilibration system, we have combined and modified sample preparation procedures and analytical setups used by other researchers. We first chemically converted NO(3)(-) and NH(4)(+) into NO(2)(-) and then into N(2)O. Subsequently, the resulting gas was decomposed into N(2) and O(2) and analyzed by isotope ratio mass spectrometry (IRMS) using a pre-concentration system equipped with a gold reduction furnace. The δ(17)O, δ(18)O and δ(15)N values of nitrate and nitrite samples were acquired simultaneously in one run using a single analytical system. Most importantly, the entire spectrum of δ(17)O, δ(18)O and/or δ(15)N values was determined from atmospheric nitrate, nitric oxide, ammonia and ammonium. The obtained isotopic values for air and precipitation samples were in good agreement with those from previous studies. We have further advanced chemical approaches to sample preparation and isotope analyses of nitrogen-bearing compounds. The proposed methods are inexpensive and easily adaptable to a wide range of laboratory conditions. This will substantially contribute to further studies on sources and pathways of nitrate, nitrite and ammonium in terrestrial nitrogen cycling. Copyright © 2012 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.

  13. Stable carbon, oxygen, and nitrogen, isotope analysis of plants from a South Asian tropical forest: Implications for primatology.

    Roberts, Patrick; Blumenthal, Scott A; Dittus, Wolfgang; Wedage, Oshan; Lee-Thorp, Julia A


    Stable isotope analysis of primate tissues in tropical forest contexts is an increasingly popular means of obtaining information about niche distinctions among sympatric species, including preferences in feeding height, forest canopy density, plant parts, and trophism. However, issues of equifinality mean that feeding height, canopy density, as well as the plant parts and plant species consumed, may produce similar or confounding effects. With a few exceptions, researchers have so far relied largely on general principles and/or limited plant data from the study area as references for deducing the predominant drivers of primate isotope variation. Here, we explore variation in the stable carbon (δ 13 C), nitrogen (δ 15 N), and oxygen (δ 18 O) isotope ratios of 288 plant samples identified as important to the three primate species from the Polonnaruwa Nature Sanctuary, Sri Lanka, relative to plant part, season, and canopy height. Our results show that plant part and height have the greatest effect on the δ 13 C and δ 18 O measurements of plants of immediate relevance to the primates, Macaca sinica, Semnopithecus priam thersites, and Trachypithecus vetulus, living in this monsoonal tropical forest. We find no influence of plant part, height or season on the δ 15 N of measured plants. While the plant part effect is particularly pronounced in δ 13 C between fruits and leaves, differential feeding height, and plant taxonomy influence plant δ 13 C and δ 18 O differences in addition to plant organ. Given that species composition in different regions and forest types will differ, the results urge caution in extrapolating general isotopic trends without substantial local baselines studies. © 2017 Wiley Periodicals, Inc.

  14. Carbon and Oxygen Isotope Dendrochronology in Sub-Fossil Bog Oak Tree Rings - A Preliminary Study

    Sass, U.G.W.; Poole, I.; Wils, T.; Helle, G.; Schleser, G.H.; Bergen, van P.


    Isotope dendroclimatology is a relatively new field investigating environmental factors that control the radial growth of trees. Tree-ring series of sub-fossil bog oaks can be dated from sites across northwest Europe indicating that the environmental change(s) were regional rather than local. Bog

  15. Review of data of oxygen and hydrogen isotope composition in thermal waters in China

    Fan Zhicheng; Wang Jiyang


    Based on the data of δD and δ 18 O content from more than 600 water samples, this paper reviews the stable isotope composition of thermal waters in China. Data to be used in this paper were mostly collected from published literatures with a few by authors. 9 figs, 2 tabs

  16. Carbon and oxygen isotopic ratio bi-variate distribution for marble artifacts quarry assignment

    Pentia, M.


    Statistical description, by a Gaussian bi-variate probability distribution of 13 C/ 12 C and 18 O/ 16 O isotopic ratios in the ancient marble quarries has been done and the new method for obtaining the confidence level quarry assignment for marble artifacts has been presented. (author) 8 figs., 3 tabs., 4 refs

  17. Correlation of the Eemian (interglacial) Stage and the deep-sea oxygen-isotope stratigraphy

    Mangerud, J.; Soenstegaard, E.; Sejrup, H.-P.


    A complete interglacial sequence in coastal marine sediments in western Norway is here correlated with the Eemian Stage by means of pollen stratigraphy, and with deep-sea cores by means of marine fossils. The Eemian is correlated with isotope stage 5e. (author)

  18. Interannual variability in the oxygen isotopes of atmospheric CO2 driven by El Nino

    Welp, Lisa R.; Keeling, Ralph F.; Meijer, Harro A. J.; Bollenbacher, Alane F.; Piper, Stephen C.; Yoshimura, Kei; Francey, Roger J.; Allison, Colin E.; Wahlen, Martin


    The stable isotope ratios of atmospheric CO2 (O-18/O-16 and C-13/C-12) have been monitored since 1977 to improve our understanding of the global carbon cycle, because biosphere-atmosphere exchange fluxes affect the different atomic masses in a measurable way(1). Interpreting the O-18/O-16

  19. Ca, Sr, Mo and U isotopes evidence ocean acidification and deoxygenation during the Late Permian mass extinction

    Silva-Tamayo, Juan Carlos; Payne, Jon; Wignall, Paul; Newton, Rob; Eisenhauer, Anton; Weyer, Stenfan; Neubert, Nadja; Lau, Kim; Maher, Kate; Paytan, Adina; Lehrmann, Dan; Altiner, Demir; Yu, Meiyi


    The most catastrophic extinction event in the history of animal life occurred at the end of the Permian Period, ca. 252 Mya. Ocean acidification and global oceanic euxinia have each been proposed as causes of this biotic crisis, but the magnitude and timing of change in global ocean chemistry remains poorly constrained. Here we use multiple isotope systems - Ca, Sr, Mo and U - measured from well dated Upper Permian- Lower Triassic sedimentary sections to better constrain the magnitude and timing of change in ocean chemistry and the effects of ocean acidification and de-oxygenation through this interval. All the investigated carbonate successions (Turkey, Italy and China) exhibit decreasing δ44/40Ca compositions, from ~-1.4‰ to -2.0‰ in the interval preceding the main extinction. These values remain low during most of the Griesbachian, to finally return to -1.4‰ in the middle Dienerian. The limestone succession from southern Turkey also displays a major decrease in the δ88/86Sr values from 0.45‰ to 0.3‰ before the extinction. These values remain low during the Griesbachian and finally increase to 0.55‰ by the middle Dienerian. The paired negative anomalies on the carbonate δ44/40Ca and δ88/86Sr suggest a decrease in the carbonate precipitation and thus an episode of ocean acidification coincident with the major biotic crisis. The Mo and U isotope records also exhibit significant rapid negative anomalies at the onset of the main extinction interval, suggesting rapid expansion of anoxic and euxinic marine bottom waters during the extinction interval. The rapidity of the isotope excursions in Mo and U suggests substantially reduced residence times of these elements in seawater relative to the modern, consistent with expectations for a time of widespread anoxia. The large C-isotope variability within Lower Triassic rocks, which is similar to that of the Lower-Middle Cambrian, may reflect biologically controlled perturbations of the oceanic carbon cycle

  20. Seasonality of bottom water temperature in the northern North Sea reconstructed from the oxygen isotope composition of the bivalve Arctica islandica

    Trofimova, Tamara; Andersson, Carin; Bonitz, Fabian


    The seasonality of temperature changes is an important characteristic of climate. However, observational data for the ocean are only available for the last 150 year from a limited number of locations. Prior to 18th century information is only available from proxy reconstructions. The vast majority of such reconstructions depend on land-based archives, primarily from dendrochronology. Established marine proxy records for the ocean, especially at high latitudes, are both sparsely distributed and poorly resolved in time. Therefore, the identification and development of proxies for studying key ocean processes at sub-annual resolution that can extend the marine instrumental record is a clear priority in marine climate science. In this study, we have developed a record of early Holocene seasonal variability of bottom water temperature from the Viking Bank in the northern most North Sea. This area is of a particular interest since the hydrography is controlled by the inflow of Atlantic water. The reconstruction is based on the oxygen isotope composition of the growth increments in two sub-fossil shells of Arctica islandica (Bivalvia), dated to 9600-9335 cal. yr BP. By combining radiocarbon dating and sclerochronological techniques a floating chronology spanning over 200 years was constructed. Using the chronology as an age model, oxygen isotope measurements from 2 shells were combined into a 22-years long record. The results from this oxygen isotope record are compared with stable oxygen isotope profiles from modern shells to estimate changes in the mean state and seasonality between present and early Holocene. Shell-derived oxygen isotope values together with ice-volume corrected oxygen isotope values for the seawater were used to calculate bottom-water temperatures on a sub-annual time-scale. Preliminary results of the reconstructed early Holocene bottom water temperature indicate higher seasonality and lower minimum temperature compared to the present.

  1. Cl and C isotope analysis to assess the effectiveness of chlorinated ethene degradation by zero-valent iron: Evidence from dual element and product isotope values

    Audí-Miró, Carme; Cretnik, Stefan; Otero, Neus; Palau, Jordi; Shouakar-Stash, Orfan; Soler, Albert


    Highlights: ► TCE and cis-DCE Cl isotope fractionation was investigated for the first time with ZVI. ► A C–Cl bond is broken in the rate-limiting step during ethylene ZVI dechlorination. ► Dual C/Cl isotope plot is a promising tool to discriminate abiotic degradation. ► Product-related carbon isotopic fractionation gives evidence of abiotic degradation. ► Hydrogenolysis and β-dichloroelimination pathways occur simultaneously. - Abstract: This study investigated C and, for the first time, Cl isotope fractionation of trichloroethene (TCE) and cis-dichloroethene (cis-DCE) during reductive dechlorination by cast zero-valent iron (ZVI). Hydrogenolysis and β-dichloroelimination pathways occurred as parallel reactions, with ethene and ethane deriving from the β-dichloroelimination pathway. Carbon isotope fractionation of TCE and cis-DCE was consistent for different batches of Fe studied. Transformation of TCE and cis-DCE showed Cl isotopic enrichment factors (ε Cl ) of −2.6‰ ± 0.1‰ (TCE) and −6.2‰ ± 0.8‰ (cis-DCE), with Apparent Kinetic Isotope Effects (AKIE Cl ) for Cl of 1.008 ± 0.001 (TCE) and 1.013 ± 0.002 (cis-DCE). This indicates that a C–Cl bond breakage is rate-determining in TCE and cis-DCE transformation by ZVI. Two approaches were investigated to evaluate if isotope fractionation analysis can distinguish the effectiveness of transformation by ZVI as opposed to natural biodegradation. (i) Dual isotope plots. This study reports the first dual (C, Cl) element isotope plots for TCE and cis-DCE degradation by ZVI. The pattern for cis-DCE differs markedly from that reported for biodegradation of the same compound by KB-1, a commercially available Dehalococcoides-containing culture. The different trends suggest an expedient approach to distinguish abiotic and biotic transformation, but this needs to be confirmed in future studies. (ii) Product-related isotope fractionation. Carbon isotope ratios of the hydrogenolysis product cis

  2. Evidence of sub-10 nm aluminum-oxygen precipitates in silicon

    Moutanabbir, Oussama; Isheim, Dieter; Mao, Zugang; Seidman, David N


    In this research, ultraviolet laser-assisted atom-probe tomography (APT) was utilized to investigate precisely the behavior at the atomistic level of aluminum impurities in ultrathin epitaxial silicon layers. Aluminum atoms were incorporated in situ during the growth process. The measured average aluminum concentration in the grown layers exceeds by several orders of magnitude the equilibrium bulk solubility. Three-dimensional atom-by-atom mapping demonstrates that aluminum atoms precipitate in the silicon matrix and form nanoscopic precipitates with lateral dimensions in the 1.3 to 6.2 nm range. These precipitates were found to form only in the presence of oxygen impurity atoms, thus providing clear evidence of the long-hypothesized role of oxygen and aluminum-oxygen complexes in facilitating the precipitation of aluminum in a silicon lattice. The measured average aluminum and oxygen concentrations in the precipitates are ∼10 ± 0.5 at.% and ∼4.4 ± 0.5 at.%, respectively. This synergistic interaction is supported by first-principles calculations of the binding energies of aluminum-oxygen dimers in silicon. The calculations demonstrate that there is a strong binding between aluminum and oxygen atoms, with Al-O-Al and O-Al-Al as the energetically favorable sequences corresponding to precipitates in which the concentration of aluminum is twice as large as the oxygen concentration in agreement with APT data. (paper)

  3. Combined oxygen- and carbon-isotope records through the Early Jurassic: multiple global events and two modes of carbon-cycle/temperature coupling

    Hesselbo, Stephen P.; Korte, Christoph


    , to the extent that meaningful comparisons between these events can begin to be made. Here we present new carbon and oxygen isotope data from mollusks (bivalves and belemnites) and brachiopods collected through the marine Early Jurassic succession of NE England, including the Sinemurian-Plienbachian boundary...... GSSP. All materials have been screened by chemical analysis and scanning electron microscopy to check for diagenetic alteration. Analysis of carbon isotopes from marine calcite is supplemented by analysis of carbon-isotope values from fossil wood collected through the same section. It is demonstrated...... that both long-term and short-term carbon-isotope shifts from the UK Early Jurassic represent global changes in carbon cycle balances. The Sinemurian-Pliensbachian boundary event is an event of global significance and shows several similarities to the Toarcian OAE (relative sea-level change, carbon-isotope...

