Electronic isotope shifts, muonic atoms, and electron scattering

International Nuclear Information System (INIS)

Shera, E.B.

1982-01-01

The roles of electronic isotope shift, muonic atom, and electron scattering experiments in studying the nuclear charge distribution are discussed in terms of the potentials of each probe. Barium isotope shift data are presented as an example of a combined muonic-optical analysis and the results are compared with droplet and IBA model predictions. A survey of muonic and (e,e) results is presented with emphasis on shell-structure related features

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

Science.gov (United States)

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

2011-03-04

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.

Isotope shift of 234U, 236U, 238U in U I

International Nuclear Information System (INIS)

Gagne, J.M.; Nguyen Van, S.; Saint-Dizier, J.P.; Pianarosa, P.

1976-01-01

New and very accurate data of isotope shifts and relative isotope shifts in 234 U, 236 U, 238 U are presented. The invariance of the relative isotope shift, for the transitions we have investigated, supports the hypothesis that the so called specific mass effect is negligible in uranium

Oxygen isotopic anomalies in Allende inclusion HAL

International Nuclear Information System (INIS)

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

1980-01-01

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

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

International Nuclear Information System (INIS)

2009-01-01

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

Carbon and Oxygen isotopic composition in paleoenvironmental determination

International Nuclear Information System (INIS)

Silva, J.R.M. da.

1978-01-01

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

Major events in Neogene oxygen isotopic records

International Nuclear Information System (INIS)

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

1986-01-01

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

Isotope effect on the zero point energy shift upon condensation

International Nuclear Information System (INIS)

Kornblum, Z.C.; Ishida, T.

1977-07-01

The various isotope-dependent and independent atomic and molecular properties that pertain to the isotopic difference between the zero point energy (ZPE) shifts upon condensation were derived. The theoretical development of the change of the ZPE associated with the internal molecular vibrations, due to the condensation of the gaseous molecules, is presented on the basis of Wolfsberg's second-order perturbation treatment of the isotope-dependent London dispersion forces between liquid molecules. The isotope effect on the ZPE shift is related to the difference between the sums of the integrated intensities of the infrared absorption bands of the two gaseous isotopic molecules. The effective atomic charges are also calculated from available experimental infrared intensity data. The effects of isotopic substitutions of carbon-13 for carbon-12 and/or deuterium for protium, in ethylene, methane, and the fluorinated methanes, CH 3 F, CH 2 F 2 , CHF 3 , and CF 4 , on the ZPE shift upon condensation are calculated. These results compare well with the Bigeleisen B-factors, which are experimentally obtained from vapor pressure measurements of the isotopic species. Each of the following molecular properties will tend to increase the isotopic difference between the ZPE shifts upon condensation: (1) large number of highly polar bonds, (2) high molecular weight, (3) non-polar (preferably) or massive molecule, (4) non-hydrogenous molecule, and (5) closely packed liquid molecules. These properties will result in stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules. 36 tables, 9 figures

Constraining new physics models with isotope shift spectroscopy

Science.gov (United States)

Frugiuele, Claudia; Fuchs, Elina; Perez, Gilad; Schlaffer, Matthias

2017-07-01

Isotope shifts of transition frequencies in atoms constrain generic long- and intermediate-range interactions. We focus on new physics scenarios that can be most strongly constrained by King linearity violation such as models with B -L vector bosons, the Higgs portal, and chameleon models. With the anticipated precision, King linearity violation has the potential to set the strongest laboratory bounds on these models in some regions of parameter space. Furthermore, we show that this method can probe the couplings relevant for the protophobic interpretation of the recently reported Be anomaly. We extend the formalism to include an arbitrary number of transitions and isotope pairs and fit the new physics coupling to the currently available isotope shift measurements.

Hyperfine structure and isotope shift of the neutron-rich barium isotopes 139-146Ba and 148Ba

International Nuclear Information System (INIS)

Wendt, K.; Ahmad, S.A.; Klempt, W.; Neugart, R.; Otten, E.W.

1988-01-01

The hyperfine structure and isotope shift in the 6s 2 S 1/2 -6p 2 P 3/2 line of Ba II (455.4 nm) have been measured by collinear fast-beam laser spectroscopy for the neutron-rich isotopes 139-146 Ba and 148 Ba. Nuclear moments and mean square charge radii of these isotopes have been recalculated. The isotope shift of the isotope 148 Ba (T 1/2 = 0.64 s) could be studied for the first time, yielding δ 2 > 138,148 = 1.245(3) fm 2 . (orig.)

Isotope effect on the zero point energy shift upon condensation

International Nuclear Information System (INIS)

Kornblum, Z.C.

1977-01-01

The various isotope-dependent and independent atomic and molecular properties that pertain to the isotopic difference between the zero point energy (ZPE) shifts upon condensation have been derived. The theoretical development of the change of the ZPE associated with the internal molecular vibrations, due to the condensation of the gaseous molecules, has been presented on the basis of Wolfsberg's second-order perturbation treatment of the isotope-dependent London dispersion forces between liquid molecules. The isotope effect on the ZPE shift is related to the difference between the sums of the integrated intensities of the infrared absorption bands of the two gaseous isotopic molecules. Each intensity sum is expressed, in part, in terms of partial derivatives of the molecular dipole moment with respect to atomic cartesian coordinates. These derivatives are related to the isotope-independent effective charges of the atoms, which are theoretically calculated by means of a modified CNDO/2 computer program. The effective atomic charges are also calculated from available experimental infrared intensity data. The effects of isotopic substitutions of carbon-13 for carbon-12 and/or deuterium for protium, in ethylene, methane, and the fluorinated methanes, CH 3 F, CH 2 F 2 , CHF 3 , and CF 4 , on the ZPE shift upon condensation are calculated. These results compare well with the Bigeleisen B-factors, which are experimentally obtained from vapor pressure measurements of the isotopic species. Each of the following molecular properties will tend to increase the isotopic difference between the ZPE shifts upon condensation: (1) large number of highly polar bonds, (2) high molecular weight, (3) non-polar (preferably) or massive molecule, (4) non-hydrogenous molecule, and (5) closely packed liquid molecules. These properties will result in stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules

Isotope shift studies in gadolinium spectra

International Nuclear Information System (INIS)

Ahmad, S.A.; Saksena, G.D.; Venugopalan, A.

1975-01-01

Isotope shift studies have been carried out in the gadolinium spectrum using a recording Fabry-Perot spectrometer and gadolinium samples enriched in 156 Gd and 160 Gd isotopes. The source used is a liquid-nitrogen-cooled hollow cathode with Ne as the carrier gas and operating at about 30 mA. Isotope shifts Δsigma (156-160) have been recorded in 350 transitions of Gd I and Gd II. In the case of the Gd I spectrum, the transitions studied presently involve almost all the reported configurations assigned to the energy levels of Gd I. The odd configurations are 4f 7 5d6s 2 , 4f 7 5d 2 6s, 4f 7 5d 3 , 4f 8 6s6p, 4f 7 5d6s7s and 4f 7 6s 2 6p, and the even ones are 4f 8 6s 2 , 4f 7 5d6s6p, 4f 7 6s 2 6p, 4f 8 5d6s and 4f 7 5d 2 6p. In the case of the Gd II spectrum isotope shifts in the lines of the newly classified transition 4f 8 6s - 4f 8 6p have been studied and isotope shift ΔT (156-160) 87 mK has been obtained for the 4f 8 6s configuration. The other transitions of Gd II involve the odd configurations 4f 7 5d6s, 4f 7 6s 2 , 4f 7 5d 2 and 4f 8 6p and the even ones 4f 7 6s6p, 4f 8 5d, 4f 7 5d6p and 4f 8 6p. The ΔT (156-160) of a large number of odd and even levels of Gd I and Gd II have been evaluated. Electronic configurations have been suggested for a number of energy levels and configuration mixing has been pointed out in certain cases. A number of hitherto unreported transitions have been found and using a monoisotopic sample of Gd, that is 160 Gd, their separations from the closest listed transitions have been measured. (author)

Rate of oxygen isotope exchange between selenate and water.

Science.gov (United States)

Kaneko, Masanori; Poulson, Simon R

2012-04-17

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.

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

International Nuclear Information System (INIS)

Yakir, D.; DeNiro, M.J.

1990-01-01

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

Normalization of oxygen and hydrogen isotope data

Science.gov (United States)

Coplen, T.B.

1988-01-01

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.

Isotope effect in the Knight shift of potassium

International Nuclear Information System (INIS)

Sahm, W.; Schwenk, A.

1975-01-01

The Knight shifts of the potassium isotopes 39 K and 41 K were determined with high accuracy: Ksup((39)) = 0.274 35(10)% and Ksup((41)) = 0.274 93(12)%. The relative isotope effect ΔK/K = -0.210 (20)% is in agreement with the hyperfine structure anomaly 39 Δ 41 . (orig.) [de

Stable Oxygen-18 and Deuterium Isotopes

DEFF Research Database (Denmark)

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...

Combined stable isotope trajectories for water-rock interaction

International Nuclear Information System (INIS)

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

1981-01-01

The 'mixed' model of water-rock interaction (1980 Workshop) is explained in detail. Based on the magnitude of the oxygen isotope shifts of their recharge water, different geothermal systems can be placed in an evolutionary series, from incipient (large shift of water) to mature (small shift of water). Isotopes of different chemical elements may be combined, to yield a stringent test of whether or not a given change in rock composition may be ascribed to interaction with water (L-shaped trajectories). For the acidic eruptives of the Taupo Volcanic Zone, available strontium and oxygen isotope data practically rule out an origin by partial melting of greywacke basement

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

Science.gov (United States)

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

2012-10-01

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

Measurement of isotope shift of recycled uranium by laser induced fluorescence spectroscopy

International Nuclear Information System (INIS)

Oba, Masaki; Wakaida, Ikuo; Akaoka, Katsuaki; Miyabe, Masabumi

1999-07-01

Isotope shift of the recycled uranium atoms including the 236 U was measured by laser induced fluorescence method. Eight even levels at 2 eV and three odd levels at 4 eV were measured with isotope shifts among 238 U, 236 U and 235 U obtained. As for the measurement of the 4 eV levels, the Doppler free two photon absorption method was used, and the hyperfine structure of the 235 U was analyzed simultaneously. The isotope shift of 234 U was also observed in the three transition. (J.P.N.)

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

Science.gov (United States)

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

2007-12-01

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.

OXYGEN ISOTOPIC COMPOSITIONS OF SOLAR CORUNDUM GRAINS

International Nuclear Information System (INIS)

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

2009-01-01

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 �

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

Energy Technology Data Exchange (ETDEWEB)

Borysiuk, Maciek, E-mail: maciek.borysiuk@pixe.lth.se; Kristiansson, Per; Ros, Linus; Abdel, Nassem S.; Elfman, Mikael; Nilsson, Charlotta; Pallon, Jan

2015-04-01

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.

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

Science.gov (United States)

Price, Gregory; Grimes, Stephen

2015-04-01

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.

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

Science.gov (United States)

Michael, Dimitra-Ermioni; Dotsika, Elissavet

2017-12-01

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.

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

Science.gov (United States)

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

2002-12-01

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

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

Directory of Open Access Journals (Sweden)

Brooke eCrowley

2015-11-01

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.

The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

Science.gov (United States)

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

2014-01-01

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.

Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

International Nuclear Information System (INIS)

Sato, S.

1987-01-01

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

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

DEFF Research Database (Denmark)

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

2013-01-01

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...

Oxygen isotope fractionation in uranium oxides

International Nuclear Information System (INIS)

Zheng Yongfei

1995-01-01

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

Bulk Oxygen Isotopic Composition of Ultracarbonaceous Antarctic Micrometeorites with the NanoSIMS

Science.gov (United States)

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

2014-09-01

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.

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

Science.gov (United States)

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

2008-12-01

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

Oxygen isotope exchange on palladium catalysts

International Nuclear Information System (INIS)

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

1983-01-01

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

Isotopic shifts and configuration mixing in the dysprosium II spectrum

International Nuclear Information System (INIS)

Aufmuth, P.

1977-01-01

Using a photoelectric Fabry-Perot spectrometer with digital data acquisition, the isotopic shifts of all stable dysprosium isotopes (Z = 66, A = 156, 158, 160, 161, 162, 163, 164) have been measured in transitions from the groundstate configuration 4f 10 6s to the excited configurations 4f 9 5d6s, 4f 9 5d 2 , and 4f 10 6p of the spark spectrum. Mass and volume effects have been seperated; the results are compared with arc spectrum measurements. From the volume effect of a pure s-p transition the change of the mean electric quadratic nuclear radius delta 2 > has been calculated. In order to test fine structure calculations of the Dy II spectrum, the isotopic shifts of 29 lines of the isotopes 162 Dy and 164 Dy have been measured. Based on the sharing rule, the reported configuration mixing could be confirmed in principle; for one energy level (E = 22908 K) the asignement has been proved to be false, in the case of three other levels (E = 22467, 22672, and 28885 K) the asignement is doubtfull. For the ground state levels 4f 10 6s 6 I the influence of relativistic effects could be proved; these effects can be interpreted in the framework of a parametric representation of the isotopic shift. The order of magnitude of the crossed second order effects has been estimated. (orig.) [de

Analytical techniques for determination of framework oxygen isotope ratio of wairakite

International Nuclear Information System (INIS)

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

1990-01-01

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)

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

Science.gov (United States)

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

2018-04-01

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

Spectroscopic measurement of 204Pb isotope shift and 205Pb nuclear spin

International Nuclear Information System (INIS)

Schonberger, P.

1984-01-01

The isotope shift of 204 Pb and the nuclear spin of 1.4 X 10 7 -y 205 Pb was determined from a high-resolution optical measurement of the 6p 23 P 0 -6p7s 3 P 1 0 283.3-nm resonance line. The value of the shift, relative to 208 Pb is -140.2(8) x 10 -3 cm -1 , the negative sign indicating a shift to lower wave numbers. The precision is 3-4 times greater than that of previous measurements. The spin of 205 Pb I = 5/2 was obtained from the measurement of the relative intensities of its three hyperfine components. This method of absorption spectroscopy determination of ground state nuclear spin is applicable to any stable or long-lived isotope. High resolution optical absorption spectra were obtained with a 25.4 cm diffraction grating in a 9.1 m focal length Czerny-Turner spectrometer. A signal-averaging scanning technique was used to record the spectra. Increased precision in the isotope shift measurement was attained by using separated isotope samples of 204 Pb and 207 Pb

2H isotope effect on 13C chemical shifts of Nitro-Benzo-9-Crown-3

International Nuclear Information System (INIS)

Moghimi, A.; Rastegar, M.; Ghandi, M.; Bijanzadeh, H. R.

2002-01-01

Deuterium substitution on two ortho-substituted-OCH 2 fragments in Nitro-Benzo-9 Crown-3 induces low frequency shifts, positive m ''nΔC j, in all 13 C NMR resonances which is an indication of the increased shielding in this crown ether. The magnitude of these shifts vary from 15 ΔC 7=716 to 54 ΔC 3=15 ppb for C 7 and C 3 carbons directly attached to 2 H, respectively. The influences of concentration and solvent, CDCl 3 CD 3 COCD 3 , and C 6 D 6 , on mn ΔC j values were investigated. The mn ΔC j values depended more on the nature of the solvent than on the concentration. The order of induced isotope shifts is 15 Δ, 51 Δ > 24 Δ, 42 Δ> 34 Δ, 43 Δ > 56 Δ, 65 Δ> 45 Δ, 54 Δ. The isotope shifts observed are suggested to be a sum of contributions from low frequency shift due to inductive-type and negative hyperconjugation perturbations. The C-D bond, as a poorer electron acceptor than a C-H bond induced less positive charge on directly attached oxygens O 1 and O 2. This, in turn, causes shielding of C 1 and C 2 in C1O1CD 2 and C 2 0 2 CD 2 fragments. The difference in 34 ΔC 1 and 43 ΔC 2 values is attributed to the conformational dependence of the negative hyperconjugation. The C 1 and C 2, are in fact, not equally affected by the two CD 2 groups by negative hyperconjugation because of the existence of NO 2 group attached to the benzene ring

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

International Nuclear Information System (INIS)

Chiba, H.; Sakai, H.

1985-01-01

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)

Deuterium isotope effects on 13C chemical shifts of 10-Hydroxybenzo[h]quinolines

DEFF Research Database (Denmark)

Hansen, Poul Erik; Kamounah, Fadhil S.; Gryko, Daniel T.

2013-01-01

Deuterium isotope effects on 13C-NMR chemical shifts are investigated in a series of 10-hydroxybenzo[h]quinolines (HBQ’s) The OH proton is deuteriated. The isotope effects on 13C chemical shifts in these hydrogen bonded systems are rather unusual. The formal four-bond effects are found to be nega...

The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

Science.gov (United States)

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

2013-12-01

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

Isotope effects on chemical shifts in tautomeric systems with double proton transfer. Citronin

International Nuclear Information System (INIS)

Hansen, P.E.; Langgard, M.; Bolvig, S.

1998-01-01

Primary and secondary deuterium isotope effects on 1 H and 13 C chemical shifts are measured in citrinin, a tautomeric compound with an unusual doubly intramolecularly hydrogen bonded structure. The isotope effects are to a large extent dominated by equilibrium contributions and deuteration leads to more of the deuterated enol forms rather than the deuterated acid form. 1 H 13 C and 17 O nuclear shieldings are calculated using density functional ab initio methods. A very good correlation between calculated nuclear shieldings and experimental 1 H and 13 C chemical shifts is obtained. The tautomeric equilibrium can be analyzed based on the isotope effects on B-6 and C-8 carbons and shows an increase in the o-quinone form on lowering the temperature. Furthermore, upon deuteration the largest equilibrium shift is found for deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration is increasing at lower temperature. (author)

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

International Nuclear Information System (INIS)

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

1975-01-01

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)

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

Science.gov (United States)

Helliker, B.

2007-12-01

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

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

International Nuclear Information System (INIS)

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

1998-01-01

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)

Variations of nuclear charge radii in mercury isotopes with A = 198, 199, 200, 201, 202, and 204 from x-ray isotope shifts

International Nuclear Information System (INIS)

Lee, P.L.; Boehm, F.; Hahn, A.A.

1978-01-01

The isotope shifts of atomic K x rays were measured for pairs of the six mercury isotopes with A = 198, 199, 200, 201, 202, and 204, using a curved crystal spectrometer. The changes of the nuclear charge radii were derived in terms of delta 2 > and deltaR/sub k/ and compared with optical an muonic isotope shift data. From our results, a renormalization of the optical data was obtained

Combined oxygen- and carbon-isotope records through the Early Jurassic: multiple global events and two modes of carbon-cycle/temperature coupling

DEFF Research Database (Denmark)

Hesselbo, Stephen P.; Korte, Christoph

2010-01-01

, 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...

Oxygen isotopic signature of CO2 from combustion processes

Directory of Open Access Journals (Sweden)

W. A. Brand

2011-02-01

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

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

Science.gov (United States)

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

2012-09-30

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.

Biological fractionation of oxygen and carbon isotopes by recent benthic foraminifera

International Nuclear Information System (INIS)

Woodruff, F.; Douglas, R.G.

1980-01-01

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.)

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

Directory of Open Access Journals (Sweden)

Lisowska-Gaczorek Aleksandra

2017-03-01

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.

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

Science.gov (United States)

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

2017-08-01

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.

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

International Nuclear Information System (INIS)

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

1984-01-01

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)

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

OpenAIRE

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

2016-01-01

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...

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

OpenAIRE

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

2016-01-01

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...

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

Science.gov (United States)

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

2013-12-01

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.

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

International Nuclear Information System (INIS)

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

1998-01-01

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)

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

Science.gov (United States)

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

2015-12-01

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

Spectroscopic Measurement of LEAD-204 Isotope Shift and LEAD-205 Nuclear Spin.

Science.gov (United States)

Schonberger, Peter

The isotope shift of ('204)Pb and the nuclear spin of 1.4 x 10('7)-y ('205)Pb was determined from a high -resolution optical measurement of the 6p('2) ('3)P(,o) -6p7s('3)P(,1)('o) 283.3-nm resonance line. The value of the shift, relative to ('208)Pb is -140.2(8) x 10('-3)cm(' -1), the negative sign indicating a shift to lower wave numbers. The precision is 3-4 times greater than that of previous measurements. The spin of ('205)Pb l = 5/2 was obtained from the measurement of the relative intensities of its three hyperfine components. This method of absorption spectroscopy determination of ground state nuclear spin is applicable to any stable or longlived isotope. High resolution optical absorption spectra were obtained with a 25.4cm diffraction grating in a 9.1m focal length Czerny-Turner spectrometer. A signal-averaging scanning technique was used to record the spectra. Increased precision in the isotope shift measurement was attained by using separated isotope samples of ('204)Pb and ('207)Pb. A controlled amount of the later was incorporated in the absorption cell to provide internal calibration by its 6p7s ('3)P(,1)('o) hfs separation. Absorption spectra were recorded for several optical thicknesses of the absorber. A single spin value of increased precision was derived from the entire set of combined data.

Isotope shifts and hyperfine splittings in 144-154Sm I

International Nuclear Information System (INIS)

England, J.G.; Grant, I.S.; Newton, G.W.A.; Walker, P.M.

1990-01-01

The isotope shifts and hyperfine splittings have been measured in 144-154 Sm I using the crossed-beam laser fluorescence method. Transitions at 598.98 nm and 570.68 nm were investigated for all isotopes except 146 Sm and 153 Sm, in which measurements were only obtained at 570.68 nm. Laser-induced fluorescence has not previously been reported for 145 Sm. The magnetic dipole and electric quadrupole moments of the odd isotopes and the changes in mean square radii of the even ones are shown to be consistent with the information obtained from nuclear spectroscopy. (author)

Isotope shift studies in the spectra of gadolinium in UV region and term shifts of high even levels of Gd I

International Nuclear Information System (INIS)

Afzal, S.M.; Venugopalan, A.; Ahmad, S.A.

