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Sample records for oxygen isotope variations

  1. Oxygen isotope variations in phosphate of deer bones

    NASA Astrophysics Data System (ADS)

    Luz, Boaz; Cormie, Allison B.; Schwarcz, Henry P.

    1990-06-01

    Variations of δ 18O of bone phosphate (δ p) of white tailed deer were studied in samples with wide geographic distribution in North America. Bones from the same locality have similar isotopic values, and the difference between specimens (0.4‰) is not large relative to the measurement error (0.3‰). The total range of δ p values is about 12‰. This indicates that deer use water from a relatively small area, and thus their δ p indicates local environmental conditions. Multiple regression analysis between oxygen isotope composition of deer bone phosphate and of local relative humidity and precipitation (δ w) yields a high correlation coefficient (0.95). This correlation is significantly better than the linear correlation (0.81) between δ p and δ w of precipitation alone. Thus δ p depends on both isotopic composition of precipitation and on relative humidity. This is because deer obtain most of their water from leaves, the isotopic composition of which is partly controlled by relative humidity through evaporation/transpiration.

  2. Oxygen-isotope variations in post-glacial Lake Ontario

    NASA Astrophysics Data System (ADS)

    Hladyniuk, Ryan; Longstaffe, Fred J.

    2016-02-01

    The role of glacial meltwater input to the Atlantic Ocean in triggering the Younger Dryas (YD) cooling event has been the subject of controversy in recent literature. Lake Ontario is ideally situated to test for possible meltwater passage from upstream glacial lakes and the Laurentide Ice Sheet (LIS) to the Atlantic Ocean via the lower Great Lakes. Here, we use the oxygen-isotope compositions of ostracode valves and clam shells from three Lake Ontario sediment cores to identify glacial meltwater contributions to ancient Lake Ontario since the retreat of the LIS (∼16,500 cal [13,300 14C] BP). Differences in mineralogy and sediment grain size are also used to identify changes in the hydrologic regime. The average lakewater δ18O of -17.5‰ (determined from ostracode compositions) indicates a significant contribution from glacial meltwater. Upon LIS retreat from the St. Lawrence lowlands, ancient Lake Ontario (glacial Lake Iroquois) lakewater δ18O increased to -12‰ largely because of the loss of low-18O glacial meltwater input. A subsequent decrease in lakewater δ18O (from -12 to -14‰), accompanied by a median sediment grain size increase to 9 μm, indicates that post-glacial Lake Ontario received a final pulse of meltwater (∼13,000-12,500 cal [11,100-10,500 14C] BP) before the onset of hydrologic closure. This meltwater pulse, which is also recorded in a previously reported brief freshening of the neighbouring Champlain Valley (Cronin et al., 2012), may have contributed to a weakening of thermohaline circulation in the Atlantic Ocean. After 12,900 cal [11,020 14C] BP, the meltwater presence in the Ontario basin continued to inhibit entry of Champlain seawater into early Lake Ontario. Opening of the North Bay outlet diverted upper Great Lakes water from the lower Great Lakes causing a period (12,300-8300 cal [10,400-7500 14C] BP) of hydrologic closure in Lake Ontario (Anderson and Lewis, 2012). This change is demarcated by a shift to higher δ18Olakewater

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

    NASA Astrophysics Data System (ADS)

    Brookman, Tom H.; Ambrose, Stanley H.

    2012-09-01

    Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

  4. Carbon and oxygen isotope variations in Precambrian cherts

    SciTech Connect

    Robert, F. )

    1988-06-01

    Isotopic compositions of O in bulk Precambrian cherts and of C in the insoluble organic matter trapped in the silica have been determined. A general negative correlation relates these two variables and indicates that post-depositional alteration may have markedly modified the pristine isotopic ratios of the C compounds and their hosts. This interpretation is in good agreement with the expected isotopic trends for C and O resulting from secondary geological thermal events. Based on this correlation, a maximum {delta}{sup 13}C value of ca. {minus}33{per thousand}/PDB is proposed for the Precambrian kerogen. The difference between Proterozoic and Phanerozoic ({minus}27{per thousand}) {delta}{sup 13}C values could be linked to the flowering of life at the end of the Precambrian.

  5. Glacial-interglacial Variations of Molybdenum Isotopes in the Peruvian Oxygen Minimum Zone

    NASA Astrophysics Data System (ADS)

    Siebert, C.; Frank, M.; Scholz, F.

    2015-12-01

    Mo isotopes have been widely used as a tool to constrain redox-conditions during major global events such as the oxygenation of the oceans in the Precambrian and Cretaceous Ocean Anoxic Events. In addition, Mo isotopes have considerable, yet underexplored potential to quantitatively track local redox-variation at high resolution on shorter timescales. Here we present data from piston core M77/2-024-5 that was retrieved in the Peruvian oxygen minimum zone in the context of Collaborative Research Centre (SFB) 754 of the Deutsche Forschungs Gemeinschaft (DFG). The age model for this core is well constrained and the core covers the last 140 ka with a hiatus between 20 and 50 ky BP. The oxygen minimum zone along the Peru continental margin is thought to have been better ventilated and therefore less pronounced during glacial periods compared to interglacials. Concentrations of redox-sensitive trace elements show high-amplitude changes and indicate periods of strongly sulphidic conditions with high Mo fixation rate and oxygenated periods with limited Mo fixation (Scholz et al 2014). Mo isotopes do not show straightforward correlations with elemental redox tracers and are only weakly correlated with Mo/U and total organic carbon (TOC). However, Mo isotopes become significantly heavier around the last glacial maximum (Δ98Mo of 0.4 permil). The observed signatures indicate that the Mo isotope composition is dominated by changes in the operating Mo delivery mechanism, i.e. particulate transport versus molecular diffusion. Our results suggest that Mo isotopes can track local redox variation therefore adding to our understanding of this complex indicator for marine environmental change. Scholz et al., (2014), Nature Geosciences, Vol. 7, Pages 433-437

  6. Oxygen isotope variation in primitive achondrites: The influence of primordial, asteroidal and terrestrial processes

    NASA Astrophysics Data System (ADS)

    Greenwood, R. C.; Franchi, I. A.; Gibson, J. M.; Benedix, G. K.

    2012-10-01

    A detailed oxygen isotope study of the acapulcoites, lodranites, winonaites, brachinites and various related achondrites has been undertaken to investigate the nature of their precursor materials. High levels of terrestrial alteration displayed by many of these samples have been mitigated by leaching in ethanolamine thioglycollate (EATG) solution. Due to their high metal and sulphide content, acapulcoite, lodranite and winonaite samples show much greater isotopic shifts during weathering than brachinites. As observed in previous studies, Antarctic weathered finds are displaced to lighter oxygen isotope compositions and non-Antarctic finds to heavier values. Leached primitive achondrite residues continue to show high levels of oxygen isotope heterogeneity. This variation is reflected in the 2σ error on group mean Δ17O values, which decrease in the following order: acapulcoite-lodranite clan > brachinites > winonaites. On an oxygen three-isotope diagram, the acapulcoite--lodranite clan define a limited trend with a slope of 0.61 ± 0.08 and an intercept of -1.43 ± 0.27 (R2 = 0.78). A broad positive correlation between Δ17O and olivine fayalite contents displayed by both acapulcoite and lodranite samples may be the result of early aqueous alteration and subsequent dehydration. Winonaites experienced a greater degree of differentiation than the acapulcoite-lodranite clan and define a distinct mass fractionation line, with a slope of 0.53 ± 0.01 and an intercept of -0.53 ± 0.04 (R2 = 1). A number of samples currently classified as acapulcoites (NWA 725, NWA 1052 and Dho 1222) have oxygen isotope compositions indicating that they are winonaites. The relatively high level of oxygen isotope heterogeneity displayed by the brachinites supports their designation as primitive achondrites. A number of ungrouped olivine-rich achondrites (Divnoe, NWA 4042, NWA 4363, NWA 4518, NWA 5400, Zag (b)) as well as the unique plagioclase-rich achondrites GRA 06128 and GRA 06129 have

  7. Oxygen isotope variations in granulite-grade iron formations: constraints on oxygen diffusion and retrograde isotopic exchange

    USGS Publications Warehouse

    Sharp, Z.D.; O'Neil, J.R.; Essene, E.J.

    1988-01-01

    The oxygen isotope ratios of various minerals were measured in a granulite-grade iron formation in the Wind River Range, Wyoming. Estimates of temperature and pressure for the terrane using well calibrated geothermometers and geobarometers are 730??50?? C and 5.5??0.5 kbar. The mineral constraints on fluid compositions in the iron formation during retrogression require either very CO2-rich fluids or no fluid at all. In the iron formation, isotopic temperature estimates from quartz-magnetite fractionations are controlled by the proximity to the enclosing granitic gneiss, and range from 500?? C (??qz - mt=10.0???) within 2-3 meters of the orthogneiss contact to 600?? C (??qz - mt=8.0???) farther from the contact. Temperature estimates from other isotopic thermometers are in good agreement with those derived from the quartz-magnetite fractionations. During prograde metamorphism, the isotopic composition of the iron formation was lowered by the infiltration of an external fluid. Equilibrium was achieved over tens of meters. Closed-system retrograde exchange is consistent with the nearly constant whole-rock ??18Owr value of 8.0??0.6???. The greater ??qz-mt values in the iron formation near the orthogneiss contact are most likely due to a lower oxygen blocking temperature related to greater exchange-ability of deformed minerals at the contact. Cooling rates required to preserve the quartz-magnetite fractionations in the central portion of the iron formation are unreasonably high (???800?? C/Ma). In order to preserve the 600?? C isotopic temperature, the diffusion coefficient D (for ??-quartz) should be two orders of magnitude lower than the experimentally determined value of 2.5??10-16 cm2/s at 833 K. There are no values for the activation energy (Q) and pre-exponential diffusion coefficient (D0), consistent with the experimentally determined values, that will result in reasonable cooling rates for the Wind River iron formation. The discrepancy between the diffusion

  8. Oxygen isotopic variations in the outer margins and Wark-Lovering rims of refractory inclusions

    NASA Astrophysics Data System (ADS)

    Simon, Justin I.; Matzel, Jennifer E. P.; Simon, Steven B.; Hutcheon, Ian D.; Ross, D. Kent; Weber, Peter K.; Grossman, Lawrence

    2016-08-01

    Oxygen isotopic variations across the outer margins and Wark-Lovering (WL) rims of a diverse suite of six coarse-grained Types A and B refractory inclusions from both oxidized and reduced CV3 chondrites suggest that CAIs originated from a 16O-rich protosolar gas reservoir and were later exposed to both relatively 17,18O-rich and 16O-rich reservoirs. The O-isotope profiles of CAIs can be explained by changes in the composition of gas near the protoSun or the migration of CAIs through a heterogeneous nebula. Variability within the inclusion interiors appears to have been set prior to WL rim growth. Modeling the isotopic zoning profiles as diffusion gradients between inclusion interiors and edges establishes a range of permissible time-temperature combinations for their exposure in the nebula. At mean temperatures of 1400 K, models that match the isotope gradients in the inclusions yield timescales ranging from 5 × 103 to 3 × 105 years. Assuming CAIs originated with a relatively 16O-rich (protosolar) isotopic composition, differences among the melilite interiors and the isotopic gradients in their margins imply the existence of a number of isotopically distinct reservoirs. Evidence at the edges of some CAIs for subsequent isotopic exchange may relate to the beginning of rim formation. In the WL rim layers surrounding the interiors, spinel is relatively 16O-rich but subtly distinct among different CAIs. Melilite is often relatively 16O-poor, but rare relatively 16O-rich grains also exist. Pyroxene generally exhibits intermediate O-isotope compositions and isotopic zoning. Olivine in both WL and accretionary rims, when present, is isotopically heterogeneous. The extreme isotopic heterogeneity among and within individual WL rim layers and in particular, the observed trends of outward 16O-enrichments, suggest that rims surrounding CAIs contained in CV3 chondrites, like the inclusions themselves, formed from a number of isotopically distinct gas reservoirs. Collectively

  9. Oxygen isotopic variations in the outer margins and Wark–Lovering rims of refractory inclusions

    DOE PAGES

    Simon, Justin I.; Matzel, Jennifer E. P.; Simon, Steven B.; Hutcheon, Ian D.; Ross, D. Kent; Weber, Peter K.; Grossman, Lawrence

    2016-05-02

    Oxygen isotopic variations across the outer margins and Wark–Lovering (WL) rims of a diverse suite of six coarse-grained Types A and B refractory inclusions from both oxidized and reduced CV3 chondrites suggest that CAIs originated from a 16O-rich protosolar gas reservoir and were later exposed to both relatively 17,18O-rich and 16O-rich reservoirs. The O-isotope profiles of CAIs can be explained by changes in the composition of gas near the protoSun or the migration of CAIs through a heterogeneous nebula. Variability within the inclusion interiors appears to have been set prior to WL rim growth. Modeling the isotopic zoning profiles asmore » diffusion gradients between inclusion interiors and edges establishes a range of permissible time–temperature combinations for their exposure in the nebula. At mean temperatures of 1400 K, models that match the isotope gradients in the inclusions yield timescales ranging from 5 × 103 to 3 × 105 years. Assuming CAIs originated with a relatively 16O-rich (protosolar) isotopic composition, differences among the melilite interiors and the isotopic gradients in their margins imply the existence of a number of isotopically distinct reservoirs. In addition, evidence at the edges of some CAIs for subsequent isotopic exchange may relate to the beginning of rim formation. In the WL rim layers surrounding the interiors, spinel is relatively 16O-rich but subtly distinct among different CAIs. Melilite is often relatively 16O-poor, but rare relatively 16O-rich grains also exist. Pyroxene generally exhibits intermediate O-isotope compositions and isotopic zoning. Olivine in both WL and accretionary rims, when present, is isotopically heterogeneous. The extreme isotopic heterogeneity among and within individual WL rim layers and in particular, the observed trends of outward 16O-enrichments, suggest that rims surrounding CAIs contained in CV3 chondrites, like the inclusions themselves, formed from a number of isotopically distinct gas

  10. Diurnal variation of oxygen isotopic enrichment in asymmetric-18 ozone from the middle stratosphere to lower mesosphere

    NASA Astrophysics Data System (ADS)

    Sato, Tomohiro; Kasai, Yasuko; Yoshida, Naohiro

    2016-07-01

    Oxygen isotopic signature is a powerful tracer of chemical and physical processes in the earth's atmosphere. Ozone has the largest oxygen isotopic enrichment in other oxygen-included species and is a source of oxygen isotopic enrichment. The vertical profile of ozone isotopic enrichment has been measured; however its variation over time remains uninvestigated. As ozone isotopic enrichment is generated by the ozone formation reaction and ozone photolysis, ozone isotopic enrichment is expected to vary over the course of a day. In this paper, the diurnal variation in oxygen isotopic enrichment of asymmetric 18 heavy ozone (δ^{18}OOO) was reported from the middle stratosphere to the lower mesosphere for the first time. We used the Level 2 vertical profile data derived from the atmospheric limb emission spectra acquired by the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) with the optimized retrieval algorithm for ozone isotopic ratio by SMILES (TOROROS). In the middle stratosphere, δ^{18}OOO increased during the day with amplitudes of approximately 3.5 % and 2.2 % at 32 and 37 km, respectively. No significant variation was observed in the upper stratosphere and lower mesosphere, although δ^{18}OOO tended to decrease during the day with increasing altitude. This trend is opposite to that observed in the stratosphere. We estimated the diurnal variation in δ^{18}OOO with isotopic fractionation of ozone photolysis calculated by the photolysis rates of major and minor ozones. The estimation reproduced the daytime increase in the stratosphere and daytime decrease in the mesosphere. The contributions of ozone photolysis to the daytime increase were approximately 70 % and 80 % at 32 and 37 km, respectively. The daytime increase at an altitude of 32 km was underestimated, which indicates possible contributions from other chemical reactions such as collision with NO_x species. We concluded that ozone photolysis plays a key role in determining the diurnal

  11. Variation in oxygen isotope fractionation during cellulose synthesis: intramolecular and biosynthetic effects.

    PubMed

    Sternberg, Leonel; Pinzon, Maria Camila; Anderson, William T; Jahren, A Hope

    2006-10-01

    The oxygen isotopic composition of plant cellulose is commonly used for the interpretations of climate, ecophysiology and dendrochronology in both modern and palaeoenvironments. Further applications of this analytical tool depends on our in-depth knowledge of the isotopic fractionations associated with the biochemical pathways leading to cellulose. Here, we test two important assumptions regarding isotopic effects resulting from the location of oxygen in the carbohydrate moiety and the biosynthetic pathway towards cellulose synthesis. We show that the oxygen isotopic fractionation of the oxygen attached to carbon 2 of the glucose moieties differs from the average fractionation of the oxygens attached to carbons 3-6 from cellulose by at least 9%, for cellulose synthesized within seedlings of two different species (Triticum aestivum L. and Ricinus communis L.). The fractionation for a given oxygen in cellulose synthesized by the Triticum seedlings, which have starch as their primary carbon source, is different than the corresponding fractionation in Ricinus seedlings, within which lipids are the primary carbon source. This observation shows that the biosynthetic pathway towards cellulose affects oxygen isotope partitioning, a fact heretofore undemonstrated. Our findings may explain the species-dependent variability in the overall oxygen isotope fractionation during cellulose synthesis, and may provide much-needed insight for palaeoclimate reconstruction using fossil cellulose.

  12. Variation in oxygen isotope fractionation during cellulose synthesis: intramolecular and biosynthetic effects.

    PubMed

    Sternberg, Leonel; Pinzon, Maria Camila; Anderson, William T; Jahren, A Hope

    2006-10-01

    The oxygen isotopic composition of plant cellulose is commonly used for the interpretations of climate, ecophysiology and dendrochronology in both modern and palaeoenvironments. Further applications of this analytical tool depends on our in-depth knowledge of the isotopic fractionations associated with the biochemical pathways leading to cellulose. Here, we test two important assumptions regarding isotopic effects resulting from the location of oxygen in the carbohydrate moiety and the biosynthetic pathway towards cellulose synthesis. We show that the oxygen isotopic fractionation of the oxygen attached to carbon 2 of the glucose moieties differs from the average fractionation of the oxygens attached to carbons 3-6 from cellulose by at least 9%, for cellulose synthesized within seedlings of two different species (Triticum aestivum L. and Ricinus communis L.). The fractionation for a given oxygen in cellulose synthesized by the Triticum seedlings, which have starch as their primary carbon source, is different than the corresponding fractionation in Ricinus seedlings, within which lipids are the primary carbon source. This observation shows that the biosynthetic pathway towards cellulose affects oxygen isotope partitioning, a fact heretofore undemonstrated. Our findings may explain the species-dependent variability in the overall oxygen isotope fractionation during cellulose synthesis, and may provide much-needed insight for palaeoclimate reconstruction using fossil cellulose. PMID:16930314

  13. Triple Oxygen Isotopic Variation in Continental Waters and Potential Applications to Paleoclimate Research

    NASA Astrophysics Data System (ADS)

    Levin, N. E.; Li, S.

    2014-12-01

    18O/16O ratios are widely used in paleoclimate studies as proxies for temperature, precipitation amount and hydrologic change, but interpretations of these records are often challenged by the multiple factors that can influence them. Variation in 17O/16O ratios of Earth materials have long been assumed to covary with 18O/16O ratios in predictable and uniform ways such that they were not considered useful in studies of Phanerozoic climate. However, recent advances in the ability to measure small differences in 17O-excess, the deviation from an expected relationship between 18O/16O and 17O/16O ratios, in both waters and low-temperature minerals and rocks (e.g., carbonates, bioapatites, silicates, oxides) present the opportunity to use triple oxygen isotope measurements in hydrological and paleoclimate studies. In particular, the sensitivity of 17O-excess to kinetic fractionation means that it can be used to constrain the influence of kinetic effects on variations in δ18O. Here we review recently generated datasets on the triple oxygen isotope composition of the hydrosphere and show that there is considerably more variation in 17O-excess of continental waters than initially proposed. A compilation of 17O-excess data from precipitation, which includes snow from polar regions, tropical storms and weekly precipitation collections from mid-latitudes, shows that the 17O-excess of precipitation can range from -0.06 to +0.07‰. A continent-wide survey of tap waters from the U.S. mirrors the variation observed in precipitation. Among leaf waters, 17O-excess values range from -0.28 to +0.04‰ and can vary by as much as 0.16‰ in a plant within a single day. The mass-dependent effects associated with kinetic fractionation are likely responsible for the majority of the observed variation in waters, either during re-evaporation of rainfall at warmer temperatures, snow formation at very cold temperatures, or evapotranspiration within leaf waters. In summary, the combination of

  14. Oxygen isotopic determination of climatic variation using phosphate from beaver bone, tooth enamel, and dentine

    NASA Astrophysics Data System (ADS)

    Stuart-Williams, Hilary Le Q.; Schwarcz, Henry P.

    1997-06-01

    The δ 18O of Canadian beaver ( Castor canadensis) teeth should reflect variations in the isotopic composition of the water in which the beavers live, as their incisors grow rapidly and continuously. We observe seasonal variations in phosphate δ 18O using samples of enamel taken along the length of single teeth. In the spring the δ 18O of the enamel being deposited gradually declines, reflecting a retarded input of δ 18O depleted winter water. After mid-year, enamel δ 18O is higher than average (as represented by the δ 18O of bone phosphate from the same animal) and passes through a maximum in late summer or early fall. Overall, the amplitude of seasonal excursions in enamel δ 18O (4‰) is much smaller than the expected summer-winter range in the δ 18O of meteoric water (> 10‰). This is because hydrologic mixing processes, gradual admixing of environmental water with beaver body water, long-term plant growth, and oxygen inputs of relatively constant value (particularly atmospheric oxygen) tend to even out summer-winter differences in the δ 18O of oxygen inputs to the beaver. The δ 18O of bone from adult beavers was uniform at 11.9 ± 0.5‰ over the study area. Analyses of a Sangamon age giant beaver ( Castoroides ohioensis) incisor from Hopwood Farm, Illinois, show a slightly larger 5.5‰ seasonal cycle of δ 18O with an average enamel δ 18O of 18‰. This suggests that average temperatures were warmer during the Sangamon than today and that seasonal temperature differences and/or relative humidity variations were larger.

  15. Oxygen isotope variation in the tusks of extinct proboscideans: A measure of season of death and seasonality

    NASA Astrophysics Data System (ADS)

    Koch, Paul L.; Fisher, Daniel C.; Dettman, David

    1989-06-01

    Centimetre-scale laminae in tusk and molar dentine of late Pleistocene mastodonts and mammoths have been interpreted as annual growth bands produced, in part, by seasonal variation in growth rate. To test this interpretation, we measured the oxygen isotope composition (δ18O) of the CO3 fraction of dentinal hydroxyapatite from samples covering consecutive inferred years of growth in tusks. In mammals, changes in the δ18O value of dental tissues within individuals predominantly reflect variation in the δ18O value of body fluids, which is controlled mainly by the isotopic composition of ingested water. In Northern Hemisphere continental regions, winter precipitation has substantially lower δ18O values than does precipitation in other seasons. If ingested water tracks focal precipitation, then seasonal variations in dentinal isotope composition should result, the lowest δ18O values representing winter growth. We demonstrate that there are substantial variations in the oxygen isotope composition of proboscidean dentinal apatite, and that isotopic identifications of winter (i.e., low δ18O values) coincide with those based on growth rate (i.e., slow-growth zones). Finally, the potential of oxygen isotope analyses of terrestrial mammals for assessing the seasonality of paleoclimates is considered.

  16. Oxygen Isotopes in Meteorites

    NASA Astrophysics Data System (ADS)

    Clayton, R. N.

    2003-12-01

    Oxygen isotope abundance variations in meteorites are very useful in elucidating chemical and physical processes that occurred during the formation of the solar system (Clayton, 1993). On Earth, the mean abundances of the three stable isotopes are 16O: 99.76%, 17O: 0.039%, and 18O: 0.202%. It is conventional to express variations in abundances of the isotopes in terms of isotopic ratios, relative to an arbitrary standard, called SMOW (for standard mean ocean water), as follows:The isotopic composition of any sample can then be represented by one point on a "three-isotope plot," a graph of δ17O versus δ18O. It will be seen that such plots are invaluable in interpreting meteoritic data. Figure 1 shows schematically the effect of various processes on an initial composition at the center of the diagram. Almost all terrestrial materials lie along a "fractionation" trend; most meteoritic materials lie near a line of "16O addition" (or subtraction). (4K)Figure 1. Schematic representation of various isotopic processes shown on an oxygen three-isotope plot. Almost all terrestrial materials plot along a line of "fractionation"; most primitive meteoritic materials plot near a line of "16O addition." The three isotopes of oxygen are produced by nucleosynthesis in stars, but by different nuclear processes in different stellar environments. The principal isotope, 16O, is a primary isotope (capable of being produced from hydrogen and helium alone), formed in massive stars (>10 solar masses), and ejected by supernova explosions. The two rare isotopes are secondary nuclei (produced in stars from nuclei formed in an earlier generation of stars), with 17O coming primarily from low- and intermediate-mass stars (<8 solar masses), and 18O coming primarily from high-mass stars (Prantzos et al., 1996). These differences in type of stellar source result in large observable variations in stellar isotopic abundances as functions of age, size, metallicity, and galactic location ( Prantzos

  17. Oxygen and hydrogen isotope variations in the Pecos River of American Southwest

    NASA Astrophysics Data System (ADS)

    Yuan, F.; Miyamoto, S.

    2006-12-01

    The Pecos River is located in eastern New Mexico and western Texas, and its salinity increases downstream. Oxygen and hydrogen isotopic compositions (δ18O and δD) were measured on surface waters sampled from the Pecos River and its tributaries in March, May, and July of 2005. The measurements show considerably large variations in δ18O and δD, ranging from a δ18O of - 8.9‰ and δD of -64.5‰ in March at Salt Creek to a δ18O of 3.6‰ and δD of 1.6‰ in July at Girvin. Many surface waters except for head and tail waters have negative values of deuterium excess (dexcess=δD-8δ18O). Combined with the existing stable isotopic data from three gaging stations along the Pecos River (Santa Rosa, Red Bluff and Langtry) collected by the U.S. Geological Survey, it appears that evaporative enrichments of heavier isotopic species (O-18 and D) are more evident in the middle section than other parts of the river. δ18O and δD decrease at Langtry due to substantial increases in local runoff. The enhanced evaporation in the middle Pecos River is probably ascribed to a prolonged residence time resulting from anthropogenic perturbations (e.g., multi-cycle irrigation water uses and water impoundments in typically shallow reservoirs). Additionally, natural topographical gradients may have played a role in affecting water residence time and the amount of water evaporated from watersheds. These observations suggest that high dissolved salt contents of the Pecos River can be attributed to intense evaporation besides dissolution of geological salt deposits.

  18. Quartz-calcite oxygen isotope thermometry: A calibration based on natural isotopic variations

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Kirschner, D. L.

    1994-10-01

    An empirical calibration for the quartz-calcite thermometer was derived from measured Δ18O( qz- cc) values from greenschist-facies marbles, veins composed of cogenetic quartz and calcite and various low-grade metamorphic rocks. The Δ18O( qz- cc) values vary systematically with independently determined formation temperature and can be fit to the expression 1000 ln α( qz- cc) = 0.87(±0.06) × 10 6/ T2. In contrast, published results from direct-exchange experiments between calcite and quartz are 1000 ln α( qz- cc) = 0.38(±0.06) × 10 6/ T2, far smaller than in the present study. Application of the experimental mineral-water and especially the direct-exchange calibrations to natural samples, yields unreasonably low geological temperatures. It is difficult to envision a mechanism whereby the measured fractionations in greenschist-grade marbles can be reconciled with the very low temperature estimates obtained with the direct-exchange experimental calibration. Oxygen diffusion rates in quartz are too slow to explain the discrepancy. Postmetamorphic exchange could have occurred with a hydrothermal fluid, but it is unlikely that the δ18O( calcite) values of all samples would be shifted by an amount that would result in a linear relationship between 1000 ln α( qz- cc) and T-2. More likely, the discrepancy is due to a kinetic effect in the experiments. The very small fractionations observed in the direct-exchange experiments may have been caused by diffusion-related effects during recrystallization of the quartz and calcite. The problem of recrystallization is eliminated in mineral-CO 2 exchange experiments. Combined CO 2-calcite and CO 2-quartz glass experiments yield the expression 1000 ln α (qz-cc) = 0.78 ( 0¯.08) , in good agreement with the empirical calibration. The new empirical calibration yields reasonable temperature estimates for a wide range of samples and can be used for thermometry in rock types and over temperature intervals where other quantitative

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

    PubMed Central

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

    2013-01-01

    [1] Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings (δ18Otr). Interannual variation in δ18Otr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ13C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ18Otr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18O-depleted rain in the region and seem to have affected the δ18Otr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ18Otr of M. acantholoba can be used as a proxy for source water δ18O and that interannual variation in δ18Oprec is caused by a regional amount effect. This contrasts with δ18O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in disentangling the processes

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    Natural archives of oxygen isotopes in precipitation may be used to study changes in the hydrological cycle in the tropics, but their interpretation is not straightforward. We studied to which degree tree rings of Mimosa acantholoba from southern Mexico record variation in isotopic composition of precipitation and which climatic processes influence oxygen isotopes in tree rings (δ18Otr). Interannual variation in δ18Otr was highly synchronized between trees and closely related to isotopic composition of rain measured at San Salvador, 710 km to the southwest. Correlations with δ13C, growth, or local climate variables (temperature, cloud cover, vapor pressure deficit (VPD)) were relatively low, indicating weak plant physiological influences. Interannual variation in δ18Otr correlated negatively with local rainfall amount and intensity. Correlations with the amount of precipitation extended along a 1000 km long stretch of the Pacific Central American coast, probably as a result of organized storm systems uniformly affecting rainfall in the region and its isotope signal; episodic heavy precipitation events, of which some are related to cyclones, deposit strongly 18O-depleted rain in the region and seem to have affected the δ18Otr signal. Large-scale controls on the isotope signature include variation in sea surface temperatures of tropical north Atlantic and Pacific Ocean. In conclusion, we show that δ18Otr of M. acantholoba can be used as a proxy for source water δ18O and that interannual variation in δ18Oprec is caused by a regional amount effect. This contrasts with δ18O signatures at continental sites where cumulative rainout processes dominate and thus provide a proxy for precipitation integrated over a much larger scale. Our results confirm that processes influencing climate-isotope relations differ between sites located, e.g., in the western Amazon versus coastal Mexico, and that tree ring isotope records can help in disentangling the processes

  1. Oxygen isotope variations of phosphate in mammalian bone and tooth enamel

    NASA Astrophysics Data System (ADS)

    Delgado Huertas, Antonio; Iacumin, Paola; Stenni, Barbara; Sánchez Chillón, Begoña; Longinelli, Antonio

    1995-10-01

    About eighty specimens from ten different species of mammals, collected from different areas under different climatic and environmental conditions, were measured for the oxygen isotopic composition of their bone and tooth phosphate. The equations relating these values to the mean oxygen isotopic composition of local meteoric water were also derived. The same equation can be used for goats, roe-bucks, and mouflons, despite the biological differences among these species. Measurements were made on about fourty different specimens of rabbit and hare from Europe, Africa, and Canada, but in this case the data obtained clearly show no direct relationship between the oxygen isotopic composition of local meteoric water and the isotopic composition of the skeletal phosphate. However, there seems to be an inverse relationship between the relative humidity of the studied areas and the δ 18O(PO 43-) of the skeletal phosphate, thus suggesting the use of fossil bones of these mammal species as recorders of palaeoenvironmental relative humidity. Finally, a new equation was derived for the isotopic scale for horses, on the basis of all the previous data and of a few newly obtained results.

  2. Oxygen and Carbon Isotope Variations in a Modern Rodent Community – Implications for Palaeoenvironmental Reconstructions

    PubMed Central

    Gehler, Alexander; Tütken, Thomas; Pack, Andreas

    2012-01-01

    Background The oxygen (δ18O) and carbon (δ13C) isotope compositions of bioapatite from skeletal remains of fossil mammals are well-established proxies for the reconstruction of palaeoenvironmental and palaeoclimatic conditions. Stable isotope studies of modern analogues are an important prerequisite for such reconstructions from fossil mammal remains. While numerous studies have investigated modern large- and medium-sized mammals, comparable studies are rare for small mammals. Due to their high abundance in terrestrial ecosystems, short life spans and small habitat size, small mammals are good recorders of local environments. Methodology/Findings The δ18O and δ13C values of teeth and bones of seven sympatric modern rodent species collected from owl pellets at a single locality were measured, and the inter-specific, intra-specific and intra-individual variations were evaluated. Minimum sample sizes to obtain reproducible population δ18O means within one standard deviation were determined. These parameters are comparable to existing data from large mammals. Additionally, the fractionation between coexisting carbonate (δ18OCO3) and phosphate (δ18OPO4) in rodent bioapatite was determined, and δ18O values were compared to existing calibration equations between the δ18O of rodent bioapatite and local surface water (δ18OLW). Specific calibration equations between δ18OPO4 and δ18OLW may be applicable on a taxonomic level higher than the species. However, a significant bias can occur when bone-based equations are applied to tooth-data and vice versa, which is due to differences in skeletal tissue formation times. δ13C values reflect the rodents’ diet and agree well with field observations of their nutritional behaviour. Conclusions/Significance Rodents have a high potential for the reconstruction of palaeoenvironmental conditions by means of bioapatite δ18O and δ13C analysis. No significant disadvantages compared to larger mammals were observed. However

  3. Variation in oxygen isotope ratio of dissolved orthophosphate induced by uptake process in natural coral holobionts

    NASA Astrophysics Data System (ADS)

    Ferrera, Charissa M.; Miyajima, Toshihiro; Watanabe, Atsushi; Umezawa, Yu; Morimoto, Naoko; San Diego-McGlone, Maria Lourdes; Nadaoka, Kazuo

    2016-06-01

    A model incubation experiment using natural zooxanthellate corals was conducted to evaluate the influence of phosphate uptake by coral holobionts on oxygen isotope ratio of dissolved PO4 3- (δ18Op). Live coral samples of Acropora digitifera, Porites cylindrica, and Heliopora coerulea were collected from coral reefs around Ishigaki Island (Okinawa, Japan) and Bolinao (northern Luzon, Philippines) and incubated for 3-5 d after acclimatization under natural light conditions with elevated concentrations of PO4 3-. Phosphate uptake by corals behaved linearly with incubation time, with uptake rate depending on temperature. δ18Op usually increased with time toward the equilibrium value with respect to oxygen isotope exchange with ambient seawater, but sometimes became higher than equilibrium value at the end of incubation. The magnitude of the isotope effect associated with uptake depended on coral species; the greatest effect was in A. digitifera and the smallest in H. coerulea. However, it varied even within samples of a single coral species, which suggests multiple uptake processes with different isotope effects operating simultaneously with varying relative contributions in the coral holobionts used. In natural environments where concentrations of PO4 3- are much lower than those used during incubation, PO4 3- is presumably turned over much faster and the δ18Op easily altered by corals and other major primary producers. This should be taken into consideration when using δ18Op as an indicator of external PO4 3- sources in coastal ecosystems.

  4. The cause of the seasonal variation in the oxygen isotopic composition of precipitation along the western U.S. coast

    NASA Astrophysics Data System (ADS)

    Buenning, N. H.; Stott, L. D.; Yoshimura, K.; Berkelhammer, M. B.

    2012-12-01

    This study seeks to find the primary influence on the seasonal cycle of the oxygen isotopic composition of precipitation (δ18Op) along the western U.S. coast. Observed long-term mean seasonal variations of δ18Op from 16 different stations along the west coast are presented. The most robust features in the observations are high values in the summer and a drop in δ18Op during the winter, a feature observed at many mid-latitude locations. The Isotope-incorporated Global Spectral Model (IsoGSM) also simulates this wintertime drop in δ18Op along the west coast of the U.S. To better understand the cause of this seasonal variation, sensitivity experiments are performed with IsoGSM where individual oxygen isotope fractionation processes are turned off. These simulations reveal that the primary control on the seasonal variations is equilibrium oxygen isotopic fractionation during vapor condensation. There is almost no influence of the temperature dependence of equilibrium fractionation on the seasonal δ18Op cycle for both ocean evaporation and vapor condensation. Additional experiments (including tagging simulations) are performed to better understand why Rayleigh distillation causes the seasonal variation in δ18Op. Tagging results suggest no strong influence of seasonal moisture source variations on the seasonal δ18Op cycle, though the seasonal cycle of column-integrated water vapor δ18O values is in phase with the monthly shifts in moisture sources (in IsoGSM). The tagging simulations did however reveal that vertical oxygen isotope gradients and variations in condensation height cause the seasonal cycle in δ18Op. This results from seasonal changes in the polar jet, and subsequent changes to divergence and vertical velocities, which affects the uplift of moisture. These findings suggest that δ18Op in the western U.S. is a tracer of condensation height on seasonal timescales. The large influence of condensation height on δ18Op seasonality complicates

  5. Carbon and oxygen isotope variations of the Middle-Late Triassic Al Aziziyah Formation, northwest Libya

    NASA Astrophysics Data System (ADS)

    Moustafa, Mohamed S. H.; Pope, Michael C.; Grossman, Ethan L.; Mriheel, Ibrahim Y.

    2016-06-01

    This study presents the δ13C and δ18O records from whole rock samples of the Middle-Late Triassic (Ladinian-Carnian) Al Aziziyah Formation that were deposited on a gently sloping carbonate ramp within the Jifarah Basin of Northwest Libya. The Al Aziziyah Formation consists of gray limestone, dolomite, and dolomitic limestone interbedded with shale. The Ghryan Dome and Kaf Bates sections were sampled and analyzed for carbon and oxygen isotope chemostratigraphy to integrate high-resolution carbon isotope data with an outcrop-based stratigraphy, to provide better age control of the Al Aziziyah Formation. This study also discusses the relation between the facies architecture of the Al Aziziyah Formation and the carbon isotope values. Seven stages of relative sea level rise and fall within the Ghryan Dome were identified based on facies stacking patterns, field observations and carbon stable isotopes. The Al Aziziyah Formation δ13C chemostratigraphic curve can be partially correlated with the Triassic global δ13C curve. This correlation indicates that the Al Aziziyah Formation was deposited during the Ladinian and early Carnian. No straight-forward relationship is seen between δ13C and relative sea level probably because local influences complicated systematic environmental and diagenetic isotopic effects associated with sea level change.

  6. A controlled test of the dual-isotope approach for the interpretation of stable carbon and oxygen isotope ratio variation in tree rings.

    PubMed

    Roden, John S; Farquhar, Graham D

    2012-04-01

    Seedlings of a conifer (Pinus radiata D. Don) and a broad leaf angiosperm (Eucalyptus globulus Labill.) were grown for 100 days in two growth cabinets at 45 or 65% relative humidity. The seedlings were exposed to treatments designed to modify carbon assimilation rates and capacities, stomatal conductance and transpiration to test conceptual models that attempt to clarify the interpretation of carbon isotope discrimination (Δ(13)C) by using oxygen isotope enrichment (Δ(18)O). Differences in relative humidity and within-cabinet treatments (including lower irradiance, lower nitrogen inputs, higher leaf temperature and lower moisture status than control seedlings) produced significant differences in assimilation rates, photosynthetic capacities, stomatal conductance, leaf transpiration rates and leaf evaporative enrichment. The dual-isotope approach accurately interpreted the cause of variation in wood cellulose Δ(13)C for some of the treatments, but not for others. We also tested whether we could use Δ(13)C variation to constrain the interpretation of δ(18)O variation. Carbon isotope discrimination appears to be influenced by transpiration (providing information on leaf evaporative enrichment), but the results did not provide a clear way to interpret such variation. The dual-isotope approach appears to be valid conceptually, but more work is needed to make it operational under different scenarios. PMID:22440882

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

    SciTech Connect

    Lugaro, Maria; Liffman, Kurt; Maddison, Sarah T.

    2012-11-01

    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 {sup 16}O-rich CO and {sup 16}O-poor H{sub 2}O, where the H{sub 2}O subsequently combined with interstellar dust to form relatively {sup 16}O-poor solids within the solar nebula. Another model for creating the different reservoirs of {sup 16}O-rich gas and {sup 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 {sup 18}O/{sup 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.

  8. Strontium and oxygen isotopic variations in Mesozoic and Tertiary plutons of central Idaho

    USGS Publications Warehouse

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

    1985-01-01

    Regional variations in initial 87Sr/86Sr ratios (ri) of Mesozoic plutons in central Idaho locate the edge of Precambrian continental crust at the boundary between the late Paleozoic-Mesozoic accreted terranes and Precambrian sialic crust in western Idaho. The ri values increase abruptly but continuously from less than 0.704 in the accreted terranes to greater than 0.708 across a narrow, 5 to 15 km zone, characterized by elongate, lens-shaped, highly deformed plutons and schistose metasedimentary and metavolcanic units. The chemical and petrologic character of the plutons changes concomitantly from ocean-arc-type, diorite-tonalite-trondhjemite units to a weakly peraluminous, calcic to calcalkalic tonalite-granodiorite-granite suite (the Idaho batholith). Plutons in both suites yield Late Cretaceous ages, but Permian through Early Cretaceous bodies are confined to the accreted terranes and early Tertiary intrusions are restricted to areas underlain by Precambrian crust. The two major terranes were juxtaposed between 75 and 130 m.y. ago, probably between 80 and 95 m.y. Oxygen and strontium isotopic ratios and Rb and Sr concentrations of the plutonic rocks document a significant upper-crustal contribution to the magmas that intrude Precambrian crust. Magmas intruding the arc terranes were derived from the upper mantle/subducted oceanic lithosphere and may have been modified by anatexis of earlier island-arc volcanic and sedimentary units. Plutons near the edge of Precambrian sialic crust represent simple mixtures of the Precambrian wall-rocks with melts derived from the upper mantle or subducted oceanic lithosphere with ri of 0.7035. Rb/Sr varies linearly with ri, producing "pseudoisochrons" with apparent "ages" close to the age of the wall rocks. Measured ??18O values of the wall rocks are less than those required for the assimilated end-member by Sr-O covariation in the plutons, however, indicating that wall-rock ??18O was reduced significantly by exchange with

  9. Paleoclimatic Study of the West Pacific Warm Pool using Oxygen Isotope Variations in a Stalagmite from Guam

    NASA Astrophysics Data System (ADS)

    Moore, M. W.; Hardt, B. F.; Partin, J. W.; Banner, J. L.; Jenson, J. W.; Sinclair, D. J.; Taylor, F.

    2011-12-01

    The West Pacific Warm Pool (WPWP) is a region of the Pacific with mean seasonal sea surface temperatures > 28°C, and is a major driver of global climate. While the past ˜150 years have been instrumented and conditions have been recorded, it is unclear how much of the changes observed are due to anthropogenic effects or natural variability. In addition, this time frame may not include events that are natural but infrequent. This study investigates climate of the WPWP using oxygen isotope variations in speleothem calcite as a proxy for changes in rainfall on the island of Guam. The temperature effect on oxygen isotope ratios is relatively small in the tropics when compared to the effects of rainfall at Guam, and speleothem oxygen isotope ratios are more likely to vary in response to changes in storm tracks or rainfall amount. Previous research in the area has shown a correlation (r2 of .57) between rainfall amount and stable isotopic composition. The speleothem sample "Stumpy" being used for this study was collected in 2005 from Jinapsan Cave on Guam (13° 38' N, 144° 53' E), where annual rainfall is connected to the state of the WPWP. Samples were milled at 1 millimeter resolution, representing an average resolution of 50 years per sample. U-series analyses show that the 33-cm-long Stumpy grew from ˜18,000 ka up to present day. Oxygen isotope values range from -9.4 to -4.5 per mille, and exhibit oscillations of approximately 0.5 per mille. At 27 cm, the record shows a 3.8 per mille shift to higher values, coincident with the occurrence of a dark brown growth layer. This shift may represent a change in rainfall across a growth hiatus. The range in oxygen isotope values of 4.9 per mille in Stumpy corresponds to a difference in rainfall of 350 +/- 74 mm/month, based on previous study of rainfall in the modern system.

  10. Understanding Spatial and Temporal Variations of Arctic Circulation Using Oxygen Isotopes of Seawater

    NASA Astrophysics Data System (ADS)

    Yin, L.; Kopans-Johnson, C. R.; LeGrande, A. N.; Kelly, S.