  4. Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

    Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.


    Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation

  5. Caution on the storage of waters and aqueous solutions in plastic containers for hydrogen and oxygen stable isotope analysis.

    Spangenberg, Jorge E


    The choice of containers for storage of aqueous samples between their collection, transport and water hydrogen ((2)H) and oxygen ((18)O) stable isotope analysis is a topic of concern for a wide range of fields in environmental, geological, biomedical, food, and forensic sciences. The transport and separation of water molecules during water vapor or liquid uptake by sorption or solution and the diffusive transport of water molecules through organic polymer material by permeation or pervaporation may entail an isotopic fractionation. An experiment was conducted to evaluate the extent of such fractionation. Sixteen bottle-like containers of eleven different organic polymers, including low and high density polyethylene (LDPE and HDPE), polypropylene (PP), polycarbonate (PC), polyethylene terephthalate (PET), and perfluoroalkoxy-Teflon (PFA), of different wall thickness and size were completely filled with the same mineral water and stored for 659 days under the same conditions of temperature and humidity. Particular care was exercised to keep the bottles tightly closed and prevent loss of water vapor through the seals. Changes of up to +5‰ for δ(2)H values and +2.0‰ for δ(18)O values were measured for water after more than 1 year of storage within a plastic container, with the magnitude of change depending mainly on the type of organic polymer, wall thickness, and container size. The most important variations were measured for the PET and PC bottles. Waters stored in glass bottles with Polyseal™ cone-lined PP screw caps and thick-walled HDPE or PFA containers with linerless screw caps having an integrally molded inner sealing ring preserved their original δ(2)H and δ(18)O values. The carbon, hydrogen, and oxygen stable isotope compositions of the organic polymeric materials were also determined. The results of this study clearly show that for precise and accurate measurements of the water stable isotope composition in aqueous solutions, rigorous sampling and

  6. Stable isotope geochemical study of Pamukkale travertines: New evidences of low-temperature non-equilibrium calcite-water fractionation

    Kele, Sándor; Özkul, Mehmet; Fórizs, István; Gökgöz, Ali; Baykara, Mehmet Oruç; Alçiçek, Mehmet Cihat; Németh, Tibor


    , besides the detailed geochemical analyses along downstream sections, we present new evidences of non-equilibrium calcite-water fractionation in lower temperature range (13.3 to 51.3 °C). Our measurements and calculations on natural hot water travertine precipitations at Pamukkale and Egerszalók revealed that the δ 18O travertine is equal with the δ 18O HCO3 at the orifice of the thermal springs, which means that practically there is no oxygen isotope fractionation between these two phases. High rate of CO 2 degassing with rapid precipitation of carbonate could be responsible for this as it was theoretically supposed by O'Neil et al. (1969). Thus, for the determination of the deposition temperature of a fossil travertine deposit we propose to use the water-bicarbonate oxygen isotope equilibrium fractionation instead of the water-travertine fractionation, which can result 8-9 °C difference in the calculated values. Our study is the first detailed empirical proof of O'Neil's hypothesis on a natural carbonate depositing system. The presented observations can be used to identify more precisely the deposition temperature of fossil travertines during paleoclimate studies.

  7. Isotopic evidence of a rapid cooling and continuous sedimentation across the Eocene-Oligocene boundary of Wagapadhar and Waior, Kutch

    Sarangi, S.; Sarkar, A.; Bhattacharya, S.K.; Ray, A.K.


    High resolution oxygen isotope analysis of samples from two different Eocene Oligocene Boundary (EOB) sections of Wagapadhar and Waior of Kutch area and their correlation with DSDP sites indicate continuity of sedimentation at these sites. A rapid cooling of ∼ 6 degC across the EOB, synchronous with extinction of Eocene larger benthic foraminifera is also observed. (author)

  8. Diplodon shells from Northwest Patagonia as continental proxy archives: Oxygen isotopic results and sclerochronological analyses

    Soldati, A. L.; Beierlein, L.; Jacob, D. E.


    Freshwater mussels of the genus Diplodon (Bivalvia, Hyriidae) are the most abundant bivalve (today and in the past) in freshwater bodies at both sides of the South-Andean Cordillera. There are about 25 different Diplodon genera in Argentina and Chile that could be assigned almost completely to the species Diplodon chilensis (Gray, 1828) and two subspecies: D. ch. chilensis and D. ch. patagonicus; this latter species is found in Argentina between Mendoza (32˚ 52' S; 68˚ 51' W) and Chubut (45˚ 51' S; 67˚ 28' W), including the lakes and rivers of the target area, the Nahuel Huapi National Park (Castellanos, 1960). Despite their wide geographic distribution, Diplodon species have only rarely been used as climate archives in the southern hemisphere. Kaandorp et al. (2005) demonstrated for Diplodon longulus (Conrad 1874) collected from the Peruvian Amazonas that oxygen isotopic patterns in the shells could be used in order to reconstruct the precipitation regime and dry/wet seasonal of the monsoonal system in Amazonia. Although this study demonstrated the potential of Diplodon in climatological and ecological reconstructions in the southern hemisphere, as of yet, no systematic study of Diplodon as a multi-proxy archive has been undertaken for the Patagonian region. In this work we present sclerochronological analyses supported by ^18Oshell in recent mussel of Diplodon chilensis patagonicus (D'Orbigny, 1835) collected at Laguna El Trébol (42°S-71°W, Patagonia Argentina), one of the best studied water bodies in the region for paleoclimate analysis. Water temperature was measured every six hours for one year using a temperature sensor (Starmon mini®) placed at 5m depth in the lake, close to a mussel bank. Additionally, ^18Owater was measured monthly for the same time range.g^18Oshell values obtained by micro-milling at high spatial resolution in the growth increments of three Diplodon shells were compared to these records, and to air temperature and

  9. About the variation mechanism of the isotopic composition of oxygen and carbon through the geological ages

    Torquato, J.R.F.; Frischkorn, H.


    The variations of the Δ 180 ratio found in the carbonates are shown as being of the primary origin. In addition it is shown that these values can be preserved, through the geological ages, even it one considers the carbonates to be worked over again. Are given some subsidies about the study of the paleoenvironments through the analysis of the isotopic composition of the carbon. (A.B.) [pt

  10. Morphology, stratigraphy and oxygen isotope composition of fossil glacier ice at Ledyanaya Gora, Northwest Siberia, Russia

    Vaikmaee, R.; Michel, F.A.; Solomatin, V.I.


    Studies of the stratigraphy, sedimentology, structure and isotope composition of a buried massive ice body and its encompassing sediments at Ledyanaya Gora in northwestern Siberia demonstrate that the ice is relict glacier ice, probably emplaced during the Early Weichselian. Characteristics of this ice body should serve as a guide for the identification of other relict buried glacier ice bodies in permafrost regions. 31 refs., 9 figs., 2 tabs

  11. Oxygen and Hydrogen Isotopic Characteristics of the Kaveri River Surface Waters, Southern Peninsular India

    Achyuthan, Hema; Michelini, Marzia; Sengupta, Somasis D.; Kale, Vishwas S.; Stenni, Barbara; Flora, Onelio


    We present in this paper the spatial distribution of stable isotopic composition (δ 18 O and δD) of Kaveri River surface waters to understand how the evaporation and precipitation affect the isotopic signature and dynamics of surface river waters. In the southern peninsular India, Kaveri River is one of the longest tropical river. Our stable isotope data indicate that the upper Kaveri region is influenced strongly by the SW monsoon. There is a narrow range between the δ 18 O values found from the origin of the Kaveri River to its delta, and there is no significant orographic impact of the Western Ghats. A decreasing trend of d values is found along the course of the river. This is attributed to evaporation effects, which nevertheless are not very strong. This difference in deuterium excess due to evaporation is also an indication of the moisture recycling in the lower Kaveri area, which is primarily controlled by evaporation from the wetlands in the delta plain but also from the surface waters and as such from the rivers. (author)

  12. Design of a formaldehyde photodissociation process for carbon and oxygen isotope separation

    Stern, R.C.; Scheibner, K.F.


    The current shortage of 18 O has revived interest in using one step UV photodissociation of formaldehyde to enrich 13 C, 17 O and 18 O. The frequency doubled output of the copper laser pumped dye laser system currently in operation at LLNL can be used to drive this dissociation. The authors use a simple kinetics model and their experience with Atomic Vapor Laser Isotope Separation (AVLIS) process design to examine the relative merits of different designs for a formaldehyde photodissociation process. Given values for the molecular photoabsorption cross section, partition function, spectroscopic selectivity, collisional exchange and quenching cross sections (all as parameters), they perform a partial optimization in the space of illuminated area, formaldehyde pressure in each stage, and formaldehyde residence time in each stage. They examine the effect of cascade design (heads and tails staging) on molecule and photon utilization for each of the three isotope separation missions, and look in one case at the system's response to different ratios of laser to formaldehyde costs. Finally, they examine the relative cost of enrichment as a function of isotope and product assay. Emphasis is as much on the process design methodology, which is general, as on the specific application to formaldehyde

  13. Oxygen, hydrogen, and helium isotopes for investigating groundwater systems of the Cape Verde Islands, West Africa

    Heilweil, V.M.; Solomon, K.D.; Gingerich, S.B.; Verstraeten, Ingrid M.


    Stable isotopes (??18O, ??2H), tritium (3H), and helium isotopes (3He, 4He) were used for evaluating groundwater recharge sources, flow paths, and residence times of three watersheds in the Cape Verde Islands (West Africa). Stable isotopes indicate the predominance of high-elevation precipitation that undergoes little evaporation prior to groundwater recharge. In contrast to other active oceanic hotspots, environmental tracers show that deep geothermal circulation does not strongly affect groundwater. Low tritium concentrations at seven groundwater sites indicate groundwater residence times of more than 50 years. Higher tritium values at other sites suggest some recent recharge. High 4He and 3He/4He ratios precluded 3H/3He dating at six sites. These high 3He/4He ratios (R/Ra values of up to 8.3) are consistent with reported mantle derived helium of oceanic island basalts in Cape Verde and provided end-member constraints for improved dating at seven other locations. Tritium and 3H/3He dating shows that S??o Nicolau Island's Ribeira Faj?? Basin has groundwater residence times of more than 50 years, whereas Fogo Island's Mosteiros Basin and Santo Ant??o Island's Ribeira Paul Basin contain a mixture of young and old groundwater. Young ages at selected sites within these two basins indicate local recharge and potential groundwater susceptibility to surface contamination and/or salt-water intrusion. ?? Springer-Verlag 2009.

  14. Extreme Hf-Os Isotope Compositions in Hawaiian Peridotite Xenoliths: Evidence for an Ancient Recycled Lithosphere

    Bizimis, M.; Lassiter, J. C.; Salters, V. J.; Sen, G.; Griselin, M.


    ) melt depletion event recorded by both the low 187Os/186Os and high 176Hf/177Hf ratios in the SLC peridotites can be explained with two different scenarios. First, the SLC peridotites may represent ancient depleted lithosphere that survived subduction, remained "rafting" in the upper mantle and is now sampled beneath Oahu. However, the lack of such unradiogenic Os isotopes in both MORBs and abyssal peridotites suggests that such peridotites are rare in the upper mantle and makes their exclusive presence under Oahu a rather fortuitous coincidence. Alternatively, the SLC peridotites may represent ancient depleted recycled lithosphere brought up by the Hawaiian plume. A recycled oceanic crust origin has been previously invoked for the Koolau shield lavas. It is then conceivable that fragments of the lithospheric portion of that subducted package have remained coupled with the oceanic crust and are being brought up by the plume from the deep, but because they were previously depleted, these peridotites contribute minimally, if at all, to Hawaiian volcanism. The presence of microdiamonds and majoritic garnets in some SLC pyroxenites also corroborates a deep origin. In this case, the SLC peridotites represent the first-ever direct evidence that subducted material actually makes it back on the surface, essentially closing the subduction cycle.