1997-01-01

Isotope shift Δσ( 156 Gd- 160 Gd) is reported in 70 spectral lines of neutral gadolinium atom (Gd I) in the 3290-3920 A region providing isotope shift data in UV lines of Gd I spectrum for the first time. The measurements were carried out on a photoelectric recording Fabry-Perot Spectrometer using highly enriched isotopic samples of gadolinium. Term isotope shifts ΔT( 156 Gd- 160 Gd) have been evaluated for 48 high lying even parity energy levels of Gd I using this data; new ΔT values have been obtained for 24 levels. Electronic configurations 4f 7 5d6s6p, 4f 7 5d 2 6p and 4f 8 5d6s assigned earlier to these even levels have been either confirmed or configuration mixing pointed out in some of these levels. Probable assignment of 4f 8 5d6s configuration to 8 even levels between 32930 and 35500 cm -1 have been confirmed. (orig.)

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

Science.gov (United States)

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

2013-04-01

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.

Nitrogen and Oxygen Isotopic Studies of the Marine Nitrogen Cycle.

Science.gov (United States)

Casciotti, Karen L

2016-01-01

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.

Stable isotopic mass balance in sandstone-shale couplets. An example from the Neogene Pannonian Basin

International Nuclear Information System (INIS)

Matyas, J.; Geologisches Institut.

1996-01-01

Oxygen isotopic ratios of carbonate cements in the Neogene sandstones of the Pannonian Basin show distinct variations: early calcites 3-6 per mille lighter than the late calcites from the same location and depth. This shift is thought to be related to the isotopically heavy oxygen released from the mixed-layer illite/smectite during illitisation. For sandstones dominated by compactional flow, closed system mass balance calculations predict an isotopic shift comparable to that deducted from petrographic and geochemical observations. The model suggests that variations of geothermal gradient has little effect on isotopic evolution; much more significant is the sandstone: shale ratio in the couplets. (author)

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

International Nuclear Information System (INIS)

Torquato, J.R.F.

1980-01-01

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

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

Science.gov (United States)

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

2015-01-06

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.

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

Science.gov (United States)

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

2011-02-01

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.

Optical isotope shifts of sup(80,82)Sr from coincidence laser spectroscopy

International Nuclear Information System (INIS)

Eastham, D.A.; Walker, P.M.; Smith, J.R.H.; Griffith, J.A.R.; Evans, D.E.; Wells, S.A.; Fawcett, M.J.; Grant, I.S.

1986-01-01

The isotope shifts of radioactive sup(80,82)Sr have been measured by a new, ultrasensitive, laser fluorescence technique. The results have been used to calculate changes in nuclear charge radii. The values, together with those of nearby stable isotopes, are discussed in terms of changes in the static and dynamic nuclear deformations. (author)

Oxygen isotope exchange in La2NiO(4±δ).

Science.gov (United States)

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

2016-04-07

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.

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

Science.gov (United States)

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

2011-01-01

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,

Effects of Water Vapor on the Data Quality of the Stable Oxygen Isotopic Ratio of Atmospheric Carbon Dioxide

Science.gov (United States)

Evans, C. U.; White, J. W.; Vaughn, B.; Tans, P. P.; Pardo, L.

2007-12-01

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

Chemical shifts of oxygen-17 NMR in polyoxotungstates

International Nuclear Information System (INIS)

Kazanskij, L.P.; Fedotov, M.A.; Spitsyn, V.I.

1977-01-01

17 O NMR spectra of aqueous solutions containing paratungstate BH 2 W 12 O 42 10- and metatungstate H 2 W 12 O 40 6- anions have been measured. On the basis of the obtained data a scale of chemical shifts for oxygen atoms connected by various bonds with tungsten atoms is suggested. The obtained data are compared with the Raman spectra of crystalline salts and their aqueous solutions. Chemical shifts of 17 O NMR spectra have been also measured in other heteropolyanions

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

International Nuclear Information System (INIS)

Longinelli, A.

1984-04-01

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

Isotope shifts in odd and even energy levels of the neutral and singly ionised gadolinium atom

International Nuclear Information System (INIS)

Ahmad, S.A.; Venugopalan, A.; Saksena, G.D.

1979-01-01

Isotope shift studies in the gadolinium spectra have been extended in the region 4140 to 4535 A. Isotope shift Δσ(156 to 160) have been measured in 315 lines of the neutral and singly ionised gadolinium atom using a recording Fabry-Perot Spectrometer and gadolinium samples enriched in 156 Gd and 160 Gd isotopes. Some of the Gd I lines studied involve transitions from newly identified high odd levels of 4f 8 6s6p, 4f 7 5d6s7s and 4f 7 5d 3 configurations to low even levels of 4f 8 6s 2 and 4f 7 6s 2 6p configurations. Electronic configurations of the energy levels have been discussed on the basis of observed isotope shifts. In some cases assigned configurations have been revised and probable configurations have been suggested. (author)

Exploring Neutron-Rich Oxygen Isotopes with MoNA

International Nuclear Information System (INIS)

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.

2007-01-01

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

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

Science.gov (United States)

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

2017-10-01

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

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

Science.gov (United States)

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

2009-12-01

Bacterial reduction of dissolved sulfate (BSR) is a key process determining the natural attenuation in many contaminated aquifers. For example, in groundwater bodies affected by acid mine drainage (AMD) BSR reduces the contaminant load by producing alkalinity and facilitating a sustainable fixation of sulfur in the sediment. In aquifers contaminated with petroleum hydrocarbons sulfate may act as a terminal electron acceptor for the anaerobic oxidation of the organic contaminants to carbon dioxide and water. Due to the isotope selectivity of sulfate reducing bacteria, BSR shows the most pronounced isotope fractionation within the sulfur cycle. While sulfur displays a straightforward kinetic enrichment in the residual sulfate described by the enrichment factor epsilon (ɛ), the mechanism of oxygen isotope fractionation is still being discussed controversially. Nevertheless, it is agreed on that oxygen isotope exchange between ambient water and residual sulfate occurs during BSR in natural environments. With respect to this potential isotope exchange, the fractionation parameter theta (θ) is introduced instead of the kinetic enrichment factor epsilon (ɛ). The dual isotope system considering both sulfate-sulfur and sulfate-oxygen isotope fractionation and the respective fractionation parameters ɛ and θ provides an excellent tool for the recognition and quantification of BSR. Beyond that, the dual isotope approach may help identify and estimate interfering sulfur transformations such as re-oxidation and disproportionation processes which is especially vital for the understanding of the overall natural attenuation potential of the investigated aquifers. We present two examples from different field studies showing the benefits of applying the combination of sulfur and oxygen isotopes in dissolved sulfate to reveal the details of the sulfur cycle. The first case study is concerned with the evaluation of the potential for BSR in an AMD-affected aquifer close to an

Carbon and oxygen isotope compositions of the carbonate facies

Indian Academy of Sciences (India)

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 ...

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

International Nuclear Information System (INIS)

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

1999-01-01

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

THz spectroscopy of the 29 cm{sup -1} oxygen vibrational line in natural silicon and isotopically enriched {sup 28}Si

Energy Technology Data Exchange (ETDEWEB)

Lassmann, Kurt; Dressel, Martin [1. Physikalisches Inst., Univ. Stuttgart (Germany); Gorshunov, Boris; Zhukova, E.S. [1. Physikalisches Inst., Univ. Stuttgart (Germany); A.M. Prokhorov Gen. Phys. Inst., RAS, Moscow (Russian Federation); Moscow Inst. Physics and Technology (Russian Federation); Korolev, P.S. [A.M. Prokhorov Gen. Phys. Inst., RAS, Moscow (Russian Federation); Lomonosov Moscow State Univ. (Russian Federation); Kalinsuhkin, V.P. [A.M. Prokhorov Gen. Phys. Inst., RAS, Moscow (Russian Federation); Abrosimov, N.V. [Leibniz Inst. Kristallzuechtung, Berlin (Germany); Sennikov, P.G. [Inst. Chem. High-Purity Substances, Nizhny Novgorod (Russian Federation); Pohl, H.J. [PTB, Braunschweig (Germany); Zakel, S. [VITCON-Projektconsult, Jena (Germany)

2012-07-01

Looking for a possible host-isotope effect on the low-energy two-dimensional motion of interstitial oxygen in silicon we have measured the resonance parameters of the lowest transition of the 30 cm{sup -1} band of the Si-O-Si complex in natural Si and in isotopically enriched {sup 28}Si at temperatures between 5 K and 22 K by means of coherent-source terahertz spectroscopy. At 5.5 K we obtain for the resonance maxima 29.24 {+-} 0.003 cm{sup -1} and 29.22 {+-} 0.003 cm{sup -1} and for the line widths 0.09 {+-} 0.01 cm{sup -1} and 0.11 {+-} 0.01 cm{sup -1} for {sup 28}Si and {sup nat}Si, respectively. Both lines can be fitted by single Lorentzians, so, no obvious isotopic structure or asymmetry of the line in {sup nat}Si due to the Si neighbors in the Si-O-Si complex is detected. We therefore conclude that down-shift and broadening of the {sup nat}Si-resonance is not due to the Si isotopes in the isolated Si-O-Si complex but to an average effect of the isotopically inhomogeneous lattice.

Isotope effect on the zero point energy shift upon condensation. I. Formulation and application to ethylene, methane, and fluoromethanes

International Nuclear Information System (INIS)

Kornblum, Z.C.; Ishida, T.

1978-01-01

A method of evaluating the isotope effect (IE) on the zero point energy (ZPE) shift upon condensation due to the London dispersion forces in the liquid has been formulated. It is expressed to the first order, as a product of an isotope-independent liquid factor and a factor of isotopic differences in gas-phase properties. The theory has been tested by calculating the effective atomic charges for carbon and hydrogen in ethylene, according to the CNDO/2 molecular orbital algorithm, and it correctly predicts the magnitude of the IE on the ZPE shift and the first-order sum rules involving the isotopic ethylenes. However, it fails to explain the difference in vapor pressures of isotopic isomers. The theory has also been applied to the D/H and to the 13 C/ 12 C isotope effects in methane and fluoromethanes. The results obtained from the CNDO/2 calculations have been compared with the experimental values of the total infrared absorption intensities and of the IE on the ZPE shift of isotopic methanes. Based on these calculations, the molecular properties that enhance the stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules, and hence favor a large IE on the ZPE shift, have been deduced

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

International Nuclear Information System (INIS)

Buchardt, B.; Hansen, H.J.

1977-01-01

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)

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

Energy Technology Data Exchange (ETDEWEB)

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

1977-01-01

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.

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

Directory of Open Access Journals (Sweden)

J. Savarino

2007-01-01

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

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

International Nuclear Information System (INIS)

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

1983-01-01

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.)

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

Science.gov (United States)

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

2004-01-01

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.

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

DEFF Research Database (Denmark)

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

2017-01-01

, 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...

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

NARCIS (Netherlands)

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

2016-01-01

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

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

International Nuclear Information System (INIS)

Polevoj, A.S.

1989-01-01

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

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

Science.gov (United States)

Juillet-Leclerc, A.; Reynaud, S.

2009-04-01

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

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

International Nuclear Information System (INIS)

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

1981-01-01

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

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

Science.gov (United States)

Michael, Dimitra-Ermioni; Dotsika, Elissavet

2017-12-01

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

Estimation of the specific mass effect in the isotope shifts of energy levels in the optical spectrum of Ba I and Ba II

International Nuclear Information System (INIS)

Pendrill, L.R.

1984-01-01

A graphical method for separating mass and volume effects from purely optical isotope shift data is presented and compared with King's ''bunching'' method. Recent experimental data on isotope shifts for a wide range of spectral lines in the naturally abundant isotopes of Ba I and Ba II are analysed. Some agreement is found with muonic X-ray data concerning the nuclear size for the isotopes 136, 137 and 138, but there is disagreement (over 20%) for the other isotopes. The level isotope shifts are further parameterised in terms of a linear model, and the specific mass effect is decomposed into sums of one-electron and two-electron shift parameters with respect to the inert-gas like ground state of Ba III. (orig.)

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

Science.gov (United States)

Fricke, Henry C.; Rogers, Raymond R.

2000-09-01

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.

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

International Nuclear Information System (INIS)

Heinzinger, K.

1976-01-01

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)

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

International Nuclear Information System (INIS)

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

2008-01-01

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)

Oxygen isotope analysis of plant water without extraction procedure

International Nuclear Information System (INIS)

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

2001-01-01

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

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

Science.gov (United States)

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

1998-04-17

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.

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

Science.gov (United States)

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

2018-03-19

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.

Solvent Effects on Oxygen-17 Chemical Shifts in Amides. Quantitative Linear Solvation Shift Relationships

Science.gov (United States)

Díez, Ernesto; Fabián, Jesús San; Gerothanassis, Ioannis P.; Esteban, Angel L.; Abboud, José-Luis M.; Contreras, Ruben H.; de Kowalewski, Dora G.

1997-01-01

A multiple-linear-regression analysis (MLRA) has been carried out using the Kamlet-Abboud-Taft (KAT) solvatochromic parameters in order to elucidate and quantify the solvent effects on the17O chemical shifts ofN-methylformamide (NMF),N,N-dimethylformamide (DMF),N-methylacetamide (NMA), andN,N-dimethylacetamide (DMA). The chemical shifts of the four molecules show the same dependence (in ppm) on the solvent polarity-polarizability, i.e., -22π*. The influence of the solvent hydrogen-bond-donor (HBD) acidities is slightly larger for the acetamides NMA and DMA, i.e., -48α, than for the formamides NMF and DMF, i.e., -42α. The influence of the solvent hydrogen-bond-acceptor (HBA) basicities is negligible for the nonprotic molecules DMF and DMA but significant for the protic molecules NMF and NMA, i.e., -9β. The effect of substituting the N-H hydrogen by a methyl group amounts to -5.9 ppm in NMF and 5.4 ppm in NMA. The effect of substituting the O=C-H hydrogen amounts to 5.5 ppm in NMF and 16.8 ppm in DMF. The model of specific hydration sites of amides by I. P. Gerothanassis and C. Vakka [J. Org. Chem.59,2341 (1994)] is settled in a more quantitative basis and the model by M. I. Burgar, T. E. St. Amour, and D. Fiat [J. Phys. Chem.85,502 (1981)] is critically evaluated.17O hydration shifts have been calculated for formamide (FOR) by the ab initio LORG method at the 6-31G* level. For a formamide surrounded by the four in-plane molecules of water in the first hydration shell, the calculated17O shift change due to the four hydrogen bonds, -83.2 ppm, is smaller than the empirical hydration shift, -100 ppm. The17O shift change from each out-of-plane water molecule hydrogen-bonded to the amide oxygen is -18.0 ppm. These LORG results support the conclusion that no more than four water molecules are hydrogen-bonded to the amide oxygen in formamide.

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

Science.gov (United States)

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

2017-05-01

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.

Stratigraphy on Oxygen and Carbon Isotope of Paciran Formation East Java

International Nuclear Information System (INIS)

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

2004-01-01

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)

Isotope study in geothermal fields in Java Island

International Nuclear Information System (INIS)

Wandowo, Z.A.

1995-01-01

Study in two geothermal fields, Dieng and Kamojang, in Java island by utilizing isotope technique has been carried out. Isotopic data of wells, springs and other geothermal manifestations providing informations on the recharge area of precipitation contributed to geothermal resources, flow paths and origin of geothermal fluids. The data of oxygen shift has also provided information on the characteristic the fields. (author). 8 refs, 5 figs, 3 tabs

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

Science.gov (United States)

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

2014-06-15

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

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

Directory of Open Access Journals (Sweden)

J. Kaiser

2011-07-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-07-01

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.

Deuterium isotope shifts for backbone {sup 1}H, {sup 15}N and {sup 13}C nuclei in intrinsically disordered protein {alpha}-synuclein

Energy Technology Data Exchange (ETDEWEB)

Maltsev, Alexander S.; Ying Jinfa; Bax, Ad, E-mail: bax@nih.gov [National Institutes of Health, Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases (United States)

2012-10-15

Intrinsically disordered proteins (IDPs) are abundant in nature and characterization of their potential structural propensities remains a widely pursued but challenging task. Analysis of NMR secondary chemical shifts plays an important role in such studies, but the output of such analyses depends on the accuracy of reference random coil chemical shifts. Although uniform perdeuteration of IDPs can dramatically increase spectral resolution, a feature particularly important for the poorly dispersed IDP spectra, the impact of deuterium isotope shifts on random coil values has not yet been fully characterized. Very precise {sup 2}H isotope shift measurements for {sup 13}C{sup {alpha}}, {sup 13}C{sup {beta}}, {sup 13}C Prime , {sup 15}N, and {sup 1}H{sup N} have been obtained by using a mixed sample of protonated and uniformly perdeuterated {alpha}-synuclein, a protein with chemical shifts exceptionally close to random coil values. Decomposition of these isotope shifts into one-bond, two-bond and three-bond effects as well as intra- and sequential residue contributions shows that such an analysis, which ignores conformational dependence, is meaningful but does not fully describe the total isotope shift to within the precision of the measurements. Random coil {sup 2}H isotope shifts provide an important starting point for analysis of such shifts in structural terms in folded proteins, where they are known to depend strongly on local geometry.

Identifying Stereoisomers by ab-initio Calculation of Secondary Isotope Shifts on NMR Chemical Shieldings

Directory of Open Access Journals (Sweden)

Karl-Heinz Böhm

2014-04-01

Full Text Available We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2Hethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

Identifying stereoisomers by ab-initio calculation of secondary isotope shifts on NMR chemical shieldings.

Science.gov (United States)

Böhm, Karl-Heinz; Banert, Klaus; Auer, Alexander A

2014-04-23

We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

Oxygen isotope partitioning between rhyolitic glass/melt and CO2: An experimental study at 550-950 degrees C and 1 bar

International Nuclear Information System (INIS)

Palin, J.M.; Epstein, S.; Stolper, E.M.

1996-01-01

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

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

Science.gov (United States)

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

Stable isotope geochemistry of the Tongonan geothermal system, Leyte, Philippines

International Nuclear Information System (INIS)

Hulston, J.R.; Stewart, M.K.

1982-01-01

Stable isotope and geochemical data on samples from natural features, shallow wells and deep wells collected over a number of years from the Tongonan area of Leyte have been evaluated. The variations in the isotopic compositions of the thermal waters are used to describe natural processes occurring within the system. The effect of the ''excess enthalpy'' of the deep wells on the isotope data is formulated. Water from the deep Tongonan wells shows an oxygen-18 shift of 5 per mille, which is larger than at Wairakei and Broadlands, probably in part because of the high temperatures at Tongonan. Recent measurements indicate that the deuterium shift is very much smaller than previously thought. Isotopic measurements of methane in the gases suggests differing flows from the Eastern and Central Philippine faults

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

Digital Repository Service at National Institute of Oceanography (India)

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...

Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

Science.gov (United States)

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

2016-12-01

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.

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

Science.gov (United States)

De Bénédittis, J; Bertrand-Krajewski, J L

2005-01-01

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.

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

Science.gov (United States)

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

2012-01-01

increased significantly after ˜3.5 Ma. The oxygen isotope results from Yuanmou (Xiaohe Formation) show a positive shift after ˜8.5 Ma, which is similar in timing and magnitude to δ 18O shifts observed in horses and rhinos from the Linxia Basin and in fossils and paleosols from Pakistan and Nepal, suggesting a shift toward a drier climate at the northeast, southeast, and southern borders of the Tibetan Plateau during the late Miocene. Taken together, the carbon and oxygen isotope data indicate a general drying of the local climate over time and a change from a largely dense-forest environment at ˜8 Ma to a more open environment with a mosaic of forests and grasslands after 3-4 Ma in the Yuanmou region. Intra-tooth δ 13C and δ 18O variations within individual fossil teeth from Yuanmou suggest a stronger seasonality of rainfall at ˜1.7 Ma than in the late Miocene. The spatial and temporal δ 13C and δ 18O variations observed in mammalian teeth from Yunnan likely reflect changes in regional climate and/or tectonics, but more data are needed to fully explore the significance of the regional patterns in the δ 18O and δ 13C data in relation to climate and tectonic evolution of the region.

Triple oxygen isotope systematics of structurally bonded water in gypsum

Science.gov (United States)

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

2017-07-01

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

Triple oxygen isotopes in biogenic and sedimentary carbonates

Science.gov (United States)

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

2014-09-01

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

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

Science.gov (United States)

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

2012-01-01

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.

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

Digital Repository Service at National Institute of Oceanography (India)

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...

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

Energy Technology Data Exchange (ETDEWEB)

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)

2013-05-15

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)

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

Digital Repository Service at National Institute of Oceanography (India)

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...

EQUILIBRIUM AND KINETIC NITROGEN AND OXYGEN-ISOTOPE FRACTIONATIONS BETWEEN DISSOLVED AND GASEOUS N2O

NARCIS (Netherlands)

INOUE, HY; MOOK, WG

1994-01-01

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

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

Science.gov (United States)

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

2002-01-01

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.

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

Science.gov (United States)

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

2014-12-01

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

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

Science.gov (United States)

Keedakkadan, Habeeb Rahman; Abe, Osamu

2015-04-30

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

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

Science.gov (United States)

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

2013-04-01

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

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

Data.gov (United States)

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...

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

Data.gov (United States)

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...

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

Data.gov (United States)

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...

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

International Nuclear Information System (INIS)

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

1990-01-01

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

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

Science.gov (United States)

Ryb, U.; Eiler, J. M.

2017-12-01

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.