    2015-12-01

    The isotopic ratio of 18O to 16O in seawater (2005ppm in ocean water is defined as 𝛿18Oseawater≡0 permil or 0‰) is a fundamental ocean tracer due to its distinct linear relationship with salinity(𝛿18O -S) from regional inland freshwater sources. As opposed to salinity alone, 𝛿18O distinguishes river runoff from sea-ice melt and traces ocean circulation pathways from coastal to open waters and surface to deep waters. Observations from the past 60 years of 𝛿18O seawater were compiled into a database by Schimdt et al. (1999), and subsequently used to calculate a 3-dimensional 1°x1° 𝛿18O global gridded dataset by LeGrande and Schmidt (2006). Although the Schmidt et al. (1999) Global Seawater Oxygen-18 Database (𝛿18Oobs) contains 25,514 measurements used to calculate the global gridded dataset, LeGrande and Schmidt (2006) point out that, "data coverage varies greatly from region to region," with seasonal variability creating biases in areas where sea ice is present. Python Pandas is used to automate the addition of 2,942 records to the Schmidt et al. (1999) Global Seawater Oxygen-18 Database (𝛿18Oobs), and examine the spatial and temporal distributions of 18O in the Arctic Ocean. 10 initial water masses are defined using spatial and temporal trends, clusters of observations, and Arctic surface circulation. Jackknife slope analysis of water mass 𝛿18O -S is used to determine anomalous data points and regional hydrology, resulting in 4 distinct Arctic water masses. These techniques are used to improve the gridded 𝛿18Oseawater dataset by distinguishing unique water masses, and accounting for seasonal variability of complex high latitude areas.

  11. Factors controlling the growth rate, carbon and oxygen isotope variation in modern calcite precipitation in a subtropical cave, Southwest China

    NASA Astrophysics Data System (ADS)

    Pu, Junbing; Wang, Aoyu; Shen, Licheng; Yin, Jianjun; Yuan, Daoxian; Zhao, Heping

    2016-04-01

    A prerequisite for using cave speleothems to reconstruct palaeoenvironmental conditions is an accurate understanding of specific factors controlling calcite growth, in particular the isotopic partitioning of oxygen (δ18O) and carbon (δ13C) which are the most commonly used proxies. An in situ monitoring study from April 2008 to September 2009 at Xueyu Cave, Chongqing, SW China, provides insight into the controls on calcite growth rates, drip water composition, cave air parameters and δ18O and δ13C isotopic values of modern calcite precipitation. Both cave air PCO2 and drip water hydrochemical characteristics show obvious seasonality driven by seasonal changes in the external environment. Calcite growth rates also display clear intra-annual variation, with the lowest values occurring during wet season and peak values during the dry season. Seasonal variations of calcite growth rate are primarily controlled by variations of cave air PCO2 and drip water rate. Seasonal δ18O-VPDB and δ13C-VPDB in modern calcite precipitates vary, with more negative values in the wet season than in the dry season. Strong positive correlation of δ18O-VPDB vs. δ13C-VPDB is due to simultaneous enrichment of both isotopes in the calcite. This correlation indicates that kinetic fractionation occurs between parent drip water and depositing calcite, likely caused by the variations of cave air PCO2 and drip rate influenced by seasonal cave ventilation. Kinetic fractionation amplifies the equilibrium fractionation value of calcite δ18O (by ∼1.5‰) and δ13C (by ∼1.7‰), which quantitatively reflects surface conditions during the cave ventilation season. These results indicate that the cave monitoring of growth rate and δ18O and δ13C of modern calcite precipitation are necessary in order to use a speleothem to reconstruct palaeoenvironment.

  12. Coral oxygen isotope records of interdecadal climate variations in the South Pacific Convergence Zone region

    NASA Astrophysics Data System (ADS)

    Bagnato, Stefan; Linsley, Braddock K.; Howe, Stephen S.; Wellington, Gerard M.; Salinger, Jim

    2005-06-01

    The South Pacific Convergence Zone (SPCZ), a region of high rainfall, is a major feature of subtropical Southern Hemisphere climate and contributes to and interacts with circulation features across the Pacific, yet its past temporal variability and forcing remain only partially understood. Here we compare coral oxygen isotopic (δ18O) series (spanning A.D. 1997-1780 and A.D. 2001-1776) from two genera of hermatypic corals in Fiji, located within the SPCZ, to examine the fidelity of these corals in recording climate change and SPCZ interdecadal dynamics. One of these coral records is a new 225-year subannually resolved δ18O series from the massive coral Diploastreaheliopora. Diploastrea's use in climate reconstructions is still relatively new, but this coral has shown encouragingly similar interannual variability to Porites, the coral genus most commonly used in Pacific paleoclimate studies. In Fiji we observe that interdecadal δ18O variance is also similar in these two coral genera, and Diploastrea contains a larger-amplitude interdecadal signal that more closely tracks instrumental-based indices of Pacific interdecadal climate change and the SPCZ than Porites. Both coral δ18O series record greater interdecadal variability from ˜1880 to 1950, which is consistent with the observations of Folland et al. (2002), who reported higher variability in SPCZ position before 1945. These observations indicate that Diploastrea will likely provide a significant new source of long-term climate information from the SPCZ region.

  13. Sulfur, carbon, and oxygen isotope variations in submarine hydrothermal deposits of Guaymas Basin, Gulf of California, USA

    USGS Publications Warehouse

    Peter, J.M.; Shanks, Wayne C.

    1992-01-01

    Sulfur, carbon, and oxygen isotope values were measured in sulfide, sulfate, and carbonate from hydrothermal chimney, spire, and mound samples in the southern trough of Guaymas Basin, Gulf of California, USA. ??34S values of sulfides range from -3.7 to 4.5%. and indicate that sulfur originated from several sources: 1. (1) dissolution of 0??? sulfide contained within basaltic rocks, 2. (2) thermal reduction of seawater sulfate during sediment alteration reactions in feeder zones to give sulfide with positive ??34S, and 3. (3) entrainment or leaching of isotopically light (negative-??34S) bacteriogenic sulfide from sediments underlying the deposits. ??34S of barite and anhydrite indicate sulfur derivation mainly from unfractionated seawater sulfate, although some samples show evidence of sulfate reduction and sulfide oxidation reactions during mixing within chimneys. Oxygen isotope temperatures calculated for chimney calcites are in reasonable agreement with measured vent fluid temperatures and fluid inclusion trapping temperatures. Hydrothermal fluids that formed calcite-rich chimneys in the southern trough of Guaymas Basin were enriched in 18O with respect to seawater by about 2.4??? due to isotopic exchange with sedimentary and/or basaltic rocks. Carbon isotope values of calcite range from -9.6 to -14.0??? ??34CpDB, indicating that carbon was derived in approximately equal quantities from the dissolution of marine carbonate minerals and the oxidation of organic matter during migration of hydrothermal fluid through the underlying sediment column. Statistically significant positive, linear correlations of ??34S, ??34C, and ??18O of sulfides and calcites with geographic location within the southern trough of Guaymas Basin are best explained by variations in water/rock ( w r) ratios or sediment reactivity within subsurface alteration zones. Low w r ratios and the leaching of detrital carbonates and bacteriogenic sulfides at the southern vent sites result in relatively

  14. Assessing site-specific spatio-temporal variations in hydrogen and oxygen stable isotopes of human drinking water

    NASA Astrophysics Data System (ADS)

    Kennedy, C. D.; Bowen, G. J.; Ehleringer, J. R.

    2008-12-01

    Stable isotope ratios of hydrogen and oxygen (δ2H and δ18O) are environmental forensic tracers that can be used to constrain the origin and movement of animals, people, and products. The fundamental assumption underlying this method is that water resources at different geographic locations have distinct and characteristic isotopic signatures that are assimilated into organic tissues. Although much is known about regional-scale spatio-temporal variability in δ2H and δ18O of water, few studies have addressed the question of how distinct these geographic and seasonal patterns are for any given site. To address this question, a 2-year survey of δ2H and δ18O in tap water from across the contiguous U.S. and Canada was conducted. The data show that seasonal variability in δ2H and δ18O of tap water is generally low (<10 ‰ for δ2H), and those with the highest variability can be classified as: a) cities or towns in areas of high climate seasonality, or b) large cities in arid or seasonally arid regions which access and switch among multiple water sources throughout the year. The data suggest that inter-annual variation in tap water isotope ratios is typically low, with a median difference for month-month pairs during the 2 sampling years of 2.7 (δ2H). The results from this study confirm the existence of temporal variability in δ2H and δ18O of tap water, but suggest that this variability in human-managed systems is highly damped and may be amenable to classification, modeling, and prediction. In all, the data provide the foundation for incorporating temporal variation in predictive models of water and organic δ2H and δ18O, leading to more robust and statistically defensible tests of geographic origin.

  15. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide.

    PubMed

    Wiegel, Aaron A; Cole, Amanda S; Hoag, Katherine J; Atlas, Elliot L; Schauffler, Sue M; Boering, Kristie A

    2013-10-29

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in (17)O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the (17)O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O((1)D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of (17)O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2. PMID:23940331

  16. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

    NASA Astrophysics Data System (ADS)

    Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

    2013-10-01

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

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

    PubMed

    Lightfoot, Emma; O'Connell, Tamsin C

    2016-01-01

    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 homeland should not

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

    PubMed Central

    Lightfoot, Emma; O’Connell, Tamsin C.

    2016-01-01

    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 homeland should

  19. Intraspecific variations in carbon-isotope and oxygen-isotope compositions of a brachiopod Basiliola lucida collected off Okinawa-jima, southwestern Japan

    NASA Astrophysics Data System (ADS)

    Takayanagi, Hideko; Asami, Ryuji; Abe, Osamu; Miyajima, Toshihiro; Kitagawa, Hiroyuki; Sasaki, Keiichi; Iryu, Yasufumi

    2013-08-01

    This study presents intraspecific variations in carbon-isotope (δ13C) and oxygen-isotope (δ18O) compositions of nine specimens of a subtropical brachiopod, Basiliola lucida, collected west of Okinawa-jima, Ryukyu Islands, southwestern Japan. The δ13C values of samples collected along the maximum growth axis (ontogenetic samples) from two modern and seven older (pre-1945 cal AD) shells show no seasonal changes. The modern shells, which were collected from comparable depths, have similar δ13C values that fall within the range of calcite precipitated in isotopic equilibrium with ambient seawater (equilibrium calcite) (δ13CEC values), and their mean δ13C values are ˜1.1-1.6‰ less than those from the older shells. This decrease in δ13C values is similar in magnitude to the decreases in atmospheric CO2 and the oceanic dissolved inorganic carbon at the sea surface in recent years (13C Suess effect), suggesting that the effect can even be detected at water depths of 200-300 m in the subtropical northwestern Pacific Ocean. The δ18O values fluctuate within a narrow range (0.26-0.41‰) with no seasonal changes, and they exhibit small (0.14-0.51‰) offsets from those of equilibrium calcite (δ18OEC values). A statistically significant negative linear relationship is established between seawater temperature and mean δ18O values of the nine shells, but the slope (-0.31‰/°C) is steeper than those of equilibrium calcite (-0.23‰/°C) and other calcareous organisms (-0.15‰ to -0.26‰/°C). The cross-plots of the δ13C and δ18O values suggest that the degree of the vital effect varies among individuals in this species. The δ13C and δ18O values of B. lucida are potentially useful for reconstructing the δ13C and δ18O evolution of ancient oceans, because both values show small intraspecific variations, the former is identical to the δ13CEC values, and the latter shows small within-shell variations and small, nearly constant offsets from the δ18OEC values.

  20. Kangaroo tooth enamel oxygen and carbon isotope variation on a latitudinal transect in southern Australia: implications for palaeoenvironmental reconstruction.

    PubMed

    Brookman, Tom H; Ambrose, Stanley H

    2013-02-01

    Tooth enamel apatite carbonate carbon and oxygen isotope ratios of modern kangaroos (Macropus spp.) collected on a 900-km latitudinal transect spanning a C(3)-C(4) transition zone were analysed to create a reference set for palaeoenvironmental reconstruction in southern Australia. The carbon isotope composition of enamel carbonate reflects the proportional intake of C(3) and C(4) vegetation, and its oxygen isotope composition reflects that of ingested water. Tooth enamel forms incrementally, recording dietary and environmental changes during mineralisation. Analyses show only weak correlations between climate records and latitudinal changes in δ(13)C and δ(18)O. No species achieved the δ(13)C values (~-1.0 ‰) expected for 100 % C(4) grazing diets; kangaroos at low latitudes that are classified as feeding primarily on C(4) grasses (grazers) have δ(13)C of up to -3.5 ‰. In these areas, δ(13)C below -12 ‰ suggests a 100 % C(3) grass and/or leafy plant (browse) diet while animals from higher latitude have lower δ(13)C. Animals from semi-arid areas have δ(18)O of 34-40 ‰, while grazers from temperate areas have lower values (~28-30 ‰). Three patterns with implications for palaeoenvironmental reconstruction emerge: (1) all species in semi-arid areas regularly browse to supplement limited grass resources; (2) all species within an environmental zone have similar carbon and oxygen isotope compositions, meaning data from different kangaroo species can be pooled for palaeoenvironmental investigations; (3) relatively small regional environmental differences can be distinguished when δ(13)C and δ(18)O data are used together. These data demonstrate that diet-isotope and climate-isotope relationships should be evaluated in modern ecosystems before application to the regional fossil record.

  1. Carbon, oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England

    NASA Astrophysics Data System (ADS)

    Coleman, M. L.; Raiswell, R.

    1981-03-01

    Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ 13C PDB values of the calcite cement (-12.9 to -15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon ( δ13CPDB = -26.1 to -37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation. Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ 34S CD values of -22 to -26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of - 2.5 to - 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ 13C and δ 34S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ 18O values of the calcite in one concretion ( δ18OPDB = 2.3 to -4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter ( δ18OPDB-8.9 to -9.9%.) and large δ 18O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.

  2. Oxygen isotope ratios in eclogites from kimberlites.

    PubMed

    Garlick, G D; Macgregor, I D; Vogel, D E

    1971-06-01

    The oxygen isotope compositions (delta(18)O) of eclogitic xenoliths from the Roberts Victor kimberlite range from 2 to 8 per mil relative to SMOW (standard mean ocean water). This surprising variation appears to be due to fractional crystallization: the eclogites rich in oxygen-18 represent early crystal accumulates; the eclogites poor in oxygen-18 represent residual liquids. Crystal-melt partitioning probably exceeded 3 per mil and is interpreted to be pressure-dependent. Anomalous enrichment of oxygen-18 in cumulate eclogites relative to ultramafic xenoliths suggests that crystal-melt partitioning increased after melt-formation but prior to crystallization.

  3. Oxygen isotope ratios in eclogites from kimberlites.

    PubMed

    Garlick, G D; Macgregor, I D; Vogel, D E

    1971-06-01

    The oxygen isotope compositions (delta(18)O) of eclogitic xenoliths from the Roberts Victor kimberlite range from 2 to 8 per mil relative to SMOW (standard mean ocean water). This surprising variation appears to be due to fractional crystallization: the eclogites rich in oxygen-18 represent early crystal accumulates; the eclogites poor in oxygen-18 represent residual liquids. Crystal-melt partitioning probably exceeded 3 per mil and is interpreted to be pressure-dependent. Anomalous enrichment of oxygen-18 in cumulate eclogites relative to ultramafic xenoliths suggests that crystal-melt partitioning increased after melt-formation but prior to crystallization. PMID:17798552

  4. Theoretical calculation of oxygen equilibrium isotope fractionation factors involving various NOy molecules, radOH, and H2O and its implications for isotope variations in atmospheric nitrate

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2016-10-01

    The oxygen stable isotope composition (δ18O) of nitrogen oxides [NOx = nitric oxide (NO) + nitrogen dioxide (NO2)] and their oxidation products (NOy = NOx + nitric acid (HNO3) + particulate nitrate (p-NO3-) + nitrate radical (NO3) + dinitrogen pentoxide (N2O5) + nitrous acid (HONO) + …) have been shown to be a useful tool for inferring the proportion of NOx that is oxidized by ozone (O3). However, isotopic fractionation processes may have an influence on δ18O of various NOy molecules and other atmospheric O-bearing molecules pertinent to NOx oxidation chemistry. Here we have evaluated the impacts of O isotopic exchange involving NOy molecules, the hydroxyl radical (radOH), and water (H2O) using reduced partition function ratios (xβ) calculated by hybrid density functional theory. Assuming atmospheric isotopic equilibrium is achieved between NO and NO2 during the daytime, and NO2, NO3, and N2O5 during the nighttime, δ18O-δ15N compositions were predicted for the major atmospheric nitrate formation pathways using our calculated exchange fractionation factors and isotopic mass-balance. Our equilibrium model predicts that various atmospheric nitrate formation pathways, including NO2 + radOH → HNO3, N2O5 + H2O + surface → 2HNO3, and NO3 + R → HNO3 + Rrad will yield distinctive δ18O-δ15N compositions. Our calculated δ18O-δ15N compositions match well with previous atmospheric nitrate measurements, and will potentially help better understand the role oxidation chemistry plays on the N and O isotopic composition of atmospheric nitrate.

  5. Seasonal variations in the stable oxygen isotope ratio of wood cellulose reveal annual rings of trees in a Central Amazon terra firme forest.

    PubMed

    Ohashi, Shinta; Durgante, Flávia M; Kagawa, Akira; Kajimoto, Takuya; Trumbore, Susan E; Xu, Xiaomei; Ishizuka, Moriyoshi; Higuchi, Niro

    2016-03-01

    In Amazonian non-flooded forests with a moderate dry season, many trees do not form anatomically definite annual rings. Alternative indicators of annual rings, such as the oxygen (δ(18)Owc) and carbon stable isotope ratios of wood cellulose (δ(13)Cwc), have been proposed; however, their applicability in Amazonian forests remains unclear. We examined seasonal variations in the δ(18)Owc and δ(13)Cwc of three common species (Eschweilera coriacea, Iryanthera coriacea, and Protium hebetatum) in Manaus, Brazil (Central Amazon). E. coriacea was also sampled in two other regions to determine the synchronicity of the isotopic signals among different regions. The annual cyclicity of δ(18)Owc variation was cross-checked by (14)C dating. The δ(18)Owc showed distinct seasonal variations that matched the amplitude observed in the δ(18)O of precipitation, whereas seasonal δ(13)Cwc variations were less distinct in most cases. The δ(18)Owc variation patterns were similar within and between some individual trees in Manaus. However, the δ(18)Owc patterns of E. coriacea differed by region. The ages of some samples estimated from the δ(18)Owc cycles were offset from the ages estimated by (14)C dating. In the case of E. coriacea, this phenomenon suggested that missing or wedging rings may occur frequently even in well-grown individuals. Successful cross-dating may be facilitated by establishing δ(18)Owc master chronologies at both seasonal and inter-annual scales for tree species with distinct annual rings in each region.

  6. Oxygen Isotopes in the Terrestrial Planets

    NASA Astrophysics Data System (ADS)

    Clayton, R. N.

    2004-12-01

    Mechanisms that may account for oxygen isotope heterogeneity in meteorites on the microscopic scale do not seem adequate for explaining the similarities and differences in isotopic composition on a planetary scale. In chondrites, most of the isotopic variability can be attributed to photochemical enrichment of the two rare heavy isotopes with respect to the 16O-rich solar composition In the CO, CM, CI, and CR chondrites, an additional low-temperature aqueous alteration leads to mass-dependent further enrichment of the heavy isotopes. If the photochemical origin of the isotopic variation in chondrites is correct, then only a small fraction, represented primarily in CAIs, has the solar oxygen isotopic composition, and all other meteoritic components must have undergone photochemical processing. In addition, since the bulk isotopic compositions of the terrestrial planets and of the achondrite parent bodies are similar to those of chondrites, they too must be made of photochemically enriched matter. The photochemical reactions produce a non-equilibrium assemblage of gases, probably leading to a non-equilibrium assemblage of solids, particularly with respect to their oxidation state. These issues emphasize the importance of the measurement of oxygen isotopes in the Genesis solar wind mission. Within the Earth, oxygen isotope variations are due almost entirely to mass-dependent fractionation effects, giving a line of slope 0.52 on the three-isotope plot. The average crustal composition is 3 to 4 permil higher in delta-18O than the upper mantle. This difference is too large to be due to igneous fractionation effects alone, and reflects the larger, low-temperature isotope fractionation associated with aqueous weathering reactions at the Earth's surface. Similar effects are not observed in the intraplanetary isotopic variations in the Moon or in the parent bodies of the HED and SNC meteorites. The bulk oxygen isotopic compositions of Earth and Mars (assumed to be the SNC

  7. Isotopic Composition of Oxygen in Lunar Zircons

    NASA Technical Reports Server (NTRS)

    Nemchin, A. A.; Whitehouse, M. J.; Pidgeon, R. T.; Meyer, C.

    2005-01-01

    The recent discovery of heavy oxygen in zircons from the Jack Hills conglomerates Wilde et al. and Mojzsis et al. was interpreted as an indication of presence of liquid water on the surface of Early Earth. The distribution of ages of Jack Hills zircons and lunar zircons appears to be very similar and therefore analysis of oxygen in the lunar grains may provide a reference frame for further study of the early history of the Earth as well as give additional information regarding processes that operated on the Moon. In the present study we have analysed the oxygen isotopic composition of zircon grains from three lunar samples using the Swedish Museum of Natural History CAMECA 1270 ion microprobe. The samples were selected as likely tests for variations in lunar oxygen isotopic composition. Additional information is included in the original extended abstract.

  8. Oxygen isotope corrections for online δ34S analysis

    USGS Publications Warehouse

    Fry, B.; Silva, S.R.; Kendall, C.; Anderson, R.K.

    2002-01-01

    Elemental analyzers have been successfully coupled to stable-isotope-ratio mass spectrometers for online measurements of the δ34S isotopic composition of plants, animals and soils. We found that the online technology for automated δ34S isotopic determinations did not yield reproducible oxygen isotopic compositions in the SO2 produced, and as a result calculated δ34S values were often 1–3‰ too high versus their correct values, particularly for plant and animal samples with high C/S ratio. Here we provide empirical and analytical methods for correcting the S isotope values for oxygen isotope variations, and further detail a new SO2-SiO2 buffering method that minimizes detrimental oxygen isotope variations in SO2.

  9. Triple Oxygen Isotopes: Fundamental Relationships and Applications

    NASA Astrophysics Data System (ADS)

    Bao, Huiming; Cao, Xiaobin; Hayles, Justin A.

    2016-06-01

    The element oxygen has three stable isotopes: 16O, 17O, and 18O. For a defined process, a change in 18O/16O scales with the corresponding change in 17O/16O, or the fractionation factors 18α and 17α have a relationship of θ = ln17α/ln18α, in which the triple oxygen isotope exponent θ is relatively fixed but does vary with reaction path, temperature, and species involved. When the small variation is of interest, the distinction of three concepts—θ, S (a slope through data points in δ17O-δ18O space), and C (an arbitrary referencing number for the degree of 17O deviation)—becomes important. Triple oxygen isotope variations can be measured by modern instruments and thus offer an additional line of information on the underlying reaction processes and conditions. Analytical methods and Earth science applications have recently been developed for air oxygen, carbon dioxide, water, silicates, oxides, sulfates, carbonates, and phosphates.

  10. Triple Oxygen Isotopes: Fundamental Relationships and Applications

    NASA Astrophysics Data System (ADS)

    Bao, Huiming; Cao, Xiaobin; Hayles, Justin A.

    2016-06-01

    The element oxygen has three stable isotopes: 16O, 17O, and 18O. For a defined process, a change in 18O/16O scales with the corresponding change in 17O/16O, or the fractionation factors 18α and 17α have a relationship of θ = ln17α/ln18α, in which the triple oxygen isotope exponent θ is relatively fixed but does vary with reaction path, temperature, and species involved. When the small variation is of interest, the distinction of three concepts—θ, S (a slope through data points in δ17O–δ18O space), and C (an arbitrary referencing number for the degree of 17O deviation)—becomes important. Triple oxygen isotope variations can be measured by modern instruments and thus offer an additional line of information on the underlying reaction processes and conditions. Analytical methods and Earth science applications have recently been developed for air oxygen, carbon dioxide, water, silicates, oxides, sulfates, carbonates, and phosphates.

  11. The oxygen isotope composition, petrology and geochemistry of mare basalts: Evidence for large-scale compositional variation in the lunar mantle

    NASA Astrophysics Data System (ADS)

    Hallis, L. J.; Anand, M.; Greenwood, R. C.; Miller, M. F.; Franchi, I. A.; Russell, S. S.

    2010-12-01

    To investigate the formation and early evolution of the lunar mantle and crust we have analysed the oxygen isotopic composition, titanium content and modal mineralogy of a suite of lunar basalts. Our sample set included eight low-Ti basalts from the Apollo 12 and 15 collections, and 12 high-Ti basalts from Apollo 11 and 17 collections. In addition, we have determined the oxygen isotopic composition of an Apollo 15 KREEP (K - potassium, REE - Rare Earth Element, and P - phosphorus) basalt (sample 15386) and an Apollo 14 feldspathic mare basalt (sample 14053). Our data display a continuum in bulk-rock δ 18O values, from relatively low values in the most Ti-rich samples to higher values in the Ti-poor samples, with the Apollo 11 sample suite partially bridging the gap. Calculation of bulk-rock δ 18O values, using a combination of previously published oxygen isotope data on mineral separates from lunar basalts, and modal mineralogy (determined in this study), match with the measured bulk-rock δ 18O values. This demonstrates that differences in mineral modal assemblage produce differences in mare basalt δ 18O bulk-rock values. Differences between the low- and high-Ti mare basalts appear to be largely a reflection of mantle-source heterogeneities, and in particular, the highly variable distribution of ilmenite within the lunar mantle. Bulk δ 18O variation in mare basalts is also controlled by fractional crystallisation of a few key mineral phases. Thus, ilmenite fractionation is important in the case of high-Ti Apollo 17 samples, whereas olivine plays a more dominant role for the low-Ti Apollo 12 samples. Consistent with the results of previous studies, our data reveal no detectable difference between the Δ 17O of the Earth and Moon. The fact that oxygen three-isotope studies have been unable to detect a measurable difference at such high precisions reinforces doubts about the giant impact hypothesis as presently formulated.

  12. Tracing oxygen variations and its biogeochemical expression during the late hauterivian Faraoni Event: A multi tracers approach using paired carbon, nitrogen, sulfur isotopes and trace metallic elements

    NASA Astrophysics Data System (ADS)

    Thomazo, Christophe; Riquier, Laurent; Martinez, Mathieu; Mathieu, Olivier

    2013-04-01

    During the Cretaceous, several occurrences of Oceanic Anoxic Event (OAE) are described in the sedimentary record. Among them, the late Hauterivian Faraoni Event has been extensively studied in several locations including Italy, Switzerland, France and Spain and interpreted as a short-lived OAE from palaeontological, sedimentological and geochemical observations. However, the biogeochemical response to water column oxygen depletion is poorly documented and mostly stands on carbon carbonates isotopes during the Faraoni event. In order to bring further insights into the biogeochemical cycles modifications during O2 variations across the Faraoni Event, we performed an integrated geochemical study including C, N and S isotopes together with paleo-redox tracers (i.e. trace metallic elements and iron speciation) on about 25 samples from the Río Argos section (S.E. Spain). δ13Ccarb increases from 1.23‰ to 1.61‰ at the base of the studied section before the Faraoni event. Maximum values, ranging between 1.21‰ and 1.73‰, are observed within this event and are followed by a rapid decrease in δ13Ccarb values down to 0.50‰ toward the top of the section. δ13Corg and TOC values show a narrow range of variations around -26.3±0.3‰ and 0.15±0.3 wt.%, respectively. Only one sample records a higher TOC content up to 1.53 wt.% at the very base of the Faraoni Event while no sensible variations can be deduced form organic carbon isotopes. Bulk sediments nitrogen isotopes have a mean value of 2.3±0.2‰ and nitrogen contents vary between 320 and 790 ppm. A noticeable δ15N excursion (i.e. 0.86‰) is observed at the very base of the Faraoni Event and is associated with the highest TOC value. Sulfur contents vary between 100 and 2480 ppm, the highest content being recorded just bellow the base of the Faraoni Event. δ34S show a wide range of variations from -44.8 to -10.1‰ on a short scale without easily recognizable stratigraphic trend. Finally, slight increases of

  13. The influence of oxygen exchange between sulfite and water on the oxygen isotope composition of sulfate

    NASA Astrophysics Data System (ADS)

    Müller, I. A.; Brunner, B.

    2012-12-01

    Sulfate does not exchange oxygen with the water under most environmental conditions. Therefore, its oxygen isotope composition serves as an archive of past oxidative sulfur cycling. Studies on the oxygen isotope signature of sulfate produced from reduced sulfur compounds show varying relative contributions of two possible oxygen sources; molecular oxygen and water, and variable isotope fractionations relative to these two compounds. These discrepancies could be due to differences in the production and consumption of sulfuroxy intermediates which exchange oxygen with water. Thereby, the rate of oxygen exchange as well as the rate of oxidation depends on the pH. Studies on the oxygen isotope exchange effects between sulfuroxy intermediates and water and on the oxygen isotope effects during the oxidation of sulfuroxy intermediates are scarce, severely limiting the interpretability of oxygen isotope signatures in sulfate. Sulfite is often considered to be the last/final sulfuroxy intermediate in the oxidation of reduced sulfur compounds to sulfate and may, therefore, be pivotal in shaping the oxygen isotope signature of sulfate. We determined the oxygen isotope equilibrium fractionation between sulfite and water and used the obtained equilibrium value to determine the oxygen isotope effects in abiotic sulfite oxidation experiments. Our results demonstrate that natural variations in the oxygen isotope composition of sulfate produced by oxidative processes can be explained by differences in the interplay of the sulfite oxidation rate and oxygen isotope exchange rate between sulfite and water which both depend on pH conditions and availability of oxidizing agents (e.g. molecular oxygen or ferric iron). Our findings contribute to a more detailed mechanistic understanding of the oxidation of reduced sulfur compounds and underline the importance of sulfite as the final sulfuroxy intermediate in oxidative sulfur cycling.

  14. Tooth Enamel Oxygen and Carbon Isotope Variations in Modern Central Asian Horses: Development of a Calibration Database for the Interpretation of Stable Isotope Signals Preserved in Fossil Horse Remains from Archaeological Sites

    NASA Astrophysics Data System (ADS)

    Sikora, M. T.; Rosenmeier, M. F.; Allard, F.; Olsen, S. L.

    2005-12-01

    Recent studies of early nomadic pastoralism within Central Asia have focused on the rich archaeological history of Mongolia and specifically the examination of so-called khirigsuur sites. These monumental Bronze Age (first and second millennium B.C.) structures consist of stone constructions that contain abundant horse remains (typically skulls) and occasionally human burials. Isotopic analysis of horse remains preserved within these sites may provide a wealth of paleoclimatic information. However, the accuracy of climate reconstructions from fossil teeth collected at archaeological sites in Mongolia is currently limited by insufficient knowledge of the relationship between local environmental conditions and tooth enamel isotope ratios as well as uncertainties attributed to intra-population variability. In this study we measured the oxygen and carbon isotope (δ18O and δ13C) values of enamel samples from modern horse teeth collected along a nearly 550 km latitudinal (northwest-southeast) transect within central Mongolia. Preliminary results suggest that modern tooth enamel records local environmental conditions, although δ18O and δ13C values are not always a direct proxy for climate and vegetation cover. The modern samples serve as a baseline for interpreting isotope signals preserved in fossil horses and thereby increase the accuracy of paleoclimatic reconstructions. Approximately one-hundred individuals were examined from highly varied geographic zones (forest steppe, grassland steppe, dry steppe, and semi-desert) and compared with the δ18O of meteoric waters and δ13C values of local vegetation. Oxygen isotope ratios of bulk enamel samples (spanning the entire vertical axis of tooth growth) parallel spatial trends observed in isotopic composition of meteoric waters and major north-south gradients in temperature and precipitation. Average δ13C values similarly increase with decreasing geographic latitude and likely correspond to documented increases in the

  15. Meteorites and their parent bodies: Evidence from oxygen isotopes

    NASA Technical Reports Server (NTRS)

    Clayton, R. N.

    1978-01-01

    Isotopic abundance variations among meteorites are used to establish genetic associations between meteorite classes. Oxygen isotope distributions between group II E irons with H-group ordinary chondrites and enstatic meteorites indicate that the parent bodies were formed out of pre-solar material that was not fully mixed at the time condensation occurred within the solar nebula.

  16. Within-shell variations in carbon and oxygen isotope compositions of two modern brachiopods from a subtropical shelf environment off Amami-o-shima, southwestern Japan

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kazuyuki; Asami, Ryuji; Iryu, Yasufumi

    2010-10-01

    This study examines the fidelity of carbon (δ13C) and oxygen (δ18O) isotope compositions of two modern brachiopod species (Kikaithyris hanzawai and Basiliola lucida) to use as proxies of δ13C values of total dissolved inorganic carbon and temperature and/or δ18O values of seawater, respectively. Well-preserved shells of K. hanzawai and living individuals of B. lucida were collected from a subtropical shelf environment off Amami-o-shima, southwestern Japan. Some portions of the shells are in isotopic equilibrium with the ambient seawater, while other portions are not. The degree of disequilibrium differs between the two species and between different portions of each shell. Statistically significant positive correlations are recognized between the δ13C and δ18O values of these samples, which can be ascribed to a kinetic fractionation effect. Far from the posterior shell edge and along the axis of shell growth, the δ18O values of the secondary shell layer of K. hanzawai mostly fall within the expected range of equilibrium calcite. The δ13C values from the inner surface of the secondary shell layer in both species are relatively constant and are equivalent to or very close to equilibrium calcite. Therefore, these portions of the shells are most suitable for collecting reliable environmental proxy data. Although the δ13C and δ18O values of modern brachiopod shells are predominantly controlled by a kinetic fractionation effect, the appropriate selection of species and shell portions that reflect the isotopic composition of ambient seawater can facilitate the reconstruction of secular variations in oceanic δ13C or δ18O values.

  17. Quantitative analysis of intraspecific variations in the carbon and oxygen isotope compositions of the modern cool-temperate brachiopod Terebratulina crossei

    NASA Astrophysics Data System (ADS)

    Takayanagi, Hideko; Asami, Ryuji; Otake, Tsuguo; Abe, Osamu; Miyajima, Toshihiro; Kitagawa, Hiroyuki; Iryu, Yasufumi

    2015-12-01

    This study unravels intraspecific variations in the carbon isotope (δ13C) and oxygen isotope (δ18O) compositions of shells of the modern cool-temperate brachiopod Terebratulina crossei collected at a water depth of 70 m in Otsuchi Bay, northeastern Honshu, Japan. Brachiopod shells have been used as proxies of the δ13C values of dissolved inorganic carbon (DIC) (δ13CDIC) and seawater temperature/δ18O (δ18OSW) values to reconstruct the evolution of Phanerozoic oceans. To identify more reliable shell portions as the proxies, we conducted a rigorous time-series comparison of δ13C and δ18O values between the brachiopod shells and calcite precipitated in isotopic equilibrium with ambient seawater (equilibrium calcite) (δ13CEC and δ18OEC values, respectively). Samples were collected from the outer and inner surfaces of the secondary shell layer along the maximum growth axis (ontogenetic-series and inner-series samples, respectively). The ontogenetic-series δ13C values, which showed regular annual and irregular non-annual cycles, partly fell in but were mostly less than the range of the δ13CEC values. The δ13C cycles were often associated with one or two minor negative peaks. The peaks were likely resulted from an increased incorporation of respiration-derived 12C due to elevated metabolic activity during spawning. The ontogenetic-series δ18O values showed distinct seasonal variations and were mostly within the range of δ18OEC values. The amplitude of the δ18O profiles was relatively large during the younger fast-growth stage, and decreased during the senescent slow-growth stage. The inner-series δ13C and δ18O values of individual shells varied within narrow ranges. The inner-series δ13C values were close to the minimum δ13CEC values. The inner-series δ18O values were in the upper range of the δ18OEC values. Kinetic isotope fractionation effects were evident, but its degree varied among different shells. We identified the shell portions reliably

  18. Oxygen isotope studies and compilation of isotopic dates from Antarctica

    SciTech Connect

    Grootes, P.M.; Stuiver, M.

    1986-01-01

    The Quaternary Isotope Laboratory, alone or in collaboration with other investigators, is currently involved in a number of oxygen-isotope studies mainly in Antarctica. Studies of a drill core from the South Pole, seasonal oxygen-18 signals preserved in the Dominion Range, isotope dating of the Ross Ice Shelf, oxygen-18 profiles of the Siple Coast, McMurdo Ice Shelf sampling, and a data compilation of radiometric dates from Antarctica are discussed.

  19. Oxygen isotope geospeedometry by SIMS

    NASA Astrophysics Data System (ADS)

    Bonamici, C. E.; Valley, J. W.

    2013-12-01

    Geospeedometry, a discipline closely related and complimentary to thermochronology, exploits the phenomenon of diffusion in order to extract rate and duration information for segments of a rock's thermal history. Geospeedometry data, when anchored in absolute time by geochronologic data, allow for the construction of detailed temperature-time paths for specific terranes and geologic processes. We highlight the developing field of SIMS-based oxygen isotope geospeedometry with an application from granulites of the Adirondack Mountains (New York) and discuss potential future applications based on a recently updated and expanded modeling tool, the Fast Grain Boundary diffusion program (FGB; Eiler et al. 1994). Equilibrium oxygen isotope ratios in minerals are a function of temperature and bulk rock composition. In dynamic systems, intragrain oxygen isotope zoning can develop in response to geologic events that affect the thermal state of a rock and/or induce recrystallization, especially tectonic deformation and fluid infiltration. As an example, titanite grains from late-Grenville shear zones in the northwestern Adirondack Mountains exhibit a range of δ18O zoning patterns that record post-peak metamorphic cooling, episodic fluid infiltration, and deformation-facilitated recrystallization. Many titanite grains preserve smooth, core-to-rim decreasing, diffusional δ18O profiles, which are amenable to diffusion modeling. FGB models that best fit the measured δ18O profiles indicate cooling from ~700-500°C in just 2-5 m.y., a rapid thermal change signaling the final gravitational collapse of the late-Grenville orogen. Titanite can also be utilized as a U-Pb chronometer, and comparison of δ18O and U-Pb age zoning patterns within the Adirondack titanites pins the episode of rapid cooling inferred from the δ18O record to some time between 1054 and 1047 Ma. The expanded capabilities of FGB also allow for evaluation of a range of heating-cooling histories for the

  20. Neodymium isotopic variations in seawater

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

    Direct measurement of the isotopic composition of Nd in the Atlantic agree with the Nd content in ferromanganese sediments and differ from the observed amounts in the Pacific samples. These data indicate the existence of distinctive differences in the isotopic composition of Nd in the waters of major oceans; the average values determined from seawater and ferromanganese sediments are considerably lower than in sources with oceanic mantle affinities showing that the REE in the oceans is dominated by continental sources. The Nd isotopic variations in seawater are applied to relate the residence time of Nd and mixing rates between the oceans.

  1. Spatial and temporal variation in tree-ring α-cellulose oxygen and hydrogen isotope values as a record of water availability in the Atacama Desert

    NASA Astrophysics Data System (ADS)

    Olson, E. J.; Dodd, J. P.

    2015-12-01

    Previous studies have documented that tree ring oxygen and hydrogen isotopes primarily reflect source water; however, biosynthetic fractionation processes modify this signal and can have a varied response to environmental conditions. The degree to which source water contributes to δ2H and δ18O values of plant α-cellulose is species-specific and modern calibration studies are necessary. Here we present a calibration data set of P. tamarugo α-cellulose δ2H and δ18O values from the Atacama Desert in Northern Chile. P. tamarugo trees are endemic to the region and have adapted to the extremely arid environment where average annual precipitation is < 5mm/yr. This modern isotope chronology has been constructed from living P. tamarugo trees (n=12) from the Pampa del Tamarugal Basin in the northern Atacama. Generally, the tree-ring α-cellulose δ18O values are poorly correlated with meteorological data from coastal stations (i.e. Iquique); however, there is good agreement between regional groundwater depth and α-cellulose δ18O values. Most notably, average α-cellulose δ18O values increase by >2 ‰ over the past 20 years associated with a ~1.1 m lowering of the local groundwater table throughout the area. The correlation between a-cellulose isotope values and hydrologic conditions in modern times provides a baseline for interpretation of tree-ring isotope chronologies from the past 9.5 kya. A high-resolution Holocene (1.8-9.1 kya) age record of Prosopis sp. tree ring α-cellulose δ18O values provides a proxy for climatic and hydrologic conditions. During the early Holocene δ18O values range from 31 to 35‰ (2σ=0.58‰), while during the late Holocene values are much more variable (27.4 to 41‰; 2σ=2.64‰). Anthropogenic demand on local water sources is the most significant environmental factor affecting the variation in modern α-cellulose δ18O values; however, climate induced changes in regional water availability are the dominant driver of variability

  2. Contrasts in variations of the carbon and oxygen isotopic composition of travertines formed in pools and a ramp stream at Huanglong Ravine, China: Implications for paleoclimatic interpretations

    NASA Astrophysics Data System (ADS)

    Wang, Haijing; Yan, Hao; Liu, Zaihua

    2014-01-01

    Water samples and modern endogenic (thermogene) travertine calcite deposited on plexiglass substrates in travertine pools and a ramp stream were collected along the Huanglong Ravine, Sichuan, SW China at regular ∼10 day intervals from early May to early November in 2010, including both wet and dry conditions. Temporal and spatial variations in the δ13C and δ18O values of the modern travertine were examined to understand their potential for paleoclimatic and paleoenvironmental interpretations. It was found that δ13C and δ18O of travertine formed in the ramp stream were low in the warm rainy season and high in the cold dry season. Their positive correlation was mainly due to dilution and rainfall seasonal effects on δ13C and δ18O values, respectively, i.e., low δ13C values were caused by dilution by overland flow with depleted δ13C values and reduced CO2-degassing in the warm rainy season while low δ18O values of travertine were because of low δ18O values of water induced by seasonal variation in oxygen isotopic ratios of rainwater. Meanwhile, kinetic effect on oxygen isotopic fractionation during ramp travertine deposition existed and reduced this positive correlation. In contrast, the δ13C and δ18O values of the pool travertines displayed a converse behavior which was caused mainly by the temperature effect. Low δ18O values and high δ13C values in the warm rainy season were correlated chiefly with the higher water temperatures. Therefore, the δ13C and δ18O values of the travertine may be used for paleo-rainfall or paleotemperature reconstruction respectively. This study demonstrates that endogenic travertine, like epigenic (meteogene) tufa, may be a suitable candidate for high-resolution paleoclimatic and paleoenvironmental reconstructions. However, since travertines deposited under differing hydrodynamic conditions (e.g., pools with still water contrasted to fast flow streams) have different climatic responses, it is necessary to check the

  3. Device and method for separating oxygen isotopes

    DOEpatents

    Rockwood, Stephen D.; Sander, Robert K.

    1984-01-01

    A device and method for separating oxygen isotopes with an ArF laser which produces coherent radiation at approximately 193 nm. The output of the ArF laser is filtered in natural air and applied to an irradiation cell where it preferentially photodissociates molecules of oxygen gas containing .sup.17 O or .sup.18 O oxygen nuclides. A scavenger such as O.sub.2, CO or ethylene is used to collect the preferentially dissociated oxygen atoms and recycled to produce isotopically enriched molecular oxygen gas. Other embodiments utilize an ArF laser which is narrowly tuned with a prism or diffraction grating to preferentially photodissociate desired isotopes. Similarly, desired mixtures of isotopic gas can be used as a filter to photodissociate enriched preselected isotopes of oxygen.

  4. New constraints on the relationship between 26Al and oxygen, calcium, and titanium isotopic variation in the early Solar System from a multielement isotopic study of spinel-hibonite inclusions

    NASA Astrophysics Data System (ADS)

    Kööp, Levke; Nakashima, Daisuke; Heck, Philipp R.; Kita, Noriko T.; Tenner, Travis J.; Krot, Alexander N.; Nagashima, Kazuhide; Park, Changkun; Davis, Andrew M.

    2016-07-01

    We report oxygen, calcium, titanium and 26Al-26Mg isotope systematics for spinel-hibonite inclusions (SHIBs), a class of calcium-aluminum-rich inclusions (CAI) common in CM chondrites. In contrast to previous studies, our analyses of 33 SHIBs and four SHIB-related objects obtained with high spatial resolution demonstrate that these CAIs have a uniform Δ17O value of approximately -23‰, similar to many other mineralogically pristine CAIs from unmetamorphosed chondrites (e.g., CR, CV, and Acfer 094). Five SHIBs studied for calcium and titanium isotopes have no resolvable anomalies beyond 3σ uncertainties. This suggests that nucleosynthetic anomalies in the refractory elements had been significantly diluted in the environment where SHIBs with uniform Δ17O formed. We established internal 26Al-26Mg isochrons for eight SHIBs and found that seven of these formed with uniformly high levels of 26Al (a multi-CAI mineral isochron yields an initial 26Al/27Al ratio of ∼4.8 × 10-5), but one SHIB has a smaller initial 26Al/27Al of ∼ 2.5 × 10-5, indicating variation in 26Al/27Al ratios when SHIBs formed. The uniform calcium, titanium and oxygen isotopic characteristics found in SHIBs with both high and low initial 26Al/27Al ratios allow for two interpretations. (1) If subcanonical initial 26Al/27Al ratios in SHIBs are due to early formation, as suggested by Liu et al. (2012), our data would indicate that the CAI formation region had achieved a high degree of isotopic homogeneity in oxygen and refractory elements before a homogeneous distribution of 26Al was achieved. (2) Alternatively, if subcanonical ratios were the result of 26Al-26Mg system resetting, the clustering of SHIBs at a Δ17O value of ∼-23‰ would imply that a 16O-rich gaseous reservoir existed in the nebula until at least ∼0.7 Ma after the formation of the majority of CAIs.