  15. Oxygen and Carbon Isotopic Composition of Carbonate Rocks of the Permian Qixia Formation, Sichuan Basin: Thermal Effects of Emeishan Basalt

    Keke Huang


    Full Text Available The late Permian thermal events related to Emeishan Basalt has made a great impact on the underlying carbonate rock properties in the western margin of the Yangtze Platform. In this paper, we investigate the carbon and oxygen isotopic composition of the Qixia Formation carbonates from two sections: the Qiaoting Section in the northeastern part of the Sichuan Basin and the Changjianggou Section at the northwestern edge of the Basin. The data reveal that: (i Samples from Qiaoting section show a relatively narrow range of δ13C and δ18O, varying from 2.7‰ to 5.2‰ with an average of 4.2‰, and -3.8‰ to -7.8‰ with an average of -5.4‰, respectively. In contrast, Samples from Changjianggou section exhibit larger magnitude of variation in δ13C and δ18O, ranging from -1‰ to 3.8‰ with an average of 1.5‰, and -2.1 to -9.2‰, with an average of -6.0‰ respectively; (ii δ13C and δ18O records in carbonates from Qiaoting section are similar to those of Middle Permian seawater whereas carbonates from the Changjianggou section are depleted in 13C and 18O compared to contemporary seawater; (iii On the basis of combined petrographic and paleo-heat flow evidence, the lower carbon and oxygen isotopic composition of the carbonates from the Changjianggou section are interpreted to be the results of thermal effects of Emeishan Basalt because of its proximity to the eruption center of the basalt. The high temperature reduced the δ18O values of the carbonates and forced the organic matter to mature at an early stage, thus producing 13C-enriched carbon dioxide to participate in the formation of carbonates.     Composición Isotópica de Oxígeno y Carbón en Rocas de Carbonato de la Formación de Edad Pérmica Qixia, en la Cuenca de Sichuan: Efectos Térmicos del Basalto Emeishan   Resumen Los eventos térmicos del Pérmico tardío relacionados con el Basalto Emeishan han tenido un gran impacto en las propiedades de las rocas de carbonato

  16. A study on hydrogen, oxygen, carbon, sulfur and lead isotopes in the rich uranium deposit No.201

    Li Yuexiang; Li Tiangang; Tong Hongshou; Feng Mingyue; Xu Zhan


    The uranium deposit No.201 located in Indonesian granite is one of the richest uranium deposits of granite type in China. An attempt is made to investigate the sources of ore-forming solutions and ore-forming materials, and to presume the environment of ore formation in the light of the study on composition of stable isotopes such as hydrogen, oxygen, carbon, sulfur and lead. The research results indicate that the ore-forming fluids in the deposit is mainly composed of meteoric water, the ore-forming materials principally came from pre-Yanshanian granite Massif and possibly, partly from the lower crust, and metallogenesis was undertaken under relatively stable physicochemical conditions

  17. A study on hydrogen, oxygen, carbon, sulfur and lead isotopes in the rich uranium deposit No.201

    Yuexiang, Li; Tiangang, Li; Hongshou, Tong; Mingyue, Feng; Zhan, Xu [Beijing Research Inst. of Uranium Geology (China)


    The uranium deposit No.201 located in Indonesian granite is one of the richest uranium deposits of granite type in China. An attempt is made to investigate the sources of ore-forming solutions and ore-forming materials, and to presume the environment of ore formation in the light of the study on composition of stable isotopes such as hydrogen, oxygen, carbon, sulfur and lead. The research results indicate that the ore-forming fluids in the deposit is mainly composed of meteoric water, the ore-forming materials principally came from pre-Yanshanian granite Massif and possibly, partly from the lower crust, and metallogenesis was undertaken under relatively stable physicochemical conditions.

  18. Oxygen isotope effect in 55Mn and 95Mo NMR spectra of the permanganate and molybdate ion

    Buckler, K.U.; Haase, A.R.; Lutz, O.; Mueller, M.; Nolle, A.


    By Fourier transform NMR spectroscopy the 55 Mn and 95 Mo resonance lines in the different permanganate and molybdate species Mn 16 Osub(4-n) 18 Osub(n) - and Mo 16 Osub(4-n) 18 Osub(n) 2- (n = 0,1,2,3,4) have been resolved in aqueous solutions of potassium permanganate and sodium molybdate. An isotopic effect on the Larmor frequency for 55 Mn of (0.59+-0.02)ppm and for 95 Mo of (0.25+-0.01)ppm to lower frequency has been found for the substitution of one 16 O atom by one 18 O atom. The relaxation rates 1/T 1 of 55 Mn in the different lines of the permanganate solution are equal within the limits of error. The oxygen exchange rate for the water-permanganate system has been evaluated. (orig.) [de


    Heber, Veronika S.; Baur, Heinrich; Wieler, Rainer; Bochsler, Peter; McKeegan, Kevin D.; Neugebauer, Marcia; Reisenfeld, Daniel B.; Wiens, Roger C.


    NASA's Genesis space mission returned samples of solar wind collected over ∼2.3 years. We present elemental and isotopic compositions of He, Ne, and Ar analyzed in diamond-like carbon targets from the slow and fast solar wind collectors to investigate isotopic fractionation processes during solar wind formation. The solar wind provides information on the isotopic composition for most volatile elements for the solar atmosphere, the bulk Sun and hence, on the solar nebula from which it formed 4.6 Ga ago. Our data reveal a heavy isotope depletion in the slow solar wind compared to the fast wind composition by 63.1 ± 2.1 per mille for He, 4.2 ± 0.5 per mille amu –1 for Ne and 2.6 ± 0.5 per mille amu –1 for Ar. The three Ne isotopes suggest that isotopic fractionation processes between fast and slow solar wind are mass dependent. The He/H ratios of the collected slow and fast solar wind samples are 0.0344 and 0.0406, respectively. The inefficient Coulomb drag model reproduces the measured isotopic fractionation between fast and slow wind. Therefore, we apply this model to infer the photospheric isotopic composition of He, Ne, and Ar from our solar wind data. We also compare the isotopic composition of oxygen and nitrogen measured in the solar wind with values of early solar system condensates, probably representing solar nebula composition. We interpret the differences between these samples as being due to isotopic fractionation during solar wind formation. For both elements, the magnitude and sign of the observed differences are in good agreement with the values predicted by the inefficient Coulomb drag model.


    Heber, Veronika S.; Baur, Heinrich; Wieler, Rainer [Institute for Geochemistry and Petrology, ETH Zurich, Clausiusstrasse 25, CH-8092 Zurich (Switzerland); Bochsler, Peter [Physikalisches Institut, Universitaet Bern, Sidlerstasse 5, CH-3012 Bern (Switzerland); McKeegan, Kevin D. [Department of Earth and Space Sciences, University of California Los Angeles, 595 Charles Young Drive East, Box 951567, Los Angeles, CA 90095-1567 (United States); Neugebauer, Marcia [Lunar and Planetary Laboratory, University of Arizona, Tucson, AZ 85721-0092 (United States); Reisenfeld, Daniel B. [Department of Physics and Astronomy, University of Montana, Missoula, MT 59812 (United States); Wiens, Roger C., E-mail: [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)


    NASA's Genesis space mission returned samples of solar wind collected over {approx}2.3 years. We present elemental and isotopic compositions of He, Ne, and Ar analyzed in diamond-like carbon targets from the slow and fast solar wind collectors to investigate isotopic fractionation processes during solar wind formation. The solar wind provides information on the isotopic composition for most volatile elements for the solar atmosphere, the bulk Sun and hence, on the solar nebula from which it formed 4.6 Ga ago. Our data reveal a heavy isotope depletion in the slow solar wind compared to the fast wind composition by 63.1 {+-} 2.1 per mille for He, 4.2 {+-} 0.5 per mille amu{sup -1} for Ne and 2.6 {+-} 0.5 per mille amu{sup -1} for Ar. The three Ne isotopes suggest that isotopic fractionation processes between fast and slow solar wind are mass dependent. The He/H ratios of the collected slow and fast solar wind samples are 0.0344 and 0.0406, respectively. The inefficient Coulomb drag model reproduces the measured isotopic fractionation between fast and slow wind. Therefore, we apply this model to infer the photospheric isotopic composition of He, Ne, and Ar from our solar wind data. We also compare the isotopic composition of oxygen and nitrogen measured in the solar wind with values of early solar system condensates, probably representing solar nebula composition. We interpret the differences between these samples as being due to isotopic fractionation during solar wind formation. For both elements, the magnitude and sign of the observed differences are in good agreement with the values predicted by the inefficient Coulomb drag model.

  1. Osmium Isotopic Evidence Against an Impact at the Frasnian-Famennian Boundary

    Gordon, G. W.; Turekian, K. K.; Rockman, M.; Over, J.


    Two sections across the Frasnian-Famennian boundary were analyzed for Re and Os concentrations and 187Os/188Os ratios to evaluate evidence for a meteoritic input coincident with this boundary and its associated mass extinction. These sections are from a siltstone and shale sequence at Irish Gulf in New York, US and a calcareous shale and ferromanganese oxide sequence at La Serre in France. The Irish Gulf section, with an initial 187Os/188Os of ~0.49, does not show the characteristic meteoritic Os imprint with a 187Os/188Os value of about 0.13. Both Re and Os are retained in this section, as indicated by the construction of an isochron with an age of 388 ±41 Ma, consistent with independently determined ages for the Frasnian-Famennian boundary. Although the La Serre section, with Os concentrations as high as 33 ppb and Re concentrations ranging from 1.4 to 7.4 ppb, might be expected to show excellent evidence for a meteoritic contribution, the highly radiogenic isotopic composition (187Os/188Os ranges from 2.42-3.61) instead suggests recent massive Re loss or addition of radiogenic Os. This open system behavior prevents the reconstruction of an initial 187Os/188Os value for the boundary at La Serre. Assuming reasonable Re concentrations prior to loss, however, the Os isotopic value is inconsistent with a large meteoritic component. In addition, this study reinforces the need for Os isotopic evidence, not only enriched PGE concentrations, as substantiation for a meteoritic impact.

  2. Oxygen isotopic ratios of quartz from wind-erosive soils of southwestern United States in relation to aerosol dust

    Sridhar, K.; Jackson, M.L.; Clayton, R.N.; Gillette, D.A.; Hawley, J.W.


    The oxygen isotopic ratios (expressed as parts per thousand relative to mean ocean water, SMOW, delta/sup 18/O) of the quartz from 13 soils undergoing much wind erosion during the study period of 1972-1975 in four southwestern states and from comparison areas were determined. The delta/sup 18/O for quartz from eight Texas (TX) and Arizona (AZ) soils range from 13.0 to 15.9 /sup 0///sub 00/. The quartz of the sands and silts coarser than 20 from three of the soils had delta/sup 18/O values ranging from 13.1 to 15.1 /sup 0///sub 00/, characteristic of an ultimate igneous-metamorphic origin. The delta/sup 18/O values increase greatly with decreasing particle size of quartz from three soils ranging from loamy fine sand to loam to clay in texture. The delta/sup 18/O of the 1-10 quartz fraction (aerosol size) ranged from 19.2 to 20.2 /sup 0///sub 00/ (19.55 +- 0.28 /sup 0///sub 00/; +- sigma) for the thirteen soils most affected by dust storms. The oxygen isotopic ratios of 1-10 quartz from three Hawaiian soils and two sediments from Lake Waiau occurring at 3,970 m altitude on the Mauna Kea summit on the Island of Hawaii give a delta/sup 18/O mean of 18.3 +- 0.2 /sup 0///sub 00/.


    Akram, W.; Schönbächler, M. [School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Sprung, P. [Institut für Planetologie, Universität Münster, Wilhelm-Klemm-Strasse 10, D-48149 Münster (Germany); Vogel, N. [Institute for Geochemistry and Petrology, ETH, Clausiusstrasse 25, 8092 Zürich (Switzerland)


    Recent work based on analyses of meteorite and terrestrial whole-rock samples showed that the r- and s- process isotopes of Hf were homogeneously distributed throughout the inner solar system. We report new Hf isotope data for Calcium-Aluminum-rich inclusions (CAIs) of the CV3 carbonaceous chondrite Allende, and novel high-precision Zr isotope data for these CAIs and three carbonaceous chondrites (CM, CO, CK). Our Zr data reveal enrichments in the neutron-rich isotope {sup 96}Zr (≤1ε in {sup 96}Zr/{sup 90}Zr) for bulk chondrites and CAIs (∼2ε). Potential isotope effects due to incomplete sample dissolution, galactic and cosmic ray spallation, and the nuclear field shift are assessed and excluded, leading to the conclusion that the {sup 96}Zr isotope variations are of nucleosynthetic origin. The {sup 96}Zr enrichments are coupled with {sup 50}Ti excesses suggesting that both nuclides were produced in the same astrophysical environment. The same CAIs also exhibit deficits in r-process Hf isotopes, which provides strong evidence for a decoupling between the nucleosynthetic processes that produce the light (A ≤ 130) and heavy (A > 130) neutron-rich isotopes. We propose that the light neutron-capture isotopes largely formed in Type II supernovae (SNeII) with higher mass progenitors than the supernovae that produced the heavy r-process isotopes. In the context of our model, the light isotopes (e.g. {sup 96}Zr) are predominantly synthesized via charged-particle reactions in a high entropy wind environment, in which Hf isotopes are not produced. Collectively, our data indicates that CAIs sampled an excess of materials produced in a normal mass (12-25 M{sub ☉}) SNII.