INVESTIGATION OF DISSOLVED SULPHATE IN VARIOUS GEOTHERMAL FIELDS OF SUMATRA USING OXYGEN AND SULPHUR ISOTOPES

Directory of Open Access Journals (Sweden)

E. Ristin Pujiindiyati

2010-06-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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)

2013-07-15

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)

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

Science.gov (United States)

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

2017-08-01

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

Oxygen isotope geochemistry of The Geysers reservoir rocks, California

Energy Technology Data Exchange (ETDEWEB)

Gunderson, Richard P.; Moore, Joseph N.

1994-01-20

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

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

Science.gov (United States)

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

2018-05-01

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.

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

Science.gov (United States)

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

2017-04-01

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.

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

Energy Technology Data Exchange (ETDEWEB)

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: ruth.blake@yale.edu [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: yaojun@ustb.edu.cn [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)

2013-09-15

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.

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

Science.gov (United States)

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

2018-05-01

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.

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

Science.gov (United States)

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

2014-05-01

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

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

Science.gov (United States)

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

2017-12-01

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.

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

Science.gov (United States)

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

2014-01-01

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.

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

Science.gov (United States)

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

2016-08-01

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

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

International Nuclear Information System (INIS)

Gerster, Richard

1971-01-01

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

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

International Nuclear Information System (INIS)

Yu Xiujing; Jia Shuyuan

2000-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1989-12-01

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.

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

Science.gov (United States)

Longinelli, Antonio

1984-02-01

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.

Carbon and nitrogen isotopes from top predator amino acids reveal rapidly shifting ocean biochemistry in the outer California Current.

Directory of Open Access Journals (Sweden)

Rocio I Ruiz-Cooley

Full Text Available Climatic variation alters biochemical and ecological processes, but it is difficult both to quantify the magnitude of such changes, and to differentiate long-term shifts from inter-annual variability. Here, we simultaneously quantify decade-scale isotopic variability at the lowest and highest trophic positions in the offshore California Current System (CCS by measuring δ15N and δ13C values of amino acids in a top predator, the sperm whale (Physeter macrocephalus. Using a time series of skin tissue samples as a biological archive, isotopic records from individual amino acids (AAs can reveal the proximate factors driving a temporal decline we observed in bulk isotope values (a decline of ≥1 ‰ by decoupling changes in primary producer isotope values from those linked to the trophic position of this toothed whale. A continuous decline in baseline (i.e., primary producer δ15N and δ13C values was observed from 1993 to 2005 (a decrease of ∼4‰ for δ15N source-AAs and 3‰ for δ13C essential-AAs, while the trophic position of whales was variable over time and it did not exhibit directional trends. The baseline δ15N and δ13C shifts suggest rapid ongoing changes in the carbon and nitrogen biogeochemical cycling in the offshore CCS, potentially occurring at faster rates than long-term shifts observed elsewhere in the Pacific. While the mechanisms forcing these biogeochemical shifts remain to be determined, our data suggest possible links to natural climate variability, and also corresponding shifts in surface nutrient availability. Our study demonstrates that isotopic analysis of individual amino acids from a top marine mammal predator can be a powerful new approach to reconstructing temporal variation in both biochemical cycling and trophic structure.

Carbon and nitrogen isotopes from top predator amino acids reveal rapidly shifting ocean biochemistry in the outer California Current.

Science.gov (United States)

Ruiz-Cooley, Rocio I; Koch, Paul L; Fiedler, Paul C; McCarthy, Matthew D

2014-01-01

Climatic variation alters biochemical and ecological processes, but it is difficult both to quantify the magnitude of such changes, and to differentiate long-term shifts from inter-annual variability. Here, we simultaneously quantify decade-scale isotopic variability at the lowest and highest trophic positions in the offshore California Current System (CCS) by measuring δ15N and δ13C values of amino acids in a top predator, the sperm whale (Physeter macrocephalus). Using a time series of skin tissue samples as a biological archive, isotopic records from individual amino acids (AAs) can reveal the proximate factors driving a temporal decline we observed in bulk isotope values (a decline of ≥1 ‰) by decoupling changes in primary producer isotope values from those linked to the trophic position of this toothed whale. A continuous decline in baseline (i.e., primary producer) δ15N and δ13C values was observed from 1993 to 2005 (a decrease of ∼4‰ for δ15N source-AAs and 3‰ for δ13C essential-AAs), while the trophic position of whales was variable over time and it did not exhibit directional trends. The baseline δ15N and δ13C shifts suggest rapid ongoing changes in the carbon and nitrogen biogeochemical cycling in the offshore CCS, potentially occurring at faster rates than long-term shifts observed elsewhere in the Pacific. While the mechanisms forcing these biogeochemical shifts remain to be determined, our data suggest possible links to natural climate variability, and also corresponding shifts in surface nutrient availability. Our study demonstrates that isotopic analysis of individual amino acids from a top marine mammal predator can be a powerful new approach to reconstructing temporal variation in both biochemical cycling and trophic structure.

Isotopic Changes During Digestion: Protein

Science.gov (United States)

Tuross, N.

2013-12-01

Nutrient and hydrological inputs traverse a complicated route of pH, enzymatic and cellular processes in digestion in higher animals. The end products of digestion are the starting products for biosynthesis that are often used to interpret past life-ways. Using an artificial gut system, the isotopic changes (dD, d18O, d13C and d15N) of protein are documented. Three separate protein sources are subjected to the conditions, chemical and enzymatic, found in the stomach and upper small intestine with only a small shift in the oxygen isotopic composition of the proteins observed. Middle to lower small intestine parameters produced both greater isotopic effects and significantly lower molecular weight products. The role of the gastric enterocyte and the likely involvement of the internal milieu of this cell in the isotopic composition of amino acids that are transported to the liver are reported.

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

Data.gov (United States)

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...

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

International Nuclear Information System (INIS)

Sun Fengmei; Shi Guangyu; Wang Huiwen; Yang Shuming

2012-01-01

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)

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

International Nuclear Information System (INIS)

Sun Yanrong; Mu Zhiguo; Cui Haiting

2002-01-01

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

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

International Nuclear Information System (INIS)

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

2011-01-01

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.

Intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite measured by thermal dehydroxylation and partial fluorination

Science.gov (United States)

Girard, Jean-Pierre; Savin, Samuel M.

1996-02-01

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

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

International Nuclear Information System (INIS)

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

2002-01-01

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

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

Science.gov (United States)

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

2013-01-01

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.

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

Energy Technology Data Exchange (ETDEWEB)

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)

2015-07-01

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

Stable Isotopic Shifts in Fish Bones from Multiple Archeological Coastal Middens in Penobscot Bay, Maine

Science.gov (United States)

Harris, C.; Johnson, B.; Ambrose, W. G.; Bourque, B.; Dostie, P.; Crowley, E.

2010-12-01

The carbon and nitrogen stable isotope compositions of collagen extracted from well-preserved archeological fish bones has the potential to provide useful information on fish diets and food web dynamics over time. Previous work on the Turner Farm archaeological site in Penobscot Bay, Gulf of Maine, reveals significant shifts in fish diets have occurred since European colonization (post 1620’s). The objective of the present study was to analyze samples from other archaeological sites within Penobscot Bay to characterize the spatial extent of the isotopic shift measured at Turner Farm. Stratified cod, flounder, and sculpin bones were analyzed from eight coastal middens located approximately 50km apart from one another within Penobscot Bay. The bones were sampled from three time horizons (0kya, 0.5-1kya, and 2.2-2.4kya). All bone samples were demineralized in 0.2M HCl at 4°C for 2 to 7 days and then extracted in 0.25M NaOH at 4°C for 1 to 2 hours. After freeze-drying, the bulk isotopic composition of each sample was analyzed using the EA-IRMS. In all stratigraphic horizons analyzed, cod were more enriched in δ13C and δ15N than sculpin, and flounder were the most depleted in δ13C and δ15N . However, the isotopic offsets between the fish species decreased from 2.4kya to the present. The nitrogen isotope composition was relatively constant over time and space for all species, implying that trophic levels for the fishes analyzed have not changed significantly in Penobscot Bay for the last 2,400 years. The carbon isotope composition also appears to be constant spatially in Penobscot Bay, however, the modern signal was more depleted than the paleo signal in all three species. The difference between the modern and paleo δ13C is ~5‰ for cod and flounder, and ~9‰ for sculpin. These shifts may, in part, be explained by decreases in both primary producer and prey species diversity, as kelp forests replace eelgrass beds in the Gulf of Maine.

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

International Nuclear Information System (INIS)

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

2000-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Vickridge, I.C. E-mail: vickridge@gps.jussieu.fr; Ganem, J.-J.; Battistig, G.; Szilagyi, E

2000-03-01

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.

A hypothesis-testing framework for studies investigating ontogenetic niche shifts using stable isotope ratios.

Directory of Open Access Journals (Sweden)

Caroline M Hammerschlag-Peyer

Full Text Available Ontogenetic niche shifts occur across diverse taxonomic groups, and can have critical implications for population dynamics, community structure, and ecosystem function. In this study, we provide a hypothesis-testing framework combining univariate and multivariate analyses to examine ontogenetic niche shifts using stable isotope ratios. This framework is based on three distinct ontogenetic niche shift scenarios, i.e., (1 no niche shift, (2 niche expansion/reduction, and (3 discrete niche shift between size classes. We developed criteria for identifying each scenario, as based on three important resource use characteristics, i.e., niche width, niche position, and niche overlap. We provide an empirical example for each ontogenetic niche shift scenario, illustrating differences in resource use characteristics among different organisms. The present framework provides a foundation for future studies on ontogenetic niche shifts, and also can be applied to examine resource variability among other population sub-groupings (e.g., by sex or phenotype.

18O isotopic tracer studies of silicon oxidation in dry oxygen

International Nuclear Information System (INIS)

Han, C.J.

1986-01-01

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

A route for oxygen isotope enrichment of α-COOH groups in amino acids

International Nuclear Information System (INIS)

Steinschneidner, A.; St Armour, T.; Valentine, B.; Burgar, M.I.; Fiat, D.

1981-01-01

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)

CAN GALACTIC CHEMICAL EVOLUTION EXPLAIN THE OXYGEN ISOTOPIC VARIATIONS IN THE SOLAR SYSTEM?

International Nuclear Information System (INIS)

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

2012-01-01

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.

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

Science.gov (United States)

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

2009-07-01

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.

Isotope shifts and electronic configurations of some of the energy levels of the neutral gadolinium atom

International Nuclear Information System (INIS)

Ahmad, S.A.; Venugopalan, A.; Saksena, G.D.

1982-01-01

Isotope shift ΔT (156-160) have been evaluated for 52 odd and 90 even energy levels of the neutral gadolinium atom from the measurements carried out on 166 lines of the first spectrum in the region 4535 to 4975 A on a photoelectric recording Fabry-Perot Spectrometer and enriched samples of 156 Gd and 160 Gd. Earlier studies provide data for just two lines in this region. Assignment of electronic configurations to some of the energy levels have been either confirmed or revised; some unassigned levels have been assigned probable configurations. The present study provides, for the first time, isotope shift of the two levels of 4f 7 6s 2 7s configuration of Gd I. (author)

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

Science.gov (United States)

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

2017-12-01

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

Seasonality of bottom water temperature in the northern North Sea reconstructed from the oxygen isotope composition of the bivalve Arctica islandica

Science.gov (United States)

Trofimova, Tamara; Andersson, Carin; Bonitz, Fabian

2017-04-01

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.

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

International Nuclear Information System (INIS)

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

1979-06-01

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

Carbon and oxygen isotope analysis of leaf biomass reveals contrasting photosynthetic responses to elevated CO2 near geologic vents in Yellowstone National Park

Directory of Open Access Journals (Sweden)

D. G. Williams

2009-01-01

Full Text Available In this study we explore the use of natural CO2 emissions in Yellowstone National Park (YNP in Wyoming, USA to study responses of natural vegetation to elevated CO2 levels. Radiocarbon (14C analysis of leaf biomass from a conifer (Pinus contortus; lodgepole pine and an invasive, non-native herb (Linaria dalmatica; Dalmation toadflax was used to trace the inputs of vent CO2 and quantify assimilation-weighted CO2 concentrations experienced by individual plants near vents and in comparable locations with no geologic CO2 exposure. The carbon and oxygen isotopic composition and nitrogen percent of leaf biomass from the same plants was used to investigate photosynthetic responses of these plants to naturally elevated atmospheric CO2 concentrations. The coupled shifts in carbon and oxygen isotope values suggest that dalmation toadflax responded to elevated CO2 exposure by increasing stomatal conductance with no change in photosynthetic capacity and lodgepole pine apparently responded by decreasing stomatal conductance and photosynthetic capacity. Lodgepole pine saplings exposed to elevated levels of CO2 likewise had reduced leaf nitrogen concentrations compared to plants with no enhanced CO2 exposure, further suggesting widespread and dominant conifer down-regulated photosynthetic capacity under elevated CO2 levels near geologic vents.

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

Science.gov (United States)

Kumar, Pravin; Mal, Kedar; Rodrigues, G

2016-11-01

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.

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

International Nuclear Information System (INIS)

Sial, A.N.

1984-01-01

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

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

Science.gov (United States)

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

2017-12-01

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.

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

Science.gov (United States)

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

2010-02-24

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

Oxygen isotope fractionation between bird bone phosphate and drinking water

Science.gov (United States)

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

2017-06-01

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.

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

Science.gov (United States)

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

2015-07-01

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

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

Science.gov (United States)

Huyghe, Damien; Mouthereau, Frédéric; Emmanuel, Laurent

2012-09-01

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.

Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

Science.gov (United States)

Cao, Xiaobin; Liu, Yun

2011-12-01

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

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

Science.gov (United States)

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

2017-11-01

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

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

Digital Repository Service at National Institute of Oceanography (India)

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...

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

Directory of Open Access Journals (Sweden)

Alberta Silvestri

2017-01-01

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.

Hyperfine structure and isotope shift measurements of short-lived elements by laser spectroscopy, January 1-December 31, 1984

International Nuclear Information System (INIS)

Schuessler, H.A.

1983-09-01

Research progress is reported in the areas of stored ion spectroscopy, numerical studies of the trapping of pulse injected ions, beam tests at the TRISTAN mass separator, fluorescence line narrowing technique for Doppler-free observation, observation of the isotope shift on long-lived gold isotopes, and observation of Doppler-free signals in a fast Ar + beam

Rare-earth nuclei: Radii, isotope-shifts and deformation properties in the relativistic mean-field theory

International Nuclear Information System (INIS)

Lalazissis, G.A.; Ring, P.

1996-01-01

A systematic study of the ground-state properties of even-even rare earth nuclei has been performed in the framework of the Relativistic Mean-Field (RMF) theory using the parameter set NL-SH. Nuclear radii, isotope shifts and deformation properties of the heavier rare-earth nuclei have been obtained, which encompass atomic numbers ranging from Z=60 to Z=70 and include a large range of isospin. It is shown that RMF theory is able to provide a good and comprehensive description of the empirical binding energies of the isotopic chains. At the same time the quadrupole deformations β 2 obtained in the RMF theory are found to be in good agreement with the available empirical values. The theory predicts a shape transition from prolate to oblate for nuclei at neutron number N=78 in all the chains. A further addition of neutrons up to the magic number 82 brings about the spherical shape. For nuclei above N=82, the RMF theory predicts the well-known onset of prolate deformation at about N=88, which saturates at about N=102. The deformation properties display an identical behaviour for all the nuclear chains. A good description of the above deformation transitions in the RMF theory in all the isotopic chains leads to a successful reproduction of the anomalous behaviour of the empirical isotopic shifts of the rare-earth nuclei. The RMF theory exhibits a remarkable success in providing a unified and microscopic description of various empirical data. (orig.)

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

International Nuclear Information System (INIS)

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

2011-01-01

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)

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

Science.gov (United States)

Lyons, J R; Young, E D

2005-05-19

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.

Design and development of high-resolution atomic beam fluorescence spectroscopy facility for isotope shift and hyperfine structure measurements

International Nuclear Information System (INIS)

Acharyulu, G.V.S.G.; Sankari, M.; Kiran Kumar, P.V.; Suryanarayana, M.V.

2012-01-01

A high-resolution atomic beam fluorescence spectroscopy facility for the determination of isotope shifts and hyperfine structure in atomic species has been designed and developed. A resistively heated graphite tube atomic beam source was designed, tested and integrated into a compact interaction chamber for atomic beam fluorescence experiments. The design of the laser-atom interaction chamber and the source has been modified in a phased manner so as to achieve sub-Doppler resolution. The system has been used to record the hyperfine spectrum of the D2 transitions of Rb and K isotopes. The spectral resolution achieved is ∼ 26 MHz and is adequate to carry out high resolution measurement of isotope shifts and hyperfine structure of various atomic species. The other major advantage of the source is that it requires very small amounts of sample for achieving very good signal to noise ratio. (author)

Kalahari groundwaters: Their hydrogen, carbon and oxygen isotopes

International Nuclear Information System (INIS)

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

1974-01-01

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)

Isotopic shifts in chemical exchange systems. 1. Large isotope effects in the complexation of Na+ isotopes by macrocyclic polyethers

International Nuclear Information System (INIS)

Knoechel, A.; Wilken, R.D.

1981-01-01

The complexation of 24 Na + and 22 Na + by 18 of the most widely used macrocyclic polyethers (crown ethers and monocyclic and bicyclic aminopolyethers) has been investigated in view of possible equilibrium isotope shifts. Solvated salts and polyether complexes were distributed differently into two phases and isotope ratios determined in both phases. Chloroform/water systems were shown to be particularly suitable to the investigations allowing favorable distribution for Na + and 13 of the 18 polyethers employed. With crown ethers 24 Na + enrichment varied from nonsignficant values (for large crown ethers) up to 3.1 +- 0.4% (18-crown-6). In the case of bicyclic aminopolyethers, ligands with cages of optimum size to accommodate Na + showed 24 Na + enrichment between O (nonsignificant) (2.2/sub B/2./sub B/) and 5.2 +- 1.8% (2.2.1). In contrast, for 2.2.2. and its derivatives, being too large for Na + , 22 Na + enrichment varying from O (nonsignificant) (2.2.2.p) up to 5.4 +- 0.5% (2.2.2.) has been observed. These values are remarkably high. They are explained by different bonding in solvate structure and polyether complex by using the theoretical approach of Bigeleisen

Kinetic theory of oxygen isotopic exchange between minerals and water

Science.gov (United States)

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

1987-01-01

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.

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

International Nuclear Information System (INIS)

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

1989-01-01

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

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

Science.gov (United States)

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

2007-12-01

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

Temperature measurements of Transdanubian Mesozoic rocks by the oxygen isotope method

International Nuclear Information System (INIS)

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

1979-01-01

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.)

Hyperfine Structure and Isotope Shifts in Dy II

Directory of Open Access Journals (Sweden)

Dylan F. Del Papa

2017-01-01

Full Text Available Using fast-ion-beam laser-fluorescence spectroscopy (FIBLAS, we have measured the hyperfine structure (hfs of 14 levels and an additional four transitions in Dy II and the isotope shifts (IS of 12 transitions in the wavelength range of 422–460 nm. These are the first precision measurements of this kind in Dy II. Along with hfs and IS, new undocumented transitions were discovered within 3 GHz of the targeted transitions. These atomic data are essential for astrophysical studies of chemical abundances, allowing correction for saturation and the effects of blended lines. Lanthanide abundances are important in diffusion modeling of stellar interiors, and in the mechanisms and history of nucleosynthesis in the universe. Hfs and IS also play an important role in the classification of energy levels, and provide a benchmark for theoretical atomic structure calculations.

Seasonal Cyclicity in Trace Elements and Stable Isotopes of Modern Horse Enamel.

Science.gov (United States)

de Winter, Niels J; Snoeck, Christophe; Claeys, Philippe

2016-01-01

The study of stable isotopes in fossil bioapatite has yielded useful results and has shown that bioapatites are able to faithfully record paleo-environmental and paleo-climatic parameters from archeological to geological timescales. In an effort to establish new proxies for the study of bioapatites, intra-tooth records of enamel carbonate stable isotope ratios from a modern horse are compared with trace element profiles measured using laboratory micro X-Ray Fluorescence scanning. Using known patterns of tooth eruption and the relationship between stable oxygen isotopes and local temperature seasonality, an age model is constructed that links records from six cheek upper right teeth from the second premolar to the third molar. When plotted on this age model, the trace element ratios from horse tooth enamel show a seasonal pattern with a small shift in phase compared to stable oxygen isotope ratios. While stable oxygen and carbon isotopes in tooth enamel are forced respectively by the state of the hydrological cycle and the animal's diet, we argue that the seasonal signal in trace elements reflects seasonal changes in dust intake and diet of the animal. The latter explanation is in agreement with seasonal changes observed in carbon isotopes of the same teeth. This external forcing of trace element composition in mammal tooth enamel implies that trace element ratios may be used as proxies for seasonal changes in paleo-environment and paleo-diet.

Hyperfine structure and isotope shift analysis of singly ionized titanium

Science.gov (United States)

Bouazza, Safa

2013-04-01

The even-parity low configuration system of Ti II has been considered on the basis of the experimental data found in the literature, and its fine structure has been reanalyzed by simultaneous parameterization of one- and two-body interactions for the model space (3d + 4s)3. Furthermore, the main one-electron hyperfine structure parameters for these configurations have been evaluated. For instance, for 3d24s1, a_{3{\\rm{d}}}^{01} = - {\\rm{63}}.{\\rm{2}}\\left( {{\\rm{3}}.{\\rm{1}}} \\right)\\,{\\rm{MHz}} and a_{4{\\rm{s}}}^{10} = - {\\rm{984}}.{\\rm{1}}\\left( {{\\rm{7}}.{\\rm{1}}} \\right)\\,{\\rm{MHz}} . Field shifts (FS) and specific mass shifts (SMS) of the main Ti II configurations are deduced by means of ab initio estimates combined with a small quantity of experimental isotope shift data available in the literature: FS(3d3) = -63.3 MHz, FS(3d24p1) = -49.7 MHz, FS(3d14s2) = 98.2 MHz, FS(4s24P1) = 163.4 MHz and SMS(3d3) = 1453.3 MHz, SMS(3d14s2) = -2179.7 MHz, …, referred to 3d24s1 for the pair Ti46-Ti48.