  5. Carbon and oxygen isotope variations in diamonds and graphite eclogites from Orapa, Botswana, and the nitrogen content of their diamonds

    SciTech Connect

    Deines, P. ); Harris, J.W. ); Robinson, D.N. ); Gurney, J.J. ); Shee, S.R. )

    1991-02-01

    In eclogite xenoliths from Orapa, Botswana, {delta}{sup 13}C of graphite varies between {minus}4.6 and {minus}7.8 per thousand vs. PDB, while that of diamonds ranges from {minus}4.0 to {minus}22.3 per thousand. In graphite eclogites, {delta}{sup 18}O values of garnets fall between 5.2 and 7 per thousand vs. SMOW and those of clinopyroxenes between 4.6 and 6.5 per thousand. For diamond eclogites the respective ranges are wider, i.e., 3.9 to 9.2 per thousand and 5.2 to 8.3 per thousand. The {sup 18}O enrichment above normal mantle in which diamond is stable. Eclogites with {delta} {sup 13}C values in the range {minus}4 to {minus}8 per thousand and {delta}{sup 18}O values in the normal mantle range tend to have positive garnet-clinopyroxene {sup 18}O fractionations and lower Fe/Ca and Fe/Mg ratios than eclogites which have simultaneously {delta}{sup 13}C values lower than {minus}8 per thousand and {delta}{sup 18}O values higher than 6.5 per thousand. In these eclogites the garnet-clinopyroxene fractionations tend to be negative. Positive garnet-clinopyroxene {sup 18}O fractionations increase slightly in the sequence: diamond eclogites (0.36 {plus minus} 0.15,n = 6), graphic/diamond ecologites (0.46 {plus minus} 0.36, n = 3), and graphite eclogites (0.53 {plus minus} 0.15, n = 3). Neither igneous fractionation processes, subduction, nor metasomatic alteration can satisfactory explain all observed chemical and isotopic trends.

  6. The isotopic composition of atmospheric oxygen

    NASA Astrophysics Data System (ADS)

    Luz, Boaz; Barkan, Eugeni

    2011-09-01

    Atmospheric O2 is almost 24‰ more enriched in 18O than seawater, and this enrichment is known as the Dole effect. For a long time it has been accepted that there is no oxygen isotope fractionation in photosynthesis, and thus the Dole effect should be the result of preferential terrestrial and marine respiratory consumption of 16O over 18O, and also several permil enrichment of leaf water from which terrestrial photosynthesis produces 18O enriched O2. This concept has led to the understanding that the record of past Dole effect variations was strongly affected by changes in the ratio of photosynthetic production between land and sea. However, recent studies in our lab have led to two major new observations: (1) O2 produced by certain marine phytoplankton, representing important groups of primary producers, is significantly enriched (up to 6‰) in 18O with respect to the substrate seawater and (2) effective oxygen isotope fractionation in soil respiration is considerably smaller than the intrinsic respiratory fractionation. Here we take these two observations into account and show that the magnitudes of the terrestrial and marine components of the Dole effect are close, and both are close to the measured Dole effect. As a result, the magnitude of the global Dole effect should not be sensitive to past changes in the ratio of land-to-sea photosynthetic rates. Instead of the land-sea control, variations in low-latitude hydrology, and possibly changes of fractionations in the marine biosphere, are more important in regulating the magnitude of the Dole effect and its past variations.

  7. Variations in groundwater availability during the past 9,000 years in the Atacama Desert, Chile: A subannual record of oxygen isotope values from Prosopis tamarugo tree rings

    NASA Astrophysics Data System (ADS)

    Dodd, J. P.; Rivera, M.

    2012-12-01

    The Atacama Desert is among the driest regions on Earth; therefore, access to water is critical to human populations throughout the Pampa del Tamarugal region of northern Chile (20° to 22°S, 69° to 70°W). Presently, the region receives <5 mm of precipitation annually, and seasonal runoff and groundwater recharge from higher altitudes in the Andes Mountains is the primary source of water in the Pampa del Tamarugal. Oxygen isotope data from Prosopis tamarugo tree rings indicate that the region has become increasingly arid over the past 9ka, likely as a result of decreased water transport from these recharge areas. Oxygen isotope values from α-cellulose of P. tamarugo tree rings from the Llamara Basin (9130 ±145 and 7910 to 7870 ±10 Cal BP), Ramaditas (2615 ±135 Cal BP), and La Tirana Refresco (modern) record sub-annual variations in groundwater availability in the Pampa del Tamarugal. Low δ18O values (23.8 to 32.8‰) in the P. tamarugo samples from the Llamara Basin indicate wetter conditions prior to 7.8 ka; however, sub-annual variability in the δ18O values remains relatively high with an average range in intra-ring values of 3.0‰ (2σ=1.1‰). P. tamarugo logs that were used as building materials and grown in agricultural fields at Ramaditas (~2.6ka), an archeological site in the Pampa del Tamarugal, have a wider range of δ18O values (17.5 to 35.6‰) and greater intra-ring variability (ave. 4.5‰, 2σ=3.2‰). The greater range in interannual and subannual δ18O values most likely reflects a period with highly variable fluxes of runoff/recharge water. The development and eventual abandonment of Ramaditas and other settlements appear to coincide with changes in the availability of water in the region. Modern P. tamarugo from La Tirana Refresco collected in 2008 have δ18O values that are consistently higher (33.1 to 36.3‰) with much lower intra-ring variability (1.5‰, 2σ=0.9‰), indicating persistently drier conditions and greater evaporative

  8. Oxygen isotope relationships in iron meteorites

    NASA Technical Reports Server (NTRS)

    Clayton, R. N.; Mayeda, T. K.; Olsen, E. J.; Prinz, M.

    1983-01-01

    Iron meteorites with oxygen-bearing phases can be classified in terms of their oxygen isotopic abundances. These iron meteorite classes are isotopically similar to various stony meteorite classes, which may indicate a common origin. The group IAB and IIICD irons may be related to the winonaites; group IIE irons may be related to H chondrites; group IVA irons may be related to L or LL chondrites.

  9. Normalization of oxygen and hydrogen isotope data

    USGS Publications Warehouse

    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.

  10. Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

    PubMed

    Yurimoto, H; Ito, M; Nagasawa, H

    1998-12-01

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

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

    PubMed

    Yurimoto; Ito; Nagasawa

    1998-12-01

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

  12. Sub-seasonal oxygen and carbon isotope variations in shells of modern Radix sp. (Gastropoda) from the Tibetan Plateau: potential of a new archive for palaeoclimatic studies

    NASA Astrophysics Data System (ADS)

    Taft, Linda; Wiechert, Uwe; Riedel, Frank; Weynell, Marc; Zhang, Hucai

    2012-02-01

    Carbon and oxygen isotope ratios have been measured for nine aragonite shells of the gastropod genus Radix from the lake Bangda Co (30°29'N, 97°04'E, 4450 m a.s.l.) at the south-eastern edge and from two characteristic sites at the lake Kyaring Co (31°09'N, 88°17'E, 4650 m a.s.l.) on the central Tibetan Plateau. Radix shells were sampled for isotope ratio analysis with high spatial resolution along the ontogenetic spiral of growth providing the basis of isotope records with a sub-seasonal time-resolution. δ18O values of shells from Bangda Co are on average ˜-15.0‰ relative to PDB and the pattern exhibits a clear onset and progression of the summer monsoon precipitation indicated by a strong "amount effect". This pattern mirrors the precipitation pattern in the respective year and region as expected for a small (surface area ca 0.3 km2) and shallow (<5 m) lake or habitat with short water residence times and little evaporative 18O enrichment of the lake water. In contrast, δ18O values of Radix shells from Kyaring Co habitat A which is connected to the deep (several tens of metres) and big (surface area ca 660 km2) lake, average at ˜-13.0‰ consistent with a higher evaporation rate and longer water residence time. The latter is supported by more 18O enriched water in this habitat. The δ18O values of Radix shells from Kyaring Co habitat B are nearly as low as shells from Bangda Co due to the similar habitat characteristic but isotopic patterns of these shells exhibit a weaker "amount effect". In both lake systems δ13C values of the shells are coupled with oxygen isotopes because a large amount of isotopically light carbon is washed from mountain slopes into the lake during the rainy season. Although other processes influence the isotopic patterns, e.g. biological productivity (δ13C) or temperature (δ18O), these influences are minor compared with the monsoon signal or the effect of evaporation in the Radix shell records. The overall weaker amount effect

  13. Oxygen isotopes in deep sea spherules

    NASA Technical Reports Server (NTRS)

    Mayeda, T. K.; Clayton, R. N.; Brownlee, D. E.

    1984-01-01

    The determination of the genetic relationships between the dust and small particles in the solar system, and the meteorites and larger bodies are examined. Oxygen isotopes proved useful in the identification of such relationships between one meteorite group and another. Of the various samples of submillimeter extraterrestrial particles available for laboratory study, only the deep sea spherules are abundant enough for precise oxygen isotope analysis using existing techniques. Complications arise in interpretation of the isotopic data, since these particles were melted during passage through the Earth's atmosphere, and have been in contact with seawater for prolonged periods. Spherules that were originally silicates are considered with the originally metallic ones to deduce their preterrestrial isotopic compositions. The type 1 spherules which enter the atmosphere as metallic particles, contain only atmospheric oxygen. The type S spherules contain a mixture of atmospheric oxygen and their original extraterrestrial oxygen. It is suggested that the Earth's mesosphere is strongly enriched in heavy isotopes of oxygen at altitudes near 90 km at which the iron particles are oxidized. Fractionation due to the combined diffusion of O atoms and O2 molecules may be responsible.

  14. Oxygen-isotope fractionation between marine biogenic silica and seawater

    SciTech Connect

    Matheney, R.K.; Knauth, L.P. )

    1989-12-01

    A stepwise fluorination technique has been used to selectively react away the water component of hydrous silica in order to better investigate the oxygen-isotope fractionation between biogenic opal and seawater, and to determine whether all taxa produce opal which is suitable for oxygen isotope paleothermometry. {delta}{sup 18}O of the tetrahedrally coordinated silicate oxygen of siliceous sponge spicules grown at a wide variety of temperatures varies independently of temperature. {delta}{sup 18}O from an Eocene radiolarian ooze sample is much more enriched than would be expected from any reasonable isotopic temperature curve, given the probable growing temperature of the sample. {delta}{sup 18}O of diatom samples seems to vary systematically with temperature and to conform approximately to the isotopic temperature curve for diatom frustules obtained by Labeyrie and coworkers using an entirely different analytical technique. Sponges appear to precipitate silica in isotopic disequilibrium with seawater oxygen, and old radiolarian silica may exchange readily with could oceanic bottom water. Neither will apparently be useful for paleoclimate reconstructions. Diatoms maybe useful in deducing ancient surface-water temperatures, but the systematic variation of {alpha} with temperature for diatoms may not be related to the quartz-H{sub 2}O equilibrium isotope fractionation.

  15. Oxygen and hydrogen isotopic variations between adjacent drips in three caves at increasing elevation in a temperate coastal rainforest, Vancouver Island, Canada

    NASA Astrophysics Data System (ADS)

    Beddows, Patricia A.; Mandić, Magda; Ford, Derek C.; Schwarcz, Henry P.

    2016-01-01

    The interpretation of speleothem paleoenvironmental records requires understanding of spatial-temporal variations in vadose drip water chemistry and isotopic composition. This study reports on intra- and inter-cave differences in δD, δ18O and electrical conductivity, using 18 monthly water samples from three adjacent drips (<20 m apart) in each of three caves at increasing elevation (0, 550, and 740 m ASL) on very steep ground at the head of Tahsis Inlet fjord on the Pacific coast of Vancouver Island, British Columbia. All drips showed isotopic seasonal signals, despite varied patterns of drip hydrology. There was overlap in isotopic ranges (at 1 SD) between all three caves, in contrast with the expected δ18O depletion of -0.15 to -0.5‰/100 m of ascent observed in standard precipitation. The isotopic seasonality was approximated with sine curves, and compared to a GNIP data set from Victoria ∼300 km to the south. The δD and δ18O drip isotopes lagged the Victoria record by 155 ± 26 days and 165 ± 50 days respectively. The longest lag was at the slowest drip (sea level), while the shortest lag (87 days for δ18O, 550 m ASL) implies a short residence time, paradoxically from the drip with the highest mean electrical conductivity. Vadose residence time was less than one climatic year, reflecting a combination of negligible matrix porosity in the host rock and super-humid climatic conditions. Beneath the epikarst, drip hydrology was evidently by simple piston flow. Phase-shifted drip isotope records showed excellent agreement with sea level mean monthly air temperatures at the Tahsis meteorological station over the study period. The δD and δ18O drip amplitudes were damped on average 74% and 73% respectively compared to the Victoria data. The drips at 740 m ASL are tightly aligned to the global mean meteoric water line (GMWL) and 18O-depleted; the drips at 550 m ASL and at sea level plot along the GMWL, or between it and the Victoria LMWL, with the exception

  16. Sex-associated variations in coral skeletal oxygen and carbon isotopic composition of Porites panamensis in the southern Gulf of California

    NASA Astrophysics Data System (ADS)

    Cabral-Tena, R. A.; Sánchez, A.; Reyes-Bonilla, H.; Ruvalcaba-Díaz, A. H.; Balart, E. F.

    2015-11-01

    Coral δ18O variations are used as a proxy for changes in near sea surface temperature and seawater isotope composition. Skeletal δ13C of coral is frequently used as a proxy for solar radiation because most of its variability is controlled by an interrelationship between three processes: photosynthesis, respiration, and feeding. Coral growth rate is known to influence the δ18O and δ13C isotope record to a lesser extent. Recent published data show differences in growth parameters between female and male coral; thus, skeletal δ18O and δ13C are hypothesized to be different in each sex. To assess this difference, this study describes changes in the skeletal δ18O and δ13C record of four female and six male Porites panamensis coral collected in Bahía de La Paz, whose growth bands spanned 12 years. The isotopic data were compared to SST, precipitation, PAR, chlorophyll a, and skeletal growth parameters. Porites panamensis is a known gonochoric brooder whose growth parameters are different in females and males. Splitting the data by sexes explained 81 and 93 % of the differences of δ18O, and of δ13C, respectively, in the isotope record between colonies. Both isotope records were different between sexes. δ18O was higher in female colonies than in male colonies, with a 0.31 ‰ difference; δ13C was lower in female colonies, with a 0.28 ‰ difference. A difference in the skeletal δ18O implies an error in SST estimates of ≈ 1.0 °C to ≈ 2.6 °C. The δ18O records showed a seasonal pattern that corresponded to SST, with low correlation coefficients (-0.45, -0.32), and gentle slopes (0.09 ‰ °C-1, 0.10 ‰ °C-1) of the δ18O-SST relation. Seasonal variation in coral δ18O represents only 52.37 and 35.66 % of the SST cycle; 29.72 and 38.53 % can be attributed to δ18O variability in seawater. δ13C data did not correlate with any of the environmental variables; therefore, variations in skeletal δ13C appear to be driven mainly by metabolic effects. Our

  17. The effects of α-cellulose extraction and blue-stain fungus on retrospective studies of carbon and oxygen isotope variation in live and dead trees†

    USGS Publications Warehouse

    English, N.B.; McDowell, N.G.; Allen, C.D.; Mora, C.

    2011-01-01

    Tree-ring carbon and oxygen isotope ratios from live and recently dead trees may reveal important mechanisms of tree mortality. However, wood decay in dead trees may alter the δ13C and δ18O values of whole wood obscuring the isotopic signal associated with factors leading up to and including physiological death. We examined whole sapwood and α-cellulose from live and dead specimens of ponderosa pine (Pinus ponderosa), one-seed juniper (Juniperous monosperma), piñon pine (Pinus edulis) and white fir (Abies concolor), including those with fungal growth and beetle frass in the wood, to determine if α-cellulose extraction is necessary for the accurate interpretation of isotopic compositions in the dead trees. We found that the offset between the δ13C or δ18O values of α-cellulose and whole wood was the same for both live and dead trees across a large range of inter-annual and regional climate differences. The method of α-cellulose extraction, whether Leavitt-Danzer or Standard Brendel modified for small samples, imparts significant differences in the δ13C (up to 0.4‰) and δ18O (up to 1.2‰) of α-cellulose, as reported by other studies. There was no effect of beetle frass or blue-stain fungus (Ophiostoma) on the δ13C and δ18O of whole wood or α-cellulose. The relationships between whole wood and α-cellulose δ13C for ponderosa, piñon and juniper yielded slopes of ~1, while the relationship between δ18O of whole wood and α-cellulose was less clear. We conclude that there are few analytical or sampling obstacles to retrospective studies of isotopic patterns of tree mortality in forests of the western United States.

  18. Variation in Atmospheric Helium Isotopes

    NASA Astrophysics Data System (ADS)

    Mabry, J. C.; Marty, B.; Burnard, P.; Blard, P.

    2010-12-01

    Anthropogenic activity such as oil and gas exploitation releases crustal helium, which has excess 4He compared to atmospheric helium. This may give rise to both spatial and temporal variations in the atmospheric 3He/4He. Helium is present in trace quantities in the air (5 ppm) and has a very low ratio (3He/4Heair = 1.38 x 10-6), consequently high precision measurements of atmospheric He presents a significant analytical challenge. Recent work by Sano et al. [1] has endeavored to experimentally quantify these potential variations in the atmospheric 3He/4He by measuring the helium isotopes from air samples collected around the globe and from samples of ancient trapped atmosphere. Their results indicate an increase in the atmospheric 3He/4He from northern to southern latitudes of the order 2 - 4 ‰, which they attribute to greater use of fossil fuels in the northern hemisphere. However, since most of their data points overlap at the 2-3 ‰ (2σ) level, additional measurements (with increased precision if possible) are needed. We have constructed an automated extraction line dedicated to measuring He in samples of air which can rapidly switch between measuring aliquots of sample with standards. It additionally features an adjustable bellows on the sample aliquot volume that enables us to adjust the size of a sample aliquot to precisely match the standard, eliminating biases arising from nonlinear pressure effects in the mass spectrometer. The measurements are made using a Helix SFT multi-collector mass spectrometer. At present, repeat measurements of 3He/4He from our standard (purified air) have a reproducibility of 2‰ (2σ), while measurements of local (Nancy, France) air samples have a reproducibility of 3He/4He of 3‰ (2σ), which are at a similar level to the uncertainties reported by Sano. Modifications are underway to improve 3He measurements which are the principal source of error. We have collected atmospheric samples from around the globe over a wide

  19. Oxygen isotope fractionation in double carbonates.

    PubMed

    Zheng, Yong-Fei; Böttcher, Michael E

    2016-01-01

    Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60 °C and 100 °C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in (18)O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0-1200 °C. The calculated fractionation factors for double carbonate-water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2 and CaMg[CO3]2 against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2 and CO2 are much closer to theoretical predictions for the cerussite-CO2 system than for the magnesite-CO2 system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates.

  20. Laboratory constraints on the stability of oxygen isotopes in sulfate

    NASA Astrophysics Data System (ADS)

    Turchyn, A. V.; Rennie, V.

    2012-12-01

    The oxygen isotopic composition of sulfate (δ18OSO4) is a powerful new tool for exploring the transformations of sulfur in laboratory experiments and the natural environment. The δ18OSO4 is central to our understanding of bacterial sulfate reduction because variations in δ18OSO4 reflect differences in the rates of various metabolic steps. Additionally, the δ18OSO4 provides key information on the pathways of both biotic and abiotic sulfide oxidation. If preserved in the geological record, the δ18OSO4, along with the sulfur isotope composition of sulfate, provides unique insight into the long-term variability of the sulfur cycle. Use of the δ18OSO4 rests on the assumption that there is minimal abiotic exchange between sulfate-oxygen and water-oxygen during the variety of conditions imposed by sample storage and laboratory processing. Previous work has shown that oxygen isotope exchange between sulfate and water does occur at high temperatures (>100°C) and/or at low pH values (<1). Estimates of the timescales for exchange under laboratory temperatures and pH values have been extrapolated from highly dissimilar conditions. The controls on abiotic oxygen isotope exchange between sulfate and water under laboratory conditions thus remain enigmatic. We explore two mechanisms that could allow for isotope exchange and thus interfere with the interpretation of δ18OSO4: oxygen isotope exchange under low pH and oxygen isotope exchange in the presence of sulfide by the formation and subsequent reaction of thiosulfate complexes. Our results definitively rule out short and medium-term exchange of sulfate-oxygen with water-oxygen over a range of acidic conditions. Furthermore, although it has been suggested that thiosulfate complexes will form from coexisting aqueous sulfide and sulfate, we demonstrate that this mechanism does not facilitate sulfate-oxygen isotope exchange at low temperatures. Our results confirm that the δ18OSO4 is robust to standard laboratory conditions.

  1. Neodymium, strontium, and oxygen isotopic variations in the crust of the western United States: Origin of Proterozoic continental crust and tectonic implications

    SciTech Connect

    Bennett, V.C.

    1989-01-01

    Initial Nd isotopic ratios of crystalline rocks from an area of about 1.5 {times} 10{sup 6} km{sup 2} of the western United States have been determined in order to map Precambrian age province boundaries and thus document the growth and modification of the North American continent in the Proterozoic. Three age provinces have been delineated. It is demonstrated that large regions of Early Proterozoic continental crust were formed with anomalous isotopic compositions ({sup 143}Nd/{sup 144}Nd ratios lower than Early Proterozoic depleted-mantle). The variations in the initial {epsilon}{sub Nd} and {delta}{sup 18}O values correlate with each other, and correspond to the previously determined Nd isotopic provinces. The Pelona, Rand, Chocolate Mountain and Orocopia Schists are represented by 15 lithologically and structurally similar schist bodies exposed along the San Andreas and Garlock faults in southern California. The grayschists have measured {epsilon}{sub Nd} values from -1.7 to -11.7 with depleted-mantle model ages of 0.9 to 1.7 Ga. The Nd isotopic compositions can be modeled as variable mixtures of Early Proterozoic continental crust with a Mesozoic are component. The measured {sup 87}Sr/{sup 86}Sr ratios are from 0.7087 to 0.7129 and reflect the presence of an old continental source. Independent of age, the high initial {epsilon}{sub Nd} values ({sup +}9 {plus minus} 1.5) are consistent with derivation at an oceanic spreading center, either at a MORB or in a back-arc basin environment. The presence of both Early Proterozoic continental detritus and a younger sedimentary component in the grayschist protolith, and the MORB affinity of the metabasalts are compatible with formation of the protoliths of the Pelona and related schists in a Mesozoic basin adjacent to the southwestern United States continental margin.

  2. Sex-associated variations in coral skeletal oxygen and carbon isotopic composition of Porites panamensis in the southern Gulf of California

    NASA Astrophysics Data System (ADS)

    Cabral-Tena, Rafael A.; Sánchez, Alberto; Reyes-Bonilla, Héctor; Ruvalcaba-Díaz, Angel H.; Balart, Eduardo F.

    2016-05-01

    Coral δ18O variations are used as a proxy for changes in sea surface temperature (SST) and seawater isotope composition. Skeletal δ13C of coral is frequently used as a proxy for solar radiation because most of its variability is controlled by an interrelationship between three processes: photosynthesis, respiration, and feeding. Coral growth rate is known to influence the δ18O and δ13C isotope record to a lesser extent than environmental variables. Recent published data show differences in growth parameters between female and male coral in the gonochoric brooding coral Porites panamensis; thus, skeletal δ18O and δ13C are hypothesized to be different in each sex. To test this, this study describes changes in the skeletal δ18O and δ13C record of four female and six male Porites panamensis coral collected in Bahía de La Paz, Mexico, whose growth bands spanned 12 years. The isotopic data were compared to SST, precipitation, photosynthetically active radiation (PAR), chlorophyll a, and skeletal growth parameters. Porites panamensis is a known gonochoric brooder whose growth parameters are different in females and males. Splitting the data by sexes explained 81 and 93 % of the differences of δ18O, and of δ13C, respectively, in the isotope record between colonies. Both isotope records were different between sexes. δ18O was higher in female colonies than in male colonies, with a 0.31 ‰ difference; δ13C was lower in female colonies, with a 0.28 ‰ difference. A difference in the skeletal δ18O could introduce an error in SST estimates of ≈ 1.0 to ≈ 2.6 °C. The δ18O records showed a seasonal pattern that corresponded to SST, with low correlation coefficients (-0.45, -0.32), and gentle slopes (0.09, 0.10 ‰ °C-1) of the δ18O-SST relation. Seasonal variation in coral δ18O represents only 52.37 and 35.66 % of the SST cycle; 29.72 and 38.53 % can be attributed to δ18O variability in seawater. δ13C data did not correlate with any of the environmental

  3. Chlorine Isotope Variation in Eucrites

    NASA Astrophysics Data System (ADS)

    Barrett, T. J.; Barnes, J. J.; Anand, M.; Franchi, I. A.; Greenwood, R. C.; Charlier, B. L. A.; Grady, M. M.

    2016-08-01

    We present Cl isotopic compositions for several eucrites with a wide range of petrological and geochemical histories. Our results include some of the heaviest chlorine isotopic compositions recorded so far in the solar system.

  4. Unified picture of the oxygen isotope effect in cuprate superconductors

    PubMed Central

    Chen, Xiao-Jia; Struzhkin, Viktor V.; Wu, Zhigang; Lin, Hai-Qing; Hemley, Russell J.; Mao, Ho-kwang

    2007-01-01

    High-temperature superconductivity in cuprates was discovered almost exactly 20 years ago, but a satisfactory theoretical explanation for this phenomenon is still lacking. The isotope effect has played an important role in establishing electron–phonon interaction as the dominant interaction in conventional superconductors. Here we present a unified picture of the oxygen isotope effect in cuprate superconductors based on a phonon-mediated d-wave pairing model within the Bardeen–Cooper–Schrieffer theory. We show that this model accounts for the magnitude of the isotope exponent as functions of the doping level as well as the variation between different cuprate superconductors. The isotope effect on the superconducting transition is also found to resemble the effect of pressure on the transition. These results indicate that the role of phonons should not be overlooked for explaining the superconductivity in cuprates. PMID:17360421

  5. Oxygen isotopic anomalies in Allende inclusion HAL

    NASA Astrophysics Data System (ADS)

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

    1980-07-01

    An oxygen isotopic study which demonstrates the Allende inclusion HAL is a FUN object is discussed; the hibonite core, black inner rim and fine-grained outer rim have beem sampled. The oxygen in HAL is found to be heterogeneous, the rim samples having oxygen compositions similar to that of melilites and alteration products in other Allende inclusions including the FUN inclusion EK1-4-1, while the oxygen in the hibonite core shows the most extreme deviation from the AD line so far observed. The oxygen in HAL hibonite, in ED1-4-1 spinel and in spinels of usual Allende inclusions form an approximate linear array with a slope close to 1/2. With regard to the fractionation process, it is noted that the fractionation per amu for various elements does not correlate inversely with mass and that fractionation is elementally selective, probably according to volatility.

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

    PubMed

    Flanagan, Lawrence B; Farquhar, Graham D

    2014-02-01

    Measurements of the carbon (δ(13) Cm ) and oxygen (δ(18) Om ) isotope composition of C3 plant tissue provide important insights into controls on water-use efficiency. We investigated the causes of seasonal and inter-annual variability in water-use efficiency in a grassland near Lethbridge, Canada using stable isotope (leaf-scale) and eddy covariance measurements (ecosystem-scale). The positive relationship between δ(13) Cm and δ(18) Om values for samples collected during 1998-2001 indicated that variation in stomatal conductance and water stress-induced changes in the degree of stomatal limitation of net photosynthesis were the major controls on variation in δ(13) Cm and biomass production during this time. By comparison, the lack of a significant relationship between δ(13) Cm and δ(18) Om values during 2002, 2003 and 2006 demonstrated that water stress was not a significant limitation on photosynthesis and biomass production in these years. Water-use efficiency was higher in 2000 than 1999, consistent with expectations because of greater stomatal limitation of photosynthesis and lower leaf ci /ca during the drier conditions of 2000. Calculated values of leaf-scale water-use efficiency were 2-3 times higher than ecosystem-scale water-use efficiency, a difference that was likely due to carbon lost in root respiration and water lost during soil evaporation that was not accounted for by the stable isotope measurements. PMID:23862667

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

    PubMed

    Flanagan, Lawrence B; Farquhar, Graham D

    2014-02-01

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

  8. Oxygen and carbon isotope disequilibria in Galapagos corals: isotopic thermometry and calcification physiology

    SciTech Connect

    McConnaughey, T.A.

    1986-01-01

    Biological carbonate skeletons are built largely from carbon dioxide, which reacts to form carbonate ion within thin extracellular solutions. The light isotopes of carbon and oxygen react faster than the heavy isotopes, depleting the resulting carbonate ions in /sup 13/C and /sup 18/O. Calcium carbonate precipitation occurs sufficiently fast that the skeleton remains out of isotopic equilibrium with surrounding fluids. This explanation for isotopic disequilibrium in biological carbonates was partially simulated in vitro, producing results similar to those seen in non-photosynthetic corals. Photosynthetic corals have higher /sup 13/C//sup 12/C ratios due to the preferential removal of /sup 12/C (as organic carbon) from the reservoir of dissolved inorganic carbon. The oxygen isotopic variations in corals can be used to reconstruct past sea surface temperatures to an accuracy of about 0.5/sup 0/C. The carbon isotopic content of photosynthetic corals provides an indication of cloudiness. Using isotopic data from Galapagos corals, it was possible to construct proxy histories of the El Nino phenomenon. The physiology of skeletogenesis appears to be surprisingly similar in calcium carbonate, calcium phosphate, and silica precipitating systems.

  9. Coupled silicon-oxygen isotope fractionation traces Archaean silicification

    NASA Astrophysics Data System (ADS)

    Abraham, K.; Hofmann, A.; Foley, S. F.; Cardinal, D.; Harris, C.; Barth, M. G.; André, L.

    2011-01-01

    Silica alteration zones and cherts are a conspicuous feature of Archaean greenstone belts worldwide and provide evidence of extensive mobilisation of silica in the marine environment of the early Earth. In order to understand the process(es) of silicification we measured the silicon and oxygen isotope composition of sections of variably silicified basalts and overlying bedded cherts from the Theespruit, Hooggenoeg and Kromberg Formations of the Barberton Greenstone Belt, South Africa. The δ30Si and δ18O values of bulk rock increase with increasing amount of silicification from unsilicified basalts (-0.64‰ < δ30Si < -0.01‰ and + 8.6‰ < δ18O < + 11.9‰) to silicified basalts (δ30Si and δ18O values as high as + 0.81‰ and + 15.6‰, respectively). Cherts generally have positive isotope ratios (+ 0.21‰ < δ30Si < + 1.05‰ and + 10.9 < δ18O < + 17.1), except two cherts, which have negative δ30Si values, but high δ18O (up to + 19.5‰). The pronounced positive correlations between δ30Si, δ18O and SiO2 imply that the isotope variation is driven by the silicification process which coevally introduced both 18O and 30Si into the basalts. The oxygen isotope variation in the basalts from about 8.6‰ to 15.6‰ is likely to represent temperature-dependent isotope fractionation during alteration. Our proposed model for the observed silicon isotope variation relies on a temperature-controlled basalt dissolution vs. silica deposition process.

  10. Oxygen Isotope Trajectories of Crystallizing Arc Magmas

    NASA Astrophysics Data System (ADS)

    Bucholz, C. E.; Jagoutz, O. E.; VanTongeren, J. A.; Wang, Z.

    2014-12-01

    Oxygen isotopes are essential to quantify mantle-derived versus 'recycled' crustal contributions to arc magmas. High δ18O values in igneous rocks (i.e., δ18OSMOW > ~5.7) are generally used to identify supra-crustal inputs, but a melt can also become enriched in 18O due to magmatic differentiation [1,2]. To assess magmatic δ18O values of plutonic rocks, δ18Ozircon values, which are resilient to secondary alteration, are often used. Thus, to disentangle the effects of assimilation versus fractionation, both the absolute increase in melt δ18O due to differentiation and ∆18O(WR-zircon) must be determined. However, existing constraints on the effect of magmatic fractionation on melt δ18O are model-based [2] and calculated relationships between WR SiO2, δ18Ozircon, and δ18Omelt do not incorporate complex melt SiO2, H2O, and temperature (T) relationships [3]. To build upon these initial constraints, we combine the first high-precision δ18O data set on natural samples documenting changes in δ18O melt values with increasing extent of differentiation and modeling which incorporates experimentally constrained melt SiO2, H2O, and T relationships. We analyzed 55 mineral separates with infrared laser-fluorination [4] across large fractionation intervals of two well-studied cumulate sequences: (I) a relatively dry (~1 wt.% H2O initial) tholeiitic sequence (analyzed minerals include plag, opx, cpx, & Fe-rich ol) from the Bushveld Complex and (II) a hydrous high-K sequence (analyzed minerals include ol, cpx, bt, fsp, & qtz) from the Dariv paleoarc in Mongolia. Our results indicate that multiple per mil increases in melt δ18O can occur during magmatic fractionation that in detail depend strongly on melt composition and T. Calculated relationships between WR SiO2 and δ18Ozircon for experimental melt compositions show that wet, 'cool' and dry, 'hot' melts are characterized by larger and smaller ∆18O (melt-zircon) fractionations, respectively. Applying our results to

  11. Oxygen Isotope Systematics of Almahata Sitta

    NASA Technical Reports Server (NTRS)

    Kita, N. T.; Goodrich, C. A.; Herrin, J. S.; Shaddad, M. H.; Jenniskens, P.

    2011-01-01

    The Almahata Sitta (hereafter "AHS") meteorite was derived from an impact of asteroid 2008TC3 on Earth and is classified as an anomalous polymict ureilite. More than 600 meteorite fragments have been recovered from the strewnfield. Previous reports indicate that these fragments consist mainly of ureilitic materials with textures and compositions, while some fragments are found to be chondrites of a wide range of chemical classes. Bulk oxygen three isotope analyses of ureilitic fragments from AHS fall close to the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line similar to ureilites. In order to further compare AHS with known ureilites, we performed high precision SIMS (Secondary Ion Mass Spectrometer) oxygen isotope analyses of some AHS samples

  12. Oxygen isotope partitioning between phosphate and carbonate in mammalian apatite

    NASA Astrophysics Data System (ADS)

    Daniel Bryant, J.; Koch, Paul L.; Froelich, Philip N.; Showers, William J.; Genna, Bernard J.

    1996-12-01

    The oxygen isotope compositions of phosphate and structural carbonate in mammalian enamel and bone apatite are linked to that of body water at constant body temperature near 37°C, but the isotope systematics of oxygen in structural carbonate are not well understood. Using coupled measurements of the oxygen isotope composition of structural carbonate and phosphate from horse tooth enamel, the apparent oxygen isotope fractionation factor between structural carbonate and body water is estimated to be 1.0263 ± 0.0014. These estimates provide a quantitative basis for using the oxygen isotope composition of structural carbonate in mammalian biogenic apatite for ecological, climatological, and physiological reconstruction.

  13. Oxygen and hydrogen isotope geochemistry of zeolites

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

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

  14. Planetary Accretion, Oxygen Isotopes and the Central Limit Theorem

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A., III; Hill, Hugh G. M.; Vondrak, Richard R. (Technical Monitor)

    2001-01-01

    The accumulation of presolar dust into increasingly larger aggregates (CAIs and Chondrules, Asteroids, Planets) should result in a very drastic reduction in the numerical spread in oxygen isotopic composition between bodies of similar size, in accord with the Central Limit Theorem. Observed variations in oxygen isotopic composition are many orders of magnitude larger than would be predicted by a simple, random accumulation model that begins in a well-mixed nebula - no matter which size-scale objects are used as the beginning or end points of the calculation. This discrepancy implies either that some as yet unspecified process acted on the solids in the Solar Nebula to increase the spread in oxygen isotopic composition during each and every stage of accumulation or that the nebula was heterogeneous and maintained this heterogeneity throughout most of nebular history. Large-scale nebular heterogeneity would have significant consequences for many areas of cosmochemistry, including the application of some well-known isotopic systems to the dating of nebular events or the prediction of bulk compositions of planetary bodies on the basis of a uniform cosmic abundance.

  15. Isotope-abundance variations of selected elements (IUPAC technical report)

    USGS Publications Warehouse

    Coplen, T.B.; Böhlke, J.K.; De Bievre, P.; Ding, T.; Holden, N.E.; Hopple, J.A.; Krouse, H.R.; Lamberty, A.; Peiser, H.S.; Revesz, K.; Rieder, S.E.; Rosman, K.J.R.; Roth, E.; Taylor, P.D.P.; Vocke, R.D.; Xiao, Y.K.

    2002-01-01

    Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

  16. A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings.

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  17. Oxygen isotope composition of trinitite postdetonation materials.

    PubMed

    Koeman, Elizabeth C; Simonetti, Antonio; Chen, Wei; Burns, Peter C

    2013-12-17

    Trinitite is the melt glass produced subsequent the first nuclear bomb test conducted on July 16, 1945, at White Sands Range (Alamagordo, NM). The geological background of the latter consists of arkosic sand that was fused with radioactive debris and anthropogenic materials at ground zero subsequent detonation of the device. Postdetonation materials from historic nuclear weapon test sites provide ideal samples for development of novel forensic methods for attribution and studying the chemical/isotopic effects of the explosion on the natural geological environment. In particular, the latter effects can be evaluated relative to their spatial distribution from ground zero. We report here δ(18)O(‰) values for nonmelted, precursor minerals phases (quartz, feldspar, calcite), "feldspathic-rich" glass, "average" melt glass, and bulk (natural) unmelted sand from the Trinity site. Prior to oxygen isotope analysis, grains/crystals were examined using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) to determine their corresponding major element composition. δ(18)O values for bulk trinitite samples exhibit a large range (11.2-15.5‰) and do not correlate with activity levels for activation product (152)Eu; the latter levels are a function of their spatial distribution relative to ground zero. Therefore, the slow neutron flux associated with the nuclear explosion did not perturb the (18)O/(16)O isotope systematics. The oxygen isotope values do correlate with the abundances of major elements derived from precursor minerals present within the arkosic sand. Hence, the O isotope ratios documented here for trinitite melt glass can be attributed to a mixture of the respective signatures for precursor minerals at the Trinity site prior to the nuclear explosion.

  18. Oxygen isotope composition of trinitite postdetonation materials.

    PubMed

    Koeman, Elizabeth C; Simonetti, Antonio; Chen, Wei; Burns, Peter C

    2013-12-17

    Trinitite is the melt glass produced subsequent the first nuclear bomb test conducted on July 16, 1945, at White Sands Range (Alamagordo, NM). The geological background of the latter consists of arkosic sand that was fused with radioactive debris and anthropogenic materials at ground zero subsequent detonation of the device. Postdetonation materials from historic nuclear weapon test sites provide ideal samples for development of novel forensic methods for attribution and studying the chemical/isotopic effects of the explosion on the natural geological environment. In particular, the latter effects can be evaluated relative to their spatial distribution from ground zero. We report here δ(18)O(‰) values for nonmelted, precursor minerals phases (quartz, feldspar, calcite), "feldspathic-rich" glass, "average" melt glass, and bulk (natural) unmelted sand from the Trinity site. Prior to oxygen isotope analysis, grains/crystals were examined using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) to determine their corresponding major element composition. δ(18)O values for bulk trinitite samples exhibit a large range (11.2-15.5‰) and do not correlate with activity levels for activation product (152)Eu; the latter levels are a function of their spatial distribution relative to ground zero. Therefore, the slow neutron flux associated with the nuclear explosion did not perturb the (18)O/(16)O isotope systematics. The oxygen isotope values do correlate with the abundances of major elements derived from precursor minerals present within the arkosic sand. Hence, the O isotope ratios documented here for trinitite melt glass can be attributed to a mixture of the respective signatures for precursor minerals at the Trinity site prior to the nuclear explosion. PMID:24304329

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

  20. Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

    USGS Publications Warehouse

    Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

    2007-01-01

    Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in "mixed" samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant. ?? 2007 American Chemical Society.

  1. Oxygen isotope homogeneity and trace element variations in glass within 250-79 ka Central Plateau Member rhyolite lavas from the Yellowstone Volcanic System

    NASA Astrophysics Data System (ADS)

    Loewen, M.; Bindeman, I. N.; Befus, K. S.

    2014-12-01

    The 250-79 ka Central Plateau Member CPM) rhyolites are represented mostly by large volume lava flows with less than 10% crystals and are the youngest eruptive products inside of the 620 ka Yellowstone Caldera, formed after eruption of Lava Creek Tuff (LCT). These flows are low-δ18O requiring tens of percent of shallowly remelted hydrothermally-altered material and provide evidence into how large silicic magma systems evolve before and after major caldera-forming cycles. We have developed a technique to directly analyze small micro-domains of rhyolite glass for precise (better than 0.1 ‰) δ18O determination coupled with D/H, [H2O], trace elements, and Pb isotopes. We present evidence for striking δ18O homogeneity (4.48 ± 0.12 ‰, 2 standard deviations of all analyses) both across small (1 km3) and large (up to 70 km3) flows and between flows erupted over almost 200 ka. D/H analyses in the glasses are highly degassed and are not affected by secondary hydration (H2O = 0.05 to 0.28 wt. %, δD = -99 to -171 ‰). Trace element analyses show broad temporal compositional evolution consistent with increasing feldspar fractionation over time: the oldest Scaup Lake flow contains 8 ppm Sr, 330 ppm Rb, and 270 ppm Ba to the youngest Pitchstone Plateau flow contains 0.7-1.9 ppm Sr, 180-250 ppm Rb, 18-25 ppm Ba. We also show small but recognizable trace element heterogeneity within lava flows unrelated to long-term geochemical trends. Homogeneity of oxygen in melt from individual lava flows across the LCT caldera is consistent with convective homogenization of a large magma body generated by remelting of post and pre LCT hydrothermally-altered and likely highly variable, low- δ18O rocks. In combination with trace element data we show that the CPM rhyolites have also undergone a broad, caldera-wide differentiation trend with no evidence for significant recharge. We are reconciling diverse geochemical data streams to develop a comprehensive petrologic model for the

  2. Climatic influences on the oxygen isotopic composition of biogenic silica in prairie grass

    NASA Astrophysics Data System (ADS)

    Webb, Elizabeth A.; Longstaffe, Fred J.

    2002-06-01

    Samples of Calamovilfa longifolia were collected from across the North American prairies to investigate the relationship between the oxygen-isotope composition of biogenic silica (phytoliths) deposited in this grass and relative humidity, temperature, and the oxygen-18 enrichment of soil water relative to local precipitation. The δ 18O values of silica in nontranspiring tissues were controlled by soil-water composition and temperature, whereas the oxygen-18 content of silica formed in leaf and inflorescence tissues was enriched further by transpiration. Accurate calculation of growing temperature was possible only when the oxygen-isotope compositions of both stem silica and soil water were known. However, the oxygen-isotope values of stem phytoliths can be used to calculate the variation in the isotopic composition of soil water across a North American temperature gradient. As plant organic matter decays and phytoliths are transferred to the soil, the temperature and soil-water signals carried by the oxygen-isotope composition of silica from nontranspiring tissues can be masked by the oxygen-18 enrichment of phytoliths from transpiring tissues. However, the overall oxygen-isotope composition of a soil-phytolith assemblage can be related to temperature using an empirical relationship based on temperature and the difference between soil-phytolith and estimated soil-water oxygen-isotope compositions.

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

    NASA Astrophysics Data System (ADS)

    Borysiuk, Maciek; 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: 16O, 17O and 18O. We procured samples highly enriched with all three isotopes. Isotopes 16O and 18O were easily detected in the enriched samples, but no significant signal from 17O was detected in the same samples. The measured yield was too low to detect 18O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with 16O was clearly visible.

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

    SciTech Connect

    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

  5. Nitrogen Isotope Tracing of Eutrophication Sources on a Watershed Scale: Nitrogen and Oxygen Isotopes of Nitrate

    NASA Astrophysics Data System (ADS)

    Showers, W. J.; Genna, B.; Karr, J.

    2001-05-01

    elevated nitrogen isotopic values during all flow regimes and concentrations that decrease in the larger order streams. Oxygen isotopes show that while denitrification may occur in groundwaters, riparian buffers, and carbon-rich stream beds, the large flux of nitrogen precludes a change in the nitrogen isotopic signal measured in the river water. This indicates animal waste nitrate is present during all discharge states in this watershed. These results indicate that land use has important controls on the character of nutrient loading and isotope chemistry as expected, but that the type of animal operation is also important. High resolution nitrate concentration measurements made with a new instream nutrient analyzer system shows significant variations occur over very short (hourly) time spans, making the calculation of TMDL's problematic.

  6. Temporal Isotopic Variations of Leaf Water in Pine Needles

    NASA Astrophysics Data System (ADS)

    Shu, Y.; Feng, X.; Faiia, A. M.