  4. Nitrogen, Sulfur, and Oxygen Isotope Ratios of Animal- and Plant-Based Organic Fertilizers Used in South Korea.

    Shin, Woo-Jin; Ryu, Jong-Sik; Mayer, Bernhard; Lee, Kwang-Sik; Kim, Insu


    Organic fertilizers are increasingly used in agriculture in Asia and elsewhere. Tracer techniques are desirable to distinguish the fate of nutrients added to agroecosystems with organic fertilizers from those contained in synthetic fertilizers. Therefore, we determined the nitrogen, sulfur, and oxygen isotope ratios of nitrogen- and sulfur-bearing compounds in animal- and plant-based organic fertilizers (ABOF and PBOF, respectively) used in South Korea to evaluate whether they are isotopically distinct. The δN values of total and organic nitrogen for ABOF ranged from +7 to +19‰ and were higher than those of PBOF (generally fertilizer compounds in the plant-soil-water system, whereas PBOFs have similar δN values to synthetic fertilizers. However, δO values for nitrate (δO) from organic fertilizer samples (fertilizers. The δS values of total sulfur, organic sulfur compounds (e.g., carbon-bonded sulfur and hydriodic acid-reducible sulfur), and sulfate for ABOFs yielded wide and overlapping ranges of +0.3 to +6.3, +0.9 to +7.2, and -2.6 to +14.2‰, whereas those for PBOFs varied from -3.4 to +7.7, +1.4 to +9.4, and -4.1 to +12.5‰, respectively, making it challenging to distinguish the fate of sulfur compounds from ABOF and PBOF in the environment using sulfur isotopes. We conclude that the δN values of ABOFs and the O values of organic fertilizers are distinct from those of synthetic fertilizers and are a promising tool for tracing the fate of nutrients added by organic fertilizers to agroecosystems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.


    Yu. K. Vasil'chuk


    Full Text Available The object of this study is a recently (or in the Holocene formed thick (up 2.7 m in height buried massive ice body, exposed in 2 km South-East from the mouth of the river Akkani in the North-East of Chukotka in the vicinity of the settlement Lavrentiya. The structural-textural characteristics of ice and enclosing deposits are considered. It is shown that the overlying layers of sediments are loams with a slab structure and vertical-layer medium and thin-chill cryogenic structure and ice sockets. The ice of the body is very pure and transparent, visible to a depth of 0.5 m. There are some inclusions found in massive ice: sand and loams presented in forms of thin interlayers of particles or granules. The ice is full of bubbles. The main method of the research was the analysis of isotopes of oxygen and hydrogen within the stratified ice body, and also relationships between them as well as ratios between the deuterium excess and δ2Н. The thick and relatively contemporary massive ice layer buried under a layer of proluvial sediments had been found for the first time, and together with this, the isotope variations of the buried ice (δ2Н and δ18O were determined. The mean values of δ18О and δ2H in the ice are rather stable and equal to −17.1 and −128.3‰, respectively. These isotope characteristics may be used for cryogenic reconstructions of massive ice formations widely distributed in the late Quaternary deposits in Eastern Chukotka.

  6. Stable carbon and oxygen isotope studies of Late Weichselian lake sediments in southern Sweden and northern Poland, with palaeoclimatic implications

    Hammarlund, D.


    Late Weichselian lacustrine sediment sequences from southern Sweden and northern Poland were studied by means of stable isotope analysis in order to reconstruct the climatic development and climatically induced environmental changes in the respective regions. The methods used include analyses of the stable carbon isotope composition (δ 13 C) of bulk organic material, and the stable carbon and oxygen isotope compositions (δ 13 C, δ 18 O) of bulk carbonates and carbonate shells of aquatic organisms. These results were complemented and supported by lithological, chemical and biostratigraphic data (plant macrofossils, insects, molluscs). Chronological data were obtained by AMS radiocarbon dates and correlations based on pollen analysis. At c. 12.400 BP a climatic change from arctic, dry, and continental, to subarctic and more humid and maritime conditions occurred in southern Sweden. The Older Dryas stadial (c.12.200-12.000 BP) is characterized by a temporary return to generally colder , drier, and more continental conditions, followed by generally favourable (subarctic), although unstable, climatic conditions. At c. 11.300 BP a gradual transition towards a colder and more continental climate was initiated, followed by total absence of limnic carbonates during the Younger Dryas stadial (c. 11.000-10.200 BP), indicating arctic and continental conditions. The transition to the Holocene is characterized by a rapid and strong climatic warming. The results from northern Poland point to some important differences compared to this development. A climatic warming around 13.000 BP was followed by generally favourable climatic conditions enabling continuous sedimentation of limnic carbonates during the Late Weichselian. Distinct depletions of 13 C in lacustrine organic material at the transition to the Holocene were recorded in southern Sweden, also demonstrated by decreasing mean values obtained from an extensive compilation of δ 13 C data. A number of processes that may

  7. Stable isotope and DNA evidence for ritual sequences in Inca child sacrifice

    Wilson, Andrew S.; Taylor, Timothy; Ceruti, Maria Constanza; Chavez, Jose Antonio; Reinhard, Johan; Grimes, Vaughan; Meier-Augenstein, Wolfram; Cartmell, Larry; Stern, Ben; Richards, Michael P.; Worobey, Michael; Barnes, Ian; Gilbert, M. Thomas P.


    Four recently discovered frozen child mummies from two of the highest peaks in the south central Andes now yield tantalizing evidence of the preparatory stages leading to Inca ritual killing as represented by the unique capacocha rite. Our interdisciplinary study examined hair from the mummies to obtain detailed genetic and diachronic isotopic information. This approach has allowed us to reconstruct aspects of individual identity and diet, make inferences concerning social background, and gain insight on the hitherto unknown processes by which victims were selected, elevated in social status, prepared for a high-altitude pilgrimage, and killed. Such direct information amplifies, yet also partly contrasts with, Spanish historical accounts. PMID:17923675

  8. Beach rocks characterization from the southern coast of Pernambuco state based on petrography and isotopic evidences

    Assis, H.M.B. de


    The study is restricted to the occurence of three lines of beachrocks located between the Maracaipe river and Sirinhaem river, southern coast of Pernambuco state. The mineralogy and petrography, made it possible the characterization of three types of cements (micrite envelope, acicular crust and intergranular cryptocrystalline). They correspond to diagenetics microfacies which are set in different diagenetics environment. X-ray analysis, as well as sup(13)C/ sup(12)C e sup(18) O/ sup(16) O isotope analysis, show evidence of a dominantly marine precipitating fluid with a subordinate fresh water influence on a second cement generation. (author)

  9. The relationship between stable oxygen and hydrogen isotope ratios of water in astomatal plants

    Cooper, Lee W.; DeNiro, Michael J.; Keeley, Jon E.; Taylor, H. P.; O'Neil, J. R.; Kaplan, I.R.


    Isotropic fractination of leaf water during transpiration is influenced by both equilibrium and kinetic factors. Previous workers have predicted that the influence of each factor varies depending upon the path of water loss,m whether centralized through stomata, or diffuse through the cuticle. We studied the relationship between the δD and δ18O values of lead and stem waters of laurel sumac, Rhus laurina (Nutt.) T. & G., and its parasite, dodder, Cuscuta subinclusa D. & H., growing in the field. Stomatal transpiration, associated with more stagnant boundary layers, predominates in R. laurina; cuticular transpiration, associated with more turbulent boundary layers, is most important in the largely astomatal C. subinclusa. We also studied the diurnal variation in the δD and δ18O values of lead waters of two astomatal plants, Chiloschista lunifera (Rchb. F.) J.J.S. and Stylites andicola Amstutz, and two stomatal plants, Tillandsia balbisiana Schult. and Lilaeopsis schaffneriana (Schlecht.) C. & R., growing with them under the same conditions in the laboratory. Slopes, m, for the relation δD = mδ18O + b were significantly higher for stem waters in C. subinclusa that for leaf waters in R. laurina (1.77), consistent with the difference in the boundary layers through which water was lost in the two species. The magnitude of diurnal heavy isotope enrichment of tissue water was smaller in C. subinclusa than in R. laurina, which is also consistent with predictions concerning evapotranspiration through difference types of boundary layers. The slopes, m, in plant waters in the laboratory experiments, conducted at high humidity, were not different than those observed during evaporation of water from pans, regardless of plant anatomy. The observation suggests that cuticular transpiration is important in influencing isotopic fractionation of water only at low humidity. Our results indicate that the isotopic composition of water vapor released by plants in arid regions may

  10. Major, Trace Element Concentration and Triple-Oxygen Isotope Compositions of G- and I-Type Spherules from the Sør Rondane Mountains, East Antarctica

    Soens, B.; Goderis, S.; Greenwood, R. C.; McKibbin, S.; Van Ginneken, M.; Vanhaecke, F.; Debaille, V.; Franchi, I. A.; Claeys, Ph.


    We present new major, trace element concentration (LA-ICP-MS) and triple-oxygen isotope (LF-IRMS) data for G- and I-type cosmic spherules. This study suggests that both types of micrometeorites may originate from ordinary chondrite parent bodies.

  11. Geochemistry of rare earths and oxygen isotopes in granitic rocks from Monte das Gameleiras and Dona Ines, Rio Grande do Norte-Paraiba border, Brazil

    Sial, A.N.


    The study of oxygen isotopes and rare earth elements in granitic plutons of Monte das Gameleiras and Dona Ines, Rio Grande do Norte-Paraiba border, in Brazil, to define the nature of source rock of progenitor magmas, is presented. (M.C.K.) [pt

  12. Ion microprobe analyses of oxygen three-isotope ratios of chondrules from the Sayh al Uhaymir 290 CH chondrite using a multiple-hole disk

    Nakashima, D.; Ushikubo, T.; Gowda, R.N.; Kita, N.T.; Valley, J.W.; Naga, K.

    Author version: Meteorit. Planet. Sci., vol.46(6); 2011; 857-874 Ion microprobe analyses of oxygen three isotope ratios of chondrules from the Sayh al Uhaymir 290 CH chondrite using a multiple-hole disk Daisuke Nakashima 1,2,* , Takayuki Ushikubo...

  13. Planetary fertility during the past 400 ka based on the triple isotope composition of atmospheric oxygen in trapped gases from the Vostok ice core

    Blunier, T.; Bender, M. L.; Barnett, B.; von Fisher, J. C.


    The productivity of the biosphere leaves its imprint on the isotopic composition of atmospheric oxygen. Ultimately atmospheric oxygen, through photosynthesis, originates from seawater. Fractionations during the passage from seawater to atmospheric O2 and during respiration are mass dependent, affecting δ17O about half as much as δ18O. An "anomalous" (also termed mass independent) fractionation process changes δ17O about 1.7 times as much as δ18O during isotope exchange between O2 and CO2 in the stratosphere. The relative rates of biological O2 production and stratospheric processing determine the relationship between δ17O and δ18O of O2 in the atmosphere. Variations of this relationship thus allow us to estimate changes in the rate of mass dependent O2 production by photosynthesis versus the rate of mass independent O2-CO2 exchange in the stratosphere. However, the analysis of the 17O anomaly is complicated because each hydrological and biological process influencing δ17O and δ18O fractionates 17O and 18O in slightly different proportions. In this study we present oxygen data covering the last 400 kyr from the Vostok ice core. We reconstruct oxygen productivities from the triple isotope composition of atmospheric oxygen with a box model. Our steady state model for the oxygen cycle takes into account fractionation during photosynthesis and respiration of the land and ocean biosphere as well as fractionation when oxygen passes through the stratosphere. We consider changes of fractionation factors linked to climate variations taking into account the span of estimates of the main factors affecting our calculations. We find that ocean oxygen productivity was likely elevated relative to modern during glacials. However, this increase probably did not fully compensate for a reduction in land ocean productivity resulting in a slight reduction in total oxygen production during glacials.