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

Science.gov (United States)

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

2015-04-01

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

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

Science.gov (United States)

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

2013-12-01

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

Determination of spin, magnetic moment and isotopic shift of neutron rich 205Hg by optical pumping

International Nuclear Information System (INIS)

Rodriguez, J.; Bonn, J.; Huber, G.; Kluge, H.J.; Otten, E.W.; European Organisation for Nuclear Research, Geneva

1975-01-01

Neutron rich 205 Hg(Tsub(1/2) = 5.2 min) was produced and on-line mass separated at the ISOLDE facility at CERN. The polarization achieved by optical pumping via the atomic line (6s 21 S 0 - 6s6p 3 P 1 , lambda = 2,537 A) was monitored by the β decay asymmetry. Hyperfine structure and isotopic shift of the 205 Hg absorption line was determined by Zeeman scanning. In addition a magnetic resoncance was performed on the polarized 205 Hg nuclei in the atomic ground state. The results are: I( 205 Hg) = 1/2 (confirmed); μ(I, 205 Hg) = 0.5915(1)μ(N) (uncorrected for diamagnetism); isotopic shift deltaν(204/205) = ν( 205 Hg) - ν( 204 Hg) = -1.8(1)GHz. μ(I) and IS are discussed briefly in the frame of current literature. (orig.) [de

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

Czech Academy of Sciences Publication Activity Database

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

2016-01-01

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

Eastward shift and maintenance of Arabian Sea oxygen minimum zone: Understanding the paradox

Science.gov (United States)

Acharya, Shiba Shankar; Panigrahi, Mruganka K.

2016-09-01

The dominance of Oxygen Minimum Zone in the eastern part of the Arabian Sea (ASOMZ) instead of the more bio-productive and likely more oxygen consuming western part is the first part of the paradox. The sources of oxygen to the ASOMZ were evaluated through the distributions of different water masses using the extended optimum multiparameter (eOMP) analysis, whereas the sinks of oxygen were evaluated through the organic matter remineralization, using the apparent oxygen utilization (AOU). The contributions of major source waters to the Arabian Sea viz. Indian Deep water (dIDW), Indian Central water (ICW), Persian Gulf Water (PGW) and Red Sea Water (RSW) have been quantified through the eOMP analysis which shows that the PGW and RSW are significant for the eastward shift of ASOMZ instead of voluminous ICW and dIDW. The distribution of Net Primary Production (NPP) and AOU clearly suggest the transport of organic detritus from the highly productive western Arabian Sea to its eastern counterpart which adds to the eastward shifting of ASOMZ. A revised estimate of the seasonal variation of areal extent and volume occupied by ASOMZ through analysis of latest available data reveals a distinct intensification of ASOMZ by 30% and increase in its volume by 5% during the spring-summer transition. However, during this seasonal transition the productivity in the Arabian Sea shows 100% increase in mean NPP. This disparity between ASOMZ and monsoonal variation of productivity is the other part of the paradox, which has been constrained through apparent oxygen utilization, Net Primary Production along with a variation of core depths of source waters. This study reveals a subtle balance between the circulation of marginal oxygen-rich water masses from the western Arabian Sea and organic matter remineralization in the eastern Arabian Sea in different seasons that explains the maintenance of ASOMZ throughout the year.

Oxygen isotope studies of the Salton Sea geothermal field

International Nuclear Information System (INIS)

Olson, E.R.

1978-01-01

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.)

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

International Nuclear Information System (INIS)

Labeyrie, Laurent.

1979-07-01

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

Isotope effect on superconductivity and Raman phonons of Pyrochlore Cd2Re2O7

Science.gov (United States)

Razavi, F. S.; Hajialamdari, M.; Reedyk, M.; Kremer, R. K.

2018-06-01

Cd2Re2O7 is the only α-Pyrochlore exhibiting superconductivity with a transition temperature (Tc) of ∼ 1 K. In this study, we present the effect of oxygen isotope (18O) as well as combined 18O and cadmium isotope (116Cd) substitution on the superconductivity and Raman scattering spectrum of Cd2Re2O7. The change of Tc and the energy gap Δ(T) are reported using various techniques including point contact spectroscopy. The shift in Raman phonon frequencies upon isotope substitution will be compared with measurement of the isotope effect on the superconducting transition temperature.

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

International Nuclear Information System (INIS)

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

1990-01-01

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

Regime shifts and ecological catastrophes in a model of plankton-oxygen dynamics under the climate change.

Science.gov (United States)

Petrovskii, Sergei; Sekerci, Yadigar; Venturino, Ezio

2017-07-07

It is estimated that more than a half of the total atmospheric oxygen is produced in the oceans due to the photosynthetic activity of phytoplankton. Any significant decrease in the net oxygen production by phytoplankton is therefore likely to result in the depletion of atmospheric oxygen and in a global mass mortality of animals and humans. In its turn, the rate of oxygen production is known to depend on water temperature and hence can be affected by the global warming. We address this problem theoretically by considering a model of a coupled plankton-oxygen dynamics where the rate of oxygen production slowly changes with time to account for the ocean warming. We show that, when the temperature rises sufficiently high, a regime shift happens: the sustainable oxygen production becomes impossible and the system's dynamics leads to fast oxygen depletion and plankton extinction. We also consider a scenario when, after a certain period of increase, the temperature is set on a new higher yet apparently safe value, i.e. before the oxygen depletion disaster happens. We show that in this case the system dynamics may exhibit a long-term quasi-sustainable dynamics that can still result in an ecological disaster (oxygen depletion and mass extinctions) but only after a considerable period of time. Finally, we discuss the early warning signals of the approaching regime shift resulting in the disaster. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

2018-05-17

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 .

Permafrost oxygen isotope ratios and chronology of three cores from Antarctica

International Nuclear Information System (INIS)

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

1976-01-01

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)

Evaporation Induced Oxygen Isotope Fractionation in Impact Ejecta

Science.gov (United States)

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

2017-12-01

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

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

International Nuclear Information System (INIS)

Kakiuchi, M.; Matsuo, S.

1985-01-01

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

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

International Nuclear Information System (INIS)

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

2004-01-01

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

Isotope exchange in oxide-containing catalyst

Science.gov (United States)

Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

1989-01-01

A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

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

Energy Technology Data Exchange (ETDEWEB)

Kowalczyk, K

2006-05-15

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.)

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

International Nuclear Information System (INIS)

Kowalczyk, K.

2006-05-01

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.)

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

Science.gov (United States)

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

2009-06-01

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

High-resolution conodont oxygen isotope record of Ordovician climate change

Science.gov (United States)

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

2013-12-01

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.

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

International Nuclear Information System (INIS)

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

2002-01-01

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

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

Science.gov (United States)

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

2014-12-01

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

The impact of moisture sources on the oxygen isotope composition of precipitation at a continental site in central Europe

Science.gov (United States)

Krklec, Kristina; Domínguez-Villar, David; Lojen, Sonja

2018-06-01

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

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

International Nuclear Information System (INIS)

Taylor, B.E

2001-01-01

Whole-rock oxygen isotope mapping provides a useful method for the delineation and quantitative evaluation of paleo-hydrothermal systems associated with syn-volcanic intrusions and volcanic-associated massive sulfide (VMS) deposits. During the course of a four-year study of regional alteration systems associated with VMS Deposits, four syn-volcanic intrusive complexes in Canada were mapped using stable isotope techniques. The complexes included Noranda, Quebec; Clifford-Ben Nevis, Ontario; Snow Lake, Manitoba, and Sturgeon Lake, Ontario. This study was regional in extent, involving large areas and large numbers of whole-rock samples: Noranda (625 km 2 ;≥600 samples, plus others (total = 1198); Sturgeon Lake (525 km 2 ; 452 samples); Clifford-Ben Nevis (160 km 2 ; 251 samples); and Snow Lake (84 km 2 ; 575 samples). Isotopic data on whole-rock carbonates and hydrous minerals were also collected. The regional isotopic studies were carried out in concert with other studies on mineral assemblages and mineral composition, and on associated intrusive and extrusive rocks. The Clifford-Ben Nevis area was selected as a control area, in as much as it contains no known VMS deposits; all other areas are well-known, productive VMS districts. Oxygen isotope maps are, in a sense, thermal maps, illustrating the paleo-distribution of heat and fluids, and offering a potential aid to exploration. The isotopic data may be contoured to reveal zones of 18 O depletion and enrichment, relative to unaltered rocks. Zones of δ 18 O≤60% comprise rocks that have reacted with seawater at high (e.g., 300+ o C) temperatures. The volume of foot-wall rocks isotopically-depleted by water/rock interaction during the life of one or more episodes of submarine hydrothermal activity is proportional to the amount of heat available from the syn-volcanic intrusive center. These altered rocks comprise the reaction zone often inferred to have supplied metals and other constituents for the VMS deposits

Oxygen isotope fractionation between human phosphate and water revisited

DEFF Research Database (Denmark)

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

2008-01-01

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...

Probing new light force-mediators by isotope shift spectroscopy

International Nuclear Information System (INIS)

Berengut, Julian C.; Budker, Dmitry; California Univ., Berkeley, CA; Lawrence Berkeley National Laboratory, Berkeley, CA; Delaunay, Cedric

2017-04-01

In this Letter we explore the potential of probing new light force-carriers, with spin-independent couplings to the electron and the neutron, using precision isotope shift spectroscopy. We develop a formalism to interpret linear King plots as bounds on new physics with minimal theory inputs. We focus only on bounding the new physics contributions that can be calculated independently of the Standard Model nuclear effects. We apply our method to existing Ca"+ data and project its sensitivity to possibly existing new bosons using narrow transitions in other atoms and ions (specifically, Sr and Yb). Future measurements are expected to improve the relative precision by five orders of magnitude, and can potentially lead to an unprecedented sensitivity for bosons within the 10 keV to 10 MeV mass range.

Probing new light force-mediators by isotope shift spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Berengut, Julian C. [New South Wales Univ., Sydney, NSW (Australia). School of Physics; Budker, Dmitry [Mainz Univ. (Germany). Helmholtz-Inst. Mainz; California Univ., Berkeley, CA (United States). Physics Dept.; Lawrence Berkeley National Laboratory, Berkeley, CA (United States). Nuclear Science Div.; Delaunay, Cedric [Savoie Mont Blanc Univ., Annecy-le-Vieux (France). Laboratoire d' Annecy-le-Vieux de Physique Theorique LAPTh; and others

2017-04-15

In this Letter we explore the potential of probing new light force-carriers, with spin-independent couplings to the electron and the neutron, using precision isotope shift spectroscopy. We develop a formalism to interpret linear King plots as bounds on new physics with minimal theory inputs. We focus only on bounding the new physics contributions that can be calculated independently of the Standard Model nuclear effects. We apply our method to existing Ca{sup +} data and project its sensitivity to possibly existing new bosons using narrow transitions in other atoms and ions (specifically, Sr and Yb). Future measurements are expected to improve the relative precision by five orders of magnitude, and can potentially lead to an unprecedented sensitivity for bosons within the 10 keV to 10 MeV mass range.

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

Science.gov (United States)

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

2017-01-01

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

Oxygen isotopic abundances in the atmospheres of seven red giant stars

International Nuclear Information System (INIS)

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

1984-01-01

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

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

Science.gov (United States)

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

2016-12-01

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

Seasonal Cyclicity in Trace Elements and Stable Isotopes of Modern Horse Enamel.

Directory of Open Access Journals (Sweden)

Niels J de Winter

Full Text Available The study of stable isotopes in fossil bioapatite has yielded useful results and has shown that bioapatites are able to faithfully record paleo-environmental and paleo-climatic parameters from archeological to geological timescales. In an effort to establish new proxies for the study of bioapatites, intra-tooth records of enamel carbonate stable isotope ratios from a modern horse are compared with trace element profiles measured using laboratory micro X-Ray Fluorescence scanning. Using known patterns of tooth eruption and the relationship between stable oxygen isotopes and local temperature seasonality, an age model is constructed that links records from six cheek upper right teeth from the second premolar to the third molar. When plotted on this age model, the trace element ratios from horse tooth enamel show a seasonal pattern with a small shift in phase compared to stable oxygen isotope ratios. While stable oxygen and carbon isotopes in tooth enamel are forced respectively by the state of the hydrological cycle and the animal's diet, we argue that the seasonal signal in trace elements reflects seasonal changes in dust intake and diet of the animal. The latter explanation is in agreement with seasonal changes observed in carbon isotopes of the same teeth. This external forcing of trace element composition in mammal tooth enamel implies that trace element ratios may be used as proxies for seasonal changes in paleo-environment and paleo-diet.

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

Science.gov (United States)

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

2017-08-01

Conodont apatite has long been used in paleoenvironmental studies, often with minimal evaluation of the influence of diagenesis on measured elemental and isotopic signals. In this study, we evaluate diagenetic influences on conodonts using an integrated set of analytical techniques. A total of 92 points in 19 coniform conodonts from Ordovician marine units of South China were analyzed by micro-laser Raman spectroscopy (M-LRS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), high-resolution X-ray microdiffraction (HXRD), and secondary ion mass spectrometry (SIMS). Each conodont element was analyzed along its full length, including the albid crown, hyaline crown, and basal body, in either a whole specimen (i.e., reflecting the composition of its outer layer) or a split specimen (i.e., reflecting the composition of its interior). In the conodonts of this study, the outer surfaces consist of hydroxyfluorapatite and the interiors of strontian hydroxyfluorapatite. Ionic substitutions resulted in characteristic Raman spectral shifts in the position (SS1) and width (SS2) of the ν1-PO43- stretching band. Although multiple elements were enriched (Sr2+, Mg2+) and depleted (Fe3+, Mn2+, Ca2+) during diagenesis, geochemical modeling constraints and known Raman spectral patterns suggest that Sr uptake was the dominant influence on diagenetic redshifts of SS1. All study specimens show lower SS2 values than modern bioapatite and synthetic apatite, suggesting that band width decreases with time in ancient bioapatite, possibly through an annealing process that produces larger, more uniform crystal domains. Most specimens consist mainly of amorphous or poorly crystalline apatite, which is inferred to represent the original microstructure of conodonts. In a subset of specimens, some tissues (especially albid crown) exhibit an increased degree of crystallinity developed through aggrading neomorphism. However, no systematic relationship was observed between

Early-Middle Pleistocene benthic turnover and oxygen isotope stratigraphy from the Central Mediterranean (Valle di Manche, Crotone Basin, Italy): Data and trends

OpenAIRE

Michele Azzarone; Patrizia Ferretti; Veronica Rossi; Daniele Scarponi; Luca Capraro; Patrizia Macrì; John W. Huntley; Costanza Faranda

2018-01-01

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...

Probing new intra-atomic force with isotope shifts

Energy Technology Data Exchange (ETDEWEB)

Mikami, Kyoko; Tanaka, Minoru [Osaka University, Department of Physics, Graduate School of Science, Toyonaka, Osaka (Japan); Yamamoto, Yasuhiro [Yonsei University, Department of Physics and IPAP, Seoul (Korea, Republic of)

2017-12-15

In the development of atomic clocks, some atomic transition frequencies are measured with remarkable precision. These measured spectra may include the effects of a new force mediated by a weakly interacting boson. Such effects might be distilled out from possible violation of a linear relation in isotope shifts between two transitions, as known as King's linearity, with relatively suppressed theoretical uncertainties. We discuss the experimental sensitivity to a new force in the test of the linearity as well as the linearity violation owing to higher-order effects within the Standard Model. The sensitivity to new physics is limited by such effects. We have found that, for Yb{sup +}, the higher-order effect is in the reach of future experiments. The sensitivity to a heavy mediator is also discussed. It is analytically clarified that the sensitivity becomes weaker than that in the literature. Our numerical results of the sensitivity are compared with other weak force search experiments. (orig.)

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

Science.gov (United States)

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

2015-03-03

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.

Tellurium Stable Isotopes as a Paleoredox Proxy

Science.gov (United States)

Wasserman, N.; Johnson, T. M.

2017-12-01

Despite arguments for variably-oxygenated shallow waters and anoxic deep marine waters, which delayed animal development until the Neoproterozoic Oxidation Event, the magnitude of atmospheric oxygen during the Proterozoic is still uncertain [1]. The evidence for low pO2 (<0.1-1% PAL) is based on geochemical and isotopic proxies, which track the mobilization of Fe and Mn on the continents. For example, large chromium isotope shifts occur at the Neoproterozoic Oxidation Event due to the initiation of Cr redox cycling, but this proxy is insensitive to fluctuations in the lower-pO2 conditions at other times during the Proterozoic. Tellurium, a metalloid with a lower threshold to oxidation, may be sensitive to pO2 shifts in a lower range. In the reduced forms, Te(-II) and Te(0), the element is insoluble and immobile. However, in the more oxidized phases, Te(IV) and Te(VI), Te can form soluble oxyanions (though it tends to adsorb to Fe-oxyhydroxides and clays) [2]. Te stable isotopes have been shown to fractionate during abiotic or biologic reduction of Te(VI) or Te(IV) to elemental Te(0) [3, 4]. Utilizing hydride generation MC-ICP-MS, we are able to obtain high precision (2σ 0.04‰) measurements of δ128Te/125Te for natural samples containing < 10 ng of Te. A suite of Phanerozoic and Proterozoic ironstones show significant variation in δ128Te/125Te (<0.5‰), suggesting that the Te redox cycle was active during the Proterozoic. Future directions will include Te isotope measurements of Precambrian paleosols to determine natural isotope variation before the Great Oxidation Event and experiments to determine fractionation during adsorption to Fe-oxyhydroxides. [1] Planavsky et al. (2014) Science 346 (6209), pp. 635-638 [2] Qin et al. (2017) Environmental Science and Technology 51 (11), pp 6027-6035 [3] Baesman et al. (2007) Applied Environmental Microbiology 73 (7), pp 2135-2143 [4] Smithers and Krause (1968) Canadian Journal of Chemistry 46(4): pp 583-591

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

CSIR Research Space (South Africa)

Waterhouse, JS

2002-07-30

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...

Oxygen and carbon isotopic compositions of gases respired by humans

International Nuclear Information System (INIS)

Epstein, S.; Zeiri, L.

1988-01-01

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

Optogalvanic measurement of isotope shifts of doubly ionized uranium (U III) made using natural-U samples

International Nuclear Information System (INIS)

Piyakis, K.N.; Gagne, J.

1989-01-01

An efficient method of identifying 235 U III (in natural-U samples), with the help of the optogalvanic effect in a hollow-cathode discharge, is presented. The use of this method enabled us to carry out the measurement of isotope shifts and the preliminary investigation of hyperfine structures of U III. The 238 U-- 235 U shifts for the 591.313-, 586.045-, and 610.497-nm U III lines are found to be 921(3), 417(6), and 392(12) mK, respectively

Stable isotopes as signposts of fluid throughput in Rotokawa and other geothermal fields, and the difficulty of identifying magmatic fingerprints

International Nuclear Information System (INIS)

Blattner, P.; Woldemichael, S.; Auckland Univ.; Browne, P.R.L.; Auckland Univ.

1994-01-01

We present a background for water-rock interaction generally, and new data on the Rotokawa geothermal field. The oxygen isotope shift of total rock samples allow the deduction of past flowpaths and total fluid throughput. Estimates of any input true exsolved magmatic water are difficult as the lithosphere can act as an effective isotopic screen. (authors). 1 fig., 6 refs

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

International Nuclear Information System (INIS)

Blattner, P.

1982-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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)

2004-10-13

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.

Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands)

Science.gov (United States)

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

2016-10-01

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.

On the Use of Biomineral Oxygen Isotope Data to Identify Human Migrants in the Archaeological Record: Intra-Sample Variation, Statistical Methods and Geographical Considerations.

Directory of Open Access Journals (Sweden)

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

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

DEFF Research Database (Denmark)

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

2015-01-01

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...

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

Digital Repository Service at National Institute of Oceanography (India)

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...

Laser spectroscopic studies along the Al isotopic chain and the isomer-shift of the self-conjugate $^{26}$Al nucleus

CERN Multimedia

We propose to measure the isomer shift in the self-conjugate $^{26}$Al ($\\textit{N = Z}$ = 13) nucleus along with the isotope shifts of $^{24-33}$Al using bunched-beam collinear laser spectroscopy at the COLLAPS beam line at ISOLDE. These isomer and isotope shifts allow the extraction of precise mean-square charge radii, in particular the difference in charge radius between the $\\textit{I}$ = 5$^{+}$; $\\textit{T}$ = 0 ground state and $\\textit{I}$= 0$^{+}$;$\\textit{T}$= 1 isomer in $^{26}$Al. This charge radius difference, in comparison with the odd-even staggering in the Al-chain, is an excellent probe to study proton-neutron pairing correlations, as was previously illustrated for $^{38}_{19}$K$_{19}$. Furthermore, accurate knowledge of the mean-square charge radius in $^{26m}$Al is essential to reliably calculate its isospin-symmetry-breaking correction which is important to extract the CKM matrix element V$_{ud}$ from the 0$^{+}$ $\\rightarrow$ 0$^{+}$ super-allowed $\\beta$-decay data. Finally, the charge ...