    2005-05-01

    Understanding the isotopic variations in a plant's leaf water is important for a number of climatological and biogeochemical studies. Leaf water isotopic composition is affected by the isotopic composition of the source water and the relative humidity of the air, both of which are related to climate. This dependency is the basis for climate reconstruction using isotopic compositions of tree-ring cellulose. The isotopic composition of leaf water is also important for the assessment of terrestrial biological productivity and the quantification of the Dole effect. We have studied the oxygen and hydrogen isotopic variations in leaf water of biennial needles from red pine (Pinus resinosa) and white pine (Pinus strobes) in Hanover, New Hampshire, USA. We have examined the leaf water δD and δ18O values along pine needles from base to tip, and the isotopic differences between young and old leaves. Within a needle, progressive enrichments of both oxygen-18 and deuterium were observed toward the tip, ranging for δD from -60.1 to 9.4 permil in white pine and -67.1 to -34.9 permil in red pine, and for δ18O from -3.1 to 19.1 for white pine and -7.3 to 5.5 permil in red pine. For both species, δD and δ18O were higher in old leaves than in young leaves. The isotopic difference between old and young leaves was most pronounced earlier in the growing season; the gap narrowed with time and finally disappeared in early fall. Early in the growing season, the δD values of young needles were -21 and -30 permil in white and red pine, respectively, and that of old needles were -3.0 and -8.0 permil, respectively. The δ18O values showed similar trends, and the δD vs. δ18O slope for the young leaves decreased from 3.6 in spring to ~1 in early autumn. Our observations can be simulated using the progressive isotopic enrichment model proposed by Barnes and Farquhar for monocotyledoneous leaves. Two variables, the transpiration rate and length of the needle, can explain the observed

  7. Controls on ostracod valve geochemistry: Part 2. Carbon and oxygen isotope compositions

    NASA Astrophysics Data System (ADS)

    Decrouy, Laurent; Vennemann, Torsten Walter; Ariztegui, Daniel

    2011-11-01

    The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in 18O of more than 3‰ relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in 18O for these species of 1.7 to 2.3‰. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens' δ 13C values are mainly controlled by seasonal variations in δ 13C DIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of CO32- at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate

  8. The oxygen isotope equilibrium fractionation between sulfite species and water

    NASA Astrophysics Data System (ADS)

    Müller, Inigo A.; Brunner, Benjamin; Breuer, Christian; Coleman, Max; Bach, Wolfgang

    2013-11-01

    Sulfite is an important sulfoxy intermediate in oxidative and reductive sulfur cycling in the marine and terrestrial environment. Different aqueous sulfite species exist, such as dissolved sulfur dioxide (SO2), bisulfite (HSO3-), pyrosulfite (S2O52-) and sulfite sensu stricto (SO32-), whereas their relative abundance in solution depends on the concentration and the pH. Conversion of one species into another is rapid and involves in many cases incorporation of oxygen from, or release of oxygen to, water (e.g. SO2 + H2O ↔ HSO3- + H+), resulting in rapid oxygen isotope exchange between sulfite species and water. Consequently, the oxygen isotope composition of sulfite is strongly influenced by the oxygen isotope composition of water. Since sulfate does not exchange oxygen isotopes with water under most earth surface conditions, it can preserve the sulfite oxygen isotope signature that it inherits via oxidative and reductive sulfur cycling. Therefore, interpretation of δO values strongly hinges on the oxygen isotope equilibrium fractionation between sulfite and water which is poorly constrained. This is in large part due to technical difficulties in extraction of sulfite from solution for oxygen isotope analysis.

  9. Carbonate Ion Effects on Coccolith Carbon and Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Ziveri, P.; Probert, I.; Stoll, H. M.

    2006-12-01

    The stable oxygen and carbon isotopic composition of biogenic calcite constitutes one of the primary tools used in paleoceanographic reconstructions. The δ18O of shells of ocean floor microfossils and corals reflects the composition of the paleo-seawater as they use the oxygen to build up their calcite and aragonite shells. The δ13C is used to reconstruct variations in the carbon isotopic composition of dissolved inorganic carbon in the ocean, which is controlled by biological productivity through the removal of isotopically light carbon in organic matter. To be effective and sensitive tools for understanding photic zone processes it is first necessary to understand the various biological fractionations associated with carbonate precipitation. To date, isotopic fractionation models are mainly based on foraminifera and corals but not on coccoliths, tiny plates produced by coccolithophore algae, which are often the most dominant carbonate contributors to pelagic sediments. As photosynthetic organisms, their chemistry can provide a sensitive tool for understanding photic zone processes. Coccoliths may be the most important carbonate phase for geochemical analysis in sediments where foraminifera are less common and/or core material is limited, such as in subpolar regions and for Early Cenozoic and Mesozoic sediments. Here we report experimental results on a common living coccolithophore species showing that the 13C/12C and 18O/16O ratios decrease with the increase of HCO^{3-} (CO32-). The selected species are among the heaviest calcifying extant coccolithophores and are major contributors to present coccolith carbonate export production. Because coccolithophores are photosynthetic organisms that calcify intracellularly in specialized vesicles, the challenge lies in ascertaining how kinetic and thermodynamic processes of isotopic fractionation are linked to cellular carbon "transport" and carbonate precipitation. This is a daunting challenge since studies have not

  10. Spatial Variations in Vitreous Oxygen Consumption

    PubMed Central

    Murali, Karthik; Kang, Dongyang; Nazari, Hossein; Scianmarello, Nicholas; Cadenas, Enrique; Tai, Yu-Chong; Kashani, Amir; Humayun, Mark

    2016-01-01

    We investigated the spatial variation of vitreous oxygen consumption in enucleated porcine eyes. A custom made oxygen source was fabricated that could be localized to either the mid or posterior vitreous cavity and steady state vitreous oxygen tension was measured as a function of distance from the source using a commercially available probe. The reaction rate constant of ascorbate oxidation was estimated ex vivo by measuring the change in oxygen tension over time using vitreous harvested from porcine eyes. Vitreous ascorbate from mid and posterior vitreous was measured spectrophotometrically. When the oxygen source was placed in either the mid-vitreous (N = 6) or the posterior vitreous (N = 6), we measured a statistically significant decrease in vitreous oxygen tension as a function of distance from the oxygen source when compared to control experiments without an oxygen source; (p<0.005 for mid-vitreous and p<0.018 for posterior vitreous at all distances). The mid-vitreous oxygen tension change was significantly different from the posterior vitreous oxygen tension change at 2 and 3mm distances from the respective oxygen source (p<0.001). We also found a statistically significant lower concentration of ascorbate in the mid-vitreous as compared to posterior vitreous (p = 0.02). We determined the reaction rate constant, k = 1.61 M-1s-1 ± 0.708 M-1s-1 (SE), of the oxidation of ascorbate which was modeled following a second order rate equation. Our data demonstrates that vitreous oxygen consumption is higher in the posterior vitreous compared to the mid-vitreous. We also show spatial variations in vitreous ascorbate concentration. PMID:26930281

  11. Spatial Variations in Vitreous Oxygen Consumption.

    PubMed

    Murali, Karthik; Kang, Dongyang; Nazari, Hossein; Scianmarello, Nicholas; Cadenas, Enrique; Tai, Yu-Chong; Kashani, Amir; Humayun, Mark

    2016-01-01

    We investigated the spatial variation of vitreous oxygen consumption in enucleated porcine eyes. A custom made oxygen source was fabricated that could be localized to either the mid or posterior vitreous cavity and steady state vitreous oxygen tension was measured as a function of distance from the source using a commercially available probe. The reaction rate constant of ascorbate oxidation was estimated ex vivo by measuring the change in oxygen tension over time using vitreous harvested from porcine eyes. Vitreous ascorbate from mid and posterior vitreous was measured spectrophotometrically. When the oxygen source was placed in either the mid-vitreous (N = 6) or the posterior vitreous (N = 6), we measured a statistically significant decrease in vitreous oxygen tension as a function of distance from the oxygen source when compared to control experiments without an oxygen source; (p<0.005 for mid-vitreous and p<0.018 for posterior vitreous at all distances). The mid-vitreous oxygen tension change was significantly different from the posterior vitreous oxygen tension change at 2 and 3mm distances from the respective oxygen source (p<0.001). We also found a statistically significant lower concentration of ascorbate in the mid-vitreous as compared to posterior vitreous (p = 0.02). We determined the reaction rate constant, k = 1.61 M(-1) s(-1) ± 0.708 M(-1) s(-1) (SE), of the oxidation of ascorbate which was modeled following a second order rate equation. Our data demonstrates that vitreous oxygen consumption is higher in the posterior vitreous compared to the mid-vitreous. We also show spatial variations in vitreous ascorbate concentration.

  12. Thermophysiology of Tyrannosaurus rex: Evidence from Oxygen Isotopes.

    PubMed

    Barrick, R E; Showers, W J

    1994-07-01

    The oxygen isotopic composition of vertebrate bone phosphate (delta(p)) is related to ingested water and to the body temperature at which the bone forms. The delta(p) is in equilibrium with the individual's body water, which is at a physiological steady state throughout the body. Therefore, intrabone temperature variation and the mean interbone temperature differences of well-preserved fossil vertebrates can be determined from the deltap variation. Values of delta(p) from a well-preserved Tyrannosaurus rex suggest that this species maintained homeothermy with less than 4 degrees C of variability in body temperature. Maintenance of homeothermy implies a relatively high metabolic rate that is similar to that of endotherms.

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

    SciTech Connect

    Yakir, D.; DeNiro, M.J. )

    1990-05-01

    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.

  14. Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa.

    PubMed

    Beukes, N J; Klein, C; Kaufman, A J; Hayes, J M

    1990-01-01

    The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic

  15. Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

    NASA Technical Reports Server (NTRS)

    Beukes, N. J.; Klein, C.; Kaufman, A. J.; Hayes, J. M.

    1990-01-01

    The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic

  16. Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa.

    PubMed

    Beukes, N J; Klein, C; Kaufman, A J; Hayes, J M

    1990-01-01

    The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic

  17. Oxygen Isotope Variability within Nautilus Shell Growth Bands

    PubMed Central

    2016-01-01

    Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis of oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. To create the observed range of δ18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands. PMID:27100183

  18. Oxygen Isotope Variability within Nautilus Shell Growth Bands.

    PubMed

    Linzmeier, Benjamin J; Kozdon, Reinhard; Peters, Shanan E; Valley, John W

    2016-01-01

    Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis of oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. To create the observed range of δ18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands. PMID:27100183

  19. Temporal variation of oxygen isotope ratios (δ18O) in drinking water: implications for specifying location of origin with human scalp hair.

    PubMed

    Kennedy, Casey D; Bowen, Gabriel J; Ehleringer, James R

    2011-05-20

    Previous work suggests that δ(18)O values of human hair can be used to constrain the region-of-origin of unknown individuals, but robust assessments of uncertainties in this method are lacking. Here we assess one source of uncertainty - temporal variation in the δ(18)O value of drinking water - using a monthly tap water survey of δ(18)O to develop geospatial models (i.e., maps) of the intra-annual variation (seasonality) in tap water δ(18)O for the contiguous USA. Temporal variation in tap water δ(18)O was correlated with water-supply type, and was related to geographic patterns of precipitation δ(18)O seasonality and water residence time. The maps were applied in a Bayesian framework to identify the geographic origin of an unidentified woman found in Utah, based on measured δ(18)O of scalp hair. The results are robust in specifying parts of the western USA as the most likely region-of-origin. Incorporation of tap water δ(18)O seasonality in the analysis reduces the precision of geographic assignments, but other sources of uncertainty (e.g., spatial interpolation uncertainty) have an equal or larger effect.

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

    NASA Astrophysics Data System (ADS)

    Waterhouse, J. S.; Switsur, V. R.; Barker, A. C.; Carter, A. H. C.; Robertson, I.

    2002-07-01

    We have measured annual oxygen and hydrogen isotope ratios in the α-cellulose of the latewood of oak ( Quercus robur L.) growing on well-drained ground in Norfolk, UK. We compare the observed values of isotope ratios with those calculated using equations that allow for isotopic fractionation during the transfer of oxygen and hydrogen from source water taken by the tree to cellulose laid down in the cambium. The equations constitute a model in which isotopic fractionation occurs during evaporative enrichment within the leaf and during isotopic change between carbohydrates and water in the trunk during cellulose synthesis. From the relationship between isotope ratios in precipitation and α-cellulose, we deduce that the source water used by the tree comprises a constant mixture of groundwater and precipitation, chiefly from the months of May, June and July of the growth year. By selection of isotopic fractionation factors and the degree of isotope exchange within the trunk, we are able to model the observed annual values of oxygen isotope ratios of α-cellulose to a significant level ( r=0.77, P<0.01). When we apply the same model to hydrogen isotope ratios, however, we find that, although we can predict the average value over the time series, we can no longer predict the year-to-year variation. We suggest that this loss of environmental signal in the hydrogen isotopes is caused by differences in the kinetic isotope effects of the biochemical reactions involved in the fixation of hydrogen in different positions of the glucose molecule. Owing to these effects, the hydrogen isotope ratios of cellulose can vary in a way not anticipated in current models and hence may induce non-climatic 'noise' in the hydrogen isotope time series.

  1. Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes

    NASA Astrophysics Data System (ADS)

    Frei, Robert; Gaucher, Claudio; Poulton, Simon W.; Canfield, Don E.

    2009-09-01

    Geochemical data suggest that oxygenation of the Earth's atmosphere occurred in two broad steps. The first rise in atmospheric oxygen is thought to have occurred between ~2.45 and 2.2Gyr ago, leading to a significant increase in atmospheric oxygen concentrations and concomitant oxygenation of the shallow surface ocean. The second increase in atmospheric oxygen appears to have taken place in distinct stages during the late Neoproterozoic era (~800-542Myr ago), ultimately leading to oxygenation of the deep ocean ~580Myr ago, but details of the evolution of atmospheric oxygenation remain uncertain. Here we use chromium (Cr) stable isotopes from banded iron formations (BIFs) to track the presence of Cr(VI) in Precambrian oceans, providing a time-resolved picture of the oxygenation history of the Earth's atmosphere-hydrosphere system. The geochemical behaviour of Cr is highly sensitive to the redox state of the surface environment because oxidative weathering processes produce the oxidized hexavalent [Cr(VI)] form. Oxidation of reduced trivalent [Cr(III)] chromium on land is accompanied by an isotopic fractionation, leading to enrichment of the mobile hexavalent form in the heavier isotope. Our fractionated Cr isotope data indicate the accumulation of Cr(VI) in ocean surface waters ~2.8 to 2.6Gyr ago and a likely transient elevation in atmospheric and surface ocean oxygenation before the first great rise of oxygen 2.45-2.2Gyr ago (the Great Oxidation Event). In ~1.88-Gyr-old BIFs we find that Cr isotopes are not fractionated, indicating a decline in atmospheric oxygen. Our findings suggest that the Great Oxidation Event did not lead to a unidirectional stepwise increase in atmospheric oxygen. In the late Neoproterozoic, we observe strong positive fractionations in Cr isotopes (δ53Cr up to +4.9‰), providing independent support for increased surface oxygenation at that time, which may have stimulated rapid evolution of macroscopic multicellular life.

  2. Hafnium isotope variations in oceanic basalts.

    USGS Publications Warehouse

    Patchett, P.J.; Tatsumoto, M.

    1980-01-01

    Routine low-blank chemistry and 0.01-0.04% precision on the ratio 176Hf/177Hf allows study of Hf isotopic variations, generated by beta --decay of 176Lu, in volcanic rocks derived from the suboceanic mantle. Normalized to 176Hf/177Hf = 0.7325, 176Hf/177Hf ranges 0.2828-0.2835, based on 24 basalt samples. 176Hf/177Hf is positively correlated with 143Nd/144Nd, and negatively correlated with 87Sr/86Sr and 206Pb/204Pb. Along the Iceland-Reykjanes ridge traverse, 176Hf/177Hf increases southwards. The coherence of Hf, Nd and Sr isotopes in the oceanic mantle allows an approximate bulk Earth 176Hf/177Hf of 0.28295 to be inferred from the bulk Earth 143Nd/144Nd. This requires the bulk Earth Lu/Hf to be 0.25, similar to that of the Juvinas eucrite. 60% of the Hf isotopic variation in oceanic basalts occurs among mid-ocean ridge samples. Lu-Hf fractionation probably decouples from Sm-Nd and Rb-Sr fractionation in very depleted source regions, with high Lu/Hf, and consequent high 176Hf/177Hf ratios developing in mantle residual from partial melting. (Authors' abstract) -T.R.

  3. Silicon and oxygen isotopic trends in Mesozoic radiolarites

    NASA Astrophysics Data System (ADS)

    Bôle, Maximlien; Baumgartner Peter, O.; Lukas, Baumgartner; Anne-Sophie, Bouvier; Rie, Hori; Masayuki, Ikeda

    2016-04-01

    Silicon and oxygen isotopes (δ30Si and δ18O) of siliceous tests (diatoms, sponges and radiolarians) preserve environmental signatures in unconsolidated sediments, but few studies show such signatures for ancient biosilicieous rocks. In Precambrian cherts from greenstone belts, small scaled isotopic variations were interpreted as a primary diagenetic feature. They were used, coupled to mean δ18O, to reconstruct seawater temperature at which cherts precipitated. Here, we examine stable isotopes in Mesozoic biogenic cherts that may also preserve an environmental signature. We measured δ30Si and δ18O in situ by SIMS, in the chalcedony of individual radiolarian tests preserved in Mesozoic radiolarites. Microanalysis of chalcedony, rather than the bulk rock isotopic composition, is likely to reveal a palaeoenvironmental signal, since it is derived from biogenic opal, the most mobile silica phase during earliest diagenesis. Our data reveal clear trends through several Mesozoic radiolarite sections from Panthalassa (Kiso River, Japan) and Western Tethys (Sogno, Italy). δ18O records measured in radiolarites show a relatively good correlation to δ18O-variations of Mesozoic low magnesium calcite shells, which are commonly used as a palaeotemperature proxy. Once these variations, attributed to seawater temperature, are removed, the residual δ18O trends are opposite to the δ30Si trends. δ30Si increases from Middle Triassic to Early Jurassic in the Kiso River sections and decrease during the Middle Jurassic in the Sogno section. The observed d30Si-trends are likely to represent a palaeoenvironmental signal, because they are not compatible with simple models of progressive diagenesis along P/T-paths (or depth below sea bottom in drill holes). Among the palaeoenvironmental factors that may have influenced these trends are the oceanic silica cycle changing though time, oceanic circulation and/or the palaeogeographic location of each studied site. Siliceous organisms are

  4. Possible evidence for fluid-rock oxygen isotope disequilibrium in hydrothermal systems

    SciTech Connect

    Cole, D.R.

    1992-01-01

    There is ample evidence from geothermal systems that isotope temperatures estimated from the oxygen isotope fractionation between alteration phases and coexisting aquifer fluids agree closely with measured bore-hole temperatures. Similar, but limited evidence is found in epithermal vein deposits where isotopes temperature agree well with fluid inclusion homogenization temperature. Conversely, many hydrothermal systems exhibit varying degrees of fluid-rock oxygen isotope equilibration. There appears to be a crude relationship between increasing degree of equilibrium and increasing temperature and salinity. The observed variations in the degree of exchange may have resulted from local, self-sealing of the fracture network prior to equilibration. The ability for fracture to remain open or to propogate allowing continued fluid flow may be the deciding factor in the attainment of isotopic equilibration.

  5. Possible evidence for fluid-rock oxygen isotope disequilibrium in hydrothermal systems

    SciTech Connect

    Cole, D.R.

    1992-04-01

    There is ample evidence from geothermal systems that isotope temperatures estimated from the oxygen isotope fractionation between alteration phases and coexisting aquifer fluids agree closely with measured bore-hole temperatures. Similar, but limited evidence is found in epithermal vein deposits where isotopes temperature agree well with fluid inclusion homogenization temperature. Conversely, many hydrothermal systems exhibit varying degrees of fluid-rock oxygen isotope equilibration. There appears to be a crude relationship between increasing degree of equilibrium and increasing temperature and salinity. The observed variations in the degree of exchange may have resulted from local, self-sealing of the fracture network prior to equilibration. The ability for fracture to remain open or to propogate allowing continued fluid flow may be the deciding factor in the attainment of isotopic equilibration.

  6. Holocene precipitation seasonality captured by a dual hydrogen and oxygen isotope approach at Steel Lake, Minnesota

    NASA Astrophysics Data System (ADS)

    Henderson, Anna K.; Nelson, David M.; Hu, Feng Sheng; Huang, Yongsong; Shuman, Bryan N.; Williams, John W.

    2010-12-01

    Middle-Holocene (8 to 4 ka BP) warmth and aridity are well recorded in sediment archives from midcontinental North America. However, neither the climatic driver nor the seasonal character of precipitation during this period is well understood because of the limitations of available proxy indicators. For example, an important challenge is to distinguish among the interacting effects of evaporation, temperature, or precipitation seasonality in existing δ 18O records from the region. Here we combine hydrogen isotopes of palmitic acid and oxygen isotopes of carbonate to derive lake-water isotopic values during the Holocene at Steel Lake in north-central Minnesota. In combination, these data enable us to separate variations in evaporation from variations in the isotopic composition of input-waters to lake. Variations in evaporation are used as a proxy for aridity and lake-water input isotopic values are used as a proxy for the isotopic values of meteoric precipitation. Our results suggest that lake-water input isotopic values were more negative during the middle Holocene than at present. To test whether these more negative values are related to temperature or precipitation seasonality, we compare pollen-inferred temperatures and the expected isotopic value of precipitation resulting from these temperatures to the reconstructed precipitation isotopic values. Results suggest that middle Holocene warmth and aridity were associated with increased evaporation rates and decreased summer precipitation. These inferences are consistent with climate simulations that highlight the role of seasonal insolation and sea surface temperatures in driving variations in precipitation seasonality during the Holocene. Results also suggest that changes in Holocene precipitation seasonality may have influenced the expansion of the prairie-forest border in Minnesota as well as regional variations in grassland community composition. This study demonstrates the efficacy of the dual hydrogen and

  7. Chromium Isotopes Record Fluctuations in Precambrian Biospheric Oxygenation

    NASA Astrophysics Data System (ADS)

    Frei, R.; Gaucher, C.; Poulton, S. W.; Canfield, D. E.

    2009-12-01

    There is a direct relationship between life, oxygen, and the surface chemistry of the Earth. Geochemical data suggest that oxygenation of the Earth's atmosphere occurred in two broad steps, near the beginning and the end of the Proterozoic Eon (2500 to 542 million years ago), but the details of this history are unclear. The geochemical behaviour of chromium (Cr) is highly sensitive to the redox state of the surface environment as oxidative weathering processes produce the oxidised hexavalent [Cr(VI)] form. Oxidation of reduced trivaltent [Cr(III)] chromium on land is accompanied by an isotopic fractionation, leading to enrichment of the mobile hexavalent form in the heavier isotope. The fractionated Cr isotope signature is then tranfered by riverine transport to the sea. Here, we use Cr stable isotopes from banded iron formations (BIFs) to track the presence of Cr(VI) in Precambrian oceans, providing a time-resolved picture of the oxygenation history of Earth’s atmosphere-hydrosphere system. Fractionated Cr isotopes indicate the accumulation of Cr(VI) in ocean surface waters ~2.8 to 2.6 billion years (Gyr) ago and a likely transient elevation in atmospheric and surface ocean oxygen prior to the first great rise of oxygen 2.45-2.2 Gyr ago (the Great Oxidation Event; GOE). In contrast, Cr isotopes in ~1.88 Gyr old BIFs are not fractionated, indicating a major decline in atmospheric oxygen and demonstrating that the GOE did not lead to a unidirectional stepwise increase in atmospheric oxygen. In the late Neoproterozoic, ~800 to 542 million years (Myr) ago, we observe strong positive fractionations in Cr isotopes (δ53Cr up to +4.9 ‰) providing independent support for increased surface oxygenation at this time. This may have stimulated rapid evolution of macroscopic multicellular life. Our chromium isotope data thus provide new insights into the oxygenation history of the Earth, and highlight its use as a powerful redox tracer in aquatic systems.

  8. Simulating oxygen isotope ratios in tree ring cellulose using a dynamic global vegetation model

    NASA Astrophysics Data System (ADS)

    Keel, Sonja G.; Joos, Fortunat; Spahni, Renato; Saurer, Matthias; Weigt, Rosemarie B.; Klesse, Stefan

    2016-07-01

    Records of stable oxygen isotope ratios in tree rings are valuable tools to reconstruct past climatic conditions and investigate the response of trees to those conditions. So far the use of stable oxygen isotope signatures of tree rings has not been systematically evaluated in dynamic global vegetation models (DGVMs). DGVMs integrate many hydrological and physiological processes and their application could improve proxy-model comparisons and the interpretation of oxygen isotope records. Here we present an approach to simulate leaf water and stem cellulose δ18O of trees using the LPX-Bern DGVM (LPX-Bern). Our results lie within a few per mil of measured tree ring δ18O of 31 different forest stands mainly located in Europe. Temporal means over the last 5 decades as well as interannual variations for a subset of sites in Switzerland are captured. A sensitivity analysis reveals that relative humidity, temperature, and the water isotope boundary conditions have the largest influence on simulated stem cellulose δ18O, followed by all climatic factors combined, whereas increasing atmospheric CO2 and nitrogen deposition exert no impact. We conclude that simulations with LPX-Bern are useful for investigating large-scale oxygen isotope patterns of tree ring cellulose to elucidate the importance of different environmental factors on isotope variations and therefore help to reduce uncertainties in the interpretation of δ18O of tree rings.

  9. The triple isotopic composition of oxygen in leaf water

    NASA Astrophysics Data System (ADS)

    Landais, A.; Barkan, E.; Yakir, D.; Luz, B.

    2006-08-01

    The isotopic composition of atmospheric O 2 depends on the rates of oxygen cycling in photosynthesis, respiration, photochemical reactions in the stratosphere and on δ17O and δ18O of ocean and leaf water. While most of the factors affecting δ17O and δ18O of air O 2 have been studied extensively in recent years, δ17O of leaf water—the substrate for all terrestrial photosynthesis—remained unknown. In order to understand the isotopic composition of atmospheric O 2 at present and in fossil air in ice cores, we studied leaf water in field experiments in Israel and in a European survey. We measured the difference in δ17O and δ18O between stem and leaf water, which is the result of isotope enrichment during transpiration. We calculated the slopes of the lines linking the isotopic compositions of stem and leaf water. The obtained slopes in ln( δ17O + 1) vs. ln( δ18O + 1) plots are characterized by very high precision (˜0.001) despite of relatively large differences between duplicates in both δ17O and δ18O (0.02-0.05‰). This is so because the errors in δ18O and δ17O are mass-dependent. The slope of the leaf transpiration process varied between 0.5111 ± 0.0013 and 0.5204 ± 0.0005, which is considerably smaller than the slope linking liquid water and vapor at equilibrium (0.529). We further found that the slope of the transpiration process decreases with atmospheric relative humidity ( h) as 0.522-0.008 × h, for h in the range 0.3-1. This slope is neither influenced by the plant species, nor by the environmental conditions where plants grow nor does it show strong variations along long leaves.

  10. Oxygen and hydrogen isotope signatures of Northeast Atlantic water masses

    NASA Astrophysics Data System (ADS)

    Voelker, Antje H. L.; Colman, Albert; Olack, Gerard; Waniek, Joanna J.; Hodell, David

    2015-06-01

    Only a few studies have examined the variation of oxygen and hydrogen isotopes of seawater in NE Atlantic water masses, and data are especially sparse for intermediate and deep-water masses. The current study greatly expands this record with 527 δ18O values from 47 stations located throughout the mid- to low-latitude NE Atlantic. In addition, δD was analyzed in the 192 samples collected along the GEOTRACES North Atlantic Transect GA03 (GA03_e=KN199-4) and the 115 Iberia-Forams cruise samples from the western and southern Iberian margin. An intercomparison study between the two stable isotope measurement techniques (cavity ring-down laser spectroscopy and magnetic-sector isotope ratio mass spectrometry) used to analyze GA03_e samples reveals relatively good agreement for both hydrogen and oxygen isotope ratios. The surface (0-100 m) and central (100-500 m) water isotope data show the typical, evaporation related trend of increasing values equatorward with the exception for the zonal transect off Cape Blanc, NW Africa. Off Cape Blanc, surface water isotope signatures are modified by the upwelling of fresher Antarctic Intermediate Water (AAIW) that generally has isotopic values of 0.0 to 0.5‰ for δ18O and 0 to 2‰ for δD. Along the Iberian margin the Mediterranean Outflow Water (MOW) is clearly distinguished by its high δ18O (0.5-1.1‰) and δD (3-6‰) values that can be traced into the open Atlantic. Isotopic values in the NE Atlantic Deep Water (NEADW) are relatively low (δ18O: -0.1 to 0.5‰; δD: -1 to 4‰) and show a broader range than observed previously in the northern and southern convection areas. The NEADW is best observed at GA03_e Stations 5 and 7 in the central NE Atlantic basin. Antarctic Bottom Water isotope values are relatively high indicating modification of the original Antarctic source water along the flow path. The reconstructed δ18O-salinity relationship for the complete data set has a slope of 0.51, i.e., slightly steeper than the 0

  11. Galena oxidation investigations on oxygen and sulphur isotopes.

    PubMed

    Heidel, Claudia; Tichomirowa, Marion

    2011-06-01

    Batch experiments with the lead sulphide ore mineral galena were carried out in order to get information about the oxidation mechanisms and to contribute to the understanding of field data, especially those obtained from the mining-affected sites. Results indicate that oxygen and sulphur isotopes of dissolved sulphate may be useful tools for the investigation of galena oxidation mechanisms. However, some methodological modifications are necessary to obtain sufficient sulphate yields, which are a prerequisite for the reduction of the analytical uncertainty. Surface and hydrochemical investigations indicated that galena was dissolved non-oxidatively during the experiment at initial pH 2, whereas the oxidative dissolution of galena dominated in experiments at initial pH 6 and 8. No isotope results could be obtained from the experiment at initial pH 2 due to the low sulphate production. The oxidative dissolution of galena resulted in somewhat higher sulphate yields. Thus, the oxygen isotope composition of sulphate produced from galena oxidation could be determined for the first time. Oxygen in sulphate derived largely from water molecules; but minor amounts of molecular oxygen could be also observed. Both molecular oxygen and ferric iron may act as oxidants of galena. A variety of intermediate reactions allow for a variable oxygen isotope composition of sulphate. Sulphur isotopes of sulphate showed an enrichment of (32)S in sulphate (relative to galena), which increases with increasing pH. Sulphur isotope enrichment processes may be associated with the formation of anglesite.

  12. Divergent Biochemical Fractionation, Not Convergent Temperature, Explains Cellulose Oxygen Isotope Enrichment across Latitudes

    PubMed Central

    Sternberg, Leonel; Ellsworth, Patricia Fernandes Vendramini

    2011-01-01

    Recent findings based on the oxygen isotope ratios of tree trunk cellulose indicate that the temperature of biomass production in biomes ranging from boreal to subtropical forests converge to an average leaf temperature of 21.4°C. The above conclusion has been drawn under the assumption that biochemically related isotopic fractionations during cellulose synthesis are not affected by temperature. Here we test the above assumption by heterotrophically generating cellulose at different temperatures and measuring the proportion of carbohydrate oxygen that exchange with water during cellulose synthesis and the average biochemical fractionation associated with this exchange. We observed no variation in the proportion of oxygen that exchange with different temperatures, which averaged 0.42 as it has been observed in other studies. On the other hand, the biochemical oxygen isotope fractionation during cellulose synthesis is affected by temperature and can be described by a 2nd order polynomial equation. The biochemical fractionation changes little between temperatures of 20 and 30°C averaging 26‰ but increases at lower temperatures to values of 31‰. This temperature sensitive biochemical fractionation explains the pattern of cellulose oxygen isotope ratios of aquatic plants encompassing several latitudes. The observed temperature sensitive biochemical fractionation also indicates that divergent biochemical fractionation and not convergent leaf temperature explains the increase in oxygen isotope enrichment of cellulose across several biomes. PMID:22132203

  13. Oxygen isotope fractionation in stratospheric CO2

    NASA Technical Reports Server (NTRS)

    Thiemens, M. H.; Jackson, T.; Mauersberger, K.; Schueler, B.; Morton, J.

    1991-01-01

    A new cryogenic collection system has been flown on board a balloon gondola to obtain separate samples of ozone and carbon dioxide without entrapping major atmospheric gases. Precision laboratory isotopic analysis of CO2 samples collected between 26 and 35.5 km show a mass-independent enrichment in both O-17 and O-18 of about 11 per mil above tropospheric values. Ozone enrichment in its heavy isotopes was 9 to 16 percent in O3-50 and 8 to 11 percent in O3-49, respectively (Schueler et al., 1990). A mechanism to explain the isotope enrichment in CO2 has been recently proposed by Yung et al. (1991). The model is based on the isotope exchange between CO2 and O3 via O(1D), resulting in a transfer of the ozone isotope enrichment to carbon dioxide. Predicted enrichment and measured values agree well.

  14. What does the oxygen isotope composition of rodent teeth record?

    NASA Astrophysics Data System (ADS)

    Royer, Aurélien; Lécuyer, Christophe; Montuire, Sophie; Amiot, Romain; Legendre, Serge; Cuenca-Bescós, Gloria; Jeannet, Marcel; Martineau, François

    2013-01-01

    Oxygen isotope compositions of tooth phosphate (δ18Op) were measured in 107 samples defined on the basis of teeth obtained from 375 specimens of extant rodents. These rodents were sampled from pellets collected in Europe from 38°N (Portugal) to 65°N (Finland) with most samples coming from sites located in France and Spain. Large oxygen isotopic variability in δ18Op is observed both at the intra- and inter-species scale within pellets from a given location. This isotopic variability is partly explained by heterochrony in tooth formation related to the short time of mineralization for all rodent species as well as the duration of mineralization that is species-dependent. Consequently, tooth phosphate of rodents records a short seasonal interval in the oxygen isotope compositions of meteoric waters (δ18Omw). In addition, inter-species isotopic variability observed in the same pellets suggests behavioural differences implying distinct isotopic compositions for species living in the same location. At the scale of Europe, a robust linear oxygen isotope fractionation equation was determined for Muroidea between the midrange δ18Op values and δ18Omw values: δ18Op=1.21(±0.20)δ18Omw+24.76(±2.70) with R2=0.79 (n=9; p<0.0001).

  15. High Resolution Carbon and Oxygen Isotope Measurements of Laminations in Pedogenic Carbonate

    NASA Astrophysics Data System (ADS)

    Breecker, D.; Sharp, Z.

    2005-12-01

    distributions are mostly primary but that variations in δ18O occur at a much smaller scale than variations in δ13C. The apparently random oxygen isotope zoning could then be explained as the result of sampling multiple homogeneous zones with 100 μm laser pits. Detailed analyses of clast rinds from less well-developed soils may help resolve these questions.

  16. Oxygen isotope variability within Nautilus shell growth bands

    DOE PAGES

    Linzmeier, Benjamin J.; Kozdon, Reinhard; Peters, Shanan E.; Valley, John W.

    2016-04-21

    Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis ofmore » oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. In addition, to create the observed range of δ18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands.« less

  17. Hydrogen burning of the rare oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Buckner, Matthew Quinn

    2014-10-01

    At the Laboratory for Experimental Nuclear Astrophysics (LENA), two rare oxygen isotope proton capture studies were performed at low energies--- 18O(p,gamma)19F and 17O( p,gamma)18F. The goal of each study was to improve thermonuclear reaction rates at stellar plasma temperatures relevant to 18O and 17O destruction, respectively. The stellar nucleosynthesis temperature regime corresponds to very low proton bombarding energies. At these low energies, the Coulomb barrier suppresses the reaction yield in the laboratory, and environmental backgrounds dominate the detected signal, making it difficult to differentiate the gamma-cascade from background. At LENA, the electron cyclotron resonance (ECR) ion source produces intense, low-energy proton beam, and these high currents boost the reaction yield. LENA, a ``sea-level" facility dedicated to nuclear astrophysics, also has a coincidence detector setup that reduces environmental background contributions and boosts signal-to-noise. The sensitivity afforded by gammagamma-coincidence and high beam current allowed these rare oxygen isotope reactions to be probed at energies that correspond to stellar plasma temperatures. For stars with masses between 0.8 solar masses < M < 8.0 solar masses, nucleosynthesis enters its final phase during the asymptotic giant branch (AGB) stage. This is an evolutionary period characterized by grain condensation that occurs in the stellar atmosphere; the star also experiences significant mass loss during this period of instability. Presolar grain production can often be attributed to this unique stellar environment. A subset of presolar oxide grains features dramatic 18O depletion that can not be explained by the standard asymptotic giant star burning stages and dredge-up models. An extra mixing process for low-mass asymptotic giant branch stars, known as cool bottom processing (CBP), was used in the literature to explain this and other anomalies. Cool bottom processing can also occur during the

  18. Position-specific measurement of oxygen isotope ratios in cellulose: Isotopic exchange during heterotrophic cellulose synthesis

    NASA Astrophysics Data System (ADS)

    Waterhouse, John S.; Cheng, Shuying; Juchelka, Dieter; Loader, Neil J.; McCarroll, Danny; Switsur, V. Roy; Gautam, Lata

    2013-07-01

    We describe the first reported method for the measurement of oxygen isotope ratios at each position in the glucose units of the cellulose molecule. The overall process comprises a series of synthetic organic sequences, by which α-cellulose is hydrolysed to glucose, and oxygen atoms at specific positions in the glucose molecule are removed in samples of benzoic acid for measurement of δ18O. Values of δ18O at specific positions in cellulose are calculated from these δ18O values and the overall δ18O value of the cellulose. We apply the method to determine the degree to which oxygen atoms at each position undergo isotopic exchange with water during heterotrophic cellulose synthesis, such as occurs in the cambium of trees. To do this we extract α-cellulose from wheat seedlings germinated in the dark in aqueous media of differing oxygen isotope ratios. Results indicate that oxygen atoms at positions 5 and 6 (O-5 and O-6 respectively) undergo around 80% exchange with medium water, O-3 undergoes around 50% exchange, and O-2 and O-4 do not undergo isotopic exchange. The results have important implications for extracting palaeoclimatic records from oxygen isotope time series obtained from tree ring cellulose. As O-5 and O-6 undergo significant exchange with medium water during heterotrophic cellulose synthesis, oxygen isotopes at these positions in tree ring cellulose should carry a predominantly trunk (source) water signal. On the other hand, O-2 and O-4 should retain the isotopic signature of leaf water in tree ring cellulose. Our method therefore potentially enables the separate reconstruction of past temperature and humidity data from oxygen isotope ratios of tree ring cellulose - something that has hitherto not been possible. The measured degrees of isotopic exchange are to some extent unexpected and cannot be fully explained using current biochemical mechanisms, suggesting that knowledge of these processes is incomplete.

  19. Oxygen isotope signatures of transpired water vapor: the role of isotopic non-steady-state transpiration under natural conditions.

    PubMed

    Dubbert, Maren; Cuntz, Matthias; Piayda, Arndt; Werner, Christiane

    2014-09-01

    The oxygen isotope signature of water is a powerful tracer of water movement from plants to the global scale. However, little is known about the short-term variability of oxygen isotopes leaving the ecosystem via transpiration, as high-frequency measurements are lacking. A laser spectrometer was coupled to a gas-exchange chamber directly estimating branch-level fluxes in order to evaluate the short-term variability of the isotopic composition of transpiration (δE ) and to investigate the role of isotopic non-steady-state transpiration under natural conditions in cork-oak trees (Quercus suber) during distinct Mediterranean seasons. The measured δ(18) O of transpiration (δE ) deviated from isotopic steady state throughout most of the day even when leaf water at the evaporating sites was near isotopic steady state. High agreement was found between estimated and modeled δE values assuming non-steady-state enrichment of leaf water. Isoforcing, that is, the influence of the transpirational δ(18) O flux on atmospheric values, deviated from steady-state calculations but daily means were similar between steady state and non-steady state. However, strong daytime isoforcing on the atmosphere implies that short-term variations in δE are likely to have consequences for large-scale applications, for example, partitioning of ecosystem fluxes or satellite-based applications.

  20. Molecular cloud origin for the oxygen isotope heterogeneity in the solar system.

    PubMed

    Yurimoto, Hisayoshi; Kuramoto, Kiyoshi

    2004-09-17

    Meteorites and their components have anomalous oxygen isotopic compositions characterized by large variations in 18O/16O and 17O/16O ratios. On the basis of recent observations of star-forming regions and models of accreting protoplanetary disks, we suggest that these variations may originate in a parent molecular cloud by ultraviolet photodissociation processes. Materials with anomalous isotopic compositions were then transported into the solar nebula by icy dust grains during the collapse of the cloud. The icy dust grains drifted toward the Sun in the disk, and their subsequent evaporation resulted in the 17O- and 18O-enrichment of the inner disk gas. PMID:15375265

  1. The rate of oxygen isotope exchange between nitrate and water

    NASA Astrophysics Data System (ADS)

    Kaneko, Masanori; Poulson, Simon R.

    2013-10-01

    The oxygen isotope exchange rate between nitrate and water was measured at a temperature of 50-80 °C and pH -0.6 to 1.1. Oxygen isotope exchange is a first-order reaction, with the exchange rate being strongly affected by both reaction temperature and pH, with increased rates of isotope exchange at higher temperatures and lower pH values. The rate of oxygen isotope exchange under natural conditions is extremely slow, with an estimated half-life for isotope exchange of 5.5 × 109 years at 25 °C and pH 7. The extremely slow rate of oxygen isotope exchange between nitrate and water under typical environmental conditions illustrates that nitrate-δ18O signatures (and also nitrate δ17O and Δ17O signatures) associated with various nitrate sources, as well as isotope compositions produced by biogeochemical processes, will be preserved. Hence, it is valid to use the value of nitrate-δ18O to investigate the sources and biogeochemical behavior of nitrate, in a similar manner to the use of sulfate-δ18O signatures to study the sources and biogeochemical behavior of sulfate. Equilibrium oxygen isotope fractionation factors have been determined, although quantification of the nitrate-water equilibrium fractionation factor is not possible due to the presence of nitrate as both protonated (i.e. HNO3) and unprotonated forms (i.e. NO3-) under the experimental conditions, and the difficulty in accurately calculating nitrate speciation in low pH, high ionic strength solutions.

  2. Carbon dioxide and oxygen isotope anomalies in the mesosphere and stratosphere

    SciTech Connect

    Thiemens, M.H.; Jackson, T.; Zipf, E.C.

    1995-11-10

    Isotopic ({delta}{sup 17}O and {delta}{sup 18}O) measurements of stratospheric and mesospheric carbon dioxide (CO{sub 2}) and oxygen (O{sub 2}), along with trace species concentrations (N{sub 2}O, CO, and CO{sub 2}), were made in samples collected from a rocket-borne cryogenic whole air sampler. A large mass-independent isotopic anomaly was observed in CO{sub 2}, which may in part derive from photochemical coupling to ozone (O{sub 3}). The data also require an additional isotopic fractionation process, which is presently unidentified. Mesospheric O{sub 2} isotope ratios differed from those in the troposphere and stratosphere. The cause of this isotopic variation in O{sub 2} is presently unknown. The inability to account for these observations represents a fundamental gap in the understanding of the O{sub 2} chemistry in the stratosphere and mesosphere. 28 refs., 2 figs., 1 tab.

  3. Spatial Variability in Instantaneous Photosynthetic Carbon and Oxygen Isotope Discrimination

    NASA Astrophysics Data System (ADS)

    Barbour, M. M.

    2007-12-01

    Stable carbon and oxygen isotope ratios of CO2 are useful tracers in studies of carbon and water cycling between the terrestrial biosphere and the atmosphere. Interpretation of variation in 13CO2 and C16O18O relies on models describing physical and biochemical processes and their associated fractionations. A layer of complexity not currently quantified or accounted for in canopy models is spatial variation in photosynthetic discrimination within a single leaf. A new measurement technique, employing tunable diode laser absorption spectrometry coupled to an open gas exchange system, enables online measurement of photosynthetic discrimination at high temporal resolution. Using this system, photosynthetic 13C and 18O discrimination was measured along leaves of a C3 monocot. For the forage cereal Triticale, 13C discrimination increased by 2‰ and 18O by 20‰ from the base to the tip of mature leaves when measured at saturating irradiance. The increase in 13C discrimination was associated with an increase in the leaf internal conductance of CO2, and 18O discrimination with carry-forward of evaporative enrichment along the leaf. When numerical averages are compared to flux- and area-weighted averages, the portion of the leaf approximately one third of the way from the base can be shown to provide the most representative area for scaling up.

  4. Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes.