  14. Magma reservoir dynamics at Toba caldera, Indonesia, recorded by oxygen isotope zoning in quartz.

    Budd, David A; Troll, Valentin R; Deegan, Frances M; Jolis, Ester M; Smith, Victoria C; Whitehouse, Martin J; Harris, Chris; Freda, Carmela; Hilton, David R; Halldórsson, Sæmundur A; Bindeman, Ilya N


    Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ 18 O values. Overall, Toba quartz crystals exhibit comparatively high δ 18 O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ 18 O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum ∆ core-rim  = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ 18 O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ 18 O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems.

  15. Isotopic variation of oxygen in the water of river Solimoes/Amazon and its main tributaries

    Mortatti, J.; Martinelli, L.A.; Matsui, E.; Victoria, R.L.; Richey, J.E.


    Eight cruises in the Amazon Basin were realized during the period between April (1982) and August (1984). Waters of main channel of the River Solimoes/Amazon and its tributaries were sampled and analysed for sup(18)0 content by mass spectrometry. A depth integrated sampler coupled to a variable speed hydraulic winch was used. The sampling was accomplished at different river stages, at upper Solimoes, middle and lower Amazon region. The δ sup(18) 0 values obtained in these reaches showed the same seasonal variation pattern. In the dry season, δ sup(18) 0 values become higher than in the rainy season. The isotopic variability in the region may be explained by the origin and dynamics of the water vapour. The spatial variation in δ sup(18) 0 values at the main channel was compared for high and low water stages; it showed an isotopic gradient of 0.052 and 0.048 sup(0)/∞ δ sup(18) 0/100 km, respectively. (author)

  16. New manuscript guidelines for the reporting of stable hydrogen, carbon, and oxygen isotope-ratio data



    To eliminate possible confusion in the reporting of isotopic abundances on non-corresponding scales, the Commission on Atomic Weights and Isotopic Abundances recommended at the 37{sup th} General Assembly at Lisbon, Portugal that (i) {sup 2}H/{sup 1}H relative ratios of all substances be expressed relative to VSMOW (Vienna Standard Mean Ocean Water) on a scale such that {sup 2}H/{sup 1}H of SLAP (Standard Light Antartic Precipitation) is 0.572 times that of VSMOW, (ii) {sup 13}C/{sup 12}C relative ratios of all substances be expressed relative to VPDB (Vienna Peedee belemnite) on a scale such that {sup 13}C/{sup 12}C of NBS 19 carbonate is 1.00195 times that of VPDB, and (iii) {sup 18}O/{sup 16}O ratios of all substances be expressed relative to either VSMOW or VPDB on scales such that {sup 18}O/{sup 16}O of SLAP is 0.9445 times that of VSMOW. (Author)

  17. The oxygen isotopic composition of phytolith assemblages from tropical rainforest soil tops (Queensland, Australia: validation of a new paleoenvironmental tool

    A. Alexandre


    Full Text Available Phytoliths are micrometric particles of amorphous silica that form inside or between the cells of higher plant tissues throughout the life of a plant. With plant decay, phytoliths are either incorporated into soils or exported to sediments via regional watersheds. Phytolith morphological assemblages are increasingly used as proxy of grassland diversity and tree cover density in inter-tropical areas. Here, we investigate whether, along altitudinal gradients in northeast Queensland (Australia, changes in the δ18O signature of soil top phytolith assemblages reflect changes in mean annual temperature (MAT and in the oxygen isotopic composition of precipitation (δ18Oprecipitation, as predicted by equilibrium temperature coefficients previously published for silica. Oxygen isotopic analyses were performed on 16 phytolith samples, after controlled isotopic exchange (CIE, using the IR Laser-Heating Fluorination Technique. Long-term mean annual precipitation (MAP and MAT values at the sampled sites were calculated by the ANUCLIM software. δ18Oprecipitation estimates were calculated using the Bowen and Wilkinson (2002 model, slightly modified. An empirical temperature-dependant relationship was obtained: δ18Owood phytolith-precipitation (‰ vs. VSMOW = −0.4 (±0.2 t (°C + 46 (±3 (R2 = 0.4, p < 0.05; n = 12. Despite the various unknowns introduced when estimating δ18Oprecipitation values and the large uncertainties on δ18Owood phytolith values, the temperature coefficient (−0.4 ± 0.2‰ °C−1 is in the range of values previously obtained for natural quartz, fresh and sedimentary diatoms and harvested grass phytoliths (from −0.2 to −0.5‰ °C−1. The consistency supports the reliability of δ18Owood phytolith signatures for recording

  18. Intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite measured by thermal dehydroxylation and partial fluorination

    Girard, Jean-Pierre; Savin, Samuel M.


    Thermal dehydroxylation and partial fluorination techniques were used to measure intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite. Several aliquots of a well characterized, fine-grained (rates, and target temperatures. Measured δ18O values of both the liberated water and the dehydroxylated residue are consistent over a wide range of temperatures (550 850°C) when dehydroxylation is performed in a single-step fashion at a rapid heating rate (>50°C/min.). Similar dehydroxylation experiments indicate that brucite dehydroxylation occurs without any significant isotopic fractionation of the oxygen isotopes. By extrapolation we postulate that no significant fractionation occurs during single-step thermal dehydroxylation of fine-grained kaolinite, provided that dehydroxylation is performed under well controlled conditions. In contrast, gibbsite dehydroxylation is accompanied by substantial isotopic fractionation. This is probably the result of the complex, multi-pathway dehydroxylation reaction of this mineral. Similarly, thermal dehydroxylation of coarsegrained (>1 μm) kaolinites and dickites of weathering and hydrothermal origin yield results that are dependent on the temperature of dehydroxylation. We suggest that this effect may be caused by isotopic exchange during diffusion of water molecules through coarse particles. Partial fluorination of fine-grained kaolinite in the presence of excess F2 at low temperatures (rate of reaction of hydroxyl oxygen than of non-hydroxyl oxygen, but examination of the isotopic data as well as XRD and IR analyses of the residues after partial fluorination indicates that the separation between the two types of oxygen is not complete. The results, therefore, do not yield a reliable δ18O value of the hydroxyl oxygen. The results of this study suggest that the thermal dehydroxylation technique may be appropriate for analysis of OH groups in fine-grained kaolinite. The partial

  19. Carbon and oxygen isotope ratios in wood constituents of Pinus halepensis as indicators of precipitation, temperature and vapour pressure deficit

    Ferrio, J.P.; Voltas, J.


    Carbon and oxygen isotope compositions (δ 13 C, δ 18 O) in tree rings have been shown to bear relevant climatic signals. However, little is known about the interrelationship between both isotopes in wood constituents for species from other than relatively wet climates. We hypothesized that in a species adapted to temporary droughts (e.g. Pinus halepensis Mill.) the signal derived from δ 18 O in precipitation would be hidden by the strong variability in leaf transpirative enrichment. To test this assumption, we compared the effect of precipitation, temperature and vapour pressure deficit (VPD) on δ 18 O and δ 13 C along 23 sites covering the ecological range for this species. We extracted the cores from the south side of four to six adult dominant trees per aspect (north/south) within each site. For each aspect and site, fragments of the period 1975-1999 were pooled and milled to a fine powder. To further test the postulated need for cellulose purification in the assessment of climatic information, we studied these relationships in whole and extracted wood, holocellulose and lignin. In all wood fractions, δ 13 C was related to annual precipitation [r=0.58 (P 18 O only holocellulose showed consistent relationships with climatic data, being strongly significant for VPD [r=0.66 (P 18 O in precipitation, confirming that transpirative enrichment (driven by VPD) dampened the source signal in P. halepensis. The relationships between δ 13 C and δ 18 O were generally poor, regardless of the wood constituent, suggesting that although both variables were somewhat related to transpirative demand, they were relatively independent. This was further confirmed by building stepwise models using both isotopes to predict annual and seasonal precipitation [r 2 = 0.34 (P 2 = 0.15 (P 2 = 0.31 (P< 0.01) to 0.55 (P< 0.001)]. We concluded that, even when partially describing the same climate variables, the information underlying the two isotopes can be regarded as complementary

  20. Geochemical, isotopic, and zircon (U-Pb, O, Hf isotopes) evidence for the magmatic sources of the volcano-plutonic Ollo de Sapo Formation, Central Iberia

    Montero, P.; Talavera, C.; Bea, F.


    The Ollo de Sapo Formation comprises variably metamorphosed felsic peraluminous volcanic rocks and highlevel granites that crop out over some 600km from the Cantabrian coast to central Spain in the northern part of the Central Iberian Zone. The Ollo de Sapo magmatism is not obviously connected with any major tectonic or metamorphic event so its origin is controversial. Some authors, based on trace-elements, have proposed that the Ollo de Sapo magmas originated in a supra-subduction setting but others, based on abnormally high zircon inheritance and field and structural data, favored a rifting environment. Here we present new oxygen and hafnium isotope data from the very characteristic Ollo the Sapo zircons, which in most cases, consist of ca. 485Ma rims and ca. 590-615Ma cores. We found that the Cambrian-Ordovician rims yielded unimodal distributions that cluster around ∂18O = 10, typical of S-type magmas formed from melting of altered crust. The Ediacaran cores, in contrast, cluster around ∂18O = 6.5, consistent with being arc-magmas. Rims and cores have the same average Hf isotope composition, but the rims are considerably more uniform. These data, coupled with existing wholerock element and Sr and Nd isotopic data, indicate that the Ollo de Sapo were S-type magmas that resulted from anatexis of younger-than-600Ma immature sediments mostly derived from different Ediacaran igneous rocks with a wide range of Hf isotope composition.

  1. Geochemical, isotopic, and zircon (U-Pb, O, Hf isotopes) evidence for the magmatic sources of the volcano-plutonic Ollo de Sapo Formation, Central Iberia

    Montero, P.; Talavera, C.; Bea, F.


    The Ollo de Sapo Formation comprises variably metamorphosed felsic peraluminous volcanic rocks and highlevel granites that crop out over some 600km from the Cantabrian coast to central Spain in the northern part of the Central Iberian Zone. The Ollo de Sapo magmatism is not obviously connected with any major tectonic or metamorphic event so its origin is controversial. Some authors, based on trace-elements, have proposed that the Ollo de Sapo magmas originated in a supra-subduction setting but others, based on abnormally high zircon inheritance and field and structural data, favored a rifting environment. Here we present new oxygen and hafnium isotope data from the very characteristic Ollo the Sapo zircons, which in most cases, consist of ca. 485Ma rims and ca. 590-615Ma cores. We found that the Cambrian-Ordovician rims yielded unimodal distributions that cluster around ∂18O = 10, typical of S-type magmas formed from melting of altered crust. The Ediacaran cores, in contrast, cluster around ∂18O = 6.5, consistent with being arc-magmas. Rims and cores have the same average Hf isotope composition, but the rims are considerably more uniform. These data, coupled with existing wholerock element and Sr and Nd isotopic data, indicate that the Ollo de Sapo were S-type magmas that resulted from anatexis of younger-than-600Ma immature sediments mostly derived from different Ediacaran igneous rocks with a wide range of Hf isotope composition.

  2. Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

    Kao, Yu-Hsuan; Wang, Sheng-Wei; Liu, Chen-Wuing; Wang, Pei-Ling; Wang, Chung-Ho; Maji, Sanjoy Kumar


    Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using δ 34 S [SO 4 ] and δ 18 O [SO 4 ] sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of 34 S [SO 4 ] and 18 O [SO 4 ] present in Type A, caused by microbial-mediated reduction of sulfate, and high 18 O enrichment factor (ε [SO 4 -H 2 O] ), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high δ 18 O [SO 4 ] and low δ 34 S [SO 4 ] values under mildly reducing conditions. Base on 18 O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O 2 , caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: → Seawater intrusion and elevated As are the main issues of groundwater in Taiwan. → Sulfur and oxygen isotopes of sulfate were analyzed to evaluate the As mobility. → Reductive dissolution of Fe minerals and

  3. Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

    Kao, Yu-Hsuan [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Sheng-Wei [Agricultural Engineering Research Center, Chungli 320, Taiwan, ROC (China); Liu, Chen-Wuing, E-mail: [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Pei-Ling [Institute of Oceanography, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Chung-Ho [Institute of Earth Sciences, Academia Sinica, Taipei 115, Taiwan, ROC (China); Maji, Sanjoy Kumar [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China)


    Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using {delta}{sup 34}S{sub [SO{sub 4]}} and {delta}{sup 18}O{sub [SO{sub 4]}} sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of {sup 34}S{sub [SO{sub 4]}} and {sup 18}O{sub [SO{sub 4]}} present in Type A, caused by microbial-mediated reduction of sulfate, and high {sup 18}O enrichment factor ({epsilon}{sub [SO{sub 4-H{sub 2O]}}}), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high {delta}{sup 18}O{sub [SO{sub 4]}} and low {delta}{sup 34}S{sub [SO{sub 4]}} values under mildly reducing conditions. Base on {sup 18}O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O{sub 2}, caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: {yields} Seawater intrusion and elevated As are the main issues of groundwater in Taiwan

  4. Oxygen isotope composition as late glacial palaeoclimate indicators of groundwater recharge in the Baltic Basin

    Mokrik, R.; Mazeika, J.