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

Directory of Open Access Journals (Sweden)

Hannah B Vander Zanden

2016-03-01

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

Isotope shift of 40,42,44,48Ca in the 4s 2S1/2 → 4p 2P3/2 transition

Science.gov (United States)

Gorges, C.; Blaum, K.; Frömmgen, N.; Geppert, Ch; Hammen, M.; Kaufmann, S.; Krämer, J.; Krieger, A.; Neugart, R.; Sánchez, R.; Nörtershäuser, W.

2015-12-01

We report on improved isotope shift measurements of the isotopes {}{40,42,{44,48}}Ca in the 4{{s}}{ }2{{{S}}}1/2\\to 4{{p}}{ }2{{{P}}}3/2 (D2) transition using collinear laser spectroscopy. Accurately known isotope shifts in the 4{{s}}{ }2{{{S}}}1/2\\to 4{{p}}{ }2{{{P}}}1/2(D1) transition were used to calibrate the ion beam energy with an uncertainty of {{Δ }}U≈ +/- 0.25 {{V}}. The accuracy in the D2 transition was improved by a factor of 5-10. A King-plot analysis of the two transitions revealed that the field shift factor in the D2 line is about 1.8(13)% larger than in the D1 transition which is ascribed to relativistic contributions of the 4{{{p}}}1/2 wave function.

Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

Science.gov (United States)

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

2009-01-01

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.

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

Science.gov (United States)

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

2009-08-01

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.

Oxygen isotope effect on 55Mn nuclear magnetic shielding in permanganate

International Nuclear Information System (INIS)

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

1976-01-01

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

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

Science.gov (United States)

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

2009-12-01

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

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

International Nuclear Information System (INIS)

Spiegler, P.; Updegraff, D.

1983-03-01

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

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

Science.gov (United States)

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

1999-09-01

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

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

International Nuclear Information System (INIS)

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

1987-01-01

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

Surface core level shifts of clean and oxygen covered Ir(111)

Energy Technology Data Exchange (ETDEWEB)

Bianchi, M; Cassese, D; Cavallin, A; Comin, R; Orlando, F; Postregna, L [Universita degli Studi di Trieste, Via A Valerio 2, 34127, Trieste (Italy); Golfetto, E; Baraldi, A [Dipartimento di Fisica e CENMAT, Universita degli Studi di Trieste, Via A Valerio 2, 34127, Trieste (Italy); Lizzit, S [Sincrotrone Trieste S.C.p.A., S.S. 14 Km 163.5, 34012 Trieste (Italy)], E-mail: alessandro.baraldi@elettra.trieste.it

2009-06-15

We present the results of high resolution core level photoelectron spectroscopy employed to investigate the electronic structure of clean and oxygen covered Ir(111) surface. Ir 4f{sub 7/2} core level spectra are shown to be very sensitive to the local atomic environment. For the clean surface we detected two distinct components shifted by 550 meV, originated by surface and bulk atoms. The larger Gaussian width of the bulk component is explained as due to experimentally unresolved subsurface components. In order to determine the relevance of the phonon contribution we examined the thermal behaviour of the core level lineshape using the Hedin-Rosengren theory. From the phonon-induced spectral broadening we found the Debye temperature of bulk and surface atoms to be 298 and 181 K, respectively, which confirms the softening of the vibrational modes at the surface. Oxygen adsorption leads to the appearance of new surface core level components at -200 meV and +230 meV, which are interpreted as due to first-layer Ir atoms differently coordinated with oxygen. The coverage dependence of these components demonstrates that the oxygen saturation corresponds to 0.38 ML, in good agreement with recent density functional theory calculations.

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-07-15

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)

Isotopic evidence for the past climates and vegetation of southern Africa

Directory of Open Access Journals (Sweden)

J. C. Vogel

1983-11-01

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.

On-line hyperfine structure and isotope shift measurements with diffuse light collection and photon burst detection

International Nuclear Information System (INIS)

Lassen, J.; Benck, E.C.; Schuessler, H.A.

1997-01-01

An experiment is presently being set up which combines collinear-fast-beam laser spectroscopy with photon burst spectroscopy. Selectivity is provided by the large kinetic isotope shifts together with the practically Doppler free linewidth of the fluorescence from the fast atom beam. The photon burst detection, based on photon correlations in the resonance fluorescence, increases the sensitivity, so that on-line optical isotope shift and hyperfine structure measurements on low intensity radioactive beams become feasible. In order to improve photon burst detection the solid angle of detection and the observation time have to be optimized. To this end a diffuse reflecting cavity has been designed and built, which collects fluorescence over a 45 cm length of the beam and covers the full solid angle. The light collection efficiency of the cavity is calculated to be about 45%. The cavity is being tested with a 11 keV beam of krypton atoms, probing the near infrared transitions in our apparatus at Texas A ampersand M University. copyright 1997 American Institute of Physics

ANALYTICAL EMPLOYMENT OF STABLE ISOTOPES OF CARBON, NITROGEN, OXYGEN AND HYDROGEN FOR FOOD AUTHENTICATION

Directory of Open Access Journals (Sweden)

E. Novelli

2011-04-01

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.

Carbon and oxygen stable isotope and trace element studies in speleothems and across the J-K boundary, Central Italy

International Nuclear Information System (INIS)

Kudielka, G.

2001-07-01

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

The oxygen-isotope effect on the in-plane penetration depth in underdoped Y{sub 1-x} Pr{sub x} Ba{sub 2} Cu{sub 3} O{sub 7-{delta}} as revealed by muon-spin rotation

Energy Technology Data Exchange (ETDEWEB)

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

2003-01-22

The oxygen-isotope ({sup 16}O/{sup 18}O) effect (OIE) on the in-plane penetration depth {lambda}{sub ab} (0) in underdoped Y{sub 1-x} Pr{sub x} Ba{sub 2} Cu{sub 3} O{sub 7-{delta}} was studied by means of muon-spin rotation. A pronounced OIE on {lambda}{sub ab}{sup -2} (0) was observed with a relative isotope shift of {delta}{lambda}{sub ab}{sup -2} /{lambda} {sub ab}{sup -2} = -5(2)% for x=0.3 and -9(2)% for x=0.4. The OIE exponents of T{sub c} and of {lambda}{sub ab}{sup -2} (0) exhibit a relation that appears to be generic for cuprate superconductors. (letter to the editor)

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

DEFF Research Database (Denmark)

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

2012-01-01

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...

Isotopically Enriched C-13 Diamond Anvil as a Stress Sensor in High Pressure Experiments

Science.gov (United States)

Vohra, Yogesh; Qiu, Wei; Kondratyev, Andreiy; Velisavljevic, Nenad; Baker, Paul

2004-03-01

The conventional high pressure diamond anvils were modified by growing an isotopically pure C-13 diamond layer by microwave plasma chemical vapor deposition using methane/hydrogen/oxygen chemistry. The isotopically pure C-13 nature of the culet of the diamond anvil was confirmed by the Raman spectroscopy measurements. This isotopically engineered diamond anvil was used against a natural abundance diamond anvil for high pressure experiments in a diamond anvil cell. Spatial resolved Raman spectroscopy was used to measure the stress induced shift in the C-13 layer as well as the undelying C-12 layer to ultra high pressures. The observed shift and splitiing of the diamond first order Raman spectrum was correlated with the stress distribution in the diamond anvil cell. The experimental results will be compared with the finite element modeling results using NIKE-2D software in order to create a mathematical relationship between sets of the following parameters: vertical (z axis) distance; horizontal (r axis) distance; max shear stress, and pressure. The isotopically enriched diamond anvils offer unique opportunities to measure stress distribution in the diamond anvil cell devices.

Strontium isotopes provide clues for a process shift in base cation dynamics in young volcanic soils

Science.gov (United States)

Bingham, N.; Jackson, M. G.; Bookhagen, B.; Maher, K.; Chadwick, O.

2015-12-01

Despite advances in soil development theory based on studies of old soils or over long timescales, little is known about soil thresholds (dramatic changes in soil properties associated with only small shifts in external forcing factors) that might be expressed in young soils (less than 10 kyr). Therefore, we seek to understand infant soil development in a tropical environment through the sourcing of plant available base cations by measuring the strontium (Sr) isotopic composition of the soil exchange complex. Our sampling strategy spans soils in three different precipitation ranges (950-1060 mm, 1180-1210 mm, and 1450-1500) and an array of soil ages from 500 to 7500 years in the Kona region on the island of Hawaii. In Hawaiian soils, 87Sr/86Sr values are determined by a mixture of three components: a mantle-derived component from the lava (0.7034), a rainfall component (0.7093) and a component from continental dust (0.720). Elevation-controlled leaching intensity in the wettest localities produces a decline in the concentration of base cations supplied by basalt and a dilute resupply by rainfall. In the driest sites, where leaching intensity is dramatically reduced, there is a buildup of rainfall-derived extractable Sr in the soil over time. Slow rock weathering rates produce a small rock-derived cation input to the soil. Thus, Sr isotope signatures reflect both the input of rainfall-derived cations and rock-derived cations with values that fall between rainfall and basaltic signatures. Soils in the intermediate precipitation range have Sr isotopic signatures consistent with both the wet and dry trends; suggesting that they lie close to the critical precipitation amount that marks a shift between these two processes. For the Kona region, this transition seems to occur at 1200 mm /yr. In contrast to the clear-cut differentiation in strontium isotopes with precipitation shifts observed in older soils, patterns on these young soils in Kona are complicated by low soil

Automated system measuring triple oxygen and nitrogen isotope ratios in nitrate using the bacterial method and N2 O decomposition by microwave discharge.

Science.gov (United States)

Hattori, Shohei; Savarino, Joel; Kamezaki, Kazuki; Ishino, Sakiko; Dyckmans, Jens; Fujinawa, Tamaki; Caillon, Nicolas; Barbero, Albane; Mukotaka, Arata; Toyoda, Sakae; Well, Reinhard; Yoshida, Naohiro

2016-12-30

Triple oxygen and nitrogen isotope ratios in nitrate are powerful tools for assessing atmospheric nitrate formation pathways and their contribution to ecosystems. N 2 O decomposition using microwave-induced plasma (MIP) has been used only for measurements of oxygen isotopes to date, but it is also possible to measure nitrogen isotopes during the same analytical run. The main improvements to a previous system are (i) an automated distribution system of nitrate to the bacterial medium, (ii) N 2 O separation by gas chromatography before N 2 O decomposition using the MIP, (iii) use of a corundum tube for microwave discharge, and (iv) development of an automated system for isotopic measurements. Three nitrate standards with sample sizes of 60, 80, 100, and 120 nmol were measured to investigate the sample size dependence of the isotope measurements. The δ 17 O, δ 18 O, and Δ 17 O values increased with increasing sample size, although the δ 15 N value showed no significant size dependency. Different calibration slopes and intercepts were obtained with different sample amounts. The slopes and intercepts for the regression lines in different sample amounts were dependent on sample size, indicating that the extent of oxygen exchange is also dependent on sample size. The sample-size-dependent slopes and intercepts were fitted using natural log (ln) regression curves, and the slopes and intercepts can be estimated to apply to any sample size corrections. When using 100 nmol samples, the standard deviations of residuals from the regression lines for this system were 0.5‰, 0.3‰, and 0.1‰, respectively, for the δ 18 O, Δ 17 O, and δ 15 N values, results that are not inferior to those from other systems using gold tube or gold wire. An automated system was developed to measure triple oxygen and nitrogen isotopes in nitrate using N 2 O decomposition by MIP. This system enables us to measure both triple oxygen and nitrogen isotopes in nitrate with comparable precision

An experimental study on the effect of carbonic anhydrase on the oxygen isotope exchange kinetics and equilibrium in the carbonic acid system

Science.gov (United States)

Uchikawa, J.; Zeebe, R. E.

2011-12-01

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.

Isotope shift measurements in the 2s(1/2) -> 2p(3/2) transition of Be+ and extraction of the nuclear charge radii for Be-7,Be-10,Be-11

CERN Document Server

Zakova, M; Yordanov, D T; Lochmann, M; Drake, G W F; Yan, Z-C; Neugart, R; Kowalska, M; Blaum, K; Andjelkovic, Z; Kraemer, J; Bissell, M L; Neff, T; Schmidt-Kaler, F; Sanchez, R; Noertershaeuser, W; Geppert, Ch; Tiedemann, D; Zimmermann, C

2010-01-01

We have performed isotope shift measurements in the 2s(1/2) -> 2p(3/2) transition of Be+ ions using advanced collinear laser spectroscopy with two counter-propagating laser beams. Measurements involving a frequency comb for laser stabilization and absolute frequency determination allowed us to determine the isotope shifts with an accuracy of 2 MHz. From the isotope shifts between Be-9 and Be-7,Be-10,Be-11, high-accuracy mass shift calculations and the charge radius of the reference isotope Be-9 we determined nuclear charge radii for the isotopes Be-7,Be-10 and the one-neutron halo nucleus Be-11. The results are compared to nuclear-structure calculations using the fermionic molecular dynamics model which reproduce well the general trend of the radii. Decreasing charge radii from Be-7 to Be-10 are explained by the cluster structure of the nuclei. The increase from Be-10 to Be-11 is mainly caused by the halo neutron by which the Be-10 core moves relative to the center of mass. Polarization of the Be-10 core has ...

Construction of a two-photon-laser spectrometer and determination of the hyperfine splitting and isotopic shift of barium

International Nuclear Information System (INIS)

Jitschin, W.

1977-01-01

A sensitive two-photon-laser spectrometer was constructed, that allowed to measure atomic states with an energy from 31 000 up to 37500 cm -1 with about 2 MHz resolution. The large energy range and the high resolution were reached by using a wide-wavelength tunable, narrow-band dye-laser. With this spectrometer transitions could be detected at barium from the electron ground-state 6s 2 1 S 0 to 10 upper states in the 5 most common isotopes 138 Ba, 137 Ba, 136 Ba, 135 Ba and 134 Ba. The transitions could be measured precisely. It was possible to derive lower limits of the life-time of these states from the widths of the recorded resonance lines (typically several nsec), that should in fact not be smaller than the actual lifetimes. From the measured hyper-fine splitting of the 6 transitions with angular momentum J = 2 at the oddnumbered isotopes 137 Ba and 135 Ba the parameters of the hyper-fine splitting could be determined. Hereby an accuracy of about IMH 2 could be reached at the A-factor and about 5MHz at the B-factor. At the measured transitions the isotopic shifts of the particular isotope could be determined with an accuracy of a few MHz. There was only a simple theory of the isotopic shift with only few parameters worked out for the theoretical interpretation of the measured data, that describes the data even at the experimentally reached high accuracy. Two parameters of this theory depending only from atomic nucleus properties, could be determined with a 0.5 % error. (orig./WB) [de

Correlation and Stacking of Relative Paleointensity and Oxygen Isotope Data

Science.gov (United States)

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

2012-12-01

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.

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

NARCIS (Netherlands)

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

2001-01-01

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

Workshop on Oxygen in the Terrestrial Planets

Science.gov (United States)

2004-01-01

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in

Shifts in coastal sediment oxygenation cause pronounced changes in microbial community composition and associated metabolism.

Science.gov (United States)

Broman, Elias; Sjöstedt, Johanna; Pinhassi, Jarone; Dopson, Mark

2017-08-09

A key characteristic of eutrophication in coastal seas is the expansion of hypoxic bottom waters, often referred to as 'dead zones'. One proposed remediation strategy for coastal dead zones in the Baltic Sea is to mix the water column using pump stations, circulating oxygenated water to the sea bottom. Although microbial metabolism in the sediment surface is recognized as key in regulating bulk chemical fluxes, it remains unknown how the microbial community and its metabolic processes are influenced by shifts in oxygen availability. Here, coastal Baltic Sea sediments sampled from oxic and anoxic sites, plus an intermediate area subjected to episodic oxygenation, were experimentally exposed to oxygen shifts. Chemical, 16S rRNA gene, metagenomic, and metatranscriptomic analyses were conducted to investigate changes in chemistry fluxes, microbial community structure, and metabolic functions in the sediment surface. Compared to anoxic controls, oxygenation of anoxic sediment resulted in a proliferation of bacterial populations in the facultative anaerobic genus Sulfurovum that are capable of oxidizing toxic sulfide. Furthermore, the oxygenated sediment had higher amounts of RNA transcripts annotated as sqr, fccB, and dsrA involved in sulfide oxidation. In addition, the importance of cryptic sulfur cycling was highlighted by the oxidative genes listed above as well as dsvA, ttrB, dmsA, and ddhAB that encode reductive processes being identified in anoxic and intermediate sediments turned oxic. In particular, the intermediate site sediments responded differently upon oxygenation compared to the anoxic and oxic site sediments. This included a microbial community composition with more habitat generalists, lower amounts of RNA transcripts attributed to methane oxidation, and a reduced rate of organic matter degradation. These novel data emphasize that genetic expression analyses has the power to identify key molecular mechanisms that regulate microbial community responses

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

NARCIS (Netherlands)

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

2003-01-01

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

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

Directory of Open Access Journals (Sweden)

A. Wackerbarth

2012-11-01

Full Text Available Interpreting stable oxygen isotope (δ¹⁸O 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

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

DEFF Research Database (Denmark)

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

2016-01-01

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...

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

NARCIS (Netherlands)

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

2014-01-01

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

Towards isotope shift and hyperfine structure measurements of the element nobelium

Energy Technology Data Exchange (ETDEWEB)

Chhetri, Premaditya; Lautenschlaeger, Felix; Walther, Thomas [Institut fuer Angewandte Physik, TU Darmstadt, D-64289 Darmstadt (Germany); Laatiaoui, Mustapha [Helmholtz Institut Mainz, D-55099 Mainz (Germany); Block, Michael; Hessberger, Fritz-Peter [Helmholtz Institut Mainz, D-55099 Mainz (Germany); GSI, D-64291 Darmstadt (Germany); Lauth, Werner; Backe, Hartmut [Institut fuer Kernphysik, JGU Mainz, D-55122 Mainz (Germany); Kunz, Peter [TRIUMF, D-V6T2A3 Vancouver (Canada)

2014-07-01

Laser spectroscopy on the heaviest elements is of great interest as it allows the study of the evolution of relativistic effects on their atomic structure. In our experiment we exploit the Radiation Detected Resonance Ionization Spectroscopy technique and use excimer-laser pumped dye lasers to search for the first time the {sup 1}P{sub 1} level in {sup 254}No. Etalons will be used in the forthcoming experiments at GSI, Darmstadt, to narrow down the bandwidth of the dye lasers to 0.04 cm{sup -1}, for the determination of the isotope shift and hyperfine splitting of {sup 253,} {sup 255}No. In this talk results from preparatory hyperfine structure studies in nat. ytterbium and the perspectives for future experiments of the heaviest elements are discussed.

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

International Nuclear Information System (INIS)

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

2005-01-01

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

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

Science.gov (United States)

Szymanek, Marcin

2017-12-01

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

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

International Nuclear Information System (INIS)

Olausson, E.

1984-01-01

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.)

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

Science.gov (United States)

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

2017-08-01

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.

Quasi-free one nucleon knockout reactions on neutron-rich oxygen isotopes at the R3B-LAND setup

Energy Technology Data Exchange (ETDEWEB)

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

2016-07-01

Recent experiments have showed a reduction of spectroscopic strengths of about 60-70% for stable nuclei. When going to driplines 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 a secondary beam {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.

Cross-continental triple oxygen isotope analysis of tropospheric CO2

Science.gov (United States)

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

2016-12-01

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.

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

Science.gov (United States)

Schmidt, Gavin A.

1999-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Isomura, Shohei; Tonooka, Yasuhiko; Kaetsu, Hayato

1987-02-01

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.

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

International Nuclear Information System (INIS)

Isomura, Shohei; Tonooka, Yasuhiko; Kaetsu, Hayato

1987-01-01

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)

OXYGEN ISOTOPIC COMPOSITIONS OF THE ALLENDE TYPE C CAIs: EVIDENCE FOR ISOTOPIC EXCHANGE DURING NEBULAR MELTING AND ASTEROIDAL THERMAL METAMORPHISM

Energy Technology Data Exchange (ETDEWEB)

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

2008-02-21

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

Stable isotopes reveal diet shift from pre-extinction to reintroduced Przewalski's horses.

Science.gov (United States)

Kaczensky, Petra; Burnik Šturm, Martina; Sablin, Mikhail V; Voigt, Christian C; Smith, Steve; Ganbaatar, Oyunsaikhan; Balint, Boglarka; Walzer, Chris; Spasskaya, Natalia N

2017-07-20

The Przewalski's horse (Equus ferus przewalskii), the only remaining wild horse within the equid family, is one of only a handful of species worldwide that went extinct in the wild, was saved by captive breeding, and has been successfully returned to the wild. However, concerns remain that after multiple generations in captivity the ecology of the Przewalski's horse and / or the ecological conditions in its former range have changed in a way compromising the species' long term survival. We analyzed stable isotope chronologies from tail hair of pre-extinction and reintroduced Przewalski's horses from the Dzungarian Gobi and detected a clear difference in the isotopic dietary composition. The direction of the dietary shift from being a mixed feeder in winter and a grazer in summer in the past, to a year-round grazer nowadays, is best explained by a release from human hunting pressure. A changed, positive societal attitude towards the species allows reintroduced Przewalski's horses to utilize the scarce, grass-dominated pastures of the Gobi alongside local people and their livestock whereas their historic conspecifics were forced into less productive habitats dominated by browse.