    PubMed

    Frei, Robert; Gaucher, Claudio; Poulton, Simon W; Canfield, Don E

    2009-09-10

    Geochemical data suggest that oxygenation of the Earth's atmosphere occurred in two broad steps. The first rise in atmospheric oxygen is thought to have occurred between approximately 2.45 and 2.2 Gyr ago, leading to a significant increase in atmospheric oxygen concentrations and concomitant oxygenation of the shallow surface ocean. The second increase in atmospheric oxygen appears to have taken place in distinct stages during the late Neoproterozoic era ( approximately 800-542 Myr ago), ultimately leading to oxygenation of the deep ocean approximately 580 Myr ago, but details of the evolution of atmospheric oxygenation remain uncertain. Here we use chromium (Cr) stable isotopes from banded iron formations (BIFs) to track the presence of Cr(VI) in Precambrian oceans, providing a time-resolved picture of the oxygenation history of the Earth's atmosphere-hydrosphere system. The geochemical behaviour of Cr is highly sensitive to the redox state of the surface environment because oxidative weathering processes produce the oxidized hexavalent [Cr(VI)] form. Oxidation of reduced trivalent [Cr(III)] chromium on land is accompanied by an isotopic fractionation, leading to enrichment of the mobile hexavalent form in the heavier isotope. Our fractionated Cr isotope data indicate the accumulation of Cr(VI) in ocean surface waters approximately 2.8 to 2.6 Gyr ago and a likely transient elevation in atmospheric and surface ocean oxygenation before the first great rise of oxygen 2.45-2.2 Gyr ago (the Great Oxidation Event). In approximately 1.88-Gyr-old BIFs we find that Cr isotopes are not fractionated, indicating a decline in atmospheric oxygen. Our findings suggest that the Great Oxidation Event did not lead to a unidirectional stepwise increase in atmospheric oxygen. In the late Neoproterozoic, we observe strong positive fractionations in Cr isotopes (delta(53)Cr up to +4.9 per thousand), providing independent support for increased surface oxygenation at that time, which may

  5. Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes.

    PubMed

    Frei, Robert; Gaucher, Claudio; Poulton, Simon W; Canfield, Don E

    2009-09-10

    Geochemical data suggest that oxygenation of the Earth's atmosphere occurred in two broad steps. The first rise in atmospheric oxygen is thought to have occurred between approximately 2.45 and 2.2 Gyr ago, leading to a significant increase in atmospheric oxygen concentrations and concomitant oxygenation of the shallow surface ocean. The second increase in atmospheric oxygen appears to have taken place in distinct stages during the late Neoproterozoic era ( approximately 800-542 Myr ago), ultimately leading to oxygenation of the deep ocean approximately 580 Myr ago, but details of the evolution of atmospheric oxygenation remain uncertain. Here we use chromium (Cr) stable isotopes from banded iron formations (BIFs) to track the presence of Cr(VI) in Precambrian oceans, providing a time-resolved picture of the oxygenation history of the Earth's atmosphere-hydrosphere system. The geochemical behaviour of Cr is highly sensitive to the redox state of the surface environment because oxidative weathering processes produce the oxidized hexavalent [Cr(VI)] form. Oxidation of reduced trivalent [Cr(III)] chromium on land is accompanied by an isotopic fractionation, leading to enrichment of the mobile hexavalent form in the heavier isotope. Our fractionated Cr isotope data indicate the accumulation of Cr(VI) in ocean surface waters approximately 2.8 to 2.6 Gyr ago and a likely transient elevation in atmospheric and surface ocean oxygenation before the first great rise of oxygen 2.45-2.2 Gyr ago (the Great Oxidation Event). In approximately 1.88-Gyr-old BIFs we find that Cr isotopes are not fractionated, indicating a decline in atmospheric oxygen. Our findings suggest that the Great Oxidation Event did not lead to a unidirectional stepwise increase in atmospheric oxygen. In the late Neoproterozoic, we observe strong positive fractionations in Cr isotopes (delta(53)Cr up to +4.9 per thousand), providing independent support for increased surface oxygenation at that time, which may

  6. Oxygen isotope diffusion and zoning in diopside: The importance of water fugacity during cooling

    SciTech Connect

    Edwards, K.J.; Valley, J.W.

    1998-07-01

    The oxygen isotope ratio of diopside correlates with crystal size in many high grade marbles, permitting the intracrystalline self-diffusion rate of oxygen in diopside to be empirically evaluated. Small (75--300 {micro}m) and large (1.2--1.5 mm) diopside grains were analyzed in bulk for their oxygen isotope ratios by laser extraction. Cooling histories were calculated using the Fast Grain Boundary diffusion model, assuming equilibrium at peak metamorphic temperatures (700--800 C), slow cooling of 1.5--4 C/Ma, and experimentally determined diffusion coefficients for oxygen in minerals. Measurements and calculations to predict differences in {delta}{sup 18}O between large and small diopside grains lead to the following conclusions. (1) Natural diopsides in this study exhibit variations in oxygen isotope ratios between grains of different size, which are related to the peak temperature, cooling rate, and water fugacity during cooling. Diffusion distances are properly modeled by the size of an entire grain; there is no evidence for subdomains. (2) In slowly cooled high grade metamorphic terrains, water fugacity can be highly variable from rock to rock during cooling. For many rocks, water fugacity is the most important constraint on the degree of oxygen isotope retrograde exchange.

  7. The isotopic homogeneity in the early solar system: Revisiting the CAI oxygen isotopic anomaly

    NASA Astrophysics Data System (ADS)

    Ozima, M.; Yamada, A.

    2009-12-01

    Since the first discovery of the mass-independently fractionated oxygen isotopes in anhydrous, high temperature Ca-Al rich inclusion minerals in carbonaceous meteorites (CAIs) by Clayton et al. (1), their common occurrence in primitive meteorites has generally been regarded to reflect some fundamental process prevalent in the early solar nebula. The CAI oxygen isotopic composition is uniquely characterized by (i) large mass independent isotopic fractionation and (ii) their isotopic data in an oxygen three isotope plot (δ17O - δ18O (δ17O ≡ {(17O/16O)/(17O/16O)SMOW - 1} × 1000) yield nearly a straight line with a slope 1.0. In establishing these characteristics, ion microprobe analyses has played a central role, especially an isotopic mapping technique (isotopography) was crucial (e.g., 2). The extraordinary oxygen isotopic ratio in CAIs is widely attributed to the self-shielding absorption of UV radiation in CO, one of the dominant chemical compounds in the early solar nebula (3). However, the self-shielding scenario necessarily leads to the unusual prediction that a mean solar oxygen isotopic composition differs from most of planetary bodies including Earth, Moon, and Mars. If the self-shielding process were indeed responsible to the CAI oxygen isotopic anomaly, this would require a fundamental revision of the current theory of the origin of the solar system, which generally assumes the initial total vaporization of nebula material to give rise to isotopic homogenization. The GENESIS mission launched in 2001(4), which collected oxygen in the solar wind was hoped to resolve the isotopic composition of the Sun. However, because of difficulties in correcting for instrumental and more importantly for intrinsic isotopic fractionation between the SW and the Sun, a final answer is yet to be seen (5). Here, we show on the basis of the oxygen isotopic fractionation systematics that the self shielding hypothesis cannot explain the key characteristics of the CAI oxygen

  8. Leaf water oxygen isotope measurement by direct equilibration.

    PubMed

    Song, Xin; Barbour, Margaret M

    2016-08-01

    The oxygen isotope composition of leaf water imparts a signal to a range of molecules in the atmosphere and biosphere, but has been notoriously difficult to measure in studies requiring a large number of samples as a consequence of the labour-intensive extraction step. We tested a method of direct equilibration of water in fresh leaf samples with CO2 , and subsequent oxygen isotope analysis on an optical spectrometer. The oxygen isotope composition of leaf water measured by the direct equilibration technique was strongly linearly related to that of cryogenically extracted leaf water in paired samples for a wide range of species with differing anatomy, with an R(2) of 0.95. The somewhat more enriched values produced by the direct equilibration method may reflect lack of full equilibration with unenriched water in the vascular bundles, but the strong relationship across a wide range of species suggests that this difference can be adequately corrected for using a simple linear relationship.

  9. Oxygen and carbon isotopic growth record in a reef coral from the florida keys and a deep-sea coral from blake plateau

    USGS Publications Warehouse

    Emiliani, C.; Harold, Hudson J.; Shinn, E.A.; George, R.Y.

    1978-01-01

    Carbon and oxygen isotope analysis through a 30-year (1944 to 1974) growth of Montastrea annularis from Hen and Chickens Reef (Florida Keys) shows a strong yearly variation in the abundances of both carbon-13 and oxygen-18 and a broad inverse relationship between the two isotopes. Normal annual dense bands are formed during the summer and are characterized by heavy carbon and light oxygen. "Stress bands" are formed during particularly severe winters and are characterized by heavy carbon and heavy oxygen. The isotopic effect of Zooxanthellae metabolism dominates the temperature effect on the oxygen-18/oxygen-16 ratio. The isotopic results on the deep-sea solitary coral Bathypsammia tintinnabulum, where Zooxanthellae are nonexistent, indicates that the abundance of the heavy isotopes carbon-13 and oxygen-18 is inversely related to the growth rate, with both carbon and oxygen approaching equilibrium values with increasing skeletal age.

  10. Oxygen isotope fractionation in divalent metal carbonates

    USGS Publications Warehouse

    O'Neil, J.R.; Clayton, R.N.; Mayeda, T.K.

    1969-01-01

    Equilibrium fractionation factors for the distribution of 18O between alkaline-earth carbonates and water have been measured over the temperature range 0-500??C. The fractionation factors ?? can be represented by the equations CaCO3-H2O, 1000 ln??=2.78(106 T-2)-3.39, SrCO3-H 2O, 1000 ln??=2.69(106 T-2)-3.74, BaCO3-H2O, 1000 ln??=2.57(106 T -2)-4.73. Measurements on MnCO3, CdCO3, and PbCO3 were made at isolated temperatures. A statistical-mechanical calculation of the isotopic partition function ratios gives reasonably good agreement with experiment. Both cationic size and mass are important in isotopic fractionation, the former predominantly in its effect on the internal vibrations of the anion, the latter in its effect on the lattice vibrations.

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

    SciTech Connect

    Guy, R.D. ); Fogel, M.L.; Berry, J.A. )

    1993-01-01

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

  12. Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

    USGS Publications Warehouse

    Johnson, C.A.; Emsbo, P.; Poole, F.G.; Rye, R.O.

    2009-01-01

    Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a ??34S versus ??18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The ??34S versus ??18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

  13. Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

    NASA Astrophysics Data System (ADS)

    Johnson, Craig A.; Emsbo, Poul; Poole, Forrest G.; Rye, Robert O.

    2009-01-01

    Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a δ 34S versus δ 18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The δ 34S versus δ 18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H 2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

  14. Intramolecular oxygen isotope ratios of a global stem cellulose sample set: insight into a climate proxy.

    NASA Astrophysics Data System (ADS)

    Sternberg, L.; Pinzon, M. C.; Vendramini, P.; Anderson, W.; Jahren, H.; Beuning, K.

    2006-12-01

    Oxygen isotope ratios of cellulose have been used to interpret current and paleo-climate. However, our knowledge of biochemical processes leading to cellulose oxygen isotope ratios is limited. We have previously developed a technique to determine the oxygen isotope ratio of the oxygen attached to the second carbon separate from the average oxygen isotope ratio of the oxygen attached to carbon 3, 4, 5 and 6 of the cellulose glucose moieties. Cellulose, representing the average δ18O value of oxygen attached to carbon 2, 3, 4, 5 and 6, is hydrolyzed to glucose, followed by the synthesis of phenylglucosazone, which represents the average δ18O value of oxygen attached to carbon 3, 4, 5 and 6. With the δ18O values of cellulose and phenyglucosazone it is possible to calculate the δ18O value of oxygen attached to the second carbon of the cellulose glucose moieties. We use this technique to elucidate biochemical processes causing oxygen isotopic fractionation during cellulose synthesis. We show here with stem samples from several areas of the world that the changes in the δ18O value of cellulose is non linear relative to those of stem water and this lack of linearity is in part caused by changes in the biochemical fractionation during cellulose synthesis. The biochemical cause of this non-linearity is confirmed by a compilation of previously published oxygen isotope ratios of aquatic plant cellulose in relation to that of lake water showing a curvilinear relationship parallel to the δ18O value of stem cellulose vs stem water in terrestrial plants. This non linearity is, in part, caused by the large variation in the δ18O value of the oxygen attached to the second carbon which super-imposes isotopic noise on the stem cellulose isotopic signals. This conclusion is supported by examining the three best fit multiple linear regression equations between oxygen isotope ratios of stem water and relative humidity as independent factors with either δ18O values of (1) cellulose

  15. Calcium and Oxygen Isotopic Composition of Calcium Carbonates

    NASA Astrophysics Data System (ADS)

    Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

    2016-04-01

    Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h-1 m-2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in 40

  16. Calcium and Oxygen Isotopic Composition of Calcium Carbonates

    NASA Astrophysics Data System (ADS)

    Niedermayr, Andrea; Eisenhauer, Anton; Böhm, Florian; Kisakürek, Basak; Balzer, Isabelle; Immenhauser, Adrian; Jürgen Köhler, Stephan; Dietzel, Martin

    2016-04-01

    Different isotopic systems are influenced in multiple ways corresponding to the crystal structure, dehydration, deprotonation, adsorption, desorption, isotope exchange and diffusion processes. In this study we investigated the structural and kinetic effects on fractionation of stable Ca- and O-isotopes during CaCO3 precipitation. Calcite, aragonite and vaterite were precipitated using the CO2 diffusion technique[1]at a constant pH of 8.3, but various temperatures (6, 10, 25 and 40° C) and precipitation rates R (101.5 to 105 μmol h‑1 m‑2). The calcium isotopic fractionation between solution and vaterite is lower (Δ44/40Ca= -0.10 to -0.55 ‰) compared to calcite (-0.69 to -2.04 ‰) and aragonite (-0.91 to -1.55 ‰). In contrast the fractionation of oxygen isotopes is highest for vaterite (32.1 ‰), followed by aragonite (29.2 ‰) and calcite (27.6 ‰) at 25° C and equilibrium. The enrichment of 18O vs. 16O in all polymorphs decreases with increasing precipitation rate by around -0.7 ‰ per log(R). The calcium isotopic fractionation between calcite/ vaterite and aqueous Ca2+ increases with increasing precipitation rate by ˜0.45 ‰ per log(R) and ˜0.1 ‰ per log(R) at 25° C and 40° C, respectively. In contrast the fractionation of Ca-isotopes between aragonite and aqueous Ca2+ decreases with increasing precipitation rates. The large enrichment of 18O vs. 16O isotopes in carbonates is related to the strong bond of oxygen to the small and highly charged C4+-ion. In contrast equilibrium isotopic fractionation between solution and calcite or vaterite is nearly zero as the Ca-O bond length is similar for calcite, vaterite and the hydrated Ca. Aragonite incorporates preferentially the lighter 40Ca isotope as it has very large Ca-O bonds in comparison to the hydrated Ca. At the crystal surface the lighter 40Ca isotopes are preferentially incorporated as dehydration and diffusion of lighter isotopes are faster. Consequently, the surface becomes enriched in

  17. Oxygen isotopic composition and U-Pb discordance in zircon

    USGS Publications Warehouse

    Booth, A.L.; Kolodny, Y.; Chamberlain, C.P.; McWilliams, M.; Schmitt, A.K.; Wooden, J.

    2005-01-01

    We have investigated U-Pb discordance and oxygen isotopic composition of zircon using high-spatial resolution ??18O measurement by ion microprobe. ??18O in both concordant and discordant zircon grains provides an indication of the relationship between fluid interaction and discordance. Our results suggest that three characteristics of zircon are interrelated: (1) U-Pb systematics and concomitant age discordance, (2) ??18O and the water-rock interactions implied therein, and (3) zircon texture, as revealed by cathodoluminescence and BSE imaging. A key observation is that U-Pb-disturbed zircons are often also variably depleted in 18O, but the relationship between discordance and ??18O is not systematic. ??18O values of discordant zircons are generally lighter but irregular in their distribution. Textural differences between zircon grains can be correlated with both U-Pb discordance and ??18O. Discordant grains exhibit either a recrystallized, fractured, or strongly zoned CL texture, and are characteristic of 18O depletion. We interpret this to be a result of metamictization, leading to destruction of the zircon lattice and an increased susceptibility to lead loss. Conversely, grains that are concordant have less-expressed zoning and a smoother CL texture and are enriched in 18O. From this it is apparent that various stages of water-rock interaction, as evidenced by systematic variations in ??18O, leave their imprint on both the texture and U-Pb systematics of zircon. Copyright ?? 2005 Elsevier Ltd.

  18. Extreme crustal oxygen isotope signatures preserved in coesite in diamond.

    PubMed

    Schulze, Daniel J; Harte, Ben; Valley, John W; Brenan, James M; Channer, Dominic M De R

    2003-05-01

    The anomalously high and low oxygen isotope values observed in eclogite xenoliths from the upper mantle beneath cratons have been interpreted as indicating that the parent rock of the eclogites experienced alteration on the ancient sea floor. Recognition of this genetic lineage has provided the foundation for a model of the evolution of the continents whereby imbricated slabs of oceanic lithosphere underpin and promote stabilization of early cratons. Early crustal growth is thought to have been enhanced by the addition of slab-derived magmas, leaving an eclogite residuum in the upper mantle beneath the cratons. But the oxygen isotope anomalies observed in eclogite xenoliths are small relative to those in altered ocean-floor basalt and intermediate-stage subduction-zone eclogites, and this has hindered acceptance of the hypothesis that the eclogite xenoliths represent subducted and metamorphosed ocean-floor basalts. We present here the oxygen isotope composition of eclogitic mineral inclusions, analysed in situ in diamonds using an ion microprobe/secondary ion mass spectrometer. The oxygen isotope values of coesite (a polymorph of SiO2) inclusions are substantially higher than previously reported for xenoliths from the subcratonic mantle, but are typical of subduction-zone meta-basalts, and accordingly provide strong support for the link between altered ocean-floor basalts and mantle eclogite xenoliths. PMID:12721625

  19. Rapid biologically mediated oxygen isotope exchange between water and phosphate

    NASA Astrophysics Data System (ADS)

    Paytan, Adina; Kolodny, Yehoshua; Neori, Amir; Luz, Boaz

    2002-03-01

    In order to better constrain the rate of oxygen isotope exchange between water and phosphate via biochemical reactions a set of controlled experiments were conducted in 1988 at the Aquaculture Plant in Elat, Israel. Different species of algae and other organisms were grown in seawater tanks under controlled conditions, and the water temperature and oxygen isotopic composition (δ18Ow) were monitored. The oxygen isotopic composition of phosphate (δ18Op) in the organisms' food source, tissues, and the δ18Op of dissolved inorganic phosphate (DIP) were measured at different stages of the experiments. Results indicate that intracellular oxygen isotope exchange between phosphorus compounds and water is very rapid and occurs at all levels of the food chain. Through these reactions the soft tissue δ18Op values become 23-26‰ higher than δ18Ow, and δ18Op values of DIP become ~20‰ higher than δ18Ow. No correlation between δ18Op values and either temperature or P concentrations in these experiments was observed. Our data imply that biogenic recycling and intracellular phosphorus turnover, which involves kinetic fractionation effects, are the major parameters controlling the δ18Op values of P compounds dissolved in aquatic systems. This information is fundamental to any application of δ18Op of dissolved organic or inorganic phosphate to quantify the dynamics of phosphorus cycling in aquatic systems.

  20. Oxygen Isotopes and Origin of Opal in an Antarctic Ureilite

    NASA Astrophysics Data System (ADS)

    Downes, H.; Beard, A. D.; Franchi, I. A.; Greenwood, R. C.

    2016-08-01

    Fragments of opal (SiO2.nH2O) in several internal chips of a single Antarctic polymict ureilite meteorite Elephant Moraine (EET) 83309 have been studied by NanoSIMS to determine their oxygen isotope compositions and hence constrain their origin.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Oxygen isotopes and the moon-forming giant impact.

    PubMed

    Wiechert, U; Halliday, A N; Lee, D C; Snyder, G A; Taylor, L A; Rumble, D

    2001-10-12

    We have determined the abundances of 16O, 17O, and 18O in 31 lunar samples from Apollo missions 11, 12, 15, 16, and 17 using a high-precision laser fluorination technique. All oxygen isotope compositions plot within +/-0.016 per mil (2 standard deviations) on a single mass-dependent fractionation line that is identical to the terrestrial fractionation line within uncertainties. This observation is consistent with the Giant Impact model, provided that the proto-Earth and the smaller impactor planet (named Theia) formed from an identical mix of components. The similarity between the proto-Earth and Theia is consistent with formation at about the same heliocentric distance. The three oxygen isotopes (delta17O) provide no evidence that isotopic heterogeneity on the Moon was created by lunar impacts.

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

    PubMed

    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. PMID:26747521

  5. Oxygen Isotopes in Bivalve Shells record Hydrological Changes in the Siberian Land-Shelf Connection on Annual Timescales

    NASA Astrophysics Data System (ADS)

    Mueller-Lupp, T.; Bauch, H. A.; Erlenkeuser, H.

    2003-04-01

    It is now widely accepted that changes in surface ocean hydrology at northern high latitudes is a major forcing mechanism that can strongly perturbate a particular climate mode. Given the variability on subdecadal and on centennial to millennial timescales, the dispersal and fate of arctic riverine water discharge and its role on the ice regime as well as on surface water properties are central issues in the understanding of Holocene climate change in the arctic marginal seas, the Arctic Ocean, and beyond. Oxygen isotope profiles from living and fossil bivalves were investigated in order to trace modern and past hydrographical changes in the strongly coupled land-shelf system of the Laptev Sea. Detailed oxygen isotope measurements were executed on the shells along their axis of maximum growth and provide an isotopic record of hydrological and environmental changes for the lifespan of the individual bivalves. The oxygen isotopic records exhibit amplitude cycles interpreted as recording annual cycles. Based on the well-known relationship between the oxygen isotope ratio in the bivalves carbonate, the temperature and the isotopic composition of water, it is possible to relate phases of more negative (lighter) oxygen isotope values indicating summer and more positive (heavier) oxygen isotope values indicating the winter season. The main forcing factor of the oxygen isotope variations is the variability of the isotopic composition of the bottom water. Measurements of the oxygen isotope ratio in surface and bottom waters of the Laptev Sea show a linear relation of salinity and oxygen isotope ratio of the water with a coefficient of 0.50 per mill per salinity unit and document the mixing of freshwater and seawater. The oxygen isotope cycles from growing profiles of the living bivalves indicate a correspondence to seasonal hydrographic changes and can be compared with runoff data and circulation patterns in the Laptev Sea. Given the seasonal cycles in living bivalves

  6. Photosynthetic Fractionation of the Stable Isotopes of Oxygen and Carbon.

    PubMed Central

    Guy, R. D.; Fogel, M. L.; Berry, J. A.

    1993-01-01

    Isotope discrimination during photosynthetic exchange of O2 and CO2 was measured using enzyme, thylakoid, and whole cell preparations. Evolved oxygen from isolated spinach thylakoids was isotopically identical (within analytical error) to its source water. Similar results were obtained with Anacystis nidulans Richter and Phaeodactylum tricornutum Bohlin cultures purged with helium. For consumptive reactions, discrimination ([delta], where 1 + [delta]/1000 equals the isotope effect, k16/k18 or k12/k13) was determined by analysis of residual substrate (O2 or CO2). The [delta] for the Mehler reaction, mediated by ferredoxin or methylviologen, was 15.3[per mille (thousand) sign]. Oxygen isotope discrimination during oxygenation of ribulose-1,5-bisphosphate (RuBP) catalyzed by RuBP carboxylase/oxygenase (Rubisco) was 21.3[per mille (thousand) sign] and independent of enzyme source, unlike carbon isotope discrimination: 30.3[per mille (thousand) sign] for spinach enzyme and 19.6 to 23[per mille (thousand) sign] for Rhodospirillum rubrum and A. nidulans enzymes, depending on reaction conditions. The [delta] for O2 consumption catalyzed by glycolate oxidase was 22.7[per mille (thousand) sign]. The expected overall [delta] for photorespiration is about 21.7[per mille (thousand) sign]. Consistent with this, when Asparagus sprengeri Regel mesophyll cells approached the compensation point within a sealed vessel, the [delta]18O of dissolved O2 came to a steady-state value of about 21.5[per mille (thousand) sign] relative to the source water. The results provide improved estimates of discrimination factors in several reactions prominent in the global O cycle and indicate that photorespiration plays a significant part in determining the isotopic composition of atmospheric oxygen. PMID:12231663

  7. Isotope Variations in Terrestrial Carbonates and Thermal Springs as Biomarkers: Analogs for Martian Processes

    NASA Technical Reports Server (NTRS)

    Socki, Richard A.; Gibson, Everett K., Jr.; Bissada, K. K.

    2006-01-01

    Stable isotope measurements of carbonate minerals contained within ALH84001 [1] suggest that fluids were present at 3.9 Gy on Mars [2, 3, 4, 5]. Both oxygen and carbon isotopes provide independent means of deciphering paleoenvironmental conditions at the time of carbonate mineral precipitation. In terrestrial carbonate rocks oxygen isotopes not only indicate the paleotemperature of the precipitating fluid, but also provide clues to environmental conditions that affected the fluid chemistry. Carbon isotopes, on the other hand, can indicate the presence or absence of organic compounds during precipitation (i.e. biogenically vs. thermogenically-generated methane), thus serving as a potential biomarker. We have undertaken a study of micro scale stable isotope variations measured in some terrestrial carbonates and the influence of organic compounds associated with the formation of these carbonates. Preliminary results indicate that isotope variations occur within narrow and discrete intervals, providing clues to paleoenvironmental conditions that include both biological and non-biological activity. These results carry implications for deciphering Martian isotope data and therefore potential biological prospecting on the planet Mars. Recently, Fourier Transform Spectrometer observations have detected methane occurring in the Martian atmosphere [6] that could be attributed to a possible biogenic source. Indeed, Mars Express has detected the presence of methane in the Martian atmosphere [7], with evidence indicating that methane abundances are greatest above those basins with high water concentrations.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  9. Oxygen Isotope Constraints on the Origin of Georgia Tektites

    NASA Astrophysics Data System (ADS)

    Albin, E. F.

    1997-07-01

    Georgia tektites ("georgiaites") are North American tektites that occur in east-central Georgia. In this investigation small chips of tektite material was separated from 24 individual specimens for oxygen isotope analysis. Results have an analytical precision of 0.2% based on duplicate analysis of a NIST silicate standard (NBS-28) and tektites. Oxygen isotope ratios (i.e., delta (18) O - SMOW) range from + 6.9 to + 10.7 parts per mil. The mean delta (18) O for Georgia tektites is + 9.1 parts per mil. These results are consistent with a delta (18) O value reported previously on a single georgiaite [1]. It appears that the tektites have oxygen isotope ratios similar to igneous and/or metamorphic rocks. Blum and Chamberlain [2] argue that since sea water has a relatively low delta (18) O value, its addition to isotopically heavier sedimentary rocks could account for the relatively low oxygen isotope ratios determined for the tektites. Such a model would require vaporization of the target material in order to exchange oxygen between the water and silicates. However, vaporization is not a popular theory of tektite petrogenesis, and since tektites contain very little water, it is difficult to reconcile the low delta (18) O values due to mixing with sea water. An alternative explanation may be that the low delta (18) O values are derived from a crystalline basement or it may be that the sedimentary target rocks at the proposed source crater (i.e., Chesapeake Bay crater) have delta (18) O values similar to that of the tektites. To resolve the issue, it will be necessary to melt samples of the proposed target material and make delta (18) O measurements on the resulting glass and then compare the results to the tektites. References: [1] Taylor, H.P. and Epstein, S. (1969) J. Geophys. Res., 74, 6834-6844. [2] Blum J.D. and Chamberlain C.D. (1992) Science, 257, 1104-1107.

  10. Seasonal variability of soil phosphate stable oxygen isotopes in rainfall manipulation experiments

    NASA Astrophysics Data System (ADS)

    Angert, Alon; Weiner, Tal; Mazeh, Shunit; Tamburini, Federica; Frossard, Emmanuel; Bernasconi, Stefano M.; Sternberg, Marcelo

    2011-08-01

    Phosphorus (P) availability limits productivity in many ecosystems worldwide. As a result, improved understanding of P cycling through soil and plants is much desirable. The use of the oxygen isotopes associated to phosphate can be used to study the cycle of P in terrestrial systems. However, changes with time in the oxygen isotopes associated to available P have not yet been evaluated under field conditions. Here we present the variations in available-P oxygen isotopes, based on resin extractions, in a semi-arid site that included plots in which the amount of rainfall reaching the soil was modified. In addition, the oxygen isotopes in the less dynamic fraction which is extractable by HCl, were also measured. The δ 18O of the HCl-extractable phosphate shows no seasonal pattern and corresponds to the average value of the available phosphate of 16.5‰. This value is in the expected range for equilibration with soil water at the prevailing temperatures in the site. The δ 18O values of resin-extractable P showed a range of 14.5-19.1‰ (SMOW), and evidence of seasonal variability, as well as variability induced by rainfall manipulation experiments. We present a framework for analyzing the isotopic ratios in soil phosphate and explain the variability as mainly driven by phosphate equilibration with soil water, and by the isotopic effects associated with extracellular mineralization. Additional isotopic effects result from fractionation in uptake, and the input to the soil of phosphate equilibrated in leaves. These results suggest that the δ 18O of resin-extractable P is an interesting marker for the rate of biological P transformations in soil systems.

  11. The Divnoe meteorite: Petrology, chemistry, oxygen isotopes and origin

    NASA Technical Reports Server (NTRS)

    Petaev, M. I.; Barsukova, L. D.; Lipschultz, M. E.; Wang, M.-S.; Ariskin, A. A.; Clayton, R. N.; Mayeda, T. K.

    1994-01-01

    The Divnoe meteorite is an olivine-rich primitive achondrite with subchondritic chemistry and mineralogy. It has a granoblastic, coarse-grained, olivine groundmass (CGL: coarse-grained lithology) with relatively large pyroxene-plagioclase poiklitic patches (PP) and small fine-grained domains of an opaque-rich lithology (ORL). Both PP and ORL are inhomogeneously distributed and display reaction boundaries with the groundmass. Major silicates, olivine Fa(20-28) and orthopyroxyene Fs(20-28 Wo(0.5-2.5), display systematic differences in composition between CGL and ORL as well as a complicated pattern of variations within CGL. Accessory plagioclase has low K content and displays regular igneous zoning with core compositions An(40-45) and rims An(32-37). The bulk chemical composition of Divnoe is similar to that of olivine-rich primitive achondrites, except for a depletion of incompatible elements and minor enrichment of refractory siderophiles. Oxygen isotope compositions for whole-rock and separated minerals from Divnoe fall in a narrow range, with mean delta O-18 = +4.91, delta O-17 = +2.24, and Delta O-17 = -0.26 +/- 0.11. The isotopic composition is not within the range of any previously recognized group but is very close to that of the brachinites. To understand the origin of Divnoe lithologies, partial melting and crystallization were modelled using starting compositions equal to that of Divnoe and some chondritic meteorites. It was found that the Divnoe composition could be derived from a chondritic source region by approximately 20 wt% partial melting at Ta approximately 1300 C and log(fO2) = IW-1.8, followed by approximtely 60 wt% crystallization of the partial melt formed, and removal of the still-liquid portion of the partial melt. Removal of the last partial melt resulted in depletion of the Divnoe plagioclase in Na and K. In this scenario, CGL represents the residue of partial melting, and PP is a portion of the partial melt that crystallized in situ. The

  12. Oxygen isotope fractionation in phosphates: the role of dissolved complex anions in isotope exchange.

    PubMed

    Zheng, Yong-Fei

    2016-01-01

    Oxygen isotope fractionation factors for phosphates were calculated by means of the increment method. The results suggest that Ag3PO4 and BiPO4 are enriched in (18)O relative to AgPO4, and the three phosphates are consistently depleted in (18)O relative to Ba3[PO4]2; fluorapatite and chlorapatite exhibit a similar behaviour of oxygen isotope fractionation with consistent enrichment of (18)O relative to hydroxyapatite. The valence, radii and coordination of metal cations play a quantitative role in dictating the (18)O/(16)O partitioning in these phosphates of different compositions. The calculated fractionation factors for the Ag3PO4-H2O system are in agreement with experimental determinations derived from enzyme-catalysed isotope exchange between dissolved inorganic phosphate and water at the longest reaction durations at low temperatures. This demonstrates that the precipitated Ag3PO4 has completely captured the oxygen isotope fractionation in the dissolved inorganic phosphate. The calculated fractionation factors for the F/Cl-apatite-water systems are in agreement with the enzyme-catalysed experimental fractionations for the dissolved phosphate-water system at the longest reaction durations but larger than fractionations derived from bacteria-facilitated exchange and inorganic precipitation experiments as well as natural observations. For the experimental calibrations of oxygen isotope fractionation involving the precipitation of dissolved phosphate species from aqueous solutions, the fractionation between precipitate and water is primarily dictated by the isotope equilibration between the dissolved complex anions and water prior to the precipitation. Therefore, the present results provide a quantitative means to interpret the temperature dependence of oxygen isotope fractionation in inorganic and biogenic phosphates.

  13. Evaluation of Speleothem Oxygen Isotope Fractionation from a Tropical Cave on the Island of Guam

    NASA Astrophysics Data System (ADS)

    Moore, M. W.; Hardt, B. F.; Banner, J. L.; Jenson, J. W.

    2013-12-01

    Recent studies in the tropics apply oxygen isotope variations in speleothems as proxies for changes in past hydroclimate, yet little work has been done to study the modern tropical cave environment. Oxygen isotope time series in speleothems are commonly used to interpret past climate based on the assumption of equilibrium fractionation. When re-constructing paleoclimate, there are limited tools available to assess potential non-equilibrium isotope effects. One approach is to test for agreement of oxygen isotope values between parallel-milled tracks from a stalagmite. A stalagmite collected from Jinapsan Cave on the island of Guam supports the argument for equilibrium as multiple overlapping transects along the growth axis show consistent replication. However, to fully evaluate the fractionation processes relating to calcite growth, we have also studied the relationship between modern drip water and modern speleothem calcite. To accomplish this, we collected monthly dripwater samples and deployed artificial substrates under active drips to measure calcite growth rates and to assess the state of isotopic equilibrium between speleothem calcite and drip water. We evaluate the processes controlling the δ18O values of calcite formed on substrates relative to values for the dripwater feeding the site of the speleothem in Jinapsan Cave. The studied drip site shows seasonal variability in dripwater δ18O of ~1‰, with more negative composition occurring during the wet season. The δ18O of the substrate calcite sampled at the point of first growth (analogous to the growth axis in a speleothem) also shows a seasonal cycle of about 1‰, yet the values are more positive than predicted by the equilibrium equation of Kim & O'Neil 1997. In addition, carbon and oxygen isotopic composition between substrates strongly covary. Correlation of carbon and oxygen isotopes between substrates at the point of first growth may be explained by prior calcite precipitation. Carbon isotope

  14. Oxygen Isotopic Analyses of Water Extracted from Lunar Samples

    NASA Astrophysics Data System (ADS)

    Nunn Martinez, M.; Thiemens, M. H.

    2014-12-01

    Oxygen exists in lunar materials in distinct phases having unique sources and equilibration histories. The oxygen isotopic composition (δ17O, δ18O) of various components of lunar materials has been studied extensively, but analyses of water in these samples are relatively sparse [1-3]. Samples collected on the lunar surface reflect not only the composition of their source reservoirs but also contributions from asteroidal and cometary impacts, interactions with solar wind and cosmic radiation, among other surface processes. Isotopic characterization of oxygen in lunar water could help resolve the major source of water in the Earth-Moon system by revealing if lunar water is primordial, asteroidal, or cometary in origin [1]. Methods: A lunar rock/soil sample is pumped to high vacuum to remove physisorbed water before heating step-wise to 50, 150, and 1000°C to extract extraterrestrial water without terrestrial contamination. The temperature at which water is evolved is proportional to the strength with which the water is bound in the sample and the relative difficulty of exchanging oxygen atoms in that water. This allows for the isolated extraction of water bound in different phases, which could have different source reservoirs and/or histories, as evidenced by the mass (in)dependence of oxygen compositions. A low blank procedure was developed to accommodate the low water content of lunar material [4]. Results: Oxygen isotopic analyses of lunar water extracted by stepwise heating lunar basalts and breccias with a range of compositions, petrologic types, and surface exposure ages will be presented. The cosmic ray exposure age of these samples varies by two orders of magnitude, and we will consider this in discussing the effects of solar wind and cosmic radiation on the oxygen isotopic composition (Δ17O). I will examine the implications of our water analyses for the composition of the oxygen-bearing reservoir from which that water formed, the effects of surface

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Silicon and oxygen isotopes in selected Allende inclusions

    NASA Technical Reports Server (NTRS)

    Becker, R. H.; Epstein, S.

    1982-01-01

    Silicon and oxygen data are presented for a number of Allende samples. It is found that based on oxygen and silicon isotopes, Allende samples EGG-1, EGG-6, BG1a, and 3529Yc are typical, unfractionated Allende inclusions. Where magnesium data are available, they indicate the same thing. EGG-3 is fractionated in both oxygen and silicon, as it is in magnesium. Sample D7 melilite is fractionated in oxygen by several per mil along the C2-matrix line, away from typical Allende melilites. Inclusion BG10a is a FUN inclusion with an inferred original oxygen isotopic fractionation of 8-9 per mille/amu relative to the Allende line. Silicon data for two density fractions of inclusion 3A with different mineralogies show a difference of about 2 per mille, which indicates that silicon, like oxygen, has been added to at least some mineral phases in Allende inclusions from a reservoir other than the one in which the inclusion first began to form.

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

    SciTech Connect

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

    2006-02-14

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

  18. Oxygen isotopes in the early protoplanetary disk inferred from pyroxene in a classical type B CAI

    NASA Astrophysics Data System (ADS)

    Aléon, Jérôme

    2016-04-01

    A major unanswered question in solar system formation is the origin of the oxygen isotopic dichotomy between the Sun and the planets. Individual Calcium-Aluminum-rich inclusions (CAIs) from CV chondrites exhibit almost the full isotopic range, but how their composition evolved is still unclear, which prevents robust astrochemical conclusions. A key issue is notably the yet unsolved origin of the 16O-rich isotopic composition of pyroxene in type B CAIs. Here, I report an in-situ oxygen isotope study of the archetypal type B CAI USNM-3529-Z from Allende with emphasis on the isotopic composition of pyroxene and its isotopic and petrographic relationships with other major minerals. The O isotopic composition of pyroxene is correlated with indicators of magmatic growth, indicating that the pyroxene evolved from a 16O-poor composition and became progressively enriched in 16O during its crystallization, contrary to the long held assumption that pyroxene was initially 16O-rich. This variation is well explained by isotopic exchange between a 16O-poor partial melt having the isotopic composition of melilite and a 16O-rich gas having the isotopic composition of spinel, during pyroxene crystallization. The isotopic evolution of 3529-Z is consistent with formation in an initially 16O-rich environment where spinel and gehlenitic melilite crystallized, followed by a 16O-depletion associated with melilite partial melting and recrystallization and finally a return to the initial 16O-rich environment before pyroxene crystallization. This strongly suggests that the environment of CAI formation was globally 16O-rich, with local 16O-depletions systematically associated with high temperature events. The Al/Mg isotopic systematics of 3529-Z further indicates that this suite of isotopic changes occurred in the first 150 000 yr of the solar system, during the main CAI formation period. A new astrophysical setting is proposed, where the 16O-depletion occurs in an optically thin surface

  19. Hydrogen and oxygen isotope ratios in human hair are related to geography.

    PubMed

    Ehleringer, James R; Bowen, Gabriel J; Chesson, Lesley A; West, Adam G; Podlesak, David W; Cerling, Thure E

    2008-02-26

    We develop and test a model to predict the geographic region-of-origin of humans based on the stable isotope composition of their scalp hair. This model incorporates exchangeable and nonexchangeable hydrogen and oxygen atoms in amino acids to predict the delta(2)H and delta(18)O values of scalp hair (primarily keratin). We evaluated model predictions with stable isotope analyses of human hair from 65 cities across the United States. The model, which predicts hair isotopic composition as a function of drinking water, bulk diet, and dietary protein isotope ratios, explains >85% of the observed variation and reproduces the observed slopes relating the isotopic composition of hair samples to that of local drinking water. Based on the geographical distributions of the isotope ratios of tap waters and the assumption of a "continental supermarket" dietary input, we constructed maps of the expected average H and O isotope ratios in human hair across the contiguous 48 states. Applications of this model and these observations are extensive and include detection of dietary information, reconstruction of historic movements of individuals, and provision of region-of-origin information for unidentified human remains. PMID:18299562

  20. Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

    PubMed

    Chew, Gina; Walczyk, Thomas

    2013-04-01

    Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

  1. Pristine extraterrestrial material with unprecedented nitrogen isotopic variation

    PubMed Central

    Briani, Giacomo; Gounelle, Matthieu; Marrocchi, Yves; Mostefaoui, Smail; Leroux, Hugues; Quirico, Eric; Meibom, Anders

    2009-01-01

    Pristine meteoritic materials carry light element isotopic fractionations that constrain physiochemical conditions during solar system formation. Here we report the discovery of a unique xenolith in the metal-rich chondrite Isheyevo. Its fine-grained, highly pristine mineralogy has similarity with interplanetary dust particles (IDPs), but the volume of the xenolith is more than 30,000 times that of a typical IDP. Furthermore, an extreme continuum of N isotopic variation is present in this xenolith: from very light N isotopic composition (δ15NAIR = −310 ± 20‰), similar to that inferred for the solar nebula, to the heaviest ratios measured in any solar system material (δ15NAIR = 4,900 ± 300‰). At the same time, its hydrogen and carbon isotopic compositions exhibit very little variation. This object poses serious challenges for existing models for the origin of light element isotopic anomalies. PMID:19528640

  2. Pristine extraterrestrial material with unprecedented nitrogen isotopic variation.

    PubMed

    Briani, Giacomo; Gounelle, Matthieu; Marrocchi, Yves; Mostefaoui, Smail; Leroux, Hugues; Quirico, Eric; Meibom, Anders

    2009-06-30

    Pristine meteoritic materials carry light element isotopic fractionations that constrain physiochemical conditions during solar system formation. Here we report the discovery of a unique xenolith in the metal-rich chondrite Isheyevo. Its fine-grained, highly pristine mineralogy has similarity with interplanetary dust particles (IDPs), but the volume of the xenolith is more than 30,000 times that of a typical IDP. Furthermore, an extreme continuum of N isotopic variation is present in this xenolith: from very light N isotopic composition (delta(15)N(AIR) = -310 +/- 20 per thousand), similar to that inferred for the solar nebula, to the heaviest ratios measured in any solar system material (delta(15)N(AIR) = 4,900 +/- 300 per thousand). At the same time, its hydrogen and carbon isotopic compositions exhibit very little variation. This object poses serious challenges for existing models for the origin of light element isotopic anomalies. PMID:19528640

  3. Carbon and Oxygen Isotopic Ratios for Nearby Miras

    NASA Astrophysics Data System (ADS)

    Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar

    2016-07-01

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

  4. Carbon and Oxygen Isotopic Ratios for Nearby Miras

    NASA Astrophysics Data System (ADS)

    Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar

    2016-07-01

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

  5. Oxygen isotope fractionation between analcime and water: An experimental study

    SciTech Connect

    Karlsson, H.R.; Clayton, R.N. )

    1990-05-01

    The fractionation of oxygen isotopes between natural analcime ({approximately}100 {mu}m) and water has been determined at 300, 350, and 400{degree}C at fluid pressures ranging from 1.5 to 5.0 kbar. Isotope ratios were obtained for the analcime framework, the channel water, and bulk water. Analcimes from Surtsey (145{degree}C), DSDP Hole 417A (30 to 55{degree}C), and Guam (25{degree}C) were used to constrain the fractionation factors below 300{degree}C. Analcime channel water exchanged completely with external water in all runs. Although some retrograde exchange may have occurred during quenching, the results indicate that the channel water is depleted in {sup 18}O relative to bulk water by a constant value of {approximately}5{per thousand}, nearly independent of temperature. Analcime is the first hydrated mineral found to have water of hydration depleted in {sup 18}O. Analcime framework oxygen exchanged 80, 90, and 96% at 300{degree}C for 412 h, 350{degree}C for 178 h, and 400{degree}C for 120 h, respectively. Equilibrium {Delta}{sup 18}O ({per thousand}) are as follows: 2.9 (400{degree}C), 4.5 (350{degree}C), and 5.8 (300{degree}C) for the experimental runs and 12.2 (145{degree}C) and 24.2 to 28.2 (30-55{degree}C) for the empirical data. The analcime-water fractionation curve is within experimental error of that of calcite-water. The exchange had little effect on grain morphology and does not involve recrystallization. This is the fastest exchange observed for a silicate. The rapid exchange rates indicate that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. Once calibrated, zeolites may be among the best low-temperature oxygen isotope geothermometers.