    Several hypotheses were established to explain low δ 18 O values of groundwater which have been found in the Estonian Homocline. Traces of depleted groundwater were found also in other parts of the Baltic Basin near the shoreline. From data collected in this and previous studies, the δ 18 O values of groundwater in most aquifers are known to range from -7.7 to -13.9 per mille. However, the groundwater in Estonia in the Cambrian-Vendian aquifer system has significantly lower δ 18 O values, which vary mainly from -18 to -22.5 per mille. The overlying Ordovician-Cambrian aquifer is also depleted in 18 O, but, as a rule, the degree of depletion is several per mille less than in case of the Cambrian- Vendian aquifer. The thickness of the depleted water in Estonia reaches 450 m. At similar depths beneath Gotland Island (Sweden Homocline), groundwater has significantly higher δ 18 O values (from -5.7 to -6.1 per mille). A hydrogeologic model, depicting conditions during the pre Late Glacial, and accounting for hydraulic connections between the lake and river systems through taliks in permafrost, was developed to explain the observed groundwater isotope data. According to the adopted model, penetration of isotopically depleted surface waters could have reached depths of up to 500 m, with subsequent mixing between subglacial meltwater and old groundwater of Huneborg-Denekamp time. Traces of this penetration were discovered only near the shoreline, where δ 18 O values vary from -12 to -13.9 per mille and 14 C is below 4%. In the territory of the Estonian Homocline, the hydraulically close connection via the Cambrian-Vendian aquifer between talik systems of the Gulf of Riga and the Gulf of Finland existed through permafrost before the Late Glacial. This was due to subglacial recharge during the recessional Pandivere (12 ka BP) and Palivere (11.2 ka BP) phases, which is also associated with recharge of isotopically depleted groundwater. (author)

  5. Earliest isotopic evidence in the Maya region for animal management and long-distance trade at the site of Ceibal, Guatemala.

    Sharpe, Ashley E; Emery, Kitty F; Inomata, Takeshi; Triadan, Daniela; Kamenov, George D; Krigbaum, John


    This study uses a multiisotope (carbon, nitrogen, oxygen, and strontium) approach to examine early animal management in the Maya region. An analysis of faunal specimens across almost 2,000 years (1000 BC to AD 950) at the site of Ceibal, Guatemala, reveals the earliest evidence for live-traded dogs and possible captive-reared taxa in the Americas. These animals may have been procured for ceremonial functions based on their location in the monumental site core, suggesting that animal management and trade began in the Maya area to promote special events, activities that were critical in the development of state society. Isotopic evidence for animal captivity at Ceibal reveals that animal management played a greater role in Maya communities than previously believed. Copyright © 2018 the Author(s). Published by PNAS.

  6. Ice-vapor equilibrium fractionation factor of hydrogen and oxygen isotopes

    Ellehøj, Mads Dam; Steen-Larsen, Hans Christian; Johnsen, Sigfus Johann


    RATIONALE: The equilibrium fractionation factors govern the relative change in the isotopic composition during phase transitions of water. The commonly used results, which were published more than 40 years ago, are limited to a minimum temperature of -33 degrees C. This limits the reliability...... values, with a temperature dependency in accordance with theory for equilibrium fractionation. We obtain the following expressions for the temperature dependency of the fractionation coefficients: ln(alpha(delta 2H)) = 0.2133 - 203.10/T + 48888/T-2 ln(alpha(delta 18O)) = 0.0831 - 49.192/T + 8312.5/T2...... Compared with previous experimental work, a significantly larger for H-2 is obtained while, for O-18, is larger for temperatures below -20 degrees C and slightly lower for temperatures above this. CONCLUSIONS: Using the new values for alpha, a Rayleigh distillation model shows significant changes in both...

  7. Does oxygen limit thermal tolerance in arthropods? A critical review of current evidence.

    Verberk, Wilco C E P; Overgaard, Johannes; Ern, Rasmus; Bayley, Mark; Wang, Tobias; Boardman, Leigh; Terblanche, John S


    Over the last decade, numerous studies have investigated the role of oxygen in setting thermal tolerance in aquatic animals, and there has been particular focus on arthropods. Arthropods comprise one of the most species-rich taxonomic groups on Earth, and display great diversity in the modes of ventilation, circulation, blood oxygen transport, with representatives living both in water (mainly crustaceans) and on land (mainly insects). The oxygen and capacity limitation of thermal tolerance (OCLTT) hypothesis proposes that the temperature dependent performance curve of animals is shaped by the capacity for oxygen delivery in relation to oxygen demand. If correct, oxygen limitation could provide a mechanistic framework to understand and predict both current and future impacts of rapidly changing climate. In arthropods, most studies testing the OCLTT hypothesis have considered tolerance to thermal extremes. These studies likely operate from the philosophical viewpoint that if the model can predict these critical thermal limits, then it is more likely to also explain loss of performance at less extreme, non-lethal temperatures, for which much less data is available. Nevertheless, the extent to which lethal temperatures are influenced by limitations in oxygen supply remains unresolved. Here we critically evaluate the support and universal applicability for oxygen limitation being involved in lethal temperatures in crustaceans and insects. The relatively few studies investigating the OCLTT hypothesis at low temperature do not support a universal role for oxygen in setting the lower thermal limits in arthropods. With respect to upper thermal limits, the evidence supporting OCLTT is stronger for species relying on underwater gas exchange, while the support for OCLTT in air-breathers is weak. Overall, strongest support was found for increased anaerobic metabolism close to thermal maxima. In contrast, there was only mixed support for the prediction that aerobic scope

  8. Isotopic labeling study of oxygen diffusion in amorphous LaScO3 high-κ films on Si(100) and its effects on the electrical characteristics

    Lopes, J.M.J.; Littmark, U.; Roeckerath, M.; Durgun Oezben, E.; Lenk, S.; Schubert, J.; Mantl, S.; Breuer, U.; Besmehn, A.; Staerk, A.; Grande, P.L.; Sortica, M.A.; Radtke, C.


    The influence of post-deposition oxygen anneals on the properties of amorphous LaScO 3 films on Si(100) is reported. The use of an isotopically ( 18 O 2 ) enriched atmosphere allowed to investigate the 16 O- 18 O exchange and the oxygen diffusion across the dielectric layer. Such effects are connected to the formation of an interfacial layer. Oxygen annealing leads to nearly ideal capacitance-voltage curves, lower leakage currents and interface trap densities, as well as to κ-values up to 33 for the LaScO 3 films. These results are attributed to the suppression of oxygen-related trap centers and the achievement of a stoichiometric oxygen content. (orig.)

  9. Textural and Isotopic Evidence for Silica Cementation in 1.88 GA Granular Iron Formation

    Brengman, L. A.; Fedo, C.; Martin, W.


    Controls on quartz precipitation mechanisms and silicon isotope fractionation during diagenesis of Precambrian iron formation (IF) are not well constrained. The goal of this study is to identify textural evidence for the relative timing of silica cementation of granular units from the near un-metamorphosed 1.88 Ga Biwabik IF and determine the silicon isotope composition for such a silicification event. The lowermost IF (lower cherty, LC) consists of granular units associated with high-energy sedimentary structures interpreted to represent shallow-marine shelf deposition. Up-section is marked by an abrupt shift to banded units interpreted as a transition to quiescent (deeper) water, followed by a return to granular textures and shallower conditions (upper cherty, UC). We first surveyed granular samples of the lower stromatolitic (LC) and upper oncolitic facies (UC) to identify sedimentary textures and cement. LC units consist of microquartz (chert), megaquartz, hematite, carbonate, and detrital quartz, chert, and quartz/Fe-oxide intraclastic material. In UC samples, space between granular material (hematite, magnetite, quartz ooids/intraclasts) is filled by mega-quartz cement, and cross-cutting mega-quartz veins. We targeted mega-quartz cement, and veins for δ30Si analysis via secondary ion mass spectrometry. The average measured δ30Si value of cement (δ30Siavg. cement UC6b = -3.11 ± 0.21 ‰) is significantly different than associated veins (δ30Siavg. vein UC6b = 0.21 ± 0.21 ‰; δ30Siavg. vein LC4 = 0.39 ± 0.21 ‰), both within and between samples. We interpret the relative difference between cement and veins to represent quartz precipitation under different geochemical conditions, and therefore at different times. Combining isotopic and textural evidence, we interpret silica cementation to pre-date veins, and represent quartz precipitation that either varied in rate, or occurred under closed-system conditions affected by Rayleigh distillation. Both

  10. Distribution of isotopic composition of hydrogen, oxygen and carbon in the atmosphere of Croatia and Slovenia

    Krajcar Bronic, I.; Vreca, P.; Horvatincic, N.; Ogrinc, N.; Baresic, J.; Obelic, B.; Kanduc, T.


    Natural cycles of water and carbon can be studied by monitoring the isotopic composition of H 2 O and CO 2 in the atmosphere. The monitoring includes isotopes 2 H , 3 H and 1 8O in precipitation, and 1 3C and 1 4C in atmospheric CO 2 . Here we present the results of such a monitoring of the atmosphere over Croatia and Slovenia for the last several years. Monthly precipitation samples at Zagreb and Ljubljana have been collected since 1976 and 1981, respectively. In the period 2000-2003 the sampling network was extended to seven stations along the Adriatic coast of the two countries. Tritium activity in precipitation shows seasonal variations that are most pronounced at inland stations (Zagreb, Ljubljana) followed by the north-Adriatic (Portoroz, Kozina, Malinska) and mid-Adriatic stations (Zadar, Zavizan), and the smallest are at the south-Adriatic stations (Komiza, Dubrovnik). The mean annual tritium activity also decreases from the north to the south of the Adriatic coast. Seasonal variations in delta2 H and delta1 8O in precipitation follow temperature variations at the sampling stations, and the mean annual d 18O values follow mean annual temperatures. Thus, the south-Adriatic stations show the smallest variations in delta1 8O and highest mean delta1 8O values. Atmospheric CO 2 was collected on a monthly basis in Zagreb and Plitvice to record seasonal variations in both Delta1 4C and delta1 3C . Mean annual 1 4C activities in Zagreb decreased after their peak in the 1960s and approached natural pre-bomb activities. For the last three years, the mean 1 4C activity Delta1 4C has remained about 30 per mile. This study extended our knowledge about natural spatial and temporal distributions of 2 H , 3 H , 1 3C , 1 4C and 1 8O in the atmosphere over a relatively small yet rather diverse area in terms of climate and geographic features.(author)

  11. Geomorphic Drainage Capture Recorded by Oxygen Isotopes of Green River Formation Lacustrine Mudstone, Eocene, Wyoming

    Doebbert, A. C.; Booth, A. L.; Carroll, A.; Chamberlain, C.; Rhodes, M.