Dietary shift after 3600 cal yr BP and its influencing factors in northwestern China: Evidence from stable isotopes

Science.gov (United States)

Ma, Minmin; Dong, Guanghui; Jia, Xin; Wang, Hui; Cui, Yifu; Chen, Fahu

2017-04-01

:Human diets rely on natural resource availability and can reflect social and cultural values. When environments, societies, and cultures change, diets may also shift. This study traced the extent of dietary change and the factors influencing such change. Through stable carbon and nitrogen isotopic analysis of late Neolithic and early Bronze Age human and animal bone collagen, we found that significant shifts in human diets were closely associated with intercontinental cultural exchanges in Eurasia and climate change in northwestern China. The isotopic evidence indicated that human diets mainly consisted of C4 foodstuffs (presumably millet and/or animals fed with C4 foods) around 4000 calibrated years before the present (cal yr BP), corresponding to the flourishing of millet agriculture in the context of the optimal climate conditions of the mid-Holocene. Subsequently, more C3 foods (probably wheat, barley, and animals fed with C3 foods) were added to human diets post-3600 cal yr BP when the climate became cooler and drier. Such dietary variation is also consistent with the increasing intensity of long-distance exchange after 4000 cal yr BP. While many factors can lead to human dietary shifts (e.g. climate change, population growth, cultural factors, and human migration), climate may have been a key factor in Gansu and Qinghai.

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

Digital Repository Service at National Institute of Oceanography (India)

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...

Isotope heterogeneity of Pre-Holocene groundwater in Iceland

DEFF Research Database (Denmark)

Sveinbjörnsdóttir, Á.E.; Arnorsson, S.; Heinemeier, Jan

2007-01-01

In recent years, it has been shown that groundwater with a Pre-Holocene component is more common in the Icelandic bedrock than previously thought. Some of the Pre-Holocene water samples are more depleted in delta H-2 and delta O-18 than any mean annual precipitation in Iceland today due to the cold...... climate at that time. However, most often Pre-Holocene water components cannot be detected based on the water isotopes alone due to mixing with younger and isotopically heavier water. The Cl concentration in relation to the water isotopes in specific areas has proved to be a good indicator of a Pre......-Holocene component in the groundwater. The deuterium excess value may also help to identify water from a different climate regime, if no oxygen shift has occurred. The relative abundance of a Pre-Holocene water component of the Icelandic groundwater has led to the understanding that combined interpretation of water...

Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study

Science.gov (United States)

Warwick, Peter D.; Ruppert, Leslie F.

2016-01-01

The concentration of carbon dioxide (CO2) in the atmosphere has dramatically increased from the start of the industrial revolution in the mid-1700s to present levels exceeding 400 ppm. Carbon dioxide derived from fossil fuel combustion is a greenhouse gas and a major contributor to on-going climate change. Carbon and oxygen stable isotope geochemistry is a useful tool to help model and predict the contributions of anthropogenic sources of CO2 in the global carbon cycle. Surprisingly few studies have addressed the carbon and oxygen isotopic composition of CO2 derived from coal combustion. The goal of this study is to document the relationships between the carbon and oxygen isotope signatures of coal and signatures of the CO2 produced from laboratory coal combustion in atmospheric conditions.Six coal samples were selected that represent various geologic ages (Carboniferous to Tertiary) and coal ranks (lignite to bituminous). Duplicate splits of the six coal samples were ignited and partially combusted in the laboratory at atmospheric conditions. The resulting coal-combustion gases were collected and the molecular composition of the collected gases and isotopic analyses of δ13C of CO2, δ13C of CH4, and δ18O of CO2 were analysed by a commercial laboratory. Splits (~ 1 g) of the un-combusted dried ground coal samples were analyzed for δ13C and δ18O by the U.S. Geological Survey Reston Stable Isotope Laboratory.The major findings of this preliminary work indicate that the isotopic signatures of δ13C (relative to the Vienna Pee Dee Belemnite scale, VPDB) of CO2 resulting from coal combustion are similar to the δ13CVPDB signature of the bulk coal (− 28.46 to − 23.86 ‰) and are not similar to atmospheric δ13CVPDB of CO2 (~ − 8 ‰, see http://www.esrl.noaa.gov/gmd/outreach/isotopes/c13tellsus.html). The δ18O values of bulk coal are strongly correlated to the coal dry ash yields and appear to have little or no influence on the δ18O values of CO2

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

International Nuclear Information System (INIS)

Ghazi, S.; Sajid, Z.

2014-01-01

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)

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

Science.gov (United States)

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

2013-12-01

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

Can oxygen stable isotopes be used to track precipitation moisture source in vascular plant-dominated peatlands?

Science.gov (United States)

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.

2015-11-01

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

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

Science.gov (United States)

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

2011-01-01

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.

Oxygen and U-Th isotopes and the timescales of hydrothermal exchange and melting in granitoid wall rocks at Mount Mazama, Crater Lake, Oregon

Science.gov (United States)

Ankney, Meagan E.; Bacon, Charles R.; Valley, John W.; Beard, Brian L.; Johnson, Clark M.

2017-01-01

We report new whole rock U-Th and in-situ oxygen isotope compositions for partially melted (0–50 vol% melt), low-δ18O Pleistocene granitoid blocks ejected during the ∼7.7 ka caldera-forming eruption of Mt. Mazama (Crater Lake, Oregon). The blocks are interpreted to represent wall rocks of the climactic magma chamber that, prior to eruption, experienced variable amounts of exchange with meteoric hydrothermal fluids and subsequent partial melting. U-Th and oxygen isotope results allow us to examine the timescales of hydrothermal circulation and partial melting, and provide an “outside in” perspective on the buildup to the climactic eruption of Mt. Mazama. Oxygen isotope compositions measured in the cores and rims of individual quartz (n = 126) and plagioclase (n = 91) crystals, and for transects across ten quartz crystals, document zonation in quartz (Δ18OCore-Rim ≤ 0.1–5.5‰), but show homogeneity in plagioclase (Δ18OCore-Rim ≤ ±0.8‰). We propose that oxygen isotope zonation in quartz records hydrothermal exchange followed by high-temperature exchange in response to partial melting caused by injection of basaltic to andesitic recharge magma into the deeper portions of the chamber. Results of modeling of oxygen diffusion in quartz indicates that hydrothermal exchange in quartz occurred over a period of ∼1000–63,000 years. Models also suggest that the onset of melting of the granitoids occurred a minimum of ∼10–200 years prior to the Mazama climactic eruption, an inference which is broadly consistent with results for magnetite homogenization and for Zr diffusion in melt previously reported by others.Uranium-thorium isotope compositions of most granitoid blocks are in 238U excess, and are in agreement with a 238U enriched array previously measured for volcanic rocks at Mt. Mazama. Uranium excess in the granitoids is likely due to enrichment via hydrothermal circulation, given their low δ18O values. The sample with the

Environmental isotope hydrology

International Nuclear Information System (INIS)

1973-01-01

Environmental isotope hydrology is a relatively new field of investigation based on isotopic variations observed in natural waters. These isotopic characteristics have been established over a broad space and time scale. They cannot be controlled by man, but can be observed and interpreted to gain valuable regional information on the origin, turnover and transit time of water in the system which often cannot be obtained by other techniques. The cost of such investigations is usually relatively small in comparison with the cost of classical hydrological studies. The main environmental isotopes of hydrological interest are the stable isotopes deuterium (hydrogen-2), carbon-13, oxygen-18, and the radioactive isotopes tritium (hydrogen-3) and carbon-14. Isotopes of hydrogen and oxygen are ideal geochemical tracers of water because their concentrations are usually not subject to change by interaction with the aquifer material. On the other hand, carbon compounds in groundwater may interact with the aquifer material, complicating the interpretation of carbon-14 data. A few other environmental isotopes such as 32 Si and 238 U/ 234 U have been proposed recently for hydrological purposes but their use has been quite limited until now and they will not be discussed here. (author)

Anatomy of the thriple oxygen isotope Terrestrial Fractionatoin Line

Science.gov (United States)

Sharp, Z. D.; Pack, A.

2017-12-01

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

Planetary fertility during the past 400 ka based on the triple isotope composition of atmospheric oxygen in trapped gases from the Vostok ice core

Science.gov (United States)

Blunier, T.; Bender, M. L.; Barnett, B.; von Fisher, J. C.

2012-04-01

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.

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

Science.gov (United States)

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

2012-01-01

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.

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

Science.gov (United States)

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

2017-04-01

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

Oxygen isotope thermometry of quartz-Al2SiO5veins in high-grade metamorphic rocks on Naxos island (Greece)

Science.gov (United States)

Putlitz, Benita; Valley, John; Matthews, Alan; Katzir, Yaron

2002-04-01

Diffusion models predict that peak metamorphic temperatures are best recorded by the oxygen isotope fractionation between minerals in a bi-mineralic rock in which a refractory accessory mineral with slow oxygen diffusion rate is modally minor to a mineral with a faster diffusion rate. This premise is demonstrated for high-grade metamorphism on the island of Naxos, Greece, where quartz-kyanite oxygen isotope thermometry from veins in high-grade metamorphic pelites gives temperatures of 635-690 °C. These temperatures are in excellent agreement with independent thermometry for the regional M2 peak metamorphic conditions and show that the vein minerals isotopically equilibrated at the peak of metamorphism. Quartz-sillimanite fractionations in the same veins give similar temperatures (680+/-35 °C) and suggest that the veins grew near to the kyanite-sillimanite boundary, corresponding to pressures of 6.5 to 7.5 kbar for temperatures of 635-685 °C. By contrast, quartz-kyanite and quartz-biotite pairs in the host rocks yield lower temperature estimates than the veins (590-600 and 350-550 °C, respectively). These lower apparent temperatures are also predicted from calculations of diffusional resetting in the polyphase host-rock system. The data demonstrate that bimineralic vein assemblages can be used as accurate thermometers in high-temperature rocks whereas retrograde exchange remains a major problem in many polymineralic rocks.

Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

Science.gov (United States)

Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.

2017-10-01

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.

The development of a completely automated oxygen isotope mass spectrometer

International Nuclear Information System (INIS)

Ahern, T.K.

1980-01-01

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

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

OpenAIRE

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

2012-01-01

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...

Correlation of zero-point energy with molecular structure and molecular forces. 3. Approximation for H/D isotope shifts and linear frequency sum rule

International Nuclear Information System (INIS)

Oi, T.; Ishida, T.

1984-01-01

The approximation methods for the zero-point energy (ZPE) previously developed using the Lanczo's tau method have been applied to the shifts in ZPE due to hydrogen isotope substitutions. Six types of approximation methods have been compared and analyzed on the basis of a weighing function Ω(lambda) varies as lambda/sup k/ and the actual eigenvalue shift spectra. The method generated by the most general optimzation treatment yields a predictable and generally satisfactory precision of the order of 1% or better. A linear frequency sum rule has been derived, which approximately holds for the sets of isotopic molecules which satisfy the second-order frequency sum rule. 19 references, 3 figures, 3 tables

Precision Isotope Shift Measurements in Calcium Ions Using Quantum Logic Detection Schemes.

Science.gov (United States)

Gebert, Florian; Wan, Yong; Wolf, Fabian; Angstmann, Christopher N; Berengut, Julian C; Schmidt, Piet O

2015-07-31

We demonstrate an efficient high-precision optical spectroscopy technique for single trapped ions with nonclosed transitions. In a double-shelving technique, the absorption of a single photon is first amplified to several phonons of a normal motional mode shared with a cotrapped cooling ion of a different species, before being further amplified to thousands of fluorescence photons emitted by the cooling ion using the standard electron shelving technique. We employ this extension of the photon recoil spectroscopy technique to perform the first high precision absolute frequency measurement of the 2D(3/2)→2P(1/2) transition in calcium, resulting in a transition frequency of f=346 000 234 867(96)  kHz. Furthermore, we determine the isotope shift of this transition and the 2S(1/2)→2P(1/2) transition for 42Ca+, 44Ca+, and 48Ca+ ions relative to 40Ca+ with an accuracy below 100 kHz. Improved field and mass shift constants of these transitions as well as changes in mean square nuclear charge radii are extracted from this high resolution data.

Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

Energy Technology Data Exchange (ETDEWEB)

Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

2017-05-01

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.

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

Science.gov (United States)

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

2018-01-01

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.

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

Science.gov (United States)

Viswanathan, S.

1974-01-01

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.

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

Science.gov (United States)

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

2018-02-02

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.

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

International Nuclear Information System (INIS)

Vaikmaee, R.; Vassilchuk, Y.

1991-01-01

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

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

International Nuclear Information System (INIS)

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

1986-01-01

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)

A First Look at Oxygen and Silicon Isotope Variations in Diatom Silica from a Pliocene Antarctic Marine Sediment Core

Science.gov (United States)

Abbott, T.; Dodd, J. P.; Hackett, H.; Scherer, R. P.

2016-02-01

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

Isotope exchange of molecular oxygen with oxygen of La0,7Sr0,3CoO3-δ

International Nuclear Information System (INIS)

Vdovin, G.K.; Kuzin, B.L.; Kurumchin, Eh.Kh.

1991-01-01

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

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

Science.gov (United States)

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

2013-12-01

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

Isotopic geochemistry at Wairakei

International Nuclear Information System (INIS)

Stewart, M.K.

1985-12-01

Deuterium measurements on geothermal water at Wairakei are consistent with the water being derived from rainfall which has percolated down from the surface. The oxygen-18 content, however, is enriched compared to average rainfall. This 18 O shift is due to isotopic exchange between water and rock at greater-than-explored depths. The magnitude of the shift implied that the mass ration (W/R) of water that has passed through the system (W) to the rock it has exchanged with (R) is about 1 assuming open (i.e. single-pass) conditions. (The ratio is about 2 if it has been a closed system, but this is thought to be less likely). The residence time of water underground cannot be determined from tritium and carbon-14 measurements at present, but arguments based on the argon isotope and deuterium contents suggest mean residence times of a few tens of thousand years. The water-rock ratio and large natural outflow of thermal water prior to exploitation are consistent with this. The 18 O content of the water has changed only slightly, and the D content not at all, during exploitation at Wairakei (measurements from 1963, 1974 and 1981). An initial tendency for the 18 O to increase because of steam loss (also shown more clearly by chloride), has been followed by decrease of 18 O (and chloride) because of dilution with infiltrating near-surface water in parts of the field

Relationship of leaf oxygen and carbon isotopic composition with transpiration efficiency in the C4 grasses Setaria viridis and Setaria italica.

Science.gov (United States)

Ellsworth, Patrick Z; Ellsworth, Patrícia V; Cousins, Asaph B

2017-06-15

Leaf carbon and oxygen isotope ratios can potentially provide a time-integrated proxy for stomatal conductance (gs) and transpiration rate (E), and can be used to estimate transpiration efficiency (TE). In this study, we found significant relationships of bulk leaf carbon isotopic signature (δ13CBL) and bulk leaf oxygen enrichment above source water (Δ18OBL) with gas exchange and TE in the model C4 grasses Setaria viridis and S. italica. Leaf δ13C had strong relationships with E, gs, water use, biomass, and TE. Additionally, the consistent difference in δ13CBL between well-watered and water-limited plants suggests that δ13CBL is effective in separating C4 plants with different availability of water. Alternatively, the use of Δ18OBL as a proxy for E and TE in S. viridis and S. italica was problematic. First, the oxygen isotopic composition of source water, used to calculate leaf water enrichment (Δ18OLW), was variable with time and differed across water treatments. Second, water limitations changed leaf size and masked the relationship of Δ18OLW and Δ18OBL with E. Therefore, the data collected here suggest that δ13CBL but not Δ18OBL may be an effective proxy for TE in C4 grasses. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

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

Science.gov (United States)

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

2017-05-01

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.

Quantitative analysis of deuterium using the isotopic effect on quaternary {sup 13}C NMR chemical shifts

Energy Technology Data Exchange (ETDEWEB)

Darwish, Tamim A., E-mail: tamim.darwish@ansto.gov.au [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); Yepuri, Nageshwar Rao; Holden, Peter J. [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); James, Michael [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia)

2016-07-13

Quantitative analysis of specifically deuterated compounds can be achieved by a number of conventional methods, such as mass spectroscopy, or by quantifying the residual {sup 1}H NMR signals compared to signals from internal standards. However, site specific quantification using these methods becomes challenging when dealing with non-specifically or randomly deuterated compounds that are produced by metal catalyzed hydrothermal reactions in D{sub 2}O, one of the most convenient deuteration methods. In this study, deuterium-induced NMR isotope shifts of quaternary {sup 13}C resonances neighboring deuterated sites have been utilized to quantify the degree of isotope labeling of molecular sites in non-specifically deuterated molecules. By probing {sup 13}C NMR signals while decoupling both proton and deuterium nuclei, it is possible to resolve {sup 13}C resonances of the different isotopologues based on the isotopic shifts and the degree of deuteration of the carbon atoms. We demonstrate that in different isotopologues, the same quaternary carbon, neighboring partially deuterated carbon atoms, are affected to an equal extent by relaxation. Decoupling both nuclei ({sup 1}H, {sup 2}H) resolves closely separated quaternary {sup 13}C signals of the different isotopologues, and allows their accurate integration and quantification under short relaxation delays (D1 = 1 s) and hence fast accumulative spectral acquisition. We have performed a number of approaches to quantify the deuterium content at different specific sites to demonstrate a convenient and generic analysis method for use in randomly deuterated molecules, or in cases of specifically deuterated molecules where back-exchange processes may take place during work up. - Graphical abstract: The relative intensities of quaternary {sup 13}C {"1H,"2H} resonances are equal despite the different relaxation delays, allowing the relative abundance of the different deuterated isotopologues to be calculated using NMR fast

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

NARCIS (Netherlands)

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

2006-01-01

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

Charge distributions of barium isotopes from muonic X-rays

International Nuclear Information System (INIS)

Shera, E.B.; Wohlfahrt, H.D.; Hoehn, M.V.; Tanaka, Y.

1982-01-01

The results of a muonic X-ray study of the charge radii of stable barium isotopes are presented and compared with optical isotope shifts. The isotope shifts Δ 2 > of a wide range of barium isotopes are found to be in good agreement with the droplet model and with IBA calculations. (orig.)

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

Energy Technology Data Exchange (ETDEWEB)

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

1979-07-01

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.

Sulfur and Oxygen Isotopic Composition of Sulfate in the Fresh Water, King Sejong Station, King George Island, Antarctica

Science.gov (United States)

Kim, M.; Lee, I.; Lee, J.; Park, B.; Mayer, B.; Kaufman, A. J.; Park, S.; Kim, G.; Lee, K.

2008-12-01

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

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

Science.gov (United States)

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

2017-09-01

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.

Near Surface CO2 Triple Oxygen Isotope Composition

Directory of Open Access Journals (Sweden)

Sasadhar Mahata

2016-02-01

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.

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

DEFF Research Database (Denmark)

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

2013-01-01

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...

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

Science.gov (United States)

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

2005-01-01

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.

Unravelling spatiotemporal tree-ring signals in Mediterranean oaks: a variance-covariance modelling approach of carbon and oxygen isotope ratios.

Science.gov (United States)

Shestakova, Tatiana A; Aguilera, Mònica; Ferrio, Juan Pedro; Gutiérrez, Emilia; Voltas, Jordi

2014-08-01

Identifying how physiological responses are structured across environmental gradients is critical to understanding in what manner ecological factors determine tree performance. Here, we investigated the spatiotemporal patterns of signal strength of carbon isotope discrimination (Δ(13)C) and oxygen isotope composition (δ(18)O) for three deciduous oaks (Quercus faginea (Lam.), Q. humilis Mill. and Q. petraea (Matt.) Liebl.) and one evergreen oak (Q. ilex L.) co-occurring in Mediterranean forests along an aridity gradient. We hypothesized that contrasting strategies in response to drought would lead to differential climate sensitivities between functional groups. Such differential sensitivities could result in a contrasting imprint on stable isotopes, depending on whether the spatial or temporal organization of tree-ring signals was analysed. To test these hypotheses, we proposed a mixed modelling framework to group isotopic records into potentially homogeneous subsets according to taxonomic or geographical criteria. To this end, carbon and oxygen isotopes were modelled through different variance-covariance structures for the variability among years (at the temporal level) or sites (at the spatial level). Signal-strength parameters were estimated from the outcome of selected models. We found striking differences between deciduous and evergreen oaks in the organization of their temporal and spatial signals. Therefore, the relationships with climate were examined independently for each functional group. While Q. ilex exhibited a large spatial dependence of isotopic signals on the temperature regime, deciduous oaks showed a greater dependence on precipitation, confirming their higher susceptibility to drought. Such contrasting responses to drought among oak types were also observed at the temporal level (interannual variability), with stronger associations with growing-season water availability in deciduous oaks. Thus, our results indicate that Mediterranean deciduous

A high resolution photoemission study of surface core-level shifts in clean and oxygen-covered Ir(2 1 0) surfaces

Energy Technology Data Exchange (ETDEWEB)

Gladys, M.J.; Ermanoski, I.; Jackson, G.; Quinton, J.S.; Rowe, J.E.; Madey, T.E. E-mail: madey@physics.rutgers.edu

2004-04-01

High resolution soft X-ray photoemission electron spectroscopy (SXPS), using synchrotron radiation, is employed to investigate 4f core-level features of four differently-prepared Ir(2 1 0) surfaces: clean planar, oxygen-covered planar, oxygen-induced faceted, and clean faceted surfaces. Surface and bulk peak identifications are supported by measurements at different photon energies (thus probing different electron escape depths) and variable emission angles. Iridium 4f{sub 7/2} photoemission spectra are fitted with Doniach-Sunjic lineshapes. The surface components are identified with core levels positioned at lower binding energies than the bulk components, in contrast to previous reports of binding energy inversion on Ir(1 0 0) (1x1) and (5x1) surfaces. For clean planar Ir(2 1 0) three surface Ir 4f{sub 7/2} features are observed with core-level shifts of -765, -529, and -281 meV, with respect to the bulk; these are associated with the first, second and third layers of atoms, respectively, for atomically rough Ir(2 1 0). Adsorption of oxygen onto the planar Ir(2 1 0) surface is found to cause a suppression and shift of the surface features to higher binding energies. Annealing at T{>=}600 K in oxygen produces a faceted surface as verified by low energy electron diffraction (LEED). A comparison of planar and faceted oxygen-covered surfaces reveals minor differences in the normal emission SXPS spectra, while grazing emission spectra exhibit differences. The SXPS spectrum of the clean, faceted Ir(2 1 0) exhibits small differences in comparison to the clean planar case, with surface features having binding energy shifts of -710, -450, and -230 meV.