  6. Oxygen isotope constraints on the petrogenesis of Aleutian arc magmas

    SciTech Connect

    Singer, B.S.; O'Neil, J.R. ); Brophy, J.G. )

    1992-04-01

    The first measurement of {sup 18}O/{sup 16}O ratios of plagioclase, clinopyroxene, orthopyroxene, and titanomagnetite phenocrysts from modern Aleutian island-arc lavas provides new insight and independent constraints on magma sources and intracrustal processes. Basalts are heterogeneous on the scale of the entire arc and individual volcanic centers. Combined with Sr isotope and trace element data {delta}{sup 18}O{sub plag} values suggest a variable magma source characterized by differences in the mantle wedge or the subducted sediment component along the volcanic front. Seven tholeiitic basalt to rhyodacite lavas from the Seguam volcanic center have nearly identical {delta}{sup 18}O{sub plag} values of 6.0{per thousand} {plus minus} 0.2{per thousand}, reflecting extensive closed-system plagioclase-dominated crystal fractionation. Oxygen isotope thermometry and pyroxene and oxide equilibria indicate that differentiation occurred between 1,150 {plus minus} 100C (basalt) and 950 {plus minus} 100C (rhyodacite). In contrast, {delta}{sup 18}O{sub plag} values of 12 calc-alkalic basaltic andesites and andesites from the smaller Kanaga volcanic center span a broader range of 5.9{per thousand}-6.6{per thousand}, and consist of mostly higher values. Isotopic disequilibrium in the Kanaga system is manifest in two ways: two types of basaltic inclusions with contrasting {delta}{sup 18}O values occur in one andesite, and in two other andesites plagioclase-titanomagnetite and clinopyroxene-titanomagnetite oxygen isotope temperatures are inconsistent.

  7. Leaf water oxygen isotope measurement by direct equilibration.

    PubMed

    Song, Xin; Barbour, Margaret M

    2016-08-01

    The oxygen isotope composition of leaf water imparts a signal to a range of molecules in the atmosphere and biosphere, but has been notoriously difficult to measure in studies requiring a large number of samples as a consequence of the labour-intensive extraction step. We tested a method of direct equilibration of water in fresh leaf samples with CO2 , and subsequent oxygen isotope analysis on an optical spectrometer. The oxygen isotope composition of leaf water measured by the direct equilibration technique was strongly linearly related to that of cryogenically extracted leaf water in paired samples for a wide range of species with differing anatomy, with an R(2) of 0.95. The somewhat more enriched values produced by the direct equilibration method may reflect lack of full equilibration with unenriched water in the vascular bundles, but the strong relationship across a wide range of species suggests that this difference can be adequately corrected for using a simple linear relationship. PMID:27147584

  8. Oxygen isotope exchange in rocks and minerals from the Cerro Prieto geothermal system: Indicators of temperature distribution and fluid flow

    SciTech Connect

    Williams, A.E.; Elders, W.A.

    1981-01-01

    Oxygen isotopic compositions have been measured in drill cuttings and core samples from more than 40 wells ranging in depth to more than 3.5 km in the Cerro Prieto geothermal field. Profiles of isotopic ratios versus sampling depths provide information on the three-dimensional distribution of temperature and fluid flow. These parameters also indicate variations in the history of hydrothermal processes in different areas of the geothermal field.

  9. Cadmium isotope variations in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Xue, Zichen; Rehkämper, Mark; Horner, Tristan J.; Abouchami, Wafa; Middag, Rob; van de Flierd, Tina; de Baar, Hein J. W.

    2013-11-01

    Cadmium concentrations and isotope compositions were determined for 47 seawater samples from the high nutrient low chlorophyll (HNLC) zone of the Atlantic sector of the Southern Ocean. The samples include 13 surface waters from a transect of the Weddell Gyre and 3 depth profiles from the Weddell Sea and Drake Passage. The Southern Ocean mixed layer samples from this study and Abouchami et al. (2011) define a clear but broad ‘HNLC trend’ in a plot of εCd114/110 versus [Cd], which is primarily a consequence of isotopic fractionation associated with biological uptake (εCd114/110 is the deviation of the 114Cd/110Cd ratio of a sample from NIST SRM 3108 Cd in parts per 10,000). The trend is especially apparent in comparison to the large range of values shown by a global set of seawater Cd data for shallow depths. The Southern Ocean samples are also distinguished by their relatively high Cd concentrations (typically 0.2 to 0.6 nmol/kg) and moderately fractionated εCd114/110 (generally between +4 and +8) that reflect the limited biological productivity of this region. Detailed assessment reveals fine structure within the ‘HNLC trend’, which may record differences in the biological fractionation factor, different scenarios of closed and open system isotope fractionation, and/or distinct source water compositions. Southern Ocean seawater from depths ⩾1000 m has an average εCd114/110 of +2.5±0.2 (2se, n=16), and together with previous results this establishes a relatively constant εCd114/110 value of +3.0±0.3 (2se, n=27) for global deep waters. Significant isotopic variability was observed at intermediate depths in the Southern Ocean. Seawater from 200 m to 400 m in Weddell Sea has high Cd concentrations and εCd114/110 as low as +1, presumably due to remineralization of Cd from biomass that records incomplete nutrient utilization. Antarctic Intermediate Water, which was sampled at 150 to 750 m depth in the Drake Passage, features a distinct Cd isotope

  10. The triple oxygen isotope composition of leaf waters in Mpala, central Kenya

    NASA Astrophysics Data System (ADS)

    Li, S.; Levin, N.; Soderberg, K.; Dennis, K. J.; Caylor, K. K.

    2013-12-01

    evapotranspiration to explain the diurnal 17O-excess variation of the Acacia leaf waters. The results from this model indicate that 17O-excess of the leaf waters may be affected by variations in stomatal conductance, leaf water volume, and water residence time, in addition to variations in Rh. Our study emphasizes that the triple oxygen isotope composition of leaf waters is controlled both physically by Rh conditions but also by the physiological responses of a plant to its environment. The triple oxygen isotope composition of grass leaf water is a result of both evapotranspiration and mixing processes, and thus species effects should be considered in the discussion of λ(stem-leaf)-Rh relationships. A better understanding of the λ(stem-leaf)-Rh relationships could provide a framework for interpreting variations of triple oxygen isotopes of tree cellulose or fossil tissues as proxies for paleo-hydrological change.

  11. Hydrogen and Oxygen Isotope Ratios in Body Water and Hair: Modeling Isotope Dynamics in Nonhuman Primates

    PubMed Central

    O’Grady, Shannon P.; Valenzuela, Luciano O.; Remien, Christopher H.; Enright, Lindsey E.; Jorgensen, Matthew J.; Kaplan, Jay R.; Wagner, Janice D.; Cerling, Thure E.; Ehleringer, James R.

    2012-01-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water (2H/1H, 18O/16O expressed as δ2H and δ18O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ2H and δ18O values of body water and a second model to predict the δ2H and δ18O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ2H and δ18O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ2H and δ18O values of gut water and the 18O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (αow). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of αow was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. PMID:22553163

  12. Online Method for Oxygen Triple Isotope Analyses of Nitrate

    NASA Astrophysics Data System (ADS)

    Kaiser, J.; Hastings, M. G.; Houlton, B.; Roeckmann, T.; Sigman, D. M.

    2004-12-01

    Combined 17O/16O and 18O/16O isotope ratio analyses of nitrate in ground and surface waters help to understand the partitioning between atmospheric and terrestrial nitrate sources because only terrestrial nitrate shows mass-dependent relative enrichments in 17O and 18O, whereas atmospheric nitrate displays an anomalous enrichment in 17O. The 17O isotope anomaly of nitrate is therefore a sensitive tracer of fresh water pollution. Furthermore, isotope measurements of atmospheric nitrate in aerosols and precipitation provide insight into the partitioning between atmospheric NOx cycling pathways via ozone or hydroxy/peroxy radicals because only ozone has a significant non-mass dependent enrichment in 17O. Previous methods to analyze the oxygen triple isotope composition of nitrate rely on offline thermal decomposition of AgNO3 amounts in the µ mol range. We have recently developed an online (coupled gas chromatography-mass spectrometry) method that requires two to three orders of magnitude less material to achieve essentially the same analytical precision: 30 nmol of nitrate give a 1σ uncertainty of 1.0 ‰ for the δ ^{18}O value and 0.3 \\permil for the ^{17}O anomaly (\\Delta17O). The method uses a strain of bacterial denitrifiers to convert nitrate to N2O [Casciotti et al., 2002], which is then quantitatively converted to elemental nitrogen and oxygen in a gold furnace at 800° C. Both gases are separated on a molecular sieve capillary column and introduced into the isotope ratio mass spectrometer. There is no significant memory effect, but calibration via nitrate or N2O standards is required for scale normalization. This novel method was used to analyze nitrate isotopes in rain water and streams and, thanks to the low sample size requirements, will also be suitable for ice core samples, which have very low nitrate concentrations. A tight correlation between Δ 17O and δ 18O in rain water was found with a slope of about 0.3 (R2 = 0.86), which reflects the

  13. Fractionation of oxygen isotopes by root respiration: Implications for the isotopic composition of atmospheric O 2

    NASA Astrophysics Data System (ADS)

    Angert, Alon; Luz, Boaz

    2001-06-01

    The ratio of 18O/ 16O in atmospheric oxygen depends on the isotopic composition of the substrate water used in photosynthesis and on discrimination against 18O in respiratory consumption. The current understanding of the composition of air O 2 attributes the magnitude of the respiratory fractionation to biochemical mechanisms alone. Thus the discrimination against 18O is assumed as 18‰ in normal dark respiration and 25‰ to 30‰ in cyanide resistant respiration. Here we report new results on the fractionation of O 2 isotopes in root respiration. The isotopic fractionation was determined from the change in δ 18O of air due to partial uptake by roots in closed containers. The discrimination in these experiments was in the range of 11.9‰ to 20.0‰ with an average of 14.5‰. This average is significantly less than the known discrimination in dark respiration. A simple diffusion-respiration model was used to explain the isotopic discrimination in roots. Available data show that O 2 concentration inside roots is low due to slow diffusion. As a result, due to diffusion and biological uptake at the consumption site inside the root, the overall discrimination is small. Root respiration is an important component of the global oxygen uptake. Our new result that the discrimination against 18O is less than generally thought indicates that the mechanisms affecting δ 18O of atmospheric oxygen should be re-evaluated.

  14. Tunable Diode Laser Measurements of Leaf-scale Carbon Isotope Discrimination and Ecosystem Respired Carbon and Oxygen Isotope Ratios in a Semi-arid Woodland

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  15. Helium isotopic abundance variation in nature

    SciTech Connect

    Holden, N.E.

    1993-08-01

    The isotopic abundance of helium in nature has been reviewed. This atomic weight value is based on the value of helium in the atmosphere, which is invariant around the world and up to a distance of 100,000 feet. Helium does vary in natural gas, volcanic rocks and gases, ocean floor sediments, waters of various types and in radioactive minerals and ores due to {alpha} particle decay of radioactive nuclides.

  16. Constraining the oxygen isotope composition of early Cretaceous seawater

    NASA Astrophysics Data System (ADS)

    Price, Gregory; VanDeVelde, Justin; Passey, Ben; Grimes, Stephen

    2015-04-01

    The oxygen isotopic composition of well-preserved marine fossils fundamentally underpins our understanding of the evolution of the Earth's climate. However, a lack of constraint on the delta18O of seawater provides a major challenge. In this study new analyses of sub-Arctic and Boreal Cretaceous (Berriasian-late Valanginian, ca. 145-134 Ma) fossil molluscs (belemnites) have been undertaken using carbonate clumped isotopes, an approach based on the "clumping" of 13C and 18O in the carbonate mineral lattice into bonds with each other. From our analyses we infer Early Cretaceous marine temperatures ranging from 10 °C to 20 °C. We identify a cooler late Valanginian interval with temperatures consistent with regions a few degrees above freezing. Our combined temperature and delta18O belemnite data imply seawater delta18O values that have a remarkably modern profile in that they are similar to modern high-latitude seawater and much more positive than values typically assumed for Cretaceous seawater. These high oxygen isotope ratios suggest a hydrological cycle similar to the modern rather than a substantial increase towards a more vigorous hydrological cycle. Our results argue for generally warm but dynamic polar climates during Cretaceous greenhouse intervals that were punctuated by periods of ice growth.

  17. The bound coherent neutron scattering lengths of the oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Fischer, Henry E.; Simonson, J. Mike; Neuefeind, Jörg C.; Lemmel, Hartmut; Rauch, Helmut; Zeidler, Anita; Salmon, Philip S.

    2012-12-01

    The technique of neutron interferometry was used to measure the bound coherent neutron scattering length bcoh of the oxygen isotopes 17O and 18O. From the measured difference in optical path between two water samples, either H217O or H218O versus H2natO, where nat denotes the natural isotopic composition, we obtain bcoh,17O = 5.867(4) fm and bcoh,18O = 6.009(5) fm, based on the accurately known value of bcoh,natO = 5.805(4) fm which is equal to bcoh,16O within the experimental uncertainty. Our results for bcoh,17O and bcoh,18O differ appreciably from the standard tabulated values of 5.6(5) fm and 5.84(7) fm, respectively. In particular, our measured scattering-length contrast of 0.204(3) fm between 18O and natO is nearly a factor of 6 greater than the tabulated value, which renders feasible neutron diffraction experiments using 18O isotope substitution and thereby offers new possibilities for measuring the partial structure factors of oxygen-containing compounds, such as water.

  18. The bound coherent neutron scattering length of the oxygen isotopes

    SciTech Connect

    Fischer, Henry E; Simonson, J Michael {Mike}; Neuefeind, Joerg C; Lemmel, Hartmut; Rauch, Helmut; Zeidler, Anita; Salmon, Phil

    2012-01-01

    The technique of neutron interferometry was used to measure the bound coherent neutron scattering length bcoh of the oxygen isotopes 17O and 18O. From the measured difference in optical path between two water samples, either H2 17O or H2 18O versus H2 natO, where nat denotes the natural isotopic composition, we obtain bcoh , 17O = 5.867(4) fm and bcoh , 18O = 6.009(5) fm, based on the accurately known value of bcoh , natO = 5.805(4) fm which is equal to bcoh , 16O within the experimental uncertainty. Our results for bcoh , 17O and bcoh , 18O differ appreciably from the standard tabulated values of 5.6(5) fm and 5.84(7) fm, respectively. In particular, our measured scattering length contrast of 0.204(3) fm between 18O and natO is nearly a factor of 6 greater than the tabulated value, which renders feasible neutron diffraction experiments using 18O isotope substitution and thereby offers new possibilites for measuring the partial structure factors of oxygen-containing compounds, such as water.

  19. Uranium Stable Isotopes: A Proxy For Productivity Or Ocean Oxygenation?

    NASA Astrophysics Data System (ADS)

    Severmann, S.

    2015-12-01

    Uranium elemental abundances in sediments have traditionally been used to reconstruct primary productivity and carbon flux in the ocean. 238U/235U isotope compositions, in contrast, are currently understood to reflect the extent of bottom water anoxia in the ocean. A review of our current understanding of authigenic U enrichment mechanism into reducing sediments suggests that a revision of this interpretation is warranted. Specifically, the current interpretation of U isotope effects in suboxic vs. anoxic deposits has not taken into account the well-documented linear relationship with organic C burial rates. Although organic C rain rates (i.e., surface productivity) and bottom water oxygenation are clearly related, distinction between these two environmental controls is conceptually important as it relates to the mechanism of enhanced C burial and ultimately the strength of the biological pump. Here we will review new and existing data to test the hypothesis that the isotope composition of authigenic U in reducing sediments are best described by their relationship with parameters related to organic carbon delivery and burial, rather than bottom water oxygen concentration.

  20. Oxygen Isotope Fractionation During Evaporation of Mg- and Si-rich CMAS-Liquids in Vacuum

    NASA Astrophysics Data System (ADS)

    Mendybaev, R. A.; Richter, F. M.; Spicuzza, M. J.; Valley, J. W.; Davis, A. M.

    2010-03-01

    We report oxygen isotope data for the residues produced by evaporation of Mg- and Si-rich CMAS-liquids. The results on oxygen together with Mg- and Si-isotopes in the experimental run products are used to estimate the isotopic compositions of natural FUN CAIs.

  1. Isotopic variations in the rock-forming elements in meteorites

    NASA Technical Reports Server (NTRS)

    Clayton, R. N.; Hinton, R. W.; Davis, A. M.

    1988-01-01

    Variations in isotopic abundances of the major rock-forming elements can be used as tracers for chemical processes in the solar nebula, and may also provide links to the presolar cloud from which the solar nebula was derived. The paper reviews recent developments involving meteoritic abundances of the isotopes of O, Mg, Si, Ca, Ti, Cr, Fe, and Ni). Some of the effects observed are due to mass-dependent fractionation, and some are due to interaction of isotopically distinct reservoirs, reflecting incomplete homogenization of materials with different nucleosynthetic histories.

  2. Environmental and biomedical applications of natural metal stable isotope variations

    USGS Publications Warehouse

    Bullen, T.D.; Walczyk, T.

    2009-01-01

    etal stable isotopes are now being used to trace metal contaminants in the environment and as indicators of human systemic function where metals play a role. Stable isotope abundance variations provide information about metal sources and the processes affecting metals in complex natural systems, complementing information gained from surrogate tracers, such as metal abundance ratios or biochemical markers of metal metabolism. The science is still in its infancy, but the results of initial studies confirm that metal stable isotopes can provide a powerful tool for forensic and biomedical investigations.

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

    USGS Publications Warehouse

    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.

  4. Lightning and Mass Independent Oxygen Isotopic Fractionation in Nebular Silicates

    NASA Technical Reports Server (NTRS)

    Nuth, Joseph A.

    2009-01-01

    Lightning has long been postulated as the agent of Chondru|e formation in the solar nebula, but it may have an additional role to play as well. Lightning bolts of almost any scale will both vaporize dust and liberate oxygen atoms that will then interact with both nebular gases as well as the refractory silicate vapor as it re-condenses. Such processes should result in the addition of the heavy oxygen isotopes to the growing silicate grains while the light oxygen-16 becomes part of the gas phase water. This process will proceed to some extent throughout the history of any turbulent nebula and will result in the gradual increase of O-16 in the gas phase and in a much larger relative increase in the O-17 and O-18 content of the nebular dust. Laboratory experiments have demonstrated the production of such "heavy oxygen enriched", non-mass-dependently-fractionated dust grains in a high voltage discharge in a hydrogen rich gas containing small quantities of silane, pentacarbonyl iron and oxygen.

  5. Oxygenation of a Cryogenian ocean (Nanhua Basin, South China) revealed by pyrite Fe isotope compositions

    NASA Astrophysics Data System (ADS)

    Zhang, Feifei; Zhu, Xiangkun; Yan, Bin; Kendall, Brian; Peng, Xi; Li, Jin; Algeo, Thomas J.; Romaniello, Stephen

    2015-11-01

    The nature of ocean redox chemistry between the Cryogenian Sturtian and Marinoan glaciations (ca. 663-654 Ma) is important for understanding the relationship between environmental conditions and the subsequent emergence and expansion of early animals. The Cryogenian-to-Ediacaran stratigraphic succession of the Nanhua Basin in South China provides a nearly complete sedimentary record of the Cryogenian, including a continuous record of interglacial sedimentation. Here, we present a high-resolution pyrite Fe isotope record for a ∼120-m-long drill-core (ZK105) through Sturtian glacial diamictites and the overlying interglacial sediments in the Nanhua Basin to explore changes in marine chemistry during the late Cryogenian. Our pyrite Fe isotope profile exhibits significant stratigraphic variation: Interval I, comprising middle to upper Tiesi'ao diamictites (correlative with the Sturtian glaciation), is characterized by light, modern seawater-like Fe isotope compositions; Interval II, comprising uppermost Tiesi'ao diamictites and the basal organic-rich Datangpo Formation, is characterized by an abrupt shift to heavier Fe isotope compositions; and Interval III, comprising organic-poor grey shales in the middle Datangpo Formation, is characterized by the return of lighter, seawater-like Fe isotope compositions. We infer that Interval I pyrite was deposited in a predominantly anoxic glacial Nanhua Basin through reaction of dissolved Fe2+ and H2S mediated by microbial sulfate reduction (MSR). The shift to heavier pyrite Fe isotope values in Interval II is interpreted as partial oxidation of ferrous iron to ferric iron and subsequent near-quantitative reduction and transformation of Fe-oxyhydroxides to pyrite through coupling with oxidation of organic matter in the local diagenetic environment. In Interval III, near-quantitative oxidation of ferrous iron to Fe-oxyhydroxides followed by near-quantitative reduction and conversion to pyrite in the local diagenetic environment

  6. An orbital origin for large oxygen isotopic shifts and sea-level changes during the Oligocene

    NASA Astrophysics Data System (ADS)

    Pekar, S. F.; Christie-Blick, N.

    2004-12-01

    Recently, it was shown that a relatively rare orbital congruence involving low-amplitude variance in obliquity and a minimum in eccentricity coincides at the Miocene/Oligocene boundary with a large increase in oxygen isotopes (Mi1 event) and ice volume, suggesting a possible causal mechanism for such events at the million-year timescale. We tested this idea against the Oligocene oxygen isotopic and sea-level records and the astronomical timescale of Shackleton et al. (1999). As in the Miocene, large isotopic shifts (Oi events; δ 18O >0.5\\permil, with maximum values >2.7\\permil) and sea-level changes (30-70 m) occurred in the Oligocene at the million-year timescale. Smaller variations in sea level (and corresponding isotopic values) characterize obliquity (104 years) and eccentricity (105 years) timescales: 15-20 m and 20-30 m, respectively. Our analysis shows that, as with the Mi1 event, Oi events relate to the anticipated orbital congruence - resolving one of the outstanding conundrums of the late Paleogene paleoclimate. It also provides support for the robustness of the astronomical time scale of Shackleton et al. (1999) for the Oligocene Epoch.

  7. Hafnium isotope variations in oceanic basalts

    NASA Technical Reports Server (NTRS)

    Patchett, P. J.; Tatsumoto, M.

    1980-01-01

    Hafnium isotope ratios generated by the beta(-) decay of Lu-176 are investigated in volcanic rocks derived from the suboceanic mantle. Hf-176/Hf-177 and Lu/Hf ratios were determined to precisions of 0.01-0.04% and 0.5%, respectively, by routine, low-blank chemistry. The Hf-176/Hf-177 ratio is found to be positively correlated with the Nd-143/Nd-144 ratio and negatively correlated with the Sr-87/Sr-86 and Pb-206/Pb-204 ratios, and to increase southwards along the Iceland-Reykjanes ridge traverse. An approximate bulk earth Hf-176/Hf-177 ratio of 0.28295 is inferred from the bulk earth Nd-143/Nd-144 ratio, which requires a bulk earth Lu/Hf ratio of 0.25, similar to the Juvinas eucrite. Midocean ridge basalts are shown to account for 60% of the range of Hf isotope ratios, and it is suggested that Lu-Hf fractionation is decoupled from Sm-Nd and Rb-Sr fractionation in very trace-element-depleted source regions as a result of partial melting.

  8. Temperature and Oxygen Isotope Composition of The Ediacaran Ocean: Constraints From Clumped Isotope Carbonate Thermometry

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

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

    SciTech Connect

    Epstein, S.; Zeiri, L. )

    1988-03-01

    Oxygen-isotope fractionation associated with respiration in human individuals at rest is linearly related to the fraction of the O{sub 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{sub 2}/O{sub 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{sub 2} consumption in human respiration and how they are affected by related diseases.

  10. Neutron decay spectroscopy of neutron-rich oxygen isotopes

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

    Neutron decay spectroscopy of neutron-rich oxygen isotopes has been performed using the two-proton knock-out reaction 9Be( 26Ne, X) 24,23,22O. A combination of the knock-out of valence and core protons can explain the three observed spectra. These knock-out processes are selective and preferentially populate hole states. The observed narrow resonance state in 23O at an excitation energy of 2.8(1) MeV was assigned to the 5/2 state.

  11. Dentine oxygen isotopes (δ (18)O) as a proxy for odontocete distributions and movements.

    PubMed

    Matthews, Cory J D; Longstaffe, Fred J; Ferguson, Steven H

    2016-07-01

    Spatial variation in marine oxygen isotope ratios (δ (18)O) resulting from differential evaporation rates and precipitation inputs is potentially useful for characterizing marine mammal distributions and tracking movements across δ (18)O gradients. Dentine hydroxyapatite contains carbonate and phosphate that precipitate in oxygen isotopic equilibrium with body water, which in odontocetes closely tracks the isotopic composition of ambient water. To test whether dentine oxygen isotope composition reliably records that of ambient water and can therefore serve as a proxy for odontocete distribution and movement patterns, we measured δ (18)O values of dentine structural carbonate (δ (18) OSC) and phosphate (δ (18) OP) of seven odontocete species (n = 55 individuals) from regional marine water bodies spanning a surface water δ (18)O range of several per mil. Mean dentine δ (18) OSC (range +21.2 to +25.5‰ VSMOW) and δ (18) OP (+16.7 to +20.3‰) values were strongly correlated with marine surface water δ (18)O values, with lower dentine δ (18) OSC and δ (18) OP values in high-latitude regions (Arctic and Eastern North Pacific) and higher values in the Gulf of California, Gulf of Mexico, and Mediterranean Sea. Correlations between dentine δ (18) OSC and δ (18) OP values with marine surface water δ (18)O values indicate that sequential δ (18)O measurements along dentine, which grows incrementally and archives intra- and interannual isotopic composition over the lifetime of the animal, would be useful for characterizing residency within and movements among water bodies with strong δ (18)O gradients, particularly between polar and lower latitudes, or between oceans and marginal basins. PMID:27547302

  12. Oxygen isotope composition of evapotranspiration and its relation to C4 photosynthetic discrimination

    NASA Astrophysics Data System (ADS)

    Griffis, T. J.; Lee, X.; Baker, J. M.; Billmark, K.; Schultz, N.; Erickson, M.; Zhang, X.; Fassbinder, J.; Xiao, W.; Hu, N.

    2011-03-01

    The oxygen isotope of water (18O-H2O) and carbon dioxide (18O-CO2) is an important signal of global change and can provide constraints on the coupled carbon-water cycle. Here, simultaneous observations of 18O-H2O (liquid and vapor phases) and 18O-CO2 were used to investigate the relation between canopy leaf water 18O enrichment, 18O-CO2 photosynthetic discrimination (18Δ), isotope disequilibrium (Deq), and the biophysical factors that control their temporal variability in a C4 (Zea mays L.) ecosystem. Data and analyses are presented from a 74 day experiment conducted in Minnesota during summer 2009. Eddy covariance observations indicate that the oxygen isotope composition of C4 evapotranspiration (δE) ranged from about -20‰ (VSMOW scale) in the early morning to -5‰ after midday. These values were used to estimate the isotope composition at the sites of leaf water evaporation (δL,e) assuming non-steady-state conditions and revealed a strong diurnal pattern ranging from about -5‰ in the early morning to +10‰ after midday. With the addition of net ecosystem CO2 exchange measurements and carbonic anhydrase (CA) assays, we derived canopy-scale 18Δ. These estimates typically varied from 11.3 to 27.5‰ (VPDB scale) and were shown to vary significantly depending on the steady state or non-steady-state assumptions related to leaf water enrichment. We demonstrate that the impact of turbulence on kinetic fractionation and steady state assumptions result in larger estimates of 18Δ and Deq. Further, the results indicate that both leaf-scale and canopy-scale CO2 hydration efficiency may be substantially lower than that previously reported for laboratory conditions. These results may have important implications for interpreting variations in atmospheric 18O-CO2 and constraining regional carbon budgets based on the oxygen isotope tracer approach.

  13. Dentine oxygen isotopes (δ (18)O) as a proxy for odontocete distributions and movements.

    PubMed

    Matthews, Cory J D; Longstaffe, Fred J; Ferguson, Steven H

    2016-07-01

    Spatial variation in marine oxygen isotope ratios (δ (18)O) resulting from differential evaporation rates and precipitation inputs is potentially useful for characterizing marine mammal distributions and tracking movements across δ (18)O gradients. Dentine hydroxyapatite contains carbonate and phosphate that precipitate in oxygen isotopic equilibrium with body water, which in odontocetes closely tracks the isotopic composition of ambient water. To test whether dentine oxygen isotope composition reliably records that of ambient water and can therefore serve as a proxy for odontocete distribution and movement patterns, we measured δ (18)O values of dentine structural carbonate (δ (18) OSC) and phosphate (δ (18) OP) of seven odontocete species (n = 55 individuals) from regional marine water bodies spanning a surface water δ (18)O range of several per mil. Mean dentine δ (18) OSC (range +21.2 to +25.5‰ VSMOW) and δ (18) OP (+16.7 to +20.3‰) values were strongly correlated with marine surface water δ (18)O values, with lower dentine δ (18) OSC and δ (18) OP values in high-latitude regions (Arctic and Eastern North Pacific) and higher values in the Gulf of California, Gulf of Mexico, and Mediterranean Sea. Correlations between dentine δ (18) OSC and δ (18) OP values with marine surface water δ (18)O values indicate that sequential δ (18)O measurements along dentine, which grows incrementally and archives intra- and interannual isotopic composition over the lifetime of the animal, would be useful for characterizing residency within and movements among water bodies with strong δ (18)O gradients, particularly between polar and lower latitudes, or between oceans and marginal basins.

  14. Geochemistry and origin of formation waters in the western Canada sedimentary basin-I. Stable isotopes of hydrogen and oxygen

    USGS Publications Warehouse

    Hitchon, B.; Friedman, I.

    1969-01-01

    Stable isotopes of hydrogen and oxygen, together with chemical analyses, were determined for 20 surface waters, 8 shallow potable formation waters, and 79 formation waters from oil fields and gas fields. The observed isotope ratios can be explained by mixing of surface water and diagenetically modified sea water, accompanied by a process which enriches the heavy oxygen isotope. Mass balances for deuterium and total dissolved solids in the western Canada sedimentary basin demonstrate that the present distribution of deuterium in formation waters of the basin can be derived through mixing of the diagenetically modified sea water with not more than 2.9 times as much fresh water at the same latitude, and that the movement of fresh water through the basin has redistributed the dissolved solids of the modified sea water into the observed salinity variations. Statistical analysis of the isotope data indicates that although exchange of deuterium between water and hydrogen sulphide takes place within the basin, the effect is minimized because of an insignificant mass of hydrogen sulphide compared to the mass of formation water. Conversely, exchange of oxygen isotopes between water and carbonate minerals causes a major oxygen-18 enrichment of formation waters, depending on the relative masses of water and carbonate. Qualitative evidence confirms the isotopic fractionation of deuterium on passage of water through micropores in shales. ?? 1969.

  15. Syntheses with stable isotopes of carbon, nitrogen, and oxygen

    SciTech Connect

    Ott, D.G.

    1981-01-01

    Methods, techniques, ideas, information, and references to prepare compounds labeled with stable isotopes of carbon, nitrogen, and oxygen are presented, which can be used in selecting or devising synthetic schemes. By studying and comparing methods that other investigators have applied to problems in isotopic labeling, the task of deciding on suitable syntheses for incorporating isotopes into various other compounds can be considerably simplified. The major portion of the book is devoted to synthetic procedures that have been used for preparation of specific labeled compounds. The descriptions are often given in sufficient detail that they can be applied or modified without necessity for recourse to the original literature. Methods can be compared, feasibility for extensions to other isotope isomers or to related compounds can be assessed, and requirements for apparatus, materials, time, effort, and skills can be evaluated. Additional methods and speculations are presented for a number of other compounds whose syntheses are not given in detail. A few biosynthetic preparations, which afford specific products in good isotopic yield, are described; certain other applications of biological methods are considered briefly. Arrangement of the procedures into chapters according to functional groups is somewhat arbitrary; that is, not all preparations of carboxylic acids will be found in the chapter dealing with acids and derivatives; certain alcohols appear as components in multistep syntheses in the chapter on hydrocarbons; some compounds could just as well have been placed elsewhere; and so on. Thus it is important to use the index. Following the introductory chapter, the contents of this book are as follows: (1) acids, anhydrides, amids, esters, and nitriles; (2) aldehydes and ketones; (3) alcohols, ethers, and phenols; (4) amines, and hydrocarbons; (5) heterocyclic compounds; and (6) other compounds.

  16. Three-Body Forces and the Limit of Oxygen Isotopes

    SciTech Connect

    Otsuka, Takaharu; Suzuki, Toshio; Holt, Jason D.; Schwenk, Achim; Akaishi, Yoshinori

    2010-07-16

    The limit of neutron-rich nuclei, the neutron drip line, evolves regularly from light to medium-mass nuclei except for a striking anomaly in the oxygen isotopes. This anomaly is not reproduced in shell-model calculations derived from microscopic two-nucleon forces. Here, we present the first microscopic explanation of the oxygen anomaly based on three-nucleon forces that have been established in few-body systems. This leads to repulsive contributions to the interactions among excess neutrons that change the location of the neutron drip line from {sup 28}O to the experimentally observed {sup 24}O. Since the mechanism is robust and general, our findings impact the prediction of the most neutron-rich nuclei and the synthesis of heavy elements in neutron-rich environments.

  17. Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

    NASA Astrophysics Data System (ADS)

    Turchyn, Alexandra V.; Brüchert, Volker; Lyons, Timothy W.; Engel, Gregory S.; Balci, Nurgul; Schrag, Daniel P.; Brunner, Benjamin

    2010-04-01

    Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ 34S SO4 and δ 18O SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ 18O H2O and initial δ 18O SO4, all strains show 34S enrichment, whereas only six strains show significant 18O enrichment. The remaining six show no (or minimal) change in δ 18O SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO 32-), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.

  18. Inference of riverine nitrogen processing from longitudinal and diel variation in dual nitrate isotopes

    NASA Astrophysics Data System (ADS)

    Cohen, Matthew J.; Heffernan, James B.; Albertin, Andrea; Martin, Jonathan B.

    2012-03-01

    Longitudinal and diel measurements of dual isotope composition (δ15N and δ18O) in nitrate (NO3-N) were made in the Ichetucknee River, a large (˜8 m3 s-1), entirely spring-fed river in North Florida, to determine whether isotopic variation can deconvolve assimilatory and dissimilatory removal. Comparing nitrate concentrations and isotope composition during the day and night we predicted (1) daytime declines in total fractionation due to low assimilatory fractionation and (2) diurnal variation in dual isotope coupling between 1:1 (assimilation) and 2:1 (denitrification). Five daytime longitudinal transects comprising 10 sampling stations showed consistent NO3-N removal (25-35% of inputs) and modest fractionation (15ɛtotal between -2 and -6‰, enriching the residual nitrate pool). Lower fractionation (by ˜1‰) during two nighttime transects, suggests higher fractionation due to assimilation than denitrification. Total fractionation was significantly negatively associated with discharge, input [NO3-N], N mass removal, and fractional water loss. Despite well-constrained mass balance estimates that denitrification dominated total N removal, isotope coupling was consistently 1:1, both for longitudinal and diel sampling. Hourly samples on two dates at the downstream location showed significant diel variation in concentration ([NO3-N] amplitude = 60 to 90 μg N L-1) and isotope composition (δ15N amplitude = -0.7‰ to -1.6‰). Total fractionation differed between day and night only on one date but estimated assimilatory fractionation assuming constant denitrification was highly variable and implausibly large (for N, 15ɛ = -2 to -25‰), suggesting that fractionation and removal due to denitrification is not diurnally constant. Pronounced counterclockwise hysteresis in the relationship between [NO3-N] andδ15N suggests diel variation in N isotope dynamics. Together, low fractionation, isotope versus concentration hysteresis, and consistent 1:1 isotope coupling

  19. Observations of nitrogen and oxygen isotopes in the low energy cosmic rays. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Vidor, S. B.

    1975-01-01

    The isotopic composition of low-energy nitrogen and oxygen cosmic rays was measured with an electron/isotope spectrometer aboard the IMP-7 satellite to determine the possible source of the particles. Instrument calibration showed the standard range-energy tables to be inadequate to calculate the isotope response, and corrections were obtained. The low-energy nitrogen and oxygen cosmic rays were found to be primarily 14N and 16O. Upper limits were obtained for the abundances of the other stable nitrogen and oxygen isotopes. The nitrogen composition differs from higher energy measurements which indicate that 15N, which is thought to be secondary, is the dominant isotope.

  20. Origin of uranium isotope variations in early solar nebula condensates

    PubMed Central

    Tissot, François L. H.; Dauphas, Nicolas; Grossman, Lawrence

    2016-01-01

    High-temperature condensates found in meteorites display uranium isotopic variations (235U/238U), which complicate dating the solar system’s formation and whose origin remains mysterious. It is possible that these variations are due to the decay of the short-lived radionuclide 247Cm (t1/2 = 15.6 My) into 235U, but they could also be due to uranium kinetic isotopic fractionation during condensation. We report uranium isotope measurements of meteoritic refractory inclusions that reveal excesses of 235U reaching ~+6% relative to average solar system composition, which can only be due to the decay of 247Cm. This allows us to constrain the 247Cm/235U ratio at solar system formation to (1.1 ± 0.3) × 10−4. This value provides new clues on the universality of the nucleosynthetic r-process of rapid neutron capture. PMID:26973874

  1. Origin of uranium isotope variations in early solar nebula condensates.

    PubMed

    Tissot, François L H; Dauphas, Nicolas; Grossman, Lawrence

    2016-03-01

    High-temperature condensates found in meteorites display uranium isotopic variations ((235)U/(238)U), which complicate dating the solar system's formation and whose origin remains mysterious. It is possible that these variations are due to the decay of the short-lived radionuclide (247)Cm (t 1/2 = 15.6 My) into (235)U, but they could also be due to uranium kinetic isotopic fractionation during condensation. We report uranium isotope measurements of meteoritic refractory inclusions that reveal excesses of (235)U reaching ~+6% relative to average solar system composition, which can only be due to the decay of (247)Cm. This allows us to constrain the (247)Cm/(235)U ratio at solar system formation to (1.1 ± 0.3) × 10(-4). This value provides new clues on the universality of the nucleosynthetic r-process of rapid neutron capture.

  2. Origin of uranium isotope variations in early solar nebula condensates.

    PubMed

    Tissot, François L H; Dauphas, Nicolas; Grossman, Lawrence

    2016-03-01

    High-temperature condensates found in meteorites display uranium isotopic variations ((235)U/(238)U), which complicate dating the solar system's formation and whose origin remains mysterious. It is possible that these variations are due to the decay of the short-lived radionuclide (247)Cm (t 1/2 = 15.6 My) into (235)U, but they could also be due to uranium kinetic isotopic fractionation during condensation. We report uranium isotope measurements of meteoritic refractory inclusions that reveal excesses of (235)U reaching ~+6% relative to average solar system composition, which can only be due to the decay of (247)Cm. This allows us to constrain the (247)Cm/(235)U ratio at solar system formation to (1.1 ± 0.3) × 10(-4). This value provides new clues on the universality of the nucleosynthetic r-process of rapid neutron capture. PMID:26973874

  3. Oxygen isotope thermometry of basic lavas and mantle nodules

    USGS Publications Warehouse

    Kyser, T.K.; O'Neil, J.R.; Carmichael, I.S.E.

    1981-01-01

    Measurements have been made of the oxygen isotope and chemical composition of glass and phenocrysts in lavas and coexisting minerals in mantle nodules. Temperatures of formation of these assemblages have been estimated from various chemical thermometers and range from 855?? to 1,300?? C. The permil fractionations between coexisting orthopyroxene and clinopyroxene in the lavas and nodules are all near zero. The fractionations between pyroxene and olivine vary from +1.2 to -1.4 and are a smooth function of temperature over the entire range. This function is given by T(?? C)=1151-173?? (px-d)-68??2(px-d) and has an uncertainty of ??60?? (2??). At temperatures above 1,150?? C, olivine in the nodules becomes more18O-rich than coexisting clinopyroxene, orthopyroxene, and plagioclase. In combination with the experimental work of Muehlenbachs and Kushiro (1974), the olivine-pyroxene fractionations indicate that olivine also becomes substantially more18O-rich than basaltic liquids above 1,200?? C. Geothermometers based on the oxygen isotope equilibration of basaltic liquid with olivine, pyroxene, and plagioclase are presented. ?? 1981 Springer-Verlag.

  4. New views on the isotopic composition of atmospheric oxygen

    NASA Astrophysics Data System (ADS)

    Luz, B.

    2001-05-01

    Air oxygen is enriched in O-18 with respect to ocean water by about 23 permil. This enrichment is named "Dole effect" after its discoverer. Air oxygen originates from marine and terrestrial photosynthesis that produces oxygen gas without fractionation with respect to the substrate water. The O-18 enrichment results primarily from preferential removal of O-16 during respiratory uptake. However, the discrimination against O-18 in ordinary dark respiration is only 18 permil, and cannot account for the entire magnitude of the Dole effect. Part of the discrepancy may be explained by enrichment of the substrate water in terrestrial evapo-transpiration. But the existing evidence on the magnitude of this enrichment shows that this mechanism alone cannot explain the discrepancy. In an attempt to better understand the Dole effect we have studied the overall fractionation in soil and aquatic oxygen uptake. Due to slow gas diffusion in soils and roots the discrimination is smaller than in respiration. This result thus increases the discrepancy. On the other hand, our new estimates show that discrimination in aquatic oxygen uptake is considerably greater than previously assumed. Oxygen uptake in the surface waters of oceans and lakes takes place by ordinary dark respiration as well as by cyanide resistant respiration in both dark and light conditions, and by photorespiration and Mehler reaction that occur only during illumination. Thus in order to study the overall discrimination in aquatic systems it is necessary to evaluate its effects in both light and dark conditions and to separate the effect of photosynthetic production of oxygen. Such separation is possible if gross rates of oxygen production and consumption are known. We have estimated these rates from in situ incubation experiments and from the natural distribution of O-16, O-17, O-18 and the ratio of dissolved oxygen/argon. We have used isotopic and elemental budgets to derive the overall respiratory fractionation in

  5. The influence of pH on the oxygen isotope equilibrium fractionation between sulfite and water

    NASA Astrophysics Data System (ADS)

    Müller, Inigo; Brunner, Benjamin; Ferdelman, Timothy

    2010-05-01

    Currently, the value for the oxygen isotope equilibrium fractionation between water and sulfite in solution is poorly constrained. Sulfite is an important intermediate in the oxidative/reductive sulfur cycle and oxygen isotope exchange between sulfite and water is expected to leave an imprint on the isotope composition of sulfate affected by sulfur cycling. One reason for the lack of accurate information about isotope fractionation between sulfite and water are technical difficulties in extraction of sulfite from solution for oxygen isotope analysis. The pH dependent presence of multiple S(IV) species in solution, i.e. sulfur dioxide (SO2), bisulfite (HSO3-), pyrosulfite (S2O52-) and sulfite (SO32-) complicates data interpretation. For example, the oxygen isotope equilibrium fractionation between water and SO32- may be different than that between water and any of the other sulfite species in solution. We exposed sodium sulfite (Na2SO3) solutions to different pH conditions and monitored oxygen isotope exchange between sulfite and water, until isotope equilibrium was reached. The equilibrium value is determined by using two isotopically different sodium sulfite starting materials, one with a starting value lighter than the equilibrium value and one with a starting composition heavier than the equilibrium value. In this manner oxygen isotope equilibrium is approached from two directions. Sulfite from solution was precipitated as BaSO3 with a set of Ba(OH)2 solutions containing different oxygen isotope compositions. This procedure allows us to disentangle the oxygen isotope contribution from water incorporated during the precipitation from the oxygen isotope composition of sulfite in solution. We present the first results from this experimental approach and discuss the applicability of determining isotope equilibrium fractionations between water and distinct S(IV) species.

  6. Oxygen isotope perspective on Precambrian crustal growth and maturation

    SciTech Connect

    Peck, W.H.; King, E.M.; Valley, J.W.

    2000-04-01

    In this study the authors contrast insights on Precambrian crustal growth and maturation from radiogenic and oxygen isotope systematics in the Superior (3.0--2.7 Ga) and Grenville (1.3--1.0 Ga) Provinces of the Canadian shield. Oxygen isotope ratios in zircon provide the best evidence of supracrustal input into ancient orogens. Archean Superior Province zircons have relatively low {delta}{sup 18}O values and a limited range (5.7{per_thousand} {+-} 0.6{per_thousand}), while Proterozoic Grenville Province zircons have elevated {delta}{sup 18}O values and a wider range (8.2{per_thousand} {+-} 1.7{per_thousand}). These data reflect fundamental differences in crustal evolution and maturation between the Superior and the Grenville Provinces. In the Grenville Province, radiogenically juvenile supracrustal material with high {delta}{sup 18}O values was buried (or subducted) to the base of the crust within 150 m.y. of initial crust production, causing high magmatic {delta}{sup 18}O values ({delta}{sup 18}O [zircon] {ge} 8{per_thousand}) in anorthosite suite and subsequent plutons. Information about large volumes and rapid recycling of Grenville crust is not accessible from radiogenic isotope data alone. The Grenville data contrast with the restricted {delta}{sup 18}O values of Superior Province magmatism, where subtle ({approximately}1{per_thousand}) elevation in {delta}{sup 18}O occurs only in volumetrically minor, late to postorogenic (sanukitoid) plutons. Differences in sediment {delta}{sup 18}O values between the Superior and Grenville Provinces are predominantly a function of the {delta}{sup 18}O of source materials, rather than differences in chemical maturity or erosion styles. This study shows that zircon is a robust reference mineral to compare igneous processes in rocks that have undergone radically different histories.