    The isotopic composition of cement and other meteoric precipitates are increasingly being used to interpret orogenic uplift histories, based on the relationship between altitude and rainwater δ18O. However, other variables such as changing regional drainage patterns may also affect the downstream composition of surface waters, especially when multiple drainages commingle in a lake. The Green River Formation contains some of the best documented lacustrine deposits in the world, making it ideal for examining such issues. Carbonate mudstone in balanced-fill facies of the lower LaClede Bed averages 3.41‰ (PDB), and records a deep, saline to brackish lake that fluctuated near its sill. In contrast, overfilled facies of the upper LaClede Bed record a freshwater lake, and δ18O reaches values as low as -9.72‰. This transition occurred shortly after deposition of the Analcite Tuff at 48.94 ± 0.12 Ma (Smith et al., 2003), and was geologically abrupt. Based on 40Ar/39Ar-calibrated sediment accumulation rates it required no more than 200-300 ky. An almost identical transition occurs in two cores separated by about 30 km, making local diagenesis an unlikely cause. The magnitude of δ18O change is similar to that in some uplift studies, but its rapidity virtually excludes uplift as a controlling mechanism. Instead, we propose that both the change in sedimentation and the sharp decrease in δ18O are the result of a drainage capture event. The addition of a new drainage to the basin may have adjusted isotopic values in two ways: by introducing runoff with relatively low δ18O, and by decreasing residence time (and therefore evaporation) of lake water. Decreasing 87Sr/86Sr across the same transition suggests that the newly added waters may have been sourced from rising volcanic topography to the north in the Absaroka province. Although this rising topography allows for the possibility of some uplift component, the rate of change in lacustrine δ18O is consistent with

  12. Isotopic evidence for nitrous oxide production pathways in a partial nitritation-anammox reactor.

    Harris, Eliza; Joss, Adriano; Emmenegger, Lukas; Kipf, Marco; Wolf, Benjamin; Mohn, Joachim; Wunderlin, Pascal


    Nitrous oxide (N2O) production pathways in a single stage, continuously fed partial nitritation-anammox reactor were investigated using online isotopic analysis of offgas N2O with quantum cascade laser absorption spectroscopy (QCLAS). N2O emissions increased when reactor operating conditions were not optimal, for example, high dissolved oxygen concentration. SP measurements indicated that the increase in N2O was due to enhanced nitrifier denitrification, generally related to nitrite build-up in the reactor. The results of this study confirm that process control via online N2O monitoring is an ideal method to detect imbalances in reactor operation and regulate aeration, to ensure optimal reactor conditions and minimise N2O emissions. Under normal operating conditions, the N2O isotopic site preference (SP) was much higher than expected - up to 40‰ - which could not be explained within the current understanding of N2O production pathways. Various targeted experiments were conducted to investigate the characteristics of N2O formation in the reactor. The high SP measurements during both normal operating and experimental conditions could potentially be explained by a number of hypotheses: i) unexpectedly strong heterotrophic N2O reduction, ii) unknown inorganic or anammox-associated N2O production pathway, iii) previous underestimation of SP fractionation during N2O production from NH2OH, or strong variations in SP from this pathway depending on reactor conditions. The second hypothesis - an unknown or incompletely characterised production pathway - was most consistent with results, however the other possibilities cannot be discounted. Further experiments are needed to distinguish between these hypotheses and fully resolve N2O production pathways in PN-anammox systems. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Analytical Method for Carbon and Oxygen Isotope of Small Carbonate Samples with the GasBench Ⅱ-IRMS Device

    LIANG Cui-cui


    Full Text Available An analytical method for measuring carbon and oxygen isotopic compositions of trace amount carbonate (>15 μg was established by Delta V Advantage isotope Ratio MS coupled with GasBench Ⅱ. Different trace amount (5-50 μg carbonate standard samples (IAEA-CO-1 were measured by GasBench Ⅱ with 12 mL and 3.7 mL vials. When the weight of samples was less than 40 μg and it was acidified in 12 mL vials, most standard deviations of the δ13C and δ18O were more than 0.1‰, which couldn’t satisfied high-precision measurements. When the weight of samples was greater than 15 μg and it was acidified in 3.7 mL vials, standard deviations for the δ13C and δ18O were 0.01‰-0.07‰ and 0.01‰-0.08‰ respectively, which satisfied high-precision measurements. Therefore, small 3.7 mL vials were used to increase the concentration of carbon dioxide in headspace, carbonate samples even less as 15 μg can be analyzed routinely by a GasBench Ⅱ continuous-flow IRMS. Meanwhile, the linear relationship between sample’s weight and peak’s area was strong (R2>0.993 2 and it can be used to determine the carbon content of carbonate samples.

  14. Oxygen Isotopic Composition of Nitrate and Sulfate in Fog and River water in Podocarpus National Forest, Ecuador

    Brothers, L. A.; Fabian, P.; Thiemens, M. H.


    The eastern slopes of the Andean rainforests of Ecuador possess some of the highest plant biodiversity found on the planet; however, these ecosystems are in jeopardy because region is experiences one of the highest deforestation rates in South America. This rainforest characterized by high acidity and low nutrient soils and experiences natural process which are both destabilizing and stabilizing to biodiversity rendering this a unique, though sensitive environment. There is increased concern that anthropogenic activities are affecting rainforests and could lead to higher extinction rates, changes in the biodiversity and far reaching effects on the global troposphere. Measurements of nitrate and sulfate in rain and fog water have shown periods of elevated concentrations in the Podocarpus National Park near Loja, Ecuador. These high episodes contribute to annual deposition rates that are comparable to polluted central Europe. Significant anthropogenic sources near this region are lacking and it is believed that the majority of the nitrate and sulfate pollution can be attributed to biomass burning in the Amazon basin. Concentration measurements do not elucidate the source of high nitrate and sulfate pollution; however, by measuring all three stable isotopes of oxygen in nitrate and sulfate from fog and river water provides a new way to examine the impacts of biomass burning on the region. By using stable isotope techniques atmospheric nitrate and sulfate can be resolved from terrestrial sources. This provides an unique way to trace the contributions from the biomass burning and farming sources. Current research at the field station monitors sulfate and nitrate concentrations in rain and fog water by standard methods to investigate water and nutrient pathways along with data from satellite and ground based remote sensing, in-situ observations and numerical models.

  15. Oxygen and carbon isotopes of Recent calcareous nannofossils as paleoceanographic indicators

    Goodney, D.E.; Margolis, S.V.; Dudley, W.C.; Kroopnick, P.; Williams, D.F.


    Delta 18 O and delta 13 C values for several species of planktonic foraminifera and calcareous nannofossils from Recent deep-sea sediments have been studied in order to evaluate their paleoceanographic and paleotemperature potential. Nannofossils from Indian Ocean core-tops reflect isotopic temperatures as warm as, or warmer than, the temperatures reported for shallow-dwelling planktonic forminifera from the same samples. In general, deep-sea sediment samples from the world's major oceans indicate that nannofossil delta 18 O values are from 0.5 to 1 per thousand heavier than shallow-dwelling planktonic foraminifera. Although nannofossil delta 18 O values depart from thermodynamic equilibrium with oceanic surface water temperatures, the delta 18 O temperature trend parallels that of surface-dwelling planktonic foraminifera. Nannofossil delta 13 C values also depart equilibrium with surface water delta 13 C-ΣCO 2 values. A comparison of nannofossil delta 13 C data with that from planktonic foraminifera suggests that the rate of primary productivity in different water masses may be influencing the delta 13 C carbonate-secreting phytoplankton and zooplankton. (Auth.)

  16. Hydrologic control of the oxygen isotope ratio of ecosystem respiration in a semi-arid woodland

    J. H. Shim


    Full Text Available We conducted high frequency measurements of the δ18O value of atmospheric CO2 from a juniper (Juniperus monosperma woodland in New Mexico, USA, over a four-year period to investigate climatic and physiological regulation of the δ18O value of ecosystem respiration (δR. Rain pulses reset δR with the dominant water source isotope composition, followed by progressive enrichment of δR. Transpiration (ET was significantly related to post-pulse δR enrichment because the leaf water δ18O value showed strong enrichment with increasing vapor pressure deficit that occurs following rain. Post-pulse δR enrichment was correlated with both ET and the ratio of ET to soil evaporation (ET/ES. In contrast, the soil water δ18O value was relatively stable and δR enrichment was not correlated with ES. Model simulations captured the large post-pulse δR enrichments only when the offset between xylem and leaf water δ18O value was modeled explicitly and when a gross flux model for CO2 retro-diffusion was included. Drought impacts δR through the balance between evaporative demand, which enriches δR, and low soil moisture availability, which attenuates δR enrichment through reduced ET. The net result, observed throughout all four years of our study, was a negative correlation of post-precipitation δR enrichment with increasing drought.

  17. Oxygen isotope zonation at the Golden Cross low-sulfidation epithermal gold deposit, New Zealand

    Mauk, J.L.; Simpson, M.P.


    Forty-one whole rock samples from the Gold Cross low-sulfidation epithermal Au-Ag deposit have δ 18 O values that range from 4.4 to 9.3 per mil, with an average value of 7.0 per mil. Unaltered and weakly altered rocks have δ 18 O values greater than 8 per mil, and the orebody is surrounded by samples that are depleted in 18 O. A strongly silicified sample adjacent to the Empire Vein System has a δ 18 O value of 9.0 per mil, similar to previously reported analyses of vein quartz (7.0 to 11.7 per mil, average 9.4 per mil). This suggests that, in detail, Golden Cross may have a zone of 18 O-enriched wall rocks in the core of the deposit, adjacent to the main underground veins. Although some workers have suggested that stable isotope geochemistry may provide useful information for epithermal mineral deposit exploration, at Golden Cross this is not the case. Alteration minerals, major elements and trace elements all define larger, less ambiguous halos than the zone of 18 O-depleted wall rocks. (author). 21 refs., 3 figs., 1 tab

  18. Not all jellyfish are equal: isotopic evidence for inter- and intraspecific variation in jellyfish trophic ecology

    Nicholas E.C. Fleming


    Full Text Available Jellyfish are highly topical within studies of pelagic food-webs and there is a growing realisation that their role is more complex than once thought. Efforts being made to include jellyfish within fisheries and ecosystem models are an important step forward, but our present understanding of their underlying trophic ecology can lead to their oversimplification in these models. Gelatinous zooplankton represent a polyphyletic assemblage spanning >2,000 species that inhabit coastal seas to the deep-ocean and employ a wide variety of foraging strategies. Despite this diversity, many contemporary modelling approaches include jellyfish as a single functional group feeding at one or two trophic levels at most. Recent reviews have drawn attention to this issue and highlighted the need for improved communication between biologists and theoreticians if this problem is to be overcome. We used stable isotopes to investigate the trophic ecology of three co-occurring scyphozoan jellyfish species (Aurelia aurita, Cyanea lamarckii and C. capillata within a temperate, coastal food-web in the NE Atlantic. Using information on individual size, time of year and δ13C and δ15N stable isotope values, we examined: (1 whether all jellyfish could be considered as a single functional group, or showed distinct inter-specific differences in trophic ecology; (2 Were size-based shifts in trophic position, found previously in A. aurita, a common trait across species?; (3 When considered collectively, did the trophic position of three sympatric species remain constant over time? Differences in δ15N (trophic position were evident between all three species, with size-based and temporal shifts in δ15N apparent in A. aurita and C. capillata. The isotopic niche width for all species combined increased throughout the season, reflecting temporal shifts in trophic position and seasonal succession in these gelatinous species. Taken together, these findings support previous

  19. Not all jellyfish are equal: isotopic evidence for inter- and intraspecific variation in jellyfish trophic ecology.

    Fleming, Nicholas E C; Harrod, Chris; Newton, Jason; Houghton, Jonathan D R


    Jellyfish are highly topical within studies of pelagic food-webs and there is a growing realisation that their role is more complex than once thought. Efforts being made to include jellyfish within fisheries and ecosystem models are an important step forward, but our present understanding of their underlying trophic ecology can lead to their oversimplification in these models. Gelatinous zooplankton represent a polyphyletic assemblage spanning >2,000 species that inhabit coastal seas to the deep-ocean and employ a wide variety of foraging strategies. Despite this diversity, many contemporary modelling approaches include jellyfish as a single functional group feeding at one or two trophic levels at most. Recent reviews have drawn attention to this issue and highlighted the need for improved communication between biologists and theoreticians if this problem is to be overcome. We used stable isotopes to investigate the trophic ecology of three co-occurring scyphozoan jellyfish species (Aurelia aurita, Cyanea lamarckii and C. capillata) within a temperate, coastal food-web in the NE Atlantic. Using information on individual size, time of year and δ (13)C and δ (15)N stable isotope values, we examined: (1) whether all jellyfish could be considered as a single functional group, or showed distinct inter-specific differences in trophic ecology; (2) Were size-based shifts in trophic position, found previously in A. aurita, a common trait across species?; (3) When considered collectively, did the trophic position of three sympatric species remain constant over time? Differences in δ (15)N (trophic position) were evident between all three species, with size-based and temporal shifts in δ (15)N apparent in A. aurita and C. capillata. The isotopic niche width for all species combined increased throughout the season, reflecting temporal shifts in trophic position and seasonal succession in these gelatinous species. Taken together, these findings support previous assertions

  20. Intercontinental correlation of organic carbon and carbonate stable isotope records: evidence of climate and sea-evel change during the Turonian (Cretaceous)

    Jarvis, I.; Trabucho-Alexandre, J.; Gröcke, D. R.; Uličný, David; Laurin, Jiří


    Roč. 1, č. 2 (2015), s. 53-90 ISSN 2055-4877 R&D Projects: GA ČR GAP210/10/1991; GA MŠk LH12041 Institutional support: RVO:67985530 Keywords : carbon isotopes * chemostratigraphy * climate change * Cretaceous * oxygen isotopes Subject RIV: DB - Geology ; Mineralogy

  1. An experimental study on the effect of carbonic anhydrase on the oxygen isotope exchange kinetics and equilibrium in the carbonic acid system

    Uchikawa, J.; Zeebe, R. E.