Chromium isotope fractionation during coprecipitation with calcium carbonate

DEFF Research Database (Denmark)

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

The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during the Ar...... et al., 2007, Water Air Soil Poll. 179, 381-390. [2] Sánchez-Pastor et al., 2011, Cryst. Growth Des. 11, 3081-3089.......The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during...... the Archaean and Protoerozoic, needs careful assessment of the signal robustness and necessitates a thorough understanding of the Cr cycle in Earth system processes. We conducted experiments testing the incorporation and isotopic fractionation of chromate into the calcite lattice. Our experiments indicate...

A Computational Drug Metabolite Detection Using the Stable Isotopic Mass-Shift Filtering with High Resolution Mass Spectrometry in Pioglitazone and Flurbiprofen

Directory of Open Access Journals (Sweden)

Yohei Miyamoto

2013-09-01

Full Text Available The identification of metabolites in drug discovery is important. At present, radioisotopes and mass spectrometry are both widely used. However, rapid and comprehensive identification is still laborious and difficult. In this study, we developed new analytical software and employed a stable isotope as a tool to identify drug metabolites using mass spectrometry. A deuterium-labeled compound and non-labeled compound were both metabolized in human liver microsomes and analyzed by liquid chromatography/time-of-flight mass spectrometry (LC-TOF-MS. We computationally aligned two different MS data sets and filtered ions having a specific mass-shift equal to masses of labeled isotopes between those data using our own software. For pioglitazone and flurbiprofen, eight and four metabolites, respectively, were identified with calculations of mass and formulas and chemical structural fragmentation analysis. With high resolution MS, the approach became more accurate. The approach detected two unexpected metabolites in pioglitazone, i.e., the hydroxypropanamide form and the aldehyde hydrolysis form, which other approaches such as metabolite-biotransformation list matching and mass defect filtering could not detect. We demonstrated that the approach using computational alignment and stable isotopic mass-shift filtering has the ability to identify drug metabolites and is useful in drug discovery.

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, I

Science.gov (United States)

2004-01-01

The Special Session: Oxygen in the Solar System, I, included the following reports:Oxygen in the Solar System: Origins of Isotopic and Redox Complexity; The Origin of Oxygen Isotope Variations in the Early Solar System; Solar and Solar-Wind Oxygen Isotopes and the Genesis Mission; Solar 18O/17O and the Setting for Solar Birth; Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites; Insight into Primordial Solar System Oxygen Reservoirs from Returned Cometary Samples; Tracing Meteorites to Their Sources Through Asteroid Spectroscopy; Redox Conditions Among the Terrestrial Planets; Redox Complexity in Martian Meteorites: Implications for Oxygen in the Terrestrial Planets; Implications of Sulfur Isotopes for the Evolution of Atmospheric Oxygen; Oxygen in the Outer Solar System; and On the Oxidation States of the Galilean Satellites: Implications for Internal Structures.

Multiple stable isotope fronts during non-isothermal fluid flow

Science.gov (United States)

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

2018-02-01

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

Oxygen isotopes in tree rings are a good proxy for Amazon precipitation and El Niño-Southern Oscillation variability

Science.gov (United States)

Brienen, Roel J. W.; Helle, Gerd; Pons, Thijs L.; Guyot, Jean-Loup; Gloor, Manuel

2012-10-01

We present a unique proxy for the reconstruction of variation in precipitation over the Amazon: oxygen isotope ratios in annual rings in tropical cedar (Cedrela odorata). A century-long record from northern Bolivia shows that tree rings preserve the signal of oxygen isotopes in precipitation during the wet season, with weaker influences of temperature and vapor pressure. Tree ring δ18O correlates strongly with δ18O in precipitation from distant stations in the center and west of the basin, and with Andean ice core δ18O showing that the signal is coherent over large areas. The signal correlates most strongly with basin-wide precipitation and Amazon river discharge. We attribute the strength of this (negative) correlation mainly to the cumulative rainout processes of oxygen isotopes (Rayleigh distillation) in air parcels during westward transport across the basin. We further find a clear signature of the El Niño-Southern Oscillation (ENSO) in the record, with strong ENSO influences over recent decades, but weaker influence from 1925 to 1975 indicating decadal scale variation in the controls on the hydrological cycle. The record exhibits a significant increase in δ18O over the 20th century consistent with increases in Andean δ18O ice core and lake records, which we tentatively attribute to increased water vapor transport into the basin. Taking these data together, our record reveals a fresh path to diagnose and improve our understanding of variation and trends of the hydrological cycle of the world's largest river catchment.

Variations in stable hydrogen and oxygen isotopes in atmospheric water vapor in the marine boundary layer across a wide latitude range.

Science.gov (United States)

Liu, Jingfeng; Xiao, Cunde; Ding, Minghu; Ren, Jiawen

2014-11-01

The newly-developed cavity ring-down laser absorption spectroscopy analyzer with special calibration protocols has enabled the direct measurement of atmospheric vapor isotopes at high spatial and temporal resolution. This paper presents real-time hydrogen and oxygen stable isotope data for atmospheric water vapor above the sea surface, over a wide range of latitudes spanning from 38°N to 69°S. Our results showed relatively higher values of δ(18)O and δ(2)H in the subtropical regions than those in the tropical and high latitude regions, and also a notable decreasing trend in the Antarctic coastal region. By combining the hydrogen and oxygen isotope data with meteoric water line and backward trajectory model analysis, we explored the kinetic fractionation caused by subsiding air masses and related saturated vapor pressure in the subtropics, and the evaporation-driven kinetic fractionation in the Antarctic region. Simultaneous observations of meteorological and marine variables were used to interpret the isotopic composition characteristics and influential factors, indicating that d-excess is negatively correlated with humidity across a wide range of latitudes and weather conditions worldwide. Coincident with previous studies, d-excess is also positively correlated with sea surface temperature and air temperature (Tair), with greater sensitivity to Tair. Thus, atmospheric vapor isotopes measured with high accuracy and good spatial-temporal resolution could act as informative tracers for exploring the water cycle at different regional scales. Such monitoring efforts should be undertaken over a longer time period and in different regions of the world. Copyright © 2014. Published by Elsevier B.V.

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

Digital Repository Service at National Institute of Oceanography (India)

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...

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

Science.gov (United States)

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

2017-10-01

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.

Elucidation of oxidation and degradation products of oxygen containing fuel components by combined use of a stable isotopic tracer and mass spectrometry.

Science.gov (United States)

Frauscher, Marcella; Besser, Charlotte; Allmaier, Günter; Dörr, Nicole

2017-11-15

In order to reveal the degradation products of oxygen-containing fuel components, in particular fatty acid methyl esters, a novel approach was developed to characterize the oxidation behaviour. Combination of artificial alteration under pressurized oxygen atmosphere, a stable isotopic tracer, and gas chromatography electron impact mass spectrometry (GC-EI-MS) was used to obtain detailed information on the formation of oxidation products of (9Z), (12Z)-octadecadienoic acid methyl ester (C18:2 ME). Thereby, biodiesel simulating model compound C18:2 ME was oxidized in a rotating pressurized vessel standardized for lubricant oxidation tests (RPVOT), i.e., artificially altered, under 16 O 2 as well as 18 O 2 atmosphere. Identification of the formed degradation products, mainly carboxylic acids of various chain lengths, alcohols, ketones, and esters, was performed by means of GC-EI-MS. Comparison of mass spectra of compounds under both atmospheres revealed not only the degree of oxidation and the origin of oxygen atoms, but also the sites of oxidative attack and bond cleavage. Hence, the developed and outlined strategy based on a gas-phase stable isotopic tracer and mass spectrometry provides insight into the degradation of oxygen-containing fuels and fuel components by means of the accurate differentiation of oxygen origin in a degradation product. Copyright © 2017 Elsevier B.V. All rights reserved.

Ocean circulation and shelf processes in the Arctic, Mediterranean traced by radiogenic neodymium isotopes, rare earth elements and stable oxygen isotopes

Energy Technology Data Exchange (ETDEWEB)

Laukert, Georgi

2017-02-20

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

Isotope composition and volume of Earth's early oceans.

Science.gov (United States)

Pope, Emily C; Bird, Dennis K; Rosing, Minik T

2012-03-20

Oxygen and hydrogen isotope compositions of Earth's seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen's was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH(4) and CO(2) concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.

The isotope altitude effect reflected in groundwater: a case study from Slovenia.

Science.gov (United States)

Mezga, Kim; Urbanc, Janko; Cerar, Sonja

2014-01-01

This paper presents the stable isotope data of oxygen (δ(18)O) and hydrogen (δ(2)H) in groundwater from 83 sampling locations in Slovenia and their interpretation. The isotopic composition of water was monitored over 3 years (2009-2011), and each location was sampled twice. New findings on the isotopic composition of sampled groundwater are presented, and the data are also compared to past studies regarding the isotopic composition of precipitation, surface water, and groundwater in Slovenia. This study comprises: (1) the general characteristics of the isotopic composition of oxygen and hydrogen in groundwater in Slovenia, (2) the spatial distribution of oxygen isotope composition (δ(18)O) and d-excess in groundwater, (3) the groundwater isotope altitude effect, (4) the correlation between groundwater d-excess and the recharge area altitude of the sampling location, (5) the relation between hydrogen and oxygen isotopes in groundwater in comparison to the global precipitation isotope data, (6) the groundwater isotope effect of distance from the sea, and (7) the estimated relation between the mean temperature of recharge area and δ(18)O in groundwater.

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

Science.gov (United States)

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

2010-07-01

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.

Fractionation behavior of chromium isotopes during coprecipitation with calcium carbonate

DEFF Research Database (Denmark)

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

2015-01-01

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

Tales of volcanoes and El-Nino southern oscillations with the oxygen isotope anomaly of sulfate aerosol.

Science.gov (United States)

Shaheen, Robina; Abauanza, Mariana; Jackson, Teresa L; McCabe, Justin; Savarino, Joel; Thiemens, Mark H

2013-10-29

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.

Laser Spectroscopy of Neutron Rich Bismuth Isotopes

CERN Multimedia

2002-01-01

%IS344 :\\\\ \\\\ The aim of the experiment is to measure the optical isotope shifts and hyperfine structures of bismuth isotopes across the N=126 shell closure in order to extract the change in mean square charge radii ($\\delta\\langle r^{2}\\rangle$) and static moments. These include the first isotones of lead to be measured directly above the shell closure and will provide new information on the systematics of the kink ($\\delta\\langle r^{2}\\rangle)$ seen in the lead isotopic chain. After two very successful runs the programme has been extended to include the neutron deficient isotopes below $^{201}$Bi to study the systematics across the $i_{13/2}$ neutron sub-shell closure at N=118.\\\\ \\\\ During the initial 2 runs (9 shifts) the isotope shifts and hyperfine structures of three new isotopes, $ ^{210,212,213}$Bi and the 9$^{-}$ isomer of $^{210}$Bi have been measured. The accuracy of the previous measurements of $^{205,206,208}$Bi have been greatly improved. The samples of $ ^{208,210,210^{m}}$Bi were prepared by c...

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

International Nuclear Information System (INIS)

Garde, A.A.

1979-01-01

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.)

Human-Induced Long-Term Shifts in Gull Diet from Marine to Terrestrial Sources in North America's Coastal Pacific: More Evidence from More Isotopes (δ2H, δ34S).

Science.gov (United States)

Hobson, Keith A; Blight, Louise K; Arcese, Peter

2015-09-15

Measurements of naturally occurring stable isotopes in tissues of seabirds and their prey are a powerful tool for investigating long-term changes in marine foodwebs. Recent isotopic (δ(15)N, δ(13)C) evidence from feathers of Glaucous-winged Gulls (Larus glaucescens) has shown that over the last 150 years, this species shifted from a midtrophic marine diet to one including lower trophic marine prey and/or more terrestrial or freshwater foods. However, long-term isotopic patterns of δ(15)N and δ(13)C cannot distinguish between the relative importance of lower trophic-level marine foods and terrestrial sources. We examined 48 feather stable-hydrogen (δ(2)H) and -sulfur (δ(34)S) isotope values from this same 150-year feather set and found additional isotopic evidence supporting the hypothesis that gulls shifted to terrestrial and/or freshwater prey. Mean feather δ(2)H and δ(34)S values (± SD) declined from the earliest period (1860-1915; n = 12) from -2.5 ± 21.4 ‰ and 18.9 ± 2.7 ‰, respectively, to -35.5 ± 15.5 ‰ and 14.8 ± 2.4 ‰, respectively, for the period 1980-2009 (n = 12). We estimated a shift of ∼ 30% increase in dependence on terrestrial/freshwater sources. These results are consistent with the hypothesis that gulls increased terrestrial food inputs in response to declining forage fish availability.

Unraveling climatic changes from intraprofile variation in oxygen and hydrogen isotopic composition of goethite and kaolinite in laterites: An integrated study from Yaou, French Guiana

Energy Technology Data Exchange (ETDEWEB)

Girard, J.P.; Freyssinet, P.; Chazot, G.

2000-02-01

An integrated study of O and H isotopes in the latertic profile of Yaou, French Guiana, was undertaken to investigate the usefulness of stable isotopes as tracers of climatic changes in continental environments. The studied profile is composed of a 27 m thick saprolite, mostly developed in the past under wet-and-dry tropical climate in association with a duricrust, overlain by a 3 m thick yellow latosol formed more recently under present equatorial hot and humid climate. {delta}{sup 18}O-{delta}D values determined for weathering goethite (pseudomorphs after pyrite) and kaolinite (microcrystalline clay groundmass) throughout the 30 m deep profile reflect formation temperatures consistent with present (25 C) and realistic past climatic temperatures (20 C--30 C), indicating that weathering minerals formed in isotopic equilibrium with their genetic environment and were not subjected to significant isotope exchange after formation. A distinct shift downward from low to high {delta}{sup 18}O-{delta}D values occurs around 20 m depth in the saprolite. It is interpreted as recording the change from the past tropical to the present equatorial climate. Goethite and kaolinite in the 5--10 m thick saprolite interval immediately above the active basement weathering front are in isotopic equilibrium with modern water and must have formed under present equatorial-humid conditions. In contrast, goethite and kaolinite found higher up on the saprolite and in the duricrust formed in the past under tropical wet and dry climate from waters distinctly depleted in {sup 18}O and D relative to modern water. The marked depletion of paleo-meteoric water at Yaou most likely reflects a more contrasted or monsoonal character of the ancient tropical climate. The present study shows that ancient weathering minerals in lateritic profiles preserve their {delta}{sup 18}O-{delta}D values and carry a time signal. The time signal is best expressed in minerals formed rapidly at the weathering front and

Isotopes in heterogeneous catalysis

CERN Document Server

Hargreaves, Justin SJ

2006-01-01

The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

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

Science.gov (United States)

Bindeman, Ilya; Valley, John

2002-07-01

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

Errors of isotope conveyor weigher caused by profile variations and shift of material

International Nuclear Information System (INIS)

Machaj, B.

1977-01-01

Results of investigations of isotope conveyor weigher in transmission geometry and with long plastic scintillator as a detector are presented in the paper. The results indicate that errors caused by material shift across the conveyor belt can be decreased by forming probe sensitivity to incident radiation along its axis by means of additional radiation absorbents. The errors caused by material profile variations can effectively be diminished by increase of photon energy. Application of 60 Co instead of 137 Cs ensured more than three times lower errors caused by profile variation. Errors caused by vertical movements of the belt with material, decrease considerably, when single point source situated in the center of the measuring head is replaced at least by two point sources situated out of the center, above the edges of the belt. (author)

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

Science.gov (United States)

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

2009-04-01

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

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

International Nuclear Information System (INIS)

Costa Pinto, N.M.A.C.

1977-01-01

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

Iron isotopic fractionation during continental weathering

Energy Technology Data Exchange (ETDEWEB)

Fantle, Matthew S.; DePaolo, Donald J.

2003-10-01

The biological activity on continents and the oxygen content of the atmosphere determine the chemical pathways through which Fe is processed at the Earth's surface. Experiments have shown that the relevant chemical pathways fractionate Fe isotopes. Measurements of soils, streams, and deep-sea clay indicate that the {sup 56}Fe/{sup 54}Fe ratio ({delta}{sup 56}Fe relative to igneous rocks) varies from +1{per_thousand} for weathering residues like soils and clays, to -3{per_thousand} for dissolved Fe in streams. These measurements confirm that weathering processes produce substantial fractionation of Fe isotopes in the modern oxidizing Earth surface environment. The results imply that biologically-mediated processes, which preferentially mobilize light Fe isotopes, are critical to Fe chemistry in weathering environments, and that the {delta}{sup 56}Fe of marine dissolved Fe should be variable and negative. Diagenetic reduction of Fe in marine sediments may also be a significant component of the global Fe isotope cycle. Iron isotopes provide a tracer for the influence of biological activity and oxygen in weathering processes through Earth history. Iron isotopic fractionation during weathering may have been smaller or absent in an oxygen-poor environment such as that of the early Precambrian Earth.

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

Science.gov (United States)

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

1986-09-01

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

Measurement of the isotope shift of the 63 P 1 ↔53 D 1 transition of ytterbium by using a diode oscillator fiber amplified laser

Science.gov (United States)

Lee, L.; Park, H.; Ko, K.-H.; Jeong, D.-Y.

2010-08-01

We demonstrated a Diode Oscillator Fiber Amplification (DOFA) system in order to study the 63 P 1 ↔53 D 1 (1539 nm) transition line of a neutral ytterbium atom that is accessed by the stepwise excitation of the ground state. The frequency of the DOFA system was doubled by a MgO:PPLN crystal for the resonant excitation of the 61 S 0 ↔63 P 1 transition. The frequency of the second harmonic beam was stabilized to the 61 S 0 ↔63 P 1 transition of each isotope with the stability of about 2 MHz. We performed absorption spectroscopy on the 63 P 1 ↔53 D 1 (1539 nm) transition after the velocity selective excitation by the frequency-doubled beam. The isotope shifts in the 63 P 1 ↔53 D 1 (1539 nm) transition were directly measured for the first time. The relative isotope shifts from 174Yb were measured as -105.8 MHz and 109.7 MHz for 176Yb and 172Yb, respectively.

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

Science.gov (United States)

Baltuck, Miriam

1987-02-01

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.

Fossil mice and rats show isotopic evidence of niche partitioning and change in dental ecomorphology related to dietary shift in Late Miocene of Pakistan.

Science.gov (United States)

Kimura, Yuri; Jacobs, Louis L; Cerling, Thure E; Uno, Kevin T; Ferguson, Kurt M; Flynn, Lawrence J; Patnaik, Rajeev

2013-01-01

Stable carbon isotope analysis in tooth enamel is a well-established approach to infer C3 and C4 dietary composition in fossil mammals. The bulk of past work has been conducted on large herbivorous mammals. One important finding is that their dietary habits of fossil large mammals track the late Miocene ecological shift from C3 forest and woodland to C4 savannah. However, few studies on carbon isotopes of fossil small mammals exist due to limitations imposed by the size of rodent teeth, and the isotopic ecological and dietary behaviors of small mammals to climate change remain unknown. Here we evaluate the impact of ecological change on small mammals by fine-scale comparisons of carbon isotope ratios (δ(13)C) with dental morphology of murine rodents, spanning 13.8 to ∼2.0 Ma, across the C3 to C4 vegetation shift in the Miocene Siwalik sequence of Pakistan. We applied in-situ laser ablation GC-IRMS to lower first molars and measured two grazing indices on upper first molars. Murine rodents yield a distinct, but related, record of past ecological conditions from large herbivorous mammals, reflecting available foods in their much smaller home ranges. In general, larger murine species show more positive δ(13)C values and have higher grazing indices than smaller species inhabiting the same area at any given age. Two clades of murine rodents experienced different rates of morphological change. In the faster-evolving clade, the timing and trend of morphological innovations are closely tied to consumption of C4 diet during the vegetation shift. This study provides quantitative evidence of linkages among diet, niche partitioning, and dental morphology at a more detailed level than previously possible.

Fossil Mice and Rats Show Isotopic Evidence of Niche Partitioning and Change in Dental Ecomorphology Related to Dietary Shift in Late Miocene of Pakistan

Science.gov (United States)

Kimura, Yuri; Jacobs, Louis L.; Cerling, Thure E.; Uno, Kevin T.; Ferguson, Kurt M.; Flynn, Lawrence J.; Patnaik, Rajeev

2013-01-01

Stable carbon isotope analysis in tooth enamel is a well-established approach to infer C3 and C4 dietary composition in fossil mammals. The bulk of past work has been conducted on large herbivorous mammals. One important finding is that their dietary habits of fossil large mammals track the late Miocene ecological shift from C3 forest and woodland to C4 savannah. However, few studies on carbon isotopes of fossil small mammals exist due to limitations imposed by the size of rodent teeth, and the isotopic ecological and dietary behaviors of small mammals to climate change remain unknown. Here we evaluate the impact of ecological change on small mammals by fine-scale comparisons of carbon isotope ratios (δ13C) with dental morphology of murine rodents, spanning 13.8 to ∼2.0 Ma, across the C3 to C4 vegetation shift in the Miocene Siwalik sequence of Pakistan. We applied in-situ laser ablation GC-IRMS to lower first molars and measured two grazing indices on upper first molars. Murine rodents yield a distinct, but related, record of past ecological conditions from large herbivorous mammals, reflecting available foods in their much smaller home ranges. In general, larger murine species show more positive δ13C values and have higher grazing indices than smaller species inhabiting the same area at any given age. Two clades of murine rodents experienced different rates of morphological change. In the faster-evolving clade, the timing and trend of morphological innovations are closely tied to consumption of C4 diet during the vegetation shift. This study provides quantitative evidence of linkages among diet, niche partitioning, and dental morphology at a more detailed level than previously possible. PMID:23936324

Fossil mice and rats show isotopic evidence of niche partitioning and change in dental ecomorphology related to dietary shift in Late Miocene of Pakistan.