  7. A non-mass-dependent oxygen isotope effect in the production of ozone from molecular oxygen - The role of molecular symmetry in isotope chemistry

    NASA Technical Reports Server (NTRS)

    Heidenreich, J. E., III; Thiemens, M. H.

    1986-01-01

    It was previously reported that the reaction products from the synthesis of ozone in an electric discharge through molecular oxygen display a nonmass-dependent (NoMaDic) oxygen isotope effect. In this paper, a detailed characterization of the isotope effect, including the effect of molecular oxygen pressure, and the presence of a chemically inert third body (helium), is reported. The NoMaDic effect is due to an isotopically selective stabilization of the O3 formation reaction intermediate, possibly resulting from the ability of the different isotopomers to exhibit different molecular symmetries.

  8. Oxygenation of Ediacaran Ocean recorded by iron isotopes

    NASA Astrophysics Data System (ADS)

    Fan, Haifeng; Zhu, Xiangkun; Wen, Hanjie; Yan, Bin; Li, Jin; Feng, Lianjun

    2014-09-01

    The increase in atmospheric oxygen during the late Neoproterozoic Era (ca. 800-542 Ma) may have stimulated the oxygenation of the deep oceans and the evolution of macroscopic multicellular organisms. However, the mechanism and magnitude of Neoproterozoic oxygenation remain uncertain. We present Fe isotopes, Fe species and other geochemical data for two sections of the Doushantuo Formation (ca. 635-551 Ma) deposited after the Nantuo glacial episode in the Yangtze Gorge area, South China. It is highlighted that highly positive δ56Fe values reflect a lower oxidation rate of Fe(II)aq under ferruginous conditions, and in turn near zero δ56Fe values indicate oxidizing conditions. Our study suggests that during the deposition of the bottom of Member II of the Doushantuo Formation the shallow seawater was oxic, but the deep water was characterized by ferruginous conditions, which is consistent with a redox chemical stratification model. Subsequent anoxic conditions under shallow seawater, represented by positive δ56Fe and negative δ13Ccarb excursions, should be ascribed to the upwelling of Fe(II)aq and dissolved organic carbon (DOC)-rich anoxic deep seawater. The oxidation of Fe (II)aq and DOC-rich anoxic deep seawater upon mixing with oxic shallow water provides an innovative explanation for the well-known negative δ13Ccarb excursions (ENC2) and positive δ56Fe excursions in the middle of Doushantuo Formation. Meanwhile, the upwelling Fe (II)aq- and DOC-rich anoxic deep seawater could increase photosynthetic activity. The balance between oxygen consumption and production was most important criteria for the oxygenation of Early Ediacaran Ocean and diversity of eukaryotic organisms.

  9. Delineating the effect of El-Nino Southern Oscillations using oxygen and sulfur isotope anomalies of sulfate aerosols

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Abaunza Quintero, M. M.; Jackson, T.; McCabe, J.; Savarino, J. P.; Thiemens, M. H.

    2013-12-01

    Sulfate aerosols, unlike greenhouse gases, contribute to global cooling by acting as cloud condensation nuclei in the troposphere and by directly reflecting solar radiation in the stratosphere. To understand the long-term effect of natural and anthropogenic sulfate aerosol on the climate cycle, it is critical to obtain a clear picture of the factors controlling the transport and transformation of sulfate aerosols. We have employed both oxygen triple isotopes and sulfur quadruple isotopes on sulfates from Antarctic ice samples to define the oxidation history, long range transport dynamics, and sources of sulfate aerosols over time. The measurements are used to deconvolve the impact of natural and anthropogenic aerosols on the stratospheric sulfate aerosol composition. Sulfate aerosols were extracted from a snow pit at the South Pole (1979-2002) with a high resolution temporal (6 month) record of the winter and summer seasons covering two largest volcanic events, Pinatubo and El-chichon and three largest ENSO events of the century. All three oxygen and four sulfur isotopes were measured on the extracted sulfate (Shaheen et al., 2013). The high temperature pyrolysis (1000oC) of silver sulfate yielded O2 and SO2. The oxygen triple isotopic composition of the O2 gas was used to determine the oxidation history of sulfate aerosol and SO2 gas obtained during this reaction was utilized to measure sulfur quadruple isotopes following appropriate reaction chemistry (Farquhar et al., 2001). The data revealed that oxygen isotope anomalies in Antarctic aerosols (Δ17O = 0.8-3.7‰) from 1990 to 2001 are strongly linked to the variation in ozone levels in the upper stratosphere/lower stratosphere. The variations in ozone levels are reflective of the intensity of the ENSO events and changes in relative humidity in the atmosphere during this time period. Sulfate concentrations and sulfur quadruple isotopic composition and associated anomalies were used to elucidate the sources of

  10. Oxygen Isotope Anomalies in Orgueil Corundum: Confirmation of Presolar Origin

    NASA Astrophysics Data System (ADS)

    Huss, G. R.; Hutcheon, I. D.; Fahey, A. J.; Wasserburg, G. J.

    1993-07-01

    In a study of Mg isotopes in oxide grains from an Orgueil SiC-spinel-rich residue, [1] reported a corundum grain with ^26Mg*/^27Al = 8.9 x 10^-4, a value ~18 times greater than the canonical 5 x 10^-5 value characteristic of refractory phases formed in the solar nebula. Comparable ratios had previously been found only in carbon-rich interstellar materials, SiC and graphite, [2] leading [1] to suggest that Orgueil corundum B is a pre-solar oxide grain. Subsequently, [3] discovered Murchison corundum 83-5 with a sirnilar ^26Mg*/^27Al of 8.7 x 10^-4; the very unusual oxygen isotope composition (delta^17O = 1072 +- 59 per mil, delta^18O = -244 per mil) led [3] to conclude 83-5 is an interstellar oxide grain. The Panurge ion probe was used to determine ^170/^160 and ^180/^160 ratios in 27 Orgueil oxide grains--16 corundum, 2 hibonite, and 9 spinel--and in 6 Allende spinels. Orgueil corundum B has an extreme ^17O excess (delta^17O = 1394 +- 178 per mil (2sigma(mean)) and a hint of an ^18O depletion (delta^18O = -65 +- 64 per mil) (Fig. 1). The extraordinary enrichments in ^26Mg* and ^17O identify Orgueil B as an interstellar oxide grain. Orgueil B and Murchison 83-5 have remarkably similar O- and Mg-isotope compositions. Red giant stars are enriched in ^17O with ^17O/^18O >~ 1 [4], suggesting these stars are a likely source of the interstellar corundum. Production of ^26Al during H-burning in AGB stars also appears to account for the ^26Mg* excess [5,6]. Condensation of corundum in the circumstellar envelope must occur before dredge up of processed material from the stellar interior decreases ^17O/^16O and creates a C-rich atmosphere. The oxygen isotope compositions of the remaining oxide grains fall into three groups (Fig. 1). All but six corundums and one Orgueil spinel exhibit ^16O excesses and lie along the ^16O-mixing line with compositions similar to those of corundum and spinel from Murchison LS, LU, and CFO(sub)c [7]. Data from Allende spinels cluster about a

  11. Natural variations of lithium isotopes in a mammalian model.

    PubMed

    Balter, Vincent; Vigier, Nathalie

    2014-03-01

    Despite lithium's extensive clinical applications, the cellular and molecular basis for the therapeutic effects remains to be elucidated. The large difference in mass between the two lithium isotopes ((6)Li and (7)Li) has prompted biochemists to explore the metabolism of Li by using pure (6)Li and (7)Li labeled drugs. However, experiments were carried out at very high Li concentrations, which did not reflect natural conditions. In the present study, we consider, for the first time, the natural variations of the (7)Li/(6)Li ratio in the organs and body fluids of an animal model, sheep. Each organ seems to be characterized by a specific Li isotope composition. So far, the range of the (7)Li/(6)Li ratio in the sheep body, expressed as δ permil variations relative to the L-SVEC standard (δ(7)Li), is about 40‰, between muscles (∼40‰) and kidney (∼0‰). Relative to a dietary δ(7)Li value of ∼+17‰, serum, red blood cells, muscle, liver, brain and kidney have a (7)Li enrichment of -12‰, -14‰, +22‰, +5‰, -3‰ and -15‰, respectively. The Li isotope composition is likely to be fractionated during intestinal absorption, with a greater absorption of (6)Li relative to (7)Li. According to previous conclusions obtained with (6)Li and (7)Li labeled chemicals, (6)Li appears to diffuse into erythrocytes faster than does (7)Li. However, this does not hold for myocytes and hepatocytes, because these two tissues have a higher δ(7)Li level than serum. Purely diffusive isotopic fractionation would leave all organs (7)Li-depleted relative to the serum, which is not the case, suggesting that active, molecule-specific, isotopic fractionation occurs in the body. Our preliminary results suggest that natural Li isotope variations can shed light on its regulation in the body, being active or passive.

  12. Triple oxygen isotopes in biogenic and sedimentary carbonates

    NASA Astrophysics Data System (ADS)

    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

  13. Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

    USGS Publications Warehouse

    Truesdell, A.H.

    1974-01-01

    Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275??C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO2 which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl2 and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (103 ln ??) between 1 molal solutions and pure water at 25, 100, and 275??C are: NaCl 0.0, -1.5, +1.0; KCl 0.0, -1.0, +2.0; LiCl -1.0, -0.6, -0.5; CaCl2 -0.4, -1.8, +0.8; MgCl2 -1.1, -0.7, -0.3; MgSO4 -1.1, +0.1, -; NaF (0.8 m) 0.0, -1.5, -0.3; and NH4Cl (0.55 m) 0.0, -1.2, -1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required. ?? 1974.

  14. Spatially Controlled Fe Isotope Variations at Torres del Paine

    NASA Astrophysics Data System (ADS)

    Gajos, N.; Lundstrom, C.

    2013-12-01

    Recent advances in mass-spectrometry have identified systematic trends of non-traditional stable isotope variation in igneous rocks with differentiation index. We present new Fe isotope data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of a 1 km vertical exposure of homogenous granite overlying a contemporaneous and possibly cogenetic 0.5 km mafic gabbro suite. Whereas previous isotopic investigations do little to address variations across important magmatic contacts, this study focuses on a first-of-its-kind spatially dependent non-traditional stable isotope investigation of an igneous pluton. Samples were collected at Torres del Paine in spatially significant transects, focusing on major contacts between country rock, granite and mafic units. Results collected by bracketed double spike MC-ICP-MS (2s precision of ×0.03) show an increase in δ56Fe towards the high silica margins of the pluton with values as high as δ56Fe 0.36. Additionally, the data show a decrease in δ56Fe toward the mafic center of the pluton with δ56Fe values ranging from δ56Fe -0.05 to 0.18. Samples collected on the contact between the granite and mafic complex show intermediate values of δ56Fe= 0.18(×) 0.03. Country rock samples in contact with granite show an isotopically light signature of δ56Fe=0.04 (×) 0.03. Analysis of 50 samples in total show a trend of increasing δ56Fe with SiO2 content. The process responsible for Fe isotope variations remains debated but is suggested to reflect four mechanisms: (1) crustal assimilation, (2) fractional crystallization, (3) late stage fluid exsolution [1] and (4) thermal migration [3]. Preliminary results show that mechanisms #1 and #2 would produce isotopic signatures opposite of those seen at Torres del Paine and other plutonic rocks. Isotopically light Torres country rock samples reveal that assimilation of rocks would not produce the isotopically heavy granites seen at Torres. Based on

  15. Geographic variation of stable isotopes in African elephant ivory

    NASA Astrophysics Data System (ADS)

    Ziegler, S.; Merker, S.; Jacob, D.

    2012-04-01

    In 1989, the international community listed the African elephant in Appendix I of the Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES) thus prohibiting commercial ivory trade. Recent surveillance data show that the illegal trade in ivory has been growing worldwide. Long-term preservation of many of the African elephant populations can be supported with a control mechanism that helps with the implementation of remedial conservation action. Therefore, setting up a reference database that predicts the origin of ivory specimens can assist in determining smuggling routes and the provenance of illegal ivory. Our research builds on earlier work to seek an appropriate method for determining the area of origin for individual tusks. Several researchers have shown that the provenance of elephant ivory can be traced by its isotopic composition, but this is the first attempt to produce an integrated isotopic reference database of elephant ivory provenance. We applied a combination of various routine geochemical analyses to measure the stable isotope ratios of hydrogen, carbon, nitrogen, oxygen, and sulphur. Up to now, we analysed 606 ivory samples of known geographical origin from African range states, museums and private collections, comprising 22 African elephant range states. The isotopic measurements were superimposed with data layers from vegetation, geology and climate. A regression function for the isotope composition of the water isotopes in precipitation and collagen in ivory was developed to overcome the problem of imprecise origin of some of the sampled material. Multivariate statistics, such as nearest neighborhood and discriminate analysis were applied to eventually allow a statistical determination of the provenance for ivory of unknown origin. Our results suggest that the combination of isotopic parameters have the potential to provide predictable and complementary markers for estimating the origin of seized elephant ivory.

  16. Vertical distribution of triple oxygen isotopic composition of dissolved oxygen in the northwestern Pacific

    NASA Astrophysics Data System (ADS)

    Abe, Osamu; Honda, Makio; Saino, Toshiro

    2013-04-01

    Oxygen-17 excess of dissolved oxygen calculated from δ18O and δ17O is not affected by oxygen consumption process but controlled only by processes of primary production and air-water gas transfer. Evaluating gross primary productivity using the 17O-excess in ocean surface water are one of the most advanced geochemical researches for last 10 years. Oxygen-17 excess below ocean mixed/photic layer has not been much investigated because it might be out of focus for estimating present primary productivity, except for the purpose to correct diapycnal mixing effect on surface water. In principle, water mass which has not been affected both by photosynthesis and gas transfer after its separation from ocean surface could preserve 17O-excess value where the water mass was at the surface. The purpose of this study is to determine the vertical distribution of 17O-excess from the surface to the bottom of northwestern Pacific to know whether 17O-excess could really preserve its "original" value after the long and dark travel. Near stations K2 and KNOT, water mass which has a density of 26.8 ?? is observed at depth between 100 and 300 m. This water mass is mainly originated from bottom water in the Okhotsk Sea and spreading widely to entire northwestern Pacific, which is called North Pacific Intermediate Water (NPIW). NPIW is found at depth of 700 m at station S1. Samplings were conducted by two R/V Mirai cruises (MR10-06, Oct-Nov 2010; MR11-02, Feb-Mar 2011). Dissolved oxygen gas was purified by the method of Sarma et al. (2003) and its isotopic composition was determined by dual-inlet isotope ratio mass spectrometer (Thermo Scientific Delta Plus). Gross primary productivities at mixed layer estimated by 17O-excess were well consistent with those by conventional light and dark bottle incubations for stations K2 and S1.

  17. An oxygen isotope study of Wark-Lovering rims on type A CAIs in primitive carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Bodénan, Jean-David; Starkey, Natalie A.; Russell, Sara S.; Wright, Ian P.; Franchi, Ian A.

    2014-09-01

    Calcium-aluminium-rich Inclusions (CAIs) and the thin Wark-Lovering (WL) rims of minerals surrounding them offer a record of the nature of changing conditions during the earliest stages of Solar System formation. Considerable heterogeneity in the gas composition in the immediate vicinity of the proto-Sun had previously been inferred from oxygen isotopic variations in the WL rim of a CAI from Allende (Simon et al., 2011). However, high precision and high spatial resolution oxygen isotope measurements presented in this study show that WL rim and pristine core minerals of individual CAIs from meteorites that had experienced only low degrees of alteration or low grade metamorphism (one from Léoville (reduced CV3), two in QUE 99177 (CR3.0) and two in ALHA 77307 (CO3.0)) are uniformly 16O-rich. This indicates that the previously observed variations are the result of secondary processes, most likely on the asteroid parent body, and that there were no temporal or spatial variations in oxygen isotopic composition during CAI and WL rim formation. Such homogeneity across three groups of carbonaceous chondrites lends further support for a common origin for the CAIs in all chondrites. 16O-poor oxygen reservoirs such as those associated with chondrule formation, were probably generated by UV photo-dissociation involving self-shielding mechanisms and must have occurred elsewhere in outer regions of the solar accretion disk.

  18. Oxygen isotope evidence for shallow emplacement of Adirondack anorthosite

    USGS Publications Warehouse

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

    1982-01-01

    Oxygen isotopic analysis of wollastonites from the Willsboro Mine, Adirondack Mountains, New York reveals a 400-ft wide zone of 18O depletion at anorthosite contacts. Values of ??18O vary more sharply with distance and are lower (to -1.3) than any yet reported for a granulite fades terrain. Exchange with circulating hot meteoric water best explains these results and implies that the anorthosite was emplaced at relatively shallow depths, <10 km, in marked contrast to the depth of granulite fades metamorphism (23 km). These 18O depletions offer the first strong evidence for shallow emplacement of anorthosite within the Grenville Province and suggest that regional metamorphism was a later and tectonically distinct event. ?? 1982 Nature Publishing Group.

  19. Oxygen isotopes and emerald trade routes since antiquity

    PubMed

    Giuliani; Chaussidon; Schubnel; Piat; Rollion-Bard; France-Lanord; Giard; de Narvaez D; Rondeau

    2000-01-28

    Oxygen isotopic compositions of historical emerald artifacts from the Gallo-Roman period to the 18th century indicate that during historical times, artisans worked emeralds originating from deposits supposedly discovered in the 20th century. In antiquity, Pakistani and Egyptian emeralds were traded by way of the Silk Route. Together with Austrian stones, they were the only source of gem-quality emeralds. Immediately after the discovery of the Colombian mines by Spaniards in the 16th century, a new trade route was established, first via Spain to Europe and India and then directly via the Philippines to India. Since then, Colombian emeralds have dominated the emerald trade, and most of the high-quality emeralds cut in the 18th century in India originated from Colombia. PMID:10649992

  20. Oxygen isotopes and emerald trade routes since antiquity

    PubMed

    Giuliani; Chaussidon; Schubnel; Piat; Rollion-Bard; France-Lanord; Giard; de Narvaez D; Rondeau

    2000-01-28

    Oxygen isotopic compositions of historical emerald artifacts from the Gallo-Roman period to the 18th century indicate that during historical times, artisans worked emeralds originating from deposits supposedly discovered in the 20th century. In antiquity, Pakistani and Egyptian emeralds were traded by way of the Silk Route. Together with Austrian stones, they were the only source of gem-quality emeralds. Immediately after the discovery of the Colombian mines by Spaniards in the 16th century, a new trade route was established, first via Spain to Europe and India and then directly via the Philippines to India. Since then, Colombian emeralds have dominated the emerald trade, and most of the high-quality emeralds cut in the 18th century in India originated from Colombia.

  1. Oxygen Isotopes and Emerald Trade Routes Since Antiquity

    NASA Astrophysics Data System (ADS)

    Giuliani, Gaston; Chaussidon, Marc; Schubnel, Henri-Jean; Piat, Daniel H.; Rollion-Bard, Claire; France-Lanord, Christian; Giard, Didier; de Narvaez, Daniel; Rondeau, Benjamin

    2000-01-01

    Oxygen isotopic compositions of historical emerald artifacts from the Gallo-Roman period to the 18th century indicate that during historical times, artisans worked emeralds originating from deposits supposedly discovered in the 20th century. In antiquity, Pakistani and Egyptian emeralds were traded by way of the Silk Route. Together with Austrian stones, they were the only source of gem-quality emeralds. Immediately after the discovery of the Colombian mines by Spaniards in the 16th century, a new trade route was established, first via Spain to Europe and India and then directly via the Philippines to India. Since then, Colombian emeralds have dominated the emerald trade, and most of the high-quality emeralds cut in the 18th century in India originated from Colombia.

  2. Nd isotopic variations in Precambrian banded iron formations

    NASA Technical Reports Server (NTRS)

    Jacobsen, Stein B.; Pimentel-Klose, Mario R.

    1988-01-01

    The isotopic composition of Nd is reported for eight banded iron formations (BIFs) ranging in age from 0.65 to 3.4 Ga. The data suggest a trend of increasingly positive epsilon(Nd) values with age which is interpreted to reflect isotopic variations in Precambrian seawater. The Urucum (0.65 Ga) and the Gunflint (1.9 Ga) BIFs yield negative epsilon(Nd) values between -6 and 0. The remaining BIFs, with ages of 1.84 to 3.4 Ga, have predominantly positive values between -1 and +4. The Nd isotopic signature of BIFs changes from a principally continental source to a dominantly depleted mantle source from the present into the Archean.

  3. Oxygen-18 Carbon Dioxide Isotope Ratio in Mars Atmosphere

    NASA Astrophysics Data System (ADS)

    Kostiuk, T.; Livengood, T. A.; Hewagama, T.; Smith, R.; Fast, K. E.; Annen, J.; Sonnabend, G.; Sornig, M.

    2012-09-01

    The determination of isotopic ratios on Mars is important to the study of atmospheric evolution [1]. The relative abundance of isotopes of CO2 provides insight into the loss of Mars' primordial atmosphere. Isotopic ratios also provide markers in the study of geochemistry of Mars meteorites and future returned samples formed in equilibrium with ambient atmosphere, and are probes of biogenic and abiotic chemistry, which differ in isotope fractionation. Due to its lesser gravity and relatively thin residual atmosphere, Mars' atmosphere should be enriched in heavy isotopes [1]. However Viking [2] results indicated an Earth-like singly substituted oxygen-18 CO2 isotopic ratio, 18OCO/OCO, with δ18O = 0±50‰ relative to Vienna Standard Mean Ocean Water (VSMOW). By comparison, isotopic ratios in Earth atmospheric CO2 are not uniquely defined due to seasonal and biotic variability, but have a range 0-41‰ relative to VSMOW [3, 4]. Phoenix lander TEGA [3] measurements found a modest enrichment of δ18O = 31.0±5.7‰. Only the Viking and Phoenix landers have carried a mass spectrometer to Mars, so far, until the arrival of Mars Science Laboratory in August 2012. Using ground-based spectroscopic techniques Krasnopolsky et al. [5] also found modest enrichment δ18O = 18±18‰. We present results from fully resolved spectroscopic measurements near 10.6 μm of both the normal and singly substituted oxygen- 18 CO2 lines, taken with the Goddard Space Flight Center Heterodyne Instrument for Planetary Winds And Composition (HIPWAC) at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. Measurements with spectral resolving power λ/Δλ=107 were obtained in October 2007 with an instantaneous field-of-view on the planet of ~1 arcsec, at the locations shown in Fig. 1 as open squares. The solid and broken line tracks show Mars SPICAM measurements of ozone corresponding to ozone measurements also obtained with HIPWAC and shown as hatched and solid regions [6]. Figure 1

  4. In Situ Carbon and Oxygen Isotope Analyses of Calcite in CM1 Chondrites

    NASA Astrophysics Data System (ADS)

    Telus, M.; Alexander, C. M. O.'D.; Wang, J.; Hauri, E. H.

    2016-08-01

    We present results from in situ C and O isotope analyses of calcite from CM1 chondrites. There are large isotope variations on small spatial scales. This provides some insight into the evolution of fluids in chondrite parent bodies.

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

    NASA Astrophysics Data System (ADS)

    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

  6. SIMS Oxygen Isotope Study of Chondrules in the Least Metamorphosed CV3 Chondrite Kaba

    NASA Astrophysics Data System (ADS)

    Hertwig, A.; Defouilloy, C.; Kita, N. T.

    2016-08-01

    High-precision SIMS oxygen three isotope analyses of chondrules in Kaba CV3 show that most chondrules are internally homogeneous in oxygen isotopes and dominated by high Mg# (≥98) and Δ17O from –6‰ to –4‰.

  7. Oxygen isotopic composition of opaline phytoliths: Potential for terrestrial climatic reconstruction

    SciTech Connect

    Shahack-Gross, R.; Weiner, S.; Shemesh, A.; Yakir, D.

    1996-10-01

    Opaline mineralized bodies are produced by many terrestrial plants and accumulate in certain soils and archaeological sites. Analyses of the oxygen isotopic compositions of these so-called phytoliths from stems and leaves of wheat plants grown in a greenhouse showed a linear relationship with stem and leaf water isotopic compositions and hence, indirectly, rain water isotopic composition. Analyses of wheat plants grown in fields showed that stem phytoliths isotopic composition directly reflects the seasonal air temperature change, whereas leaf phytoliths isotopic composition reflects both temperature and relative humidity. Temperature and the oxygen isotopic composition of stem phytoliths were related by an equation similar to that proposed for marine opal. Oxygen isotopic compositions of fossil phytoliths, and in particular those from stems, could be valuable for reconstructing past terrestrial climate change.

  8. Exploring antimony isotope ratio variations for provenancing purposes

    NASA Astrophysics Data System (ADS)

    Lobo, L.; Degryse, P.; Vanhaecke, F.

    2012-04-01

    Production sites and trade routes of Roman glass have received much attention over the past decade. It is assumed that raw glass was produced in primary workshops near the raw material sources used, to be transported to secondary glass houses. Colourless glass was a particularly prestigious material in this process, difficult to make. It has been looked at from the perspective of the provenance of its sand and flux, but rarely from the perspective of the origin of the decolourizing material. In effect, for the production of early Roman colourless glass, antimony was used, deliberately added under the form of Sb-bearing minerals. Isotopic analysis of Sb ores could help identify the origin of the decolorizing agent present in Roman glasses and, consequently, to reconstruct how such material was traded and transported, and how this can be integrated in the network of primary and secondary glass producers. In this work, variations in the isotopic composition of Sb in different ore sources (stibnites) are explored using multi-collector ICP - mass spectrometry. A new method is proposed, where Sb is directly analysed for its isotopic composition using MC-ICP-MS after chromatographic isolation of the target element from a sample digest. The isotopic composition of the selected materials shows variations up to 6 ?-units relative to an antimony standard solution. Indium was used as internal standard for correction for instrumental mass discrimination and an external precision for the 123Sb/121Sb ratio of 0.01% RSD was obtained

  9. Oxygen isotope heterogeneity in chondrules from the Mokoia CV3 carbonaceous chondrite

    NASA Astrophysics Data System (ADS)

    Jones, Rhian H.; Leshin, Laurie A.; Guan, Yunbin; Sharp, Zachary D.; Durakiewicz, Tomasz; Schilk, Alan J.

    2004-08-01

    We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ 17O ˜ -2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ 18O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ 18O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ 18O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ 18O values (-7.5‰ and -11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ 17O, δ 18O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the

  10. Oxygen-18 Carbon Dioxide Isotope Ratio in Mars Atmosphere

    NASA Astrophysics Data System (ADS)

    Kostiuk, T.; Livengood, T. A.; Hewagama, T.; Smith, R.; Fast, K. E.; Annen, J.; Sonnabend, G.; Sornig, M.

    2012-09-01

    The determination of isotopic ratios on Mars is important to the study of atmospheric evolution [1]. The relative abundance of isotopes of CO2 provides insight into the loss of Mars' primordial atmosphere. Isotopic ratios also provide markers in the study of geochemistry of Mars meteorites and future returned samples formed in equilibrium with ambient atmosphere, and are probes of biogenic and abiotic chemistry, which differ in isotope fractionation. Due to its lesser gravity and relatively thin residual atmosphere, Mars' atmosphere should be enriched in heavy isotopes [1]. However Viking [2] results indicated an Earth-like singly substituted oxygen-18 CO2 isotopic ratio, 18OCO/OCO, with δ18O = 0±50‰ relative to Vienna Standard Mean Ocean Water (VSMOW). By comparison, isotopic ratios in Earth atmospheric CO2 are not uniquely defined due to seasonal and biotic variability, but have a range 0-41‰ relative to VSMOW [3, 4]. Phoenix lander TEGA [3] measurements found a modest enrichment of δ18O = 31.0±5.7‰. Only the Viking and Phoenix landers have carried a mass spectrometer to Mars, so far, until the arrival of Mars Science Laboratory in August 2012. Using ground-based spectroscopic techniques Krasnopolsky et al. [5] also found modest enrichment δ18O = 18±18‰. We present results from fully resolved spectroscopic measurements near 10.6 μm of both the normal and singly substituted oxygen- 18 CO2 lines, taken with the Goddard Space Flight Center Heterodyne Instrument for Planetary Winds And Composition (HIPWAC) at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. Measurements with spectral resolving power λ/Δλ=107 were obtained in October 2007 with an instantaneous field-of-view on the planet of ~1 arcsec, at the locations shown in Fig. 1 as open squares. The solid and broken line tracks show Mars SPICAM measurements of ozone corresponding to ozone measurements also obtained with HIPWAC and shown as hatched and solid regions [6]. Figure 1

  11. Relative Humidity Recorded in the hydrogen and oxygen isotopic compositions of treerings

    NASA Astrophysics Data System (ADS)

    Shu, Y.; Feng, X.

    2002-12-01

    Many paleoclimate proxies have been developed to reconstruct continental surface temperatures. Examples are oxygen or hydrogen isotope ratios in ice cores, groundwater, and treerings, oxygen isotopes in stalagmites, tree-ring width and density, and pollen distributions in lake sediment cores. Several proxies listed above are also indicative of amount of precipitation. However, to our knowledge, a proxy indicator for air humidity does not yet exist. Humidity is related to the moisture content in the atmosphere, which plays an important role in the energy budget determining the planetary climate. Here we describe a study of oxygen and hydrogen isotopic compositions in modern treerings collected from trees growing along a transect of precipitation in Olympic Peninsula, Washington, USA. We are consciously optimistic that reconstruction of relative humidity may be possible if both oxygen and hydrogen isotopic compositions in tree cellulose are determined. Douglas-fir (Pseudotsuga menziesii) and subalpine fir (Abies lasiocarpa) trees were sampled at five sites within the Olympic Mountains. Among these sites, the annual precipitation varies from over three meters on the westside of the mountains to less than one meter on the eastside. The δ18O and δD in the surface water of these sites follow the trend of precipitation, decreasing from west to east. Annual treerings from seven trees were analyzed for δ18O and δD values. The number of rings from each tree ranges from 23 (1963-1985) to 48 (1949-1996). No significant correlation was found between the δD and δ18O values within each tree. This is expected because the range of variation in the isotopic ratios of source water at a given site is limited, and other factors such as humidity and soil hydrology may upset the one-to-one relationship between the δD and δ18O in the source water and those in treerings. However, the mean δD and δ18O values from each tree are weakly correlated with a slope of 19. This slope is

  12. Oxygen isotope systematics in magmatic and subsolidus epidote

    NASA Astrophysics Data System (ADS)

    Morrison, J.; Anderson, J. L.

    2003-04-01

    Magmatic epidote in broadly granitic plutonic rocks can be used to quantify parameters such as depth of crystallization and rates of pluton ascent. However, the textural criteria used to distinguish magmatic epidote from epidote grown at temperatures and pressures below the solidus can be equivocal. Oxygen isotope systematics of epidote and associated minerals in 6 broadly granitic lithologies have been used to 1) evaluate available calibrations of the temperature dependent fractionations involving epidote and 2) constrain the magmatic versus subsolidus origins of epidote in a variety of well characterized lithologies. Oxygen isotope compositions of epidote (Ep), quartz (Qt), plagioclase (Pl) and biotite (Bt) were measured using a CO_2 laser microprobe system. We measured Δ18O values in 2 distinct rapidly-cooled or "quenched" lithologies: a biotite rhyolite of the Pleistocene Sutter Buttes volcano of California and Late Cretaceous rhyodacite dikes from Boulder County, Colorado. The biotite rhyolite contains phenocrysts of magmatic epidote, quartz, plagioclase and biotite and is virtually devoid of alteration minerals. Discrete but spatially related Ep, Qt, Pl and Bt from 6 samples yield an average ΔQt-Ep of 3.10±0.12 ppm (n=5), DletaPl-Ep = 1.75 ppm, and ΔEp-Bt = -0.44 ppm. In the rhyodacite, ΔQt-Ep = 3.12±0.06 ppm and ΔEp-Bt = 1.47±0.34 ppm. Both of these lithologies likely crystallized at temperatures of ˜750^oC. Temperatures inferred from these ΔQt-Ep values are ˜550^oC. In contrast, the 3 Late Cretaceous tonalitic plutons in which Zen and Hammarstrom (1984) originally documented magmatic epidote, plus the Ordovician Ellicott City granodiorite, yield distinct values: ΔQt-Ep = 4.19±0.17 ppm, ΔPl-Ep = 1.64±0.19 ppm, ΔEp-Amph = 0.54±0.25 ppm, and ΔEp-Bt = 0.85±0.24 ppm. All 4 of these lithologies underwent slow, post-crystallization cooling. Cation exchange thermometry indicates that these plutons crystallized at temperatures from ˜680^o to

  13. Germanium isotopic variations in igneous rocks and marine sediments

    NASA Astrophysics Data System (ADS)

    Rouxel, Olivier; Galy, Albert; Elderfield, Henry

    2006-07-01

    A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICPMS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/ 70Ge ratios are expressed as δ74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2‰ for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4‰ in δ74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/ 70Ge, 73Ge/ 70Ge and 72Ge/ 70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of δ74Ge in igneous rocks is only 0.25‰ without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a δ74Ge of 1.3 ± 0.2‰ can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher δ74Ge values between 2.0‰ and 3.0‰. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the δ74Ge of the seawater to +3.0‰.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have δ74Ge values ranging from 0.7‰ to 2.0‰. The variable values of the cherts cannot be explained by binary mixing

  14. Physiological and environmental factors related to carbon isotopic variations in mollusc shell carbonate

    SciTech Connect

    Krantz, D.E.; Williams, D.F.; Jones, D.S.

    1985-01-01

    The carbon isotopic composition of mollusc shell carbonate has been used as a general environmental indicator in numerous studies, but relatively little is known of the factors which affect within-shell variation. Primary control of delta/sup 13/C values in shell carbonate comes from the dissolved bicarbonate source, particularly as related to marine versus fresh water. Present models explain cyclic variations in the delta/sup 13/C profiles of mollusc shells due to upwelling, phytoplankton productivity and stratification, disequilibrium with rapid shell growth, and infaunal versus epifaunal habitat. Carbon and oxygen isotopic profiles in this study were obtained from specimens of Spisula solidissima (surf clam) and Placopecten magellanicus (sea scallop) collected alive from 14 to 57 m water depths off the Virginia coast. Three main factors appear to affect the delta/sup 13/C profiles in these specimens. Isotopically light values commonly associated with the spring and occasionally the fall correspond with seasonal phytoplankton productivity. A significant negative delta/sup 13/C offset of the infaunal Spisula relative to the epifaunal Placopecten probably relates to the inclusion of isotopically more negative pore-water bicarbonate by Spisula. Additionally, occasional transient spikes in both the delta/sup 18/O and delta/sup 13/C profiles correspond to intrusion of reduced-salinity water.

  15. Identifying Oxygen Isotopic Signatures of ENSO Dynamics Through Isotope-Enabled Regional Ocean Modeling

    NASA Astrophysics Data System (ADS)

    Stevenson, S.; Powell, B.; Merrifield, M. A.; Cobb, K. M.; Nusbaumer, J. M.; Noone, D. C.

    2015-12-01

    Coral oxygen isotope (δ18O) records provide important constraints on past variability in the El Nino/Southern Oscillation (ENSO). However, the relationship between ENSO activity and δ18O anomalies is subject to a high degree of uncertainty owing to both observational limitations and poorly understood dynamical processes. The isotope-enabled Regional Ocean Modeling System (isoROMS) is designed to address some of these uncertainties; isoROMS is a flexible modeling framework capable of simulating δ18O over an arbitrary domain at a variety of spatial resolutions. Initial results for isoROMS simulations at the central equatorial Pacific Line Islands chain over the 1979-2009 period are presented, using water isotopologue fluxes taken from the isotope-enabled NCAR Community Atmosphere Model (iCAM). Mesoscale ocean processes can significantly impact temperature and seawater δ18O variability under certain conditions, particularly during strong La Nina events. The variability in the ENSO/δ18O relationship is then investigated over the 20th century using a suite of isoROMS simulations conducted with combinations of atmosphere and ocean reanalysis products, in an effort to determine the optimal form of 'forward models' for predicting δ18O given local conditions. Implications for our ability to quantitatively reconstruct ENSO amplitude and the properties of El Nino/La Nina events are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  17. Episodic growth of the Gondwana supercontinent from hafnium and oxygen isotopes in zircon.

    PubMed

    Kemp, A I S; Hawkesworth, C J; Paterson, B A; Kinny, P D

    2006-02-01

    It is thought that continental crust existed as early as 150 million years after planetary accretion, but assessing the rates and processes of subsequent crustal growth requires linking the apparently contradictory information from the igneous and sedimentary rock records. For example, the striking global peaks in juvenile igneous activity 2.7, 1.9 and 1.2 Gyr ago imply rapid crustal generation in response to the emplacement of mantle 'super-plumes', rather than by the continuous process of subduction. Yet uncertainties persist over whether these age peaks are artefacts of selective preservation, and over how to reconcile episodic crust formation with the smooth crustal evolution curves inferred from neodymium isotope variations of sedimentary rocks. Detrital zircons encapsulate a more representative record of igneous events than the exposed geology and their hafnium isotope ratios reflect the time since the source of the parental magmas separated from the mantle. These 'model' ages are only meaningful if the host magma lacked a mixed or sedimentary source component, but the latter can be diagnosed by oxygen isotopes, which are strongly fractionated by rock-hydrosphere interactions. Here we report the first study that integrates hafnium and oxygen isotopes, all measured in situ on the same, precisely dated detrital zircon grains. The data reveal that crust generation in part of Gondwana was limited to major pulses at 1.9 and 3.3 Gyr ago, and that the zircons crystallized during repeated reworking of crust formed at these times. The implication is that the mechanisms of crust formation differed from those of crustal differentiation in ancient orogenic belts. PMID:16452978

  18. Episodic growth of the Gondwana supercontinent from hafnium and oxygen isotopes in zircon.

    PubMed

    Kemp, A I S; Hawkesworth, C J; Paterson, B A; Kinny, P D

    2006-02-01

    It is thought that continental crust existed as early as 150 million years after planetary accretion, but assessing the rates and processes of subsequent crustal growth requires linking the apparently contradictory information from the igneous and sedimentary rock records. For example, the striking global peaks in juvenile igneous activity 2.7, 1.9 and 1.2 Gyr ago imply rapid crustal generation in response to the emplacement of mantle 'super-plumes', rather than by the continuous process of subduction. Yet uncertainties persist over whether these age peaks are artefacts of selective preservation, and over how to reconcile episodic crust formation with the smooth crustal evolution curves inferred from neodymium isotope variations of sedimentary rocks. Detrital zircons encapsulate a more representative record of igneous events than the exposed geology and their hafnium isotope ratios reflect the time since the source of the parental magmas separated from the mantle. These 'model' ages are only meaningful if the host magma lacked a mixed or sedimentary source component, but the latter can be diagnosed by oxygen isotopes, which are strongly fractionated by rock-hydrosphere interactions. Here we report the first study that integrates hafnium and oxygen isotopes, all measured in situ on the same, precisely dated detrital zircon grains. The data reveal that crust generation in part of Gondwana was limited to major pulses at 1.9 and 3.3 Gyr ago, and that the zircons crystallized during repeated reworking of crust formed at these times. The implication is that the mechanisms of crust formation differed from those of crustal differentiation in ancient orogenic belts.

  19. Millennial-Scale Variations in Oxygen-18 of Atmospheric Molecular Oxygen

    NASA Astrophysics Data System (ADS)

    Severinghaus, J. P.; Beaudette, R.; Brook, E. J.

    2006-12-01

    The oxygen-18 content of atmospheric dioxygen (δ18Oatm) is known from ice core trapped air records to vary on orbital timescales, primarily the ~21,000 year periodicity. The cause is thought to be a combination of 1) ice sheet growth and consequent variation in O-18 of ocean water, the original source of all substrate H2O used for photosynthetic O2, and 2) changes in the biogeochemical fractionation of O2 relative to ocean water, known as the Dole Effect. Because the turnover time of O2 in the atmosphere is ~1000 years, variations on shorter timescales are not expected and previous studies have not searched for them. Here we present a new record of δ18Oatm at approximately 100-year resolution from the Siple Dome ice core, Antarctica, covering the past 95 kyr. The record shows evidence of artifactual fractionation during gas loss, in the form of an inverse correlation of O2/N2 and δ18Oatm in pair differences with slope of -0.01, probably due to poor core quality (low O2/N2 is associated with highly fractured pieces of ice). The light isotope O-16 appears to escape more readily from the bubbles during leakage of gas out of the ice, leaving the remaining gas enriched in O-18. An empirical correction for gas loss fractionation is made using the measured δO2/N2 and a slope of -0.01. Both raw and corrected records show distinct millennial-duration positive anomalies in δ18Oatm, suggesting that the anomalies are real features of the paleo-atmosphere. They occur at times of Antarctic warmth (designated A1, A2, etc.), which are also times of weak Asian monsoons and Heinrich events or `mystery intervals' in the northern hemisphere. The anomalies typically have an amplitude of +0.15‰, which compares with analytical error of ±0.02‰. We speculate that the anomalies are caused by the increase in O-18 of terrestrial precipitation associated with the weak monsoons, as seen in Asian and Brazilian speleothem records, in addition to evaporative enrichment of leaf water O-18

  20. Partitioning water and carbon fluxes in a Mediterranean oak woodland using stable oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Dubbert, Maren; Piayda, Arndt; Cuntz, Matthias; Correia, Alexandra; Silva, Filipe Costa e.; Pereira, Joao; Werner, Christiane

    2014-05-01

    evaporation (Dubbert et al. 2013). Moreover, we found continuously strong deviations from isotopic steady-state in plant transpiration combined with large isoforcing on the atmosphere. This implies that assuming plant transpiration to be in the steady-state can have a huge impact at least for studies that distinguish relatively short time intervals (hours, e.g. partitioning studies). Finally. partitioning ecosystem ET and NEE into its three sources revealed a strong contribution of soil evaporation (E) and herbaceous transpiration (T) to ecosystem ET during spring and fall. In contrast, soil respiration (R) and herbaceous net carbon gain contributed to a lesser amount to ecosystem NEE during spring and fall, leading to consistently smaller water use efficiencies (WUE) of the herbaceous understory compared to the cork-oaks. Craig H, Gordon, LI. 1965. Deuterium and oxygen-18 variations in the ocean and the marine atmosphere. Paper presented at the Stable Isotopes in Oceanographic Studies and Paleotemperatures, Spoleto, Italy. Dubbert M, Cuntz M, Piayda A, Maguas C, Werner C, 2013: Partitioning evapotranspiration - Testing the Craig and Gordon model with field measurements of oxygen isotope ratios of evaporative fluxes. J Hydrol.

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

    NASA Astrophysics Data System (ADS)

    Versteegh, E. A. A.; Blicher, M. E.; Mortensen, J.; Rysgaard, S.; Als, T. D.; Wanamaker, A. D., Jr.

    2012-09-01

    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 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 kitchen middens from previous Holocene warm periods, this species may be ideal in reconstructing past meltwater dynamics. We investigate 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 during the years 2007 to 2010. Results show that δ18Ow values were not recorded at very low salinities (< ~19), because the mussels appear to cease growing. This implies that M. edulis δ18Oc values are suitable in reconstructing past meltwater amounts in most cases, but care has to be taken that shells are collected not too close to a glacier, but rather in the mid region or mouth of the fjord. The focus of future research will expand on the geographical and temporal range of the shell measurements by sampling mussels in other fjords in Greenland along a south-north gradient, and by sampling shells from raised shorelines and kitchen middens from prehistoric settlements in Greenland.

  2. Phosphate oxygen isotope ratios as a tracer for sources and cycling of phosphate in North San Francisco Bay, California

    USGS Publications Warehouse

    McLaughlin, K.; Kendall, C.; Silva, S.R.; Young, M.; Paytan, A.

    2006-01-01

    A seasonal analysis assesing variations in the oxygen isotopic composition of dissolved inorganic phosphate (DIP) was conducted in the San Francisco Bay estuarine system, California. Isotopic fractionation of oxygen in DIP (exchange of oxygen between phosphate and environmental water) at surface water temperatures occurs only as a result of enzyme-mediated, biological reactions. Accordingly, if phospate demand is low relative to input and phosphate is not heavily cycled in the ecosystem, the oxygen isotopic composition of DIP (?? 18Op) will reflect the isotopic composition of the source of phosphate to the system. Such is the case for the North San Francisco Bay, an anthropogenically impacted estuary with high surface water phosphate concentrations. Variability in the ?? 18Op in the bay is primarily controlled by mixing of water masses with different ??18Op signatures. The ??18Op values range from 11.4??? at the Sacramento River to 20.1??? at the Golden Gate. Deviations from the two-component mixing model for the North Bay reflect additional, local sources of phosphate to the estuary that vary seasonally. Most notably, deviations from the mixing model occur at the confluence of a major river into the bay during periods of high river discharge and near wastewater treatment outlets. These data suggest that ??18Op can be an effective tool for identifying P point sources and understanding phosphate dynamics in estuarine systems. Copyright 2006 by the American Geophysical Union.