    Stable oxygen isotopes of marine biogenic carbonates are often depleted in 18O relative to the values expected for thermodynamic equilibrium with ambient seawater. One possibility is that 18O-depletion in carbonates is kinetically controlled. The kinetic isotope effect associated with the hydration of CO2 results in 18O-depleted HCO3-. If the HCO3- is utilized before re-establishing equilibrium with ambient water under rapid calcification, the 18O-depletion will be recorded in carbonates. But one caveat in this kinetic model is the fact that many marine calcifiers posses carbonic anhydrase, a zinc-bearing enzyme that catalyzes the CO2 hydration reaction. It is expected that this enzyme accelerates 18O-equilibration in the carbonic acid system by facilitating direct oxygen isotope exchange between HCO3- and H2O via CO2 hydration. Clearly this argues against the conceptual framework of the kinetic model. Yet the critical variable here is the effectiveness of the carbonic anhydrase, which is likely to depend on its concentration and the carbonate chemistry of the aqueous medium. It is also hitherto unknown whether the presence of carbonic anhydrase alters the equilibrium oxygen isotope fractionations between dissolved carbonate species and water. We performed a series of quantitative inorganic carbonate precipitation experiments to examine the changes in the oxygen isotope equilibration time as a function of carbonic anhydrase concentrations. We conducted experiments at pH 8.3 and 8.9. These pH values are similar to the average surface ocean pH and the elevated pH levels observed within calcification microenvironments of certain corals and planktonic foraminifera. A summary of our new experimental results will be presented.

  2. Photo-neutron cross sections for unstable neutron-rich oxygen isotopes

    Leistenschneider, A.; Aumann, T.; Boretzky, K.


    The dipole response of stable and unstable neutron-rich oxygen nuclei of masses A = 17 to A = 22 has been investigated experimentally utilizing electromagnetic excitation in heavy-ion collisions at beam energies around 600 MeV/nucleon. A kinematically complete measurement of the neutron decay channel in inelastic scattering of the secondary beam projectiles from a Pb target was performed. Differential electromagnetic excitation cross sections dσ/dE were derived up to 30 MeV excitation energy. In contrast to stable nuclei, the deduced dipole strength distribution appears to be strongly fragmented and systematically exhibits a considerable fraction of low-lying strength, exhausting up to 12% of the energy-weighted dipole sum rule at excitation energies below 15 MeV. (orig.)

  3. 100,000-year-long terrestrial record of millennial-scale linkage between eastern North American mid-latitude paleovegetation shifts and Greenland ice-core oxygen isotope trends

    Litwin, Ronald J.; Smoot, Joseph P.; Pavich, Milan J.; Markewich, Helaine Walsh; Brook, George; Durika, Nancy J.


    We document frequent, rapid, strong, millennial-scale paleovegetation shifts throughout the late Pleistocene, within a 100,000+ yr interval (~ 115–15 ka) of terrestrial sediments from the mid-Atlantic Region (MAR) of North America. High-resolution analyses of fossil pollen from one core locality revealed a continuously shifting sequence of thermally dependent forest assemblages, ranging between two endmembers: subtropical oak-tupelo-bald cypress-gum forest and high boreal spruce-pine forest. Sedimentary textural evidence indicates fluvial, paludal, and loess deposition, and paleosol formation, representing sequential freshwater to subaerial environments in which this record was deposited. Its total age"depth model, based on radiocarbon and optically stimulated luminescence ages, ranges from terrestrial oxygen isotope stages (OIS) 6 to 1. The particular core sub-interval presented here is correlative in trend and timing to that portion of the oxygen isotope sequence common among several Greenland ice cores: interstades GI2 to GI24 (≈ OIS2–5 d). This site thus provides the first evidence for an essentially complete series of "Dansgaard"Oeschger" climate events in the MAR. These data reveal that the ~ 100,000 yr preceding the Late Glacial and Holocene in the MAR of North America were characterized by frequently and dynamically changing climate states, and by vegetation shifts that closely tracked the Greenland paleoclimate sequence.

  4. Understanding the Burial and Migration Characteristics of Deep Geothermal Water Using Hydrogen, Oxygen, and Inorganic Carbon Isotopes

    Xinyi Wang


    Full Text Available Geothermal water samples taken from deep aquifers within the city of Kaifeng at depths between 800 and 1650 m were analyzed for conventional water chemical compositions and stable isotopes. These results were then combined with the deuterium excess parameter (d value, and the contribution ratios of different carbon sources were calculated along with distributional characteristics and data on the migration and transformation of geothermal water. These results included the conventional water chemical group, hydrogen, and oxygen isotopes (δD-δ18O, dissolved inorganic carbon (DIC and associated isotopes (δ13CDIC. The results of this study show that geothermal water in the city of Kaifeng is weakly alkaline, water chemistry mostly comprises a HCO3-Na type, and the range of variation of δD is between −76.12‰ and −70.48‰, (average: −74.25‰, while the range of variation of δ18O is between −11.08‰ and −9.41‰ (average: −10.15‰. Data show that values of d vary between 1.3‰ and 13.3‰ (average: 6.91‰, while DIC content is between 91.523 and 156.969 mg/L (average: 127.158 mg/L. The recorded range of δ13CDIC was between −10.160‰ and −6.386‰ (average: −9.019‰. The results presented in this study show that as depth increases, so do δD and δ18O, while d values decrease and DIC content and δ13CDIC gradually increase. Thus, δD, δ18O, d values, DIC, and δ13CDIC can all be used as proxies for the burial characteristics of geothermal water. Because data show that the changes in d values and DIC content are larger along the direction of geothermal water flow, so these proxies can be used to indicate migration. This study also shows demonstrates that the main source of DIC in geothermal water is CO2thathas a biological origin in soils, as well as the dissolution of carbonate minerals in surrounding rocks. Thus, as depth increases, the contribution of soil biogenic carbon sources to DIC decreases while the influence

  5. Source identification of N2O produced during simulated wastewater treatment under different oxygen conditions using stable isotopic analysis

    T Azzaya


    Full Text Available Nitrous oxide (N2O, a potent greenhouse gas which is important in climate change, is predicted to be the most dominant ozone depleting substance. It is mainly produced by oxidation of hydroxylamine (NH2OH or reduction of nitrite (NO2- during microbiological processes such as nitrification and denitrification. Wastewater treatment plant (WWTP is one of the anthropogenic N2O sources because inorganic and organic nitrogen compounds are converted to nitrate (NO3-, in the case of standard system or N2 (in the case of advanced system by bacterial nitrification and denitrification in WWTP. We investigated the N2O production mechanisms during batch experiments that simulate wastewater treatment with activated sludge under various dissolved oxygen (DO concentrations by stable isotope analysis. About 125mL of water was sampled from 30L incubation chamber for several times during the incubation, and concentration and isotopomer ratios of N2O and N-containing species were measured using gas chromatography/isotope ratio mass spectrometry (GC/IRMS. Ammonium (NH4+ consumption was accompanied by increment of nitrite (NO2-, and at the same time dissolved N2O concentration gradually increased to 4850 and 5650 nmol kg-1, respectively, during the four-hour incubation when DO concentrations were 0.2 and 0.5 mg L-1. Observed low SP values (0.2-8.9‰ at DO-0.2 mg L-1, -5.3-6.3‰ at DO-0.5 mg L-1, -1.0-8.3‰ at DO-0.8 mg L-1 in N2O and relationship of nitrogen isotope ratios between N2O and its potential substrates (NH4+, NO3- suggested that N2O produced under the aerobic condition derived mainly from NO2- reduction by ammonia-oxidizing bacteria (nitrifier–denitrification.DOI: Journal of Chemistry  15 (41, 2014, p4-10  

  6. Isotopic evidence for the infiltration of mantle and metamorphic CO2-H2O fluids from below in faulted rocks from the San Andreas Fault System

    Pili, E.; Kennedy, B.M.; Conrad, M.E.; Gratier, J.-P.


    To characterize the origin of the fluids involved in the San Andreas Fault (SAF) system, we carried out an isotope study of exhumed faulted rocks from deformation zones, vein fillings and their hosts and the fluid inclusions associated with these materials. Samples were collected from segments along the SAF system selected to provide a depth profile from upper to lower crust. In all, 75 samples from various structures and lithologies from 13 localities were analyzed for noble gas, carbon, and oxygen isotope compositions. Fluid inclusions exhibit helium isotope ratios ({sup 3}He/{sup 4}He) of 0.1-2.5 times the ratio in air, indicating that past fluids percolating through the SAF system contained mantle helium contributions of at least 35%, similar to what has been measured in present-day ground waters associated with the fault (Kennedy et al., 1997). Calcite is the predominant vein mineral and is a common accessory mineral in deformation zones. A systematic variation of C- and O-isotope compositions of carbonates from veins, deformation zones and their hosts suggests percolation by external fluids of similar compositions and origin with the amount of fluid infiltration increasing from host rocks to vein to deformation zones. The isotopic trend observed for carbonates in veins and deformation zones follows that shown by carbonates in host limestones, marbles, and other host rocks, increasing with increasing contribution of deep metamorphic crustal volatiles. At each crustal level, the composition of the infiltrating fluids is thus buffered by deeper metamorphic sources. A negative correlation between calcite {delta}{sup 13}C and fluid inclusion {sup 3}He/{sup 4}He is consistent with a mantle origin for a fraction of the infiltrating CO{sub 2}. Noble gas and stable isotope systematics show consistent evidence for the involvement of mantle-derived fluids combined with infiltration of deep metamorphic H{sub 2}O and CO{sub 2} in faulting, supporting the involvement of

  7. Identification of Groundwater Nitrate Contamination from Explosives Used in Road Construction: Isotopic, Chemical, and Hydrologic Evidence.

    Degnan, James R; Böhlke, J K; Pelham, Krystle; Langlais, David M; Walsh, Gregory J


    Explosives used in construction have been implicated as sources of NO3(-) contamination in groundwater, but direct forensic evidence is limited. Identification of blasting-related NO3(-) can be complicated by other NO3(-) sources, including agriculture and wastewater disposal, and by hydrogeologic factors affecting NO3(-) transport and stability. Here we describe a study that used hydrogeology, chemistry, stable isotopes, and mass balance calculations to evaluate groundwater NO3(-) sources and transport in areas surrounding a highway construction site with documented blasting in New Hampshire. Results indicate various groundwater responses to contamination: (1) rapid breakthrough and flushing of synthetic NO3(-) (low δ(15)N, high δ(18)O) from dissolution of unexploded NH4NO3 blasting agents in oxic groundwater; (2) delayed and reduced breakthrough of synthetic NO3(-) subjected to partial denitrification (high δ(15)N, high δ(18)O); (3) relatively persistent concentrations of blasting-related biogenic NO3(-) derived from nitrification of NH4(+) (low δ(15)N, low δ(18)O); and (4) stable but spatially variable biogenic NO3(-) concentrations, consistent with recharge from septic systems (high δ(15)N, low δ(18)O), variably affected by denitrification. Source characteristics of denitrified samples were reconstructed from dissolved-gas data (Ar, N2) and isotopic fractionation trends associated with denitrification (Δδ(15)N/Δδ(18)O ≈ 1.31). Methods and data from this study are expected to be applicable in studies of other aquifers affected by explosives used in construction.

  8. No evidence of reduced collectivity in Coulomb-excited Sn isotopes

    Kumar, R.; Saxena, M.; Doornenbal, P.; Jhingan, A.; Banerjee, A.; Bhowmik, R. K.; Dutt, S.; Garg, R.; Joshi, C.; Mishra, V.; Napiorkowski, P. J.; Prajapati, S.; Söderström, P.-A.; Kumar, N.; Wollersheim, H.-J.


    In a series of Coulomb excitation experiments the first excited 2+ states in semimagic Sn 112 ,116 ,118 ,120 ,122 ,124 isotopes were excited using a 58Ni beam at safe Coulomb energy. The B (E 2 ; 0+→2+) values were determined with high precision (˜3 %) relative to 58Ni projectile excitation. These results disagree with previously reported B (E 2 ↑) values [A. Jungclaus et al., Phys. Lett. B 695, 110 (2011)., 10.1016/j.physletb.2010.11.012] extracted from Doppler-shift attenuation lifetime measurements, whereas the reported mass dependence of B (E 2 ↑) values is very similar to a recent Coulomb excitation study [J. M. Allmond et al., Phys. Rev. C 92, 041303(R) (2015), 10.1103/PhysRevC.92.041303]. The stable Sn isotopes, key nuclei in nuclear structure, show no evidence of reduced collectivity and we, thus, reconfirm the nonsymmetric behavior of reduced transition probabilities with respect to the midshell A =116 .