Directory of Open Access Journals (Sweden)

Yuri Kimura

Full Text Available Stable carbon isotope analysis in tooth enamel is a well-established approach to infer C3 and C4 dietary composition in fossil mammals. The bulk of past work has been conducted on large herbivorous mammals. One important finding is that their dietary habits of fossil large mammals track the late Miocene ecological shift from C3 forest and woodland to C4 savannah. However, few studies on carbon isotopes of fossil small mammals exist due to limitations imposed by the size of rodent teeth, and the isotopic ecological and dietary behaviors of small mammals to climate change remain unknown. Here we evaluate the impact of ecological change on small mammals by fine-scale comparisons of carbon isotope ratios (δ(13C with dental morphology of murine rodents, spanning 13.8 to ∼2.0 Ma, across the C3 to C4 vegetation shift in the Miocene Siwalik sequence of Pakistan. We applied in-situ laser ablation GC-IRMS to lower first molars and measured two grazing indices on upper first molars. Murine rodents yield a distinct, but related, record of past ecological conditions from large herbivorous mammals, reflecting available foods in their much smaller home ranges. In general, larger murine species show more positive δ(13C values and have higher grazing indices than smaller species inhabiting the same area at any given age. Two clades of murine rodents experienced different rates of morphological change. In the faster-evolving clade, the timing and trend of morphological innovations are closely tied to consumption of C4 diet during the vegetation shift. This study provides quantitative evidence of linkages among diet, niche partitioning, and dental morphology at a more detailed level than previously possible.

An oxygen isotope record from Lake Xiarinur in Inner Mongolia since the last deglaciation and its implication for tropical monsoon change

Science.gov (United States)

Sun, Qing; Chu, Guoqiang; Xie, Manman; Zhu, Qingzeng; Su, Youliang; Wang, Xisheng

2018-04-01

We present a high-resolution oxygen isotope record from authigenic carbonate (δ18Ocarb) from Lake Xiarinur (Inner Mongolia) since the last deglaciation. The lake is located at the modern northern limit of the monsoon, and is therefore sensitive to the extension of the East Asian summer monsoon. Based on calibration against the instrumental record, the δ18Ocar variation has been interpreted as changes in atmospheric circulation pattern on decadal time scales. On longer time scales, the δ18Ocarb in lake sediments could be mainly regulated by the relative contribution of nearby (remote) water-vapor sources associated with subtropical (tropical) monsoon through changes in the distance from sources to the site of precipitation. Increased remote water vapors from tropical monsoon would lead to lighter isotope value in our study site. Through time the δ18Ocarb record in Lake Xiarinur indicate a notable weak tropical monsoon during the Younger Dryas, a gradual increasing monsoon from the early Holocene and weakening monsoon after the middle Holocene. Oxygen isotope records from lakes and stalagmite in the Asian monsoon region across different localities show a general similar temporal pattern since the last deglaciation, and highlight a fundamental role of the tropical monsoon.

Oxygen isotope calibration of the onset of ice-rafting and history of glaciation in the North Atlantic region

Science.gov (United States)

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.

1984-01-01

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.

Determination Of Oxygen Isotope Ratio (18O-/16O) and Sulfur (34S-/32S) Value Of BaSO4 Din 5033 For Internal Standard

International Nuclear Information System (INIS)

Evarista Ristin, P.I.; Sidauruk, Paston; Wibagoyo; Djiono; Satrio

2000-01-01

It has been done an experiment to determine of oxygen( 18 O-/ 16 O) and Sulfur ( 34 S-/ 32 S) ) isotop value of BaSO 4 DIN 5033 (merck) for internal standard. The used technique for preparation of CO 2 gas to measure oxygen isotop ratio ratio (stated as deltaδ 18 O) is based on Rafter on Rafte method using graphite for reduction of BaSO 4 . Where the used technique for preparation of SO 2 gas to measure isotope sulphur ratio (started as δ 34 S) is based on Robinson - Kasakabe method using Cupro oxide to oxidize Ag 2 S. The result of this experiment is 11,48±0,41 0/00 and 5,00 plus minus ±0,33 o/oo for deltaδ 18 O and δ 34 S value respectively. Based on this experiment. BaSO 4 DIN 5033 can be used as internal standard because is values both oxygen and sulphur lie in the middle of range of its variation in nature. The result of interlab comparison shows that the value of this experiment is nearly similar to the value obtained from laboratorium of Pinstech-Pakistan. To acquire the result, it is necessary to carry out more interlab comparison

Sources of Holocene variability of oxygen isotopes in paleoclimate archives

Directory of Open Access Journals (Sweden)

A. N. LeGrande

2009-08-01

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.

Oxygen and silicon stable isotopes of diatom silica. Reconstructing changes in surface water hydrography and silicic acid utilization in the late Pleistocene subarctic Pacific

Energy Technology Data Exchange (ETDEWEB)

Maier, Edith

2014-03-05

Deglacial variations in upper ocean nutrient dynamics and stratification in high latitudes, as well as associated changes in thermohaline overturning circulation, are thought to have played a key role in changing atmospheric CO{sub 2} concentrations. This thesis examines the relationship between past changes in subarctic Pacific upper ocean stratification and nutrient (silicic acid) utilization, using oxygen and silicon stable isotopes of diatom silica, for the first time at millennial-scale resolution and analyzed with a new and efficient instrumentation set-up. The isotopic data, presented in three manuscripts, show a consistent picture of millennial-scale variability in upper ocean stratification and silicic acid utilization during the last ∝50 ka BP, e.g. indicating that the subarctic Pacific was a source region for atmospheric CO{sub 2} during the last deglaciation (late Heinrich Stadial 1 and the Boelling/Alleroed). The presented results demonstrate the high potential of combined diatom oxygen and silicon stable isotope analysis especially for, but not restricted to, marine regions characterized by a low biogenic carbonate content like the subarctic Pacific and the Southern Ocean.

Oxygen and silicon stable isotopes of diatom silica. Reconstructing changes in surface water hydrography and silicic acid utilization in the late Pleistocene subarctic Pacific

International Nuclear Information System (INIS)

Maier, Edith

2014-01-01

Deglacial variations in upper ocean nutrient dynamics and stratification in high latitudes, as well as associated changes in thermohaline overturning circulation, are thought to have played a key role in changing atmospheric CO 2 concentrations. This thesis examines the relationship between past changes in subarctic Pacific upper ocean stratification and nutrient (silicic acid) utilization, using oxygen and silicon stable isotopes of diatom silica, for the first time at millennial-scale resolution and analyzed with a new and efficient instrumentation set-up. The isotopic data, presented in three manuscripts, show a consistent picture of millennial-scale variability in upper ocean stratification and silicic acid utilization during the last ∝50 ka BP, e.g. indicating that the subarctic Pacific was a source region for atmospheric CO 2 during the last deglaciation (late Heinrich Stadial 1 and the Boelling/Alleroed). The presented results demonstrate the high potential of combined diatom oxygen and silicon stable isotope analysis especially for, but not restricted to, marine regions characterized by a low biogenic carbonate content like the subarctic Pacific and the Southern Ocean.

Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

Science.gov (United States)

Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

2012-01-01

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

Geochemical importance of isotopic fractionation during respiration

International Nuclear Information System (INIS)

Schleser, G.; Foerstel, H.

1975-01-01

In 1935 it was found that atmospheric oxygen contained a relatively greater abundance of the 18 O isotope than did the oxygen bound in water (Dole effect). A major contribution to the fractionation of the stable oxygen isotopes should result from the respiration of microorganisms. In this respect our interest centers on the soil because nearly all organic material produced on land is decomposed within the soil. The oceans are less important because the primary productivity on land is twice the value for the oceans. In a first approach we measured the oxygen isotope fractionation during the respiration of E. coli K12 for different respiration rates. These results, accomplished with a chemostat, indicate that the fractionation factor α of the oxygen isotopes increases with the increasing respiratory activity, measured as Q/sub O 2 /. At low dilution rates or growth rates respectively of about 0.05 h -1 , the fractionation factor amounts to 1.006 increasing to 1.017 at dilution rates of about 1.0 h -1 . The results are interpreted as a kinetic mass fractionation due to the slightly different diffusion coefficients of 16 O 2 and 18 O 16 O. The respiration rates in conjunction with the corresponding fractionation data are compared with the respiration rates of typical soil microorganisms such as Azotobacter, in order to deduce fractionation data for these organisms. This is necessary to calculate a mean global fractionation factor. Understanding the Dole effect with these fractionation processes should finally give us the opportunity to calculate gas-exchange rates between the atmosphere and the oceans, on the basis of the behavior of the stable oxygen isotopes

Neodymium isotope ratios in fish debris as a tracer for a low oxygen water mass in the equatorial Pacific across the last glacial termination.

Science.gov (United States)

Reimi Sipala, M. A.; Marcantonio, F.

2017-12-01

The deep ocean has long been suggested as a potential sink of carbon during the LGM, providing storage for the drawdown of atmospheric CO2 observed in the climate record. However, the exact location, origin and pathway of this respired carbon pool remains largely unconstrained. The equatorial Pacific is an important player in the ocean biogeochemical cycling of carbon, with many researchers focusing on the changes in iron-limited systems and potential micronutrient supply changes throughout the Pleistocene glaciation. Here we attempt to isolate the role of deep water circulation changes that may be associated with changing bottom water oxygen conditions in the Central Equatorial Pacific during the last deglaciation. We measure the variability of the Nd isotopic composition of fish debris from three sites in the Central Equatorial Pacific (CEP) along a meridional transect at approximately 160° W -- 0° 28' N (ML1208-17PC), 4° 41' N (ML1208-31BB), and 7 ° 2'N (ML1208-31BB). Nd isotopic values in fish debris reflect the Nd isotopic composition of bottom water at the time of deposition and are insensitive to moderate changes in redox conditions or pore water oxygen levels. Nd isotope ratios can, therefore, be used as an effective deep-ocean water mass tracer. This work attempts to illuminate our current understanding of changes in bottom water oxygenation conditions throughout the Equatorial Pacific over the past 25 kyr. High authigenic U concentrations during peak glacial conditions have been attributed to deep-water suboxic conditions potentially associated with increased respired carbon storage. However, it is still unclear if these changes originate in the Southern Ocean, and propagate to the equatorial Pacific through an increased in penetration of Southern Ocean Intermediate water, or if they represent a change in the efficiency of the biological pump, permitting a drawdown of oxygen in bottom water without increased nutrient availability.

The Oxygen Isotopic Composition (18O/16O) in the Dust of Comet 67P/Churyumov-Gerasimenko Measured by COSIMA On-board Rosetta

Science.gov (United States)

Paquette, J. A.; Engrand, C.; Hilchenbach, M.; Fray, N.; Stenzel, O. J.; Silen, J.; Rynö, J.; Kissel, J.

2018-03-01

The oxygen isotopic ratio 18O/16O has been measured in cometary gas for a wide variety of comets, but the only measurements in cometary dust were performed by the Stardust cometary sample return mission. Most such measurements find a value of the ratio that is consistent with Vienna Standard Mean Ocean Water (VSMOW) within errors. In this work we present the result of a measurement, using the COSIMA instrument on the Rosetta orbiter, of the oxygen isotopic ratio in dust from Comet 67P/Churyumov-Gerasimenko. Measuring the 18O/16O ratio with COSIMA is challenging for a number of reasons, but it is possible with a reasonable degree of precision. We find a result of 2.00 × 10-3 ± 1.2 × 10-4 which is consistent within errors with VSMOW.

Bayesian Nitrate Source Apportionment to Individual Groundwater Wells in the Central Valley by use of Nitrogen, Oxygen, and Boron Isotopic Tracers

Science.gov (United States)

Lockhart, K.; Harter, T.; Grote, M.; Young, M. B.; Eppich, G.; Deinhart, A.; Wimpenny, J.; Yin, Q. Z.

2014-12-01

Groundwater quality is a concern in alluvial aquifers underlying agricultural areas worldwide, an example of which is the San Joaquin Valley, California. Nitrate from land applied fertilizers or from animal waste can leach to groundwater and contaminate drinking water resources. Dairy manure and synthetic fertilizers are the major sources of nitrate in groundwater in the San Joaquin Valley, however, septic waste can be a major source in some areas. As in other such regions around the world, the rural population in the San Joaquin Valley relies almost exclusively on shallow domestic wells (≤150 m deep), of which many have been affected by nitrate. Consumption of water containing nitrate above the drinking water limit has been linked to major health effects including low blood oxygen in infants and certain cancers. Knowledge of the proportion of each of the three main nitrate sources (manure, synthetic fertilizer, and septic waste) contributing to individual well nitrate can aid future regulatory decisions. Nitrogen, oxygen, and boron isotopes can be used as tracers to differentiate between the three main nitrate sources. Mixing models quantify the proportional contributions of sources to a mixture by using the concentration of conservative tracers within each source as a source signature. Deterministic mixing models are common, but do not allow for variability in the tracer source concentration or overlap of tracer concentrations between sources. Bayesian statistics used in conjunction with mixing models can incorporate variability in the source signature. We developed a Bayesian mixing model on a pilot network of 32 private domestic wells in the San Joaquin Valley for which nitrate as well as nitrogen, oxygen, and boron isotopes were measured. Probability distributions for nitrogen, oxygen, and boron isotope source signatures for manure, fertilizer, and septic waste were compiled from the literature and from a previous groundwater monitoring project on several

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

DEFF Research Database (Denmark)

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

2012-01-01

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...

Major, Trace Element Concentration and Triple-Oxygen Isotope Compositions of G- and I-Type Spherules from the Sør Rondane Mountains, East Antarctica

Science.gov (United States)

Soens, B.; Goderis, S.; Greenwood, R. C.; McKibbin, S.; Van Ginneken, M.; Vanhaecke, F.; Debaille, V.; Franchi, I. A.; Claeys, Ph.

2017-07-01

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.

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

Science.gov (United States)

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

2010-01-01

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.

Ion microprobe analyses of oxygen three-isotope ratios of chondrules from the Sayh al Uhaymir 290 CH chondrite using a multiple-hole disk

Digital Repository Service at National Institute of Oceanography (India)

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...

Stable isotopes of authigenic minerals in variably-saturated fractured tuff

International Nuclear Information System (INIS)

Weber, D.S.; Evans, D.D.

1988-11-01

Identifying stable isotope variation and mineralogical changes in fractured rock may help establish the history of climatic and geomorphological processes that might affect the isolation properties of a waste repository site. This study examines the use of the stable isotope ratios of oxygen ( 18 O/ 16 O) and carbon ( 13 C/ 12 C) in authigenic minerals as hydrogeochemical tools tracing low-temperature rock-water interaction in variably-saturated fractured stuff. Isotopic compositions of fracture-filling and rock matrix minerals in the Apache Leap tuff, near Superior, Arizona were concordant with geothermal temperatures and in equilibrium with water isotopically similar to present-day meteoric water and groundwater. Oxygen and carbon isotope ratios of fracture-filling, in unsaturated fractured tuff, displayed an isotopic gradient believed to result from near-surface isotopic enrichment due to evaporation rather than the effects of rock-water interaction. Oxygen isotope ratios of rock matrix opal samples exhibited an isotopic gradient believed to result from, leaching and reprecipitation of silica at depth. Methods and results can be used to further define primary flowpaths and the movement of water in variably-saturated fractured rock. 71 refs., 23 figs., 3 tabs

Stable isotopes of authigenic minerals in variably-saturated fractured tuff

Energy Technology Data Exchange (ETDEWEB)

Weber, D.S.; Evans, D.D.

1988-11-01

Identifying stable isotope variation and mineralogical changes in fractured rock may help establish the history of climatic and geomorphological processes that might affect the isolation properties of a waste repository site. This study examines the use of the stable isotope ratios of oxygen ({sup 18}O/{sup 16}O) and carbon ({sup 13}C/{sup 12}C) in authigenic minerals as hydrogeochemical tools tracing low-temperature rock-water interaction in variably-saturated fractured stuff. Isotopic compositions of fracture-filling and rock matrix minerals in the Apache Leap tuff, near Superior, Arizona were concordant with geothermal temperatures and in equilibrium with water isotopically similar to present-day meteoric water and groundwater. Oxygen and carbon isotope ratios of fracture-filling, in unsaturated fractured tuff, displayed an isotopic gradient believed to result from near-surface isotopic enrichment due to evaporation rather than the effects of rock-water interaction. Oxygen isotope ratios of rock matrix opal samples exhibited an isotopic gradient believed to result from, leaching and reprecipitation of silica at depth. Methods and results can be used to further define primary flowpaths and the movement of water in variably-saturated fractured rock. 71 refs., 23 figs., 3 tabs.

Aragonite-Calcite Inversion During Biogenic Carbonate Sampling: Considerations for Interpreting Isotopic Measurements in Paleoclimate Studies

Science.gov (United States)

Waite, A. J.; Swart, P. K.

2011-12-01

As aragonite is the metastable polymorph of calcium carbonate, it lends itself to monotropic inversion to the more stable polymorph, calcite. This inversion is possible through an increase in the temperature and pressure conditions to which the sample is exposed and, although first noted nearly a century ago, has been primarily discussed in the context of sample roasting prior to analyses in paleoclimatological studies. Over the last several decades, however, researchers have found evidence to suggest that the friction associated with the sampling of biogenic carbonates via milling/drilling also induces inversion. Furthermore, this inversion may be associated with a shift in measured oxygen isotopic values and ultimately have significant implications for the interpretation of paleoclimatic reconstructions. Despite this, the isotopic heterogeneity of biogenic aragonite skeletons makes the effects of inversion challenging to test and the subject remains underrepresented in the literature. Here we present a first order study into the effects of milling on both the mineralogy and isotopic compositions measured in sclerosponges, corals, and molluscs. X-Ray diffraction analysis of samples hand ground with a mortar and pestle reveal 100% aragonitic skeletons. Conversely, samples milled with a computerized micromill show measurable inversion to calcite. On average, percent inversion of aragonite to calcite for individual specimens was 15% for sclerosponges, 16% for corals, and 9% for molluscs. Isotopic data from these specimens show that the higher the percentage of aragonite inverted to calcite, the more depleted the measured oxygen isotopic values. In the largest of the datasets (sclerosponges), it is evident that the range of oxygen isotope values from milled samples (-0.02 to +0.84%) exceeds the range in values for those samples which were hand ground and showed no inversion (+0.53 to +0.90%). This, coupled with the strong correlation between the two variables

Isotope Shifts and Hyperfine Structure in the[Xe]4f(7)5d 6s(2) D-2(J)->[Xe]4f(7)5d 6s 6p F-9(J+1) Transitions of Gadolinium

International Nuclear Information System (INIS)

Blaum, K.; Bushaw, Bruce A.; Diel, S; Geppert, Ch; Kuschnick, A; Muller, P.; Nortershauser, W.; Schmitt, A.; Wendt, K.

1999-01-01

High-resolution resonance ionization mass spectrometry has been used to measure isotope shifts and hyperfine structure in all[Xe] 4f 7 5d 6s2 9DJ ---[Xe] 4f 7 5d 6s 6p 9FJ+1 (J= 2-6) and the[Xe] 4f 7 5d 6s2 9D6---[Xe] 4f 7 5d 6s 6p 9D5 transitions of gadolinium (Gd I). Gadolinium atoms in an atomic beam were excited with a tunable single-frequency laser in the wavelength range of 422 - 429 nm. Resonant excitation was followed by photoionization with the 363.8 nm line of an argon ion laser and resulting ions were mass separated and detected with a quadrupole mass spectrometer. Isotope shifts for all stable gadolinium isotopes in these transitions have been measured for the first time. Additionally, the hyperfine structure constants of the upper states have been derived for the isotopes 155, 157Gd and are compared with previous work. Using prior experimental values for the mean nuclear charge radii, derived from the combination of muonic atoms and electron scattering data, field shift a nd specific mass shift coefficients for the investigated transitions have been determined and nuclear charge parameters l for the minor isotopes 152, 154Gd have been calculated

Study of the tensor correlation in oxygen isotopes using mean-field-type and shell model methods

International Nuclear Information System (INIS)

Sugimoto, Satoru

2007-01-01

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

Collinear laser spectroscopy on In isotopes from heavy ion fusion reactions

International Nuclear Information System (INIS)

Ulm, G.

1984-07-01

Indium isotopes 107-111 were produced by 16 O-fusion reactions and investigated in a collinear laser geometry. The hyperfine structure and isotopic shifts are measured and the deduced magnetic dipole moments are in agreement with shell model calculations. The nuclear charge radii are determined from the isotopic shifts. (WL)

Role of stable isotope mass spectroscopy in hydrological sciences

International Nuclear Information System (INIS)

Keesari, Tirumalesh

2017-01-01

Isotope Ratio Mass Spectrometry (IRMS) is a specialized technique used to provide information about a given sample about its geographic, chemical, physical and biological origin. The ability to determine the source of water molecule stems from the relative isotopic abundances of its constituent elements, viz., hydrogen and oxygen or sometimes through its dissolved elements such as carbon, nitrogen and sulphur etc. Since the isotope ratios of carbon, hydrogen, oxygen, sulfur, and nitrogen can become locally enriched or depleted through a variety of kinetic and thermodynamic factors, measurement of the isotope ratios can be used to unravel the processes and differentiate water samples which otherwise exhibit similar chemical signatures. For brevity, this article focuses mainly on measurement of water isotopes, common notation for expressing isotope data and standards, theory of isotope hydrology, field applications and advances