  3. [Hydrogen and oxygen isotopes of lake water and geothermal spring water in arid area of south Tibet].

    PubMed

    Xiao, Ke; Shen, Li-Cheng; Wang, Peng

    2014-08-01

    The condition of water cycles in Tibet Plateau is a complex process, and the hydrogen and oxygen isotopes contain important information of this process. Based on the analysis of isotopic composition of freshwater lake, saltwater lake and geothermal water in the southern Tibetan Plateau, this study investigated water cycling, composition and variation of hydrogen and oxygen isotopes and the influencing factors in the study area. The study found that the mean values of delta18O and deltaD in Daggyaima lake water (-17.0 per thousand for delta18O and -138. 6 per thousand for deltaD), Langcuo lake water (-6.4 per thousand for delta18O and -87.4 per thousand for deltaD) and Dagejia geothermal water (-19.2 per thousand for delta18 and -158.2 per thousand for deltaD) all showed negative delta18O and deltaD values in Tibetan Plateau by the influence of altitude effects. Lake water and geothermal water were influenced by evaporation effects in inland arid area, and the slope of evaporation line was less than 8. Deuterium excess parameters of lake water and geothermal water were all negative. The temperature of geothermal reservoirs in Dagejia geothermal field was high,and oxygen shift existed in the relationship of hydrogen and oxygen isotopes.

  4. Strontium isotopic variations of Neoproterozoic seawater: Implications for crustal evolution

    SciTech Connect

    Asmerom, Y.; Jacobsen, S.B.; Knoll, A.H.; Butterfield, N.J. ); Swett, K. )

    1991-10-01

    The authors report high precision Sr isotopic data on carbonates from the Neoproterozoic Shaler Group, Victoria Island, Northwest Territories, Canada. Samples with low {sup 87}Rb/{sup 86}Sr ratios (<0.01) were selected for Sr isotopic analysis. {delta}{sup 18}O, Mn, Ca, Mg, and Sr data were used to recognize altered samples. The altered samples are characterized by high Mn/Sr ({ge}2) and variable {delta}{sup 18}O; most are dolomites. The data indicate that between ca. 790-850 Ma the {sup 87}Sr/{sup 86}Sr ratio of seawater varied between 0.70676 and 0.70561. The samples show smooth and systematic variation, with the lowest {sup 87}Sr/{sup 86}Sr value of 0.70561 at ca. 830 Ma. The low {sup 87}Sr/{sup 86}Sr ratio of carbonates from the lower parts of the section is similar to a value reported for one sample from the Adrar of Mauritania ({approx}900 Ma), West African Craton. Isotopic ratios from the upper part of the Shaler section are identical to values from the lower part of the Neoproterozoic Akademikerbreen Group, Spitsbergen. Although a paucity of absolute age determinations hinders attempts at the precise correlation of Neoproterozoic successions, it is possible to draw a broad outline of the Sr isotopic composition of seawater for this period. Data from this study and the literature are used to construct a curve of the {sup 87}Sr/{sup 86}Sr ratio of Neoproterozoic seawater. The Sr isotope composition of seawater reflects primarily the balance between continental Sr input through river input and mantle input via hydrothermal circulation of seawater through mid-ocean ridges. Coupling of Nd and Sr isotopic systems allows the authors to model changes in seafloor spreading rates (or hydrothermal flux) and continental erosion. The Sr hydrothermal flux and the erosion rate (relative to present-day value) are modeled for the period 500-900 Ma.

  5. Contributions of Mycorrhizal Trees to Mg Isotopic Variations in Weathering

    NASA Astrophysics Data System (ADS)

    Bryce, J. G.; Hobbie, E. A.; Blichert-Toft, J.; Colpaert, J.; Hoff, C.; Prado, M. F.; Pettitt, E.; Telouk, P.

    2013-12-01

    Although it is well established that organisms contribute significantly to the weathering process and to the distribution of elements within continental environments, the degree to which biota actively drive weathering versus the degree to which organisms benefit from nutrients released during largely inorganic weathering processes remains shrouded in mystery. Furthermore, the relative influence of different organisms on key emerging isotopic systems, especially Mg, remains poorly understood. To address these questions, we have carried out a series of Mg isotopic investigations on semi-hydroponically cultured trees (pine, Pinus sylvestris and sugar maple, Acer saccharum) grown with appropriate mycorrhizal symbionts (ectomycorrhizal, Suillus, or arbuscular, Glomus, respectively) in different geologic substrates (carbonate and granitic) under low nutrient supply. Plant tissues and eluting solutions across these biogeochemical experiments were studied for elemental abundances and Mg isotopic signatures. Eluting solutions were most distinctive from the abiotic control for those trees grown in granite-bearing cultures, an observation we attribute to biotite weathering. Foliar and root tissues recorded distinctive isotopic compositions (e.g., differences up to 0.6 ‰ δ26/24Mg) in both the pines and sugar maples. Foliar δ26/24Mg varied amongst the trees grown in the different experiments: compared to the substrate, ectomycorrhizal pine had more depleted Mg isotopic signatures in foliage than nonmycorrhizal pine and arbuscular mycorrhizal sugar maple. Taken together our results indicate that ectomycorrhizal symbioses contribute to Mg isotopic variations during weathering and that this effect may be more pronounced in soils forming over biotite-bearing terrains.

  6. Unexpected hydrogen isotope variation in oceanic pelagic seabirds

    USGS Publications Warehouse

    Ostrom, Peggy H.; Wiley, Anne E.; Rossman, Sam; Stricker, Craig A.; James, Helen F.

    2014-01-01

    Hydrogen isotopes have significantly enhanced our understanding of the biogeography of migratory animals. The basis for this methodology lies in predictable, continental patterns of precipitation δD values that are often reflected in an organism's tissues. δD variation is not expected for oceanic pelagic organisms whose dietary hydrogen (water and organic hydrogen in prey) is transferred up the food web from an isotopically homogeneous water source. We report a 142% range in the δD values of flight feathers from the Hawaiian petrel (Pterodroma sandwichensis), an oceanic pelagic North Pacific species, and inquire about the source of that variation. We show δD variation between and within four other oceanic pelagic species: Newell's shearwater (Puffinus auricularis newellii), Black-footed albatross (Phoebastria nigripes), Laysan albatross (Phoebastria immutabilis) and Buller's shearwater (Puffinus bulleri). The similarity between muscle δD values of hatch-year Hawaiian petrels and their prey suggests that trophic fractionation does not influence δD values of muscle. We hypothesize that isotopic discrimination is associated with water loss during salt excretion through salt glands. Salt load differs between seabirds that consume isosmotic squid and crustaceans and those that feed on hyposmotic teleost fish. In support of the salt gland hypothesis, we show an inverse relationship between δD and percent teleost fish in diet for three seabird species. Our results demonstrate the utility of δD in the study of oceanic consumers, while also contributing to a better understanding of δD systematics, the basis for one of the most commonly utilized isotope tools in avian ecology.

  7. Unexpected hydrogen isotope variation in oceanic pelagic seabirds.

    PubMed

    Ostrom, Peggy H; Wiley, Anne E; Rossman, Sam; Stricker, Craig A; James, Helen F

    2014-08-01

    Hydrogen isotopes have significantly enhanced our understanding of the biogeography of migratory animals. The basis for this methodology lies in predictable, continental patterns of precipitation δD values that are often reflected in an organism's tissues. δD variation is not expected for oceanic pelagic organisms whose dietary hydrogen (water and organic hydrogen in prey) is transferred up the food web from an isotopically homogeneous water source. We report a 142‰ range in the δD values of flight feathers from the Hawaiian petrel (Pterodroma sandwichensis), an oceanic pelagic North Pacific species, and inquire about the source of that variation. We show δD variation between and within four other oceanic pelagic species: Newell's shearwater (Puffinus auricularis newellii), Black-footed albatross (Phoebastria nigripes), Laysan albatross (Phoebastria immutabilis) and Buller's shearwater (Puffinus bulleri). The similarity between muscle δD values of hatch-year Hawaiian petrels and their prey suggests that trophic fractionation does not influence δD values of muscle. We hypothesize that isotopic discrimination is associated with water loss during salt excretion through salt glands. Salt load differs between seabirds that consume isosmotic squid and crustaceans and those that feed on hyposmotic teleost fish. In support of the salt gland hypothesis, we show an inverse relationship between δD and percent teleost fish in diet for three seabird species. Our results demonstrate the utility of δD in the study of oceanic consumers, while also contributing to a better understanding of δD systematics, the basis for one of the most commonly utilized isotope tools in avian ecology. PMID:24989118

  8. Stable Isotopic Variations in Columnar Cacti: are Responses to Climate Recorded in Spines?

    NASA Astrophysics Data System (ADS)

    English, N. B.; Dettman, D. L.; Williams, D. G.

    2004-12-01

    The behavior of the North American monsoon (NAM), particularly with respect to times of continental drought and its relationship to the Pacific-North American (PNA) teleconnection pattern and the El Nino/Southern Oscillation (ENSO) is of great interest to paleoclimatologists and water managers. Long-term instrumental precipitation and tree ring records in the southwestern United States and northwestern Mexico at low elevations are sparse and this has hindered research on NAM variability at interannual timescales. Saguaro cacti (Carnegiea gigantea) and other columnar cacti in North and South America are long-lived and have the potential to record climate variability on land with high temporal and spatial resolution. The vertical sequence of spines on the saguaro's exterior represents a high resolution (4 to 6 per year), and long (over 150 years) record of environmental change. We present results from an experiment where we tracked the oxygen isotopic values in the source waters, stem tissue waters and spine tissue for three treatments over the course of three months. These data are then compared to a previously developed mechanistic model of isotopic variation that reflects the physiological responses of Saguaro to climate variation over seasonal to century long time-scales. We also present the rationale for a new method to determine the growth rate of columnar cacti using the radiocarbon bomb spike. Our measurements reveal that oxygen and hydrogen isotopic variation among the sequentially produced and persistent spines covering the saguaro body record fluctuations in saguaro water balance. The model successfully predicts isotopic variation in spines and constrains controlling variables, yielding a powerful and high-resolution stable isotope index of water stress in the low desert. The development and refinement of an isotopic model for saguaro will serve as the basis for models applied to other species of columnar cacti in North and South America. The role of the

  9. The use of the oxygen isotopes from diatom silica as a proxy for North Atlantic Oscillation reconstruction

    NASA Astrophysics Data System (ADS)

    Hernández, Armand; Leng, Melanie J.; Trigo, Ricardo M.; Vázquez-Loureiro, David; Bao, Roberto; Sloane, Hilary J.; Rubio-Inglés, Maria J.; Sánchez-López, Guiomar; Gonçalves, Vitor; Raposeiro, Pedro M.; Sáez, Alberto; Giralt, Santiago

    2015-04-01

    The North Atlantic Oscillation (NAO) is the main atmospheric circulation mode controlling climate variability in the Northern Hemisphere. Instrumental records of the NAO are relatively short, and therefore proxy approaches are essential to understand its evolution over longer time periods. Diatom oxygen isotope ratios are increasingly being used for palaeoclimatic reconstructions in lacustrine sedimentary records. However, application of this proxy to annual-to-decadal resolution lacustrine records is still in its infancy. To our knowledge, oxygen isotope ratios from diatoms at annual-to-decadal resolution has not been attempted, mainly due to the difficulty in obtaining large enough samples suitable for analysis at this temporal scale. Here we present a high-resolution, ca. 200-year-long, proxy record based on 56 oxygen isotope measurements from Lake Santiago (37° 50' N - 25° 47'W, Azores Archipelago, Portugal). This record will be compared to instrumental data of precipitation and NAO index values to test its robustness to conduct an ancient NAO reconstruction. In detail the oxygen isotope data shows an isotope depletion trend (-3o), with several interannual oscillations, from 1830 cal yr AD until present. The entire record can be divided into two intervals. The interval, from 1830 to 1938 cal yr AD, displays values above the average (+33o), whereas the interval from 1939 to 2012 cal yr AD shows values below the mean. Since Lake Santiago is a hydrologically closed lake, the oxygen isotope variations are mostly related to the precipitation-evaporation ratio. These results exhibit a good agreement with the rainfall instrumental data with an increase of net rainfall amount through the last decades in the Azores archipelago. Besides this, the short-term recorded isotope excursions (±3.5o) are related to the rainfall interannual variability. These patterns suggest that the isotope data from diatom silica in Lake Santiago sediments are directly linked to past

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

    PubMed

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

    2012-10-16

    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 δ(18)O correlates strongly with δ(18)O in precipitation from distant stations in the center and west of the basin, and with Andean ice core δ(18)O 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 δ(18)O over the 20th century consistent with increases in Andean δ(18)O 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.

  11. Petrologic and oxygen isotopic study of ALH 85085-like chondrites

    NASA Astrophysics Data System (ADS)

    Prinz, M.; Weisberg, M. K.; Clayton, R. N.; Mayeda, T. K.; Ebihara, M.

    1994-07-01

    Four meteorites (PAT 91546, PCA 91328, PCA 91452, PCA 91467) petrologically similar to ALH 85085 chondrite have now been found. Previous studies of ALH 85085 showed it be a new kind of CR-related microchondrule-bearing chondrite, although one called it a sub-chondrite. The purpose of this study is to learn more about ALH 85085-like meteorites and their relationship to CR and CR-related (LEW 85332, Acfer 182, Bencubbin) chondrites. The methods used included petrology, INA bulk chemical analysis (PAT 91546, PCA 91467), and O isotopic analyses of the whole rocks and separated chondrules and dark inclusions (DIs) from PAT 91546. Since microchondrules and fragments are approximately 20 microns it was necessary to analyze composite samples for O; one was of approximately 100 chondrules, and another was of 5 DIs. Petrologically, the four meteorites are similar to ALH 85085, and there is no basis for determining if all of them, or any combinations, are paired. Mineralogically, olivine and pyroxene are highly magnesian FeNi metal generally has 3-10% Ni, and has a positive Ni-Co correlation similar to that in CR and CR-related chondrites. Refractory inclusions are similar in size to the chondrules and have the following assemblages: (1) hibonite-perovskite, (2) melilite-fassaite-forsterite, (3) grossite (Ca-dialuminate)-melilite-perovskite, (4) spinel-melilite, and (5) spinel-pyroxene aggregates. Chemically, INA analyses indicate that PAT 91546 and PCA 91467 are generally similar to ALH 85085. Oxygen isotopic analyses of the four whole-rock compositions fall along the CR mixing line as does ALH 85085; they are also close to LEW 85332, Acfer 182, and Bencubbin. This supports the concept that these are all CR-related chondrites. Even stronger support is found in the compositions of the chondrules and DIs in PAT 91546, which also plot on or near the CR line.

  12. Recent planktic foraminifers in the Fram Strait (Arctic Ocean): carbon and oxygen stable isotope composition

    NASA Astrophysics Data System (ADS)

    Pados, T.; Spielhagen, R. F.; Bauch, D.; Meyer, H.; Segl, M.

    2012-12-01

    In paleoceanographic reconstructions the carbon isotopic compositions (δ13C) of fossil foraminifers refer to, e.g., paleoproductivity and stratification, while oxygen isotopic (δ18O) records provide information about variations in sea surface temperatures and salinities in the past. However, for a correct interpretation of the fossil data it is important to improve our understanding of the correlation between recent oceanic variability and the composition of shells of living calcareous microorganisms. For this, the upper water column and sediment surface in the Fram Strait (Arctic Ocean, 78°50'N, 5°W-8°E) were sampled for planktic foraminifer species Neogloboquadrina pachyderma (sin.) and Turborotalita quinqueloba with a large-diameter multinet and a multicorer, respectively. The δ13C and δ18O values of the shells are compared to the stable isotope composition of the ambient water and to equilibrium calcite values to define the preferred calcification depths of the foraminifers and to determine the factors controlling the isotopic signature of these calcareous microorganisms. The study area was chosen because of its high oceanographic variability: in the eastern Fram Strait the northward flowing West Spitsbergen Current (WSC) carries Atlantic Water, with a thin mixed layer on top, while in the west the upper 200 m consists of cold, low-saline Arctic outflow waters of the East Greenland Current (EGC) and warmer, saline waters of Atlantic origin underneath. Despite this variable oceanographic regime along the studied transect, the stable carbon isotope ratios of the shells do not show major differences according to their horizontal but to their vertical distribution: the δ13C values of N. pachyderma (sin.) from plankton tow samples vary roughly between -1 and -0.1‰ depending on the water depth, while the δ18O values of the tests differ more between the stations.

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

    NASA Astrophysics Data System (ADS)

    Savarino, Joël; Vicars, William C.; Legrand, Michel; Preunkert, Suzanne; Jourdain, Bruno; Frey, Markus M.; Kukui, Alexandre; Caillon, Nicolas; Gil Roca, Jaime

    2016-03-01

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

  14. Oxygen and iron isotope studies of magnetite produced by magnetotactic bacteria

    USGS Publications Warehouse

    Mandernack, K.W.; Bazylinski, D.A.; Shanks, Wayne C.; Bullen, T.D.

    1999-01-01

    A series of carefully controlled laboratory studies was carried out to investigate oxygen and iron isotope fractionation during the intracellular production of magnetite (Fe3O4) by two different species of magnetotactic bacteria at temperatures between 4??and 35??C under microaerobic and anaerobic conditions. No detectable fractionation of iron isotopes in the bacterial magnetites was observed. However, oxygen isotope measurements indicated a temperature-dependent fractionation for Fe3O4 and water that is consistent with that observed for Fe3O4 produced extracellularly by thermophilic Fe3+-reducing bacteria. These results contrast with established fractionation curves estimated from either high-temperature experiments or theoretical calculations. With the fractionation curve established in this report, oxygen-18 isotope values of bacterial Fe3O4 may be useful in paleoenvironmental studies for determining the oxygen-18 isotope values of formation waters and for inferring paleotemperatures.

  15. Mass-independent oxygen isotopic partitioning during gas-phase SiO2 formation.

    PubMed

    Chakraborty, Subrata; Yanchulova, Petia; Thiemens, Mark H

    2013-10-25

    Meteorites contain a wide range of oxygen isotopic compositions that are interpreted as heterogeneity in solar nebula. The anomalous oxygen isotopic compositions of refractory mineral phases may reflect a chemical fractionation process in the nebula, but there are no experiments to demonstrate this isotope effect during particle formation through gas-phase reactions. We report experimental results of gas-to-particle conversion during oxidation of silicon monoxide that define a mass-independent line (slope one) in oxygen three-isotope space of (18)O/(16)O versus (17)O/(16)O. This mass-independent chemical reaction is a potentially initiating step in nebular meteorite formation, which would be capable of producing silicate reservoirs with anomalous oxygen isotopic compositions. PMID:24159043

  16. Zircon megacrysts from kimberlite: oxygen isotope variability among mantle melts

    NASA Astrophysics Data System (ADS)

    Valley, John W.; Kinny, Peter D.; Schulze, Daniel J.; Spicuzza, Michael J.

    The oxygen isotope ratios of Phanerozoic zircons from kimberlite pipes in the Kaapvaal Craton of southern Africa and the Siberian Platform vary from 4.7 to 5.9‰ VSMOW. High precision, accurate analyses by laser reveal subtle pipe-to-pipe differences not previously suspected. These zircons have distinctive chemical and physical characteristics identifying them as mantle-derived megacrysts similar to zircons found associated with diamond, coesite, MARID xenoliths, Cr-diopside, K-richterite, or Mg-rich ilmenite. Several lines of evidence indicate that these 18O values are unaltered by kimberlite magmas during eruption and represent compositions preserved since crystallization in the mantle, including: U/Pb age, large crystal size, and the slow rate of oxygen exchange in non-metamict zircon. The average 18O of mantle zircons is 5.3‰, 0.1 higher and in equilibrium with values for olivine in peridotite xenoliths and oceanic basalts. Zircon megacrysts from within 250 km of Kimberley, South Africa have average 18O=5.32+/-0.17 (n=28). Small, but significant, differences among other kimberlite pipes or groups of pipes may indicate isotopically distinct reservoirs in the sub-continental lithosphere or asthenosphere, some of which are anomalous with respect to normal mantle values of 5.3+/-0.3. Precambrian zircons (2.1-2.7 Ga) from Jwaneng, Botswana have the lowest values yet measured in a mantle zircon, 18O=3.4 to 4.7‰. These zircon megacrysts originally crystallized in mafic or ultramafic rocks either through melting and metasomatism associated with kimberlite magmatism or during metamorphism. The low 18O zircons are best explained by subduction of late Archean ocean crust that exchanged with heated seawater prior to underplating as eclogite and to associated metasomatism of the mantle wedge. Smaller differences among other pipes and districts may result from variable temperatures of equilibration, mafic versus ultramafic hosts, or variable underplating. The narrow

  17. Reconstructing a Hot and High Eocene Sierra Nevada Using Oxygen and Hydrogen Isotopes in Kaolinite

    NASA Astrophysics Data System (ADS)

    Mix, H.; Ibarra, D. E.; Mulch, A.; Graham, S. A.; Chamberlain, C. P.

    2014-12-01

    Despite the broad interest in determining the topographic and climatic histories of mountain ranges, the evolution of California's Sierra Nevada remains actively debated. Prior stable isotope-based studies of Sierra Nevada have relied exclusively on hydrogen isotopes in kaolinite, hydrated volcanic glass and leaf n-alkanes. Additional constraints from the oxygen isotope composition of phyllosilicates increase the robustness of findings from a single isotope system and allow for the reconstruction of paleotemperatures. Here, we reconstruct the temperature and elevation of the Early Eocene Sierra Nevada using the oxygen isotope composition of kaolinitized granite clasts from the ancestral Yuba and American Rivers. We evaluate the possible contributions of hydrogen isotope exchange by direct comparison with more robust oxygen isotope measurements. Next, we utilize differences in the hydrogen and oxygen isotope fractionation in kaolinite to constrain paleotemperature. Oxygen isotope geochemistry of in-situ kaolinites indicates upstream (eastward) depletion of 18O in the northern Sierra Nevada. δ18O values ranging from 11.4 - 14.4 ‰ at the easternmost localities correspond to paleoelevations as high as 2400 m when simulating the orographic precipitation of moisture from a Pacific source using Eocene boundary conditions. This finding is consistent with stable isotope studies of the northern Sierra, but oxygen isotope based paleoelevation estimates are systematically ~500 - 1000 m higher than those from hydrogen-based estimates from the same samples. Kaolinite geothermometry from 16 samples measured in duplicate or triplicate produce an average Early Eocene temperature of 24.2 ± 2.0 °C (1s). This kaolinite temperature reconstruction is in agreement with paleofloral and geochemical constraints and general circulation model simulations from Eocene California. Our results confirm prior hydrogen isotope-based paleoelevations and further substantiate the existence of a

  18. Oxygen Isotopic Composition of Dissolved Inorganic Phosphate in the Monterey Bay and California Current

    NASA Astrophysics Data System (ADS)

    McLaughlin, K.; Paytan, A.; Kendall, C.

    2001-12-01

    The marine biogeochemical cycle of phosphorus (P) is intricately linked to the atmospheric abundance of CO2 through its role as an important major nutrient. Phosphorus is considered to be a limiting nutrient in some oceanic systems (Cotner et al., 1997; Karl et al., 1995; Michaels et al., 1996; Wu et al., 2000) and is possibly the ultimate limiting macronutrient for marine productivity (Broecker and Peng, 1982; Delaney, 1998; Toggweiler, 1999; Tyrrell, 1999). Despite the recognition of the important role P plays in regulating marine productivity and thus the "biological pump" relatively little is known about P cycling within the ocean. We have mapped spatial and temporal variations in the oxygen isotopic composition of phosphate within the Monterey Bay and along a transect in the California Current. The P-O bond is resistant to inorganic hydrolysis and, in the temperature range of the ocean, is only broken by enzyme mediated reactions. Therefore, the d18O of inorganic phosphate should reflect the degree of recycling of phosphate within the ecosystem where greater recycling corresponds to increased equilibration with d18O of seawater. We have applied a method for extraction of dissolved inorganic phosphate from seawater and purification to silver phosphate for oxygen isotopic analysis (McLaughlin et al., 2000). These results are the first step in determining how phosphate recycling varies spatially and throughout the water column.

  19. Reevaluation of conflicting Eocene tropical temperature estimates: Molluskan oxygen isotope evidence for warm low latitudes

    NASA Astrophysics Data System (ADS)

    Kobashi, Takuro; Grossman, Ethan L.; Yancey, Thomas E.; Dockery, David T., III

    2001-11-01

    Oxygen isotope data from planktonic foraminifera for the warm Eocene epoch suggest that tropical sea-surface temperatures (SSTs) may have been cooler than at present. Such data have stimulated various explanations involving, e.g., major changes in ocean heat transport. However, the planktonic data disagree with terrestrial climate proxies, which suggest significantly warmer low-latitude temperatures. We examined this discrepancy by analyzing seasonal oxygen isotope variations in shallow-marine mollusks from the Mississippi Embayment. Results indicate that mean annual SSTs decreased from 26 27 °C in the early Eocene to 22 23 °C in the Oligocene, agreeing well with temperatures inferred from terrestrial climate proxies. These cooling trends, with more significant winter cooling (5 °C) than summer cooling (3 °C), are consistent with the predicted consequences of decreasing atmospheric CO2 concentration through the Paleogene, suggesting that atmospheric CO2 change was a major controlling factor for Paleogene climate change. That winter SST estimates from the mollusks agree well with the foraminiferal SST estimates suggests that planktonic foraminiferal growth in low latitudes occurred mainly during the cooler winter months throughout the Eocene. We hypothesize that the unusual hydrography of Eocene oceans shifted foraminiferal productivity primarily to winter, biasing foraminiferal SST estimates of mean annual SSTs.

  20. The retention of primary oxygen isotope compositions of fossil elephant skeletal phosphate

    NASA Astrophysics Data System (ADS)

    Ayliffe, L. K.; Chivas, A. R.; Leakey, M. G.

    1994-12-01

    Fossil elephant remains from sediments of Plio-Pleistocene age in the vicinity of Lake Turkana, Kenya, provide insights into the ability of the phosphate-oxygen system to preserve original δ18O values ( δ18Op) in the depositional environment. Individual fossil specimens exhibit systematic variations in the δ18Op values of their various tooth and bone components. Differences in δ18Op values between these skeletal components can be as high as 3.6%., despite the fact that equivalent phases for individual modern elephants have δ18Op values which vary by less than 0.6%.. XRD traces of the different skeletal phases of modern and fossil samples, also infer differential preservation of primary apatite crystallinities among the various fossil phases. Fossil samples of dentine, cementum and bone have X-ray spectra with sharper and more intense peaks compared to their modern counterparts, but little change in crystallinity is observed for fossil enamel samples. A model based on the premise that the enamel phase preserves primary isotope signatures and that the accompanying skeletal phases are partially re-equilibrated with the fluids associated with the microbial decomposition of the elephant's carcass is consistent with the features of the 18O p dataset. This isotopic evidence, in conjunction with the physical and chemical attributes of enamel, has led us to postulate that enamel could be preserving primary isotope signatures while other skeletal components are affected to varying degrees by alteration processes in the burial environment.

  1. Computational modeling of oxygen isotope effects on metal-mediated O2 activation at varying temperatures.

    PubMed

    Smirnov, Valeriy V; Lanci, Michael P; Roth, Justine P

    2009-03-12

    Oxygen equilibrium isotope effects ((18)O EIEs) upon the formation of metal superoxide and peroxide structures from natural abundance O(2) are reported. The (18)O EIEs determined over a range of temperatures are compared to those calculated on the basis of vibrational frequencies. Considering all vibrational modes in a "full frequency model" is found to reproduce the empirical results better than "cut-off" models which consider only the most isotopically sensitive modes. Theoretically, the full frequency model predicts that (18)O EIEs arise from competing enthalpic and entropic influences resulting in nonlinear variations with temperature. Experimental evidence is provided for an increase in the magnitude of the EIE, in some instances implicating a change from inverse to normal values, as the temperature is raised. This finding is not easily reconciled with the common intuition that (18)O EIEs arise from a reduction of the O-O force constant and attendant changes in zero point energy level splitting. Instead a dominant entropic effect, as described here, is expected to characterize isotope effects upon reversible binding of small molecules to metal centers in enzymes and inorganic compounds.

  2. The age curves of sulfur and oxygen isotopes in marine sulfate and their mutual interpretation

    USGS Publications Warehouse

    Claypool, George E.; Holser, William T.; Kaplan, Isaac R.; Sakai, Hitoshi; Zak, Israel

    1980-01-01

    Three hundred new samples of marine evaporite sulfate, of world-wide distribution, were analyzed for δ34S, and 60 of these also for δ18O in the sulfate ion. Detailed δ34S age curves for Tertiary—Cretaceous, Permian—Pennsylvanian, Devonian, Cambrian and Proterozoic times document large variations in δ34S. A summary curve forδ18O also shows definite variations, some at different times than δ34S, and always smaller. The measured δ34S and δ18O correspond to variations in these isotopes in sulfate of the world ocean surface. The variations of δ18O are controlled by input and output fluxes of sulfur in the ocean, three of which are the same that control δ34S: deposition and erosion of sulfate, and deposition of sulfide. Erosion of sulfide differs in its effect on the S and O systems. δ18O in the sulfate does not seem to be measurably affected by equilibration with either seawater or with subsurface waters after crystallization. In principle, the simultaneous application of both δ34S and δ18O age curves should help reduce the number of assumptions in calculations of the cycles of sulfur and oxygen through geological time, and a new model involving symmetrical fluxes is introduced here to take advantage of the oxygen data. However, all previously published models as well as this one lead to anomalies, such as unreasonable calcium or oxygen depletions in the ocean—atmosphere system. In addition, most models are incapable of reproducing the sharp rises of the δ34S curve in the late Proterozoic, the Devonian and the Triassic which would be the result of unreasonably fast net sulfide deposition. This fast depletion could result from an ocean that has not always been mixed (as previously assumed in all model calculations).

  3. Thallium isotope variations in anthropogenically-affected soils

    NASA Astrophysics Data System (ADS)

    Vanek, Ales; Chrastny, Vladislav; Penizek, Vit; Mihaljevic, Martin; Komarek, Michael; Cabala, Jerzy

    2014-05-01

    Our preliminary data from soils impacted by long-term Tl deposition in the vicinity of a primary/secondary Zn smelter at Olkusz (Poland) indicate apparent variability of ɛ205Tl within soil profiles. The identified ɛ205Tl values presented for the forest soil profile reached -1.7 in the surface/organic horizon, +1.9 in the organo-mineral horizon (Ap), and +1.0 in the mineral horizon (C). This finding suggests both the enrichment of 203Tl isotope in the topsoil, as well as its preferential release during smelting operations, as "lighter" Tl tends to enter the emissions during a high-temperature process. The maximum ɛ205Tl value in the subsurface horizon Ap is in accordance with the concentration peak of oxalate-extractable Mn, indicating the presence of amorphous/poorly-crystalline Mn oxides with a potential to isotopically fractionate Tl toward the "heavier" fraction. The Tl isotope signature in the bottom horizon probably reflects the composition of a local geochemical anomaly of Tl. However, a portion of mobile (anthropogenic) Tl with negative ɛ205Tl moving downwards in the soil profile cannot be neglected. In general, there is no detailed information about the biogeochemical cycling and variations of Tl isotopes in areas affected by significant anthropogenic inputs of the metal (e.g., coal burning and primary metallurgy); the questions of the degree to which the factors such as soil (and sediment) chemistry, mineralogy, local biota, and pollution source control Tl isotope fractionation remain unresolved. Therefore, further research on the topic is needed before any principal conclusions will be made.

  4. Herbivore tooth oxygen isotope compositions: Effects of diet and physiology

    NASA Astrophysics Data System (ADS)

    Kohn, Matthew J.; Schoeninger, Margaret J.; Valley, John W.

    1996-10-01

    The applicability of rapid and precise laser probe analysis of tooth enamel for δ18O has been verified, and the method has been applied to different modern herbivores in East Africa. Sampling and pretreatment procedures involve initial bleaching and grinding of enamel to <75 μm, and elimination of adsorbed water and organic compounds with BrF 5. Typical analytical reproducibilities for 0.5-2 mg samples are ±0.08‰ (± 1σ). Chemical and spectroscopic characterization of pretreated but unanalyzed samples show no alteration compared to fresh enamel. Solid reaction products are nearly pure CaF 2 with little evidence for residual O 2. Because laser probe fluorination extracts oxygen from all sites in the apatite structure (phosphate, structural carbonate, and hydroxyl), only unaltered tooth enamel (>95% apatite) can be analyzed reliably. Different East African herbivores exhibit previously unsuspected compositional differences. Average enamel δ18O values (V-SMOW) are approximately: 25‰ (goat), 27‰ (oryx), 28‰ (dikdik and zebra), 29‰ (topi), 30‰ (gerenuk), and 32‰ (gazelle). These compositions differ from generalized theoretical models, but are broadly consistent with expected isotope effects associated with differences in how much each animal (a) drinks, (b) eats C3 vs. C4 plants, and (c) pants vs. sweats. Consideration of diet, water turnover, and animal physiology will allow the most accurate interpretation of ancient teeth and targeting of environmentally-sensitive animals in paleoclimate studies.

  5. The carbon and oxygen isotope records of reef-dwelling foraminifers subjected to five varied pCO2 seawater

    NASA Astrophysics Data System (ADS)

    Hikami, M.; Ishimura, T.; Suzuki, A.; Nojiri, Y.; Kawahata, H.

    2013-12-01

    in imperforate. For oxygen isotope ratio variation possibility among species would be caused by their Mg-content concentration in calcite shells. The distinct difference in the level of carbon isotope ratio between pure calcite and perforate foraminifera might be influenced by the degree of dependency on metabolic CO2 used for shell construction. The imperforate species would use most carbon derived from bicarbonate ion of seawater directly because the carbon isotope ratio of shell is almost same to that of pure calcite. Therefore, oxygen and carbon isotope ratio of foraminiferal test have the potential to reveal calcification mechanism of two species.

  6. A model of oxygen transport in Pt/ceria catalysts from isotope exchange

    SciTech Connect

    Holmgren, A.; Andersson, B.; Duprez, D.

    1999-03-10

    From isotope oxygen exchange reactions and simulations of these experiments, the important steps in oxygen transport in Pt/ceria were distinguished and their rates were estimated. A Pt/alumina sample was also experimentally investigated for comparison. Oxygen surface diffusion as well as oxygen spillover from Pt to ceria was found to be fast in comparison with adsorption/desorption of oxygen on the metal and oxygen bulk diffusion. The exchange rate was found to be higher on a very-low-Pt-dispersion sample than on a high-dispersion sample, which in the model was explained by the different adsorption properties of oxygen.

  7. Characterizing Variation of Isotopic Markers in Northern Alaskan Caribou Forages

    NASA Astrophysics Data System (ADS)

    VanSomeren, L.; Barboza, P. S.; Gustine, D. D.; Parrett, L. S.; Stricker, C. A.

    2013-12-01

    Isotopic markers in feces and tissues are a potential tool for monitoring the importance of feeding areas for migratory herbivores such as caribou (Rangifer tarandus). Many of these techniques are currently limited by gaps in our knowledge of how these isotopic signatures vary over the landscape. We collected seven species of preferred caribou forages along a latitudinal gradient in the summer ranges of the Central Arctic (9 sites) and Teshekpuk Lake (4 sites) caribou herds during 2011 and 2012. We analyzed forages at peak protein content and at the end of the season to characterize temporal, species-specific, and spatial variation in isotopic markers. The availability of C and N was measured by digestion in vitro. Isotopic signatures of digested samples were used to calculate fractionation that would bias the isotopic signature of feces. The range of values for isotopes (all values ‰) of nitrogen (δ15N -9.5 - +4.3), and sulfur (δ34S -3.6 - +15.5) were greater than those for carbon (δ13C -30.5 - -24.9). Small declines in forage δ13C with latitude (Carex aquatilis, Eriophorum vaginatum, Salix pulchra, and S. richardsonii [all P < 0.01]), season (all species except C. bigelowii [all P ≤ 0.01]), and season x year (S. richardsonii; P = 0.01) were probably associated with changes in water availability. Fractionation of δ13C in early season forages was 0.1 × 1.0 and positively related to C availability (58% × 15%; P < 0.01) with the greatest fractionation for the highly digestible forb Pedicularis langsdorfii (1.43 × 0.44; P < 0.01). Sedges (Carex and Eriophorum) were significantly higher in δ15N than Salix spp. and other dicots (2.0 × 1.1 vs. -2.9 × 2.2; P < 0.01). For Salix spp., δ15N was consistent over the season and between years. Fractionation of δ15N in early season forages was 0.2 × 1.8 and not related to N availability (60% × 17%). For S. pulchra, δ34S may indicate usage of coastal habitats over foothills because δ34S was higher on the

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

    NASA Astrophysics Data System (ADS)

    Nielson, Kristine E.; Bowen, Gabriel J.

    2010-03-01

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

  9. Oxygen Isotope Character of the Lake Owyhee Volcanic Field, Oregon

    NASA Astrophysics Data System (ADS)

    Blum, T.; Strickland, A.; Valley, J. W.

    2012-12-01

    Oxygen isotope analyses of zircons from lavas and tuffs from the Lake Owyhee Volcanic Field (LOVF) of east central Oregon unequivocally demonstrate the presence of mid-Miocene low-δ18O magmas (δ18Ozrc<4.7 ‰). Despite the growing data set of low-δ18O melts within, and proximal to, the Snake River Plain (SRP) Large Igneous Province, debate persists regarding both the mechanisms for low-δ18O magma petrogenesis, and their relative influence in the SRP. The LOVF is associated with widespread silicic volcanism roughly concurrent with the eruption of the Steens-Columbia River Basalt Group between ~17-15Ma. Silicic activity in the LOVF is limited to 16-15Ma, when an estimated 1100km3 of weakly peralkaline to metaluminous rhyolitic lavas and ignimbrites erupted from a series of fissures and calderas. Geographically, the LOVF overlaps the Oregon-Idaho Graben (OIG), and straddles the 87Sr/86Sr= 0.704 line which, together with the 0.706 line to the east, delineate the regional transition from the North American Precambrian continental crust to the east to younger Phanerozoic accreted terranes to the west. Here we report high accuracy ion microprobe analyses of δ18O in zircons using a 10-15μm spot, with average spot-to-spot precision ±0.28‰ (2SD), to investigate intra-grain and intra-unit δ18Ozrc trends for LOVF rhyolites. Due to its high closure temperature, chemical and physical resistance, and slow oxygen diffusion rates, zircon offers a robust record of magmatic oxygen isotope ratios during crystallization and provides constraints on the petrogenesis of Snake River Plain (SRP) low-δ18O melts. Individual zircons from LOVF rhyolites show no evidence of core-rim δ18O zoning, and populations exhibit ≤0.42‰ (2SD) intra-unit variability. Unit averages range from 2.2 to 4.3‰, with the lowest values in caldera-forming ignimbrites, but all units show evidence of crystallization from low-δ18O melts. Quartz and feldspar analyses by laser fluorination (precision

  10. Seasonal transfer of oxygen isotopes from precipitation and soil to the tree ring: source water versus needle water enrichment.

    PubMed

    Treydte, Kerstin; Boda, Sonja; Graf Pannatier, Elisabeth; Fonti, Patrick; Frank, David; Ullrich, Bastian; Saurer, Matthias; Siegwolf, Rolf; Battipaglia, Giovanna; Werner, Willy; Gessler, Arthur

    2014-05-01

    For accurate interpretation of oxygen isotopes in tree rings (δ(18) O), it is necessary to disentangle the mechanisms underlying the variations in the tree's internal water cycle and to understand the transfer of source versus leaf water δ(18) O to phloem sugars and stem wood. We studied the seasonal transfer of oxygen isotopes from precipitation and soil water through the xylem, needles and phloem to the tree rings of Larix decidua at two alpine sites in the Lötschental (Switzerland). Weekly resolved δ(18) O records of precipitation, soil water, xylem and needle water, phloem organic matter and tree rings were developed. Week-to-week variations in needle-water (18) O enrichment were strongly controlled by weather conditions during the growing season. These short-term variations were, however, not significantly fingerprinted in tree-ring δ(18) O. Instead, seasonal trends in tree-ring δ(18) O predominantly mirrored trends in the source water, including recent precipitation and soil water pools. Modelling results support these findings: seasonal tree-ring δ(18) O variations are captured best when the week-to-week variations of the leaf water signal are suppressed. Our results suggest that climate signals in tree-ring δ(18) O variations should be strongest at temperate sites with humid conditions and precipitation maxima during the growing season.

  11. Oxygen-18 content of atmospheric oxygen does not affect the oxygen isotope relationship between environmental water and cellulose in a submerged aquatic plant, Egeria densa Planch

    SciTech Connect

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

    1989-10-01

    We determined that the oxygen isotopic composition of cellulose synthesized by a submerged plant, Egeria densa Planch., is related to the isotopic composition of environmental water by a linear function, {delta}{sup 18}O cellulose = 0.48 {delta}{sup 18}O water + 24.1{per thousand}. The observation of a slope of less than 1 indicates that a portion of cellulose oxygen is derived from an isotopically constant source other than water. We tested whether this source might be molecular oxygen by growing plants in the presence of high concentrations of {sup 18}O in the form of O{sub 2} bubbled into the bottom of an aquarium. Cellulose synthesized during this experiment did not have significantly different oxygen isotope ratios than that synthesized by control plants exposed to O{sub 2} of normal {sup 18}O abundance. We propose that oxygen in organic matter recycled from senescent portions of the plant is incorporated into cellulose. Our findings indicate that paleoclimatic models linking the oxygen isotope composition of environmental water to cellulose from fossil plants will have to be modified to account for contributions of oxygen from this or other sources besides water.

  12. Holocene climate change in Newfoundland reconstructed using oxygen isotope analysis of lake sediment cores

    NASA Astrophysics Data System (ADS)

    Finkenbinder, Matthew S.; Abbott, Mark B.; Steinman, Byron A.

    2016-08-01

    Carbonate minerals that precipitate from open-basin lakes can provide archives of past variations in the oxygen isotopic composition of precipitation (δ18Oppt). Holocene δ18Oppt records from the circum- North Atlantic region exhibit large fluctuations during times of rapid ice sheet deglaciation, followed by more stable conditions when interglacial boundary conditions were achieved. However, the timing, magnitude, and climatic controls on century to millennial-scale variations in δ18Oppt in northeastern North America are unclear principally because of a dearth of paleo-proxy data. Here we present a lacustrine sediment oxygen isotope (δ18O) record spanning 10,200 to 1200 calendar years before present (cal yr BP) from Cheeseman Lake, a small, alkaline, hydrologically open lake basin located in west-central Newfoundland, Canada. Stable isotope data from regional lakes, rivers, and precipitation indicate that Cheeseman Lake water δ18O values are consistent with the isotopic composition of inflowing meteoric water. In light of the open-basin hydrology and relatively short water residence time of the lake, we interpret down-core variations in calcite oxygen isotope (δ18Ocal) values to primarily reflect changes in δ18Oppt and atmospheric temperature, although other factors such as changes in the seasonality of precipitation may be a minor influence. We conducted a series of climate sensitivity simulations with a lake hydrologic and isotope mass balance model to investigate theoretical lake water δ18O responses to climate change. Results from these experiments suggest that Cheeseman Lake δ18O values are primarily controlled by temperature and to a much lesser extent, the seasonality of precipitation. Increasing and more positive δ18Ocal values between 10,200 and 8000 cal yr BP are interpreted to reflect the waning influence of the Laurentide Ice Sheet on atmospheric circulation, warming temperatures, and rapidly changing surface ocean δ18O from the input of

  13. Oxygen isotope evidence for submarine hydrothermal alteration of the Del Puerto ophiolite, California

    USGS Publications Warehouse

    Schiffman, P.; Williams, A.E.; Evarts, R.C.

    1984-01-01

    The oxygen isotope compositions and metamorphic mineral assemblages of hydrothermally altered rocks from the Del Puerto ophiolite and overlying volcaniclastic sedimentary rocks at the base of the Great Valley sequence indicate that their alteration occurred in a submarine hydrothermal system. Whole rock ??18O compositions decrease progressively down section (with increasing metamorphic grade): +22.4??? (SMOW) to +13.8 for zeolite-bearing volcaniclastic sedimentary rocks overlying the ophiolite; +19.6 to +11.6 for pumpellyite-bearing metavolcanic rocks in the upper part of the ophiolite's volcanic member; +12.3 to +8.1 for epidote-bearing metavolcanic rocks in the lower part of the volcanic member; +8.5 to +5.7 for greenschist facies rocks from the ophiolite's plutonic member; +7.6 to +5.8 for amphibolite facies or unmetamorphosed rocks from the plutonic member. Modelling of fluid-rock interaction in the Del Puerto ophiolite indicates that the observed pattern of upward enrichment in whole rock ??18O can be best explained by isotopic exchange with discharging 18O-shifted seawater at fluid/rock mass ratios near 2 and temperatures below 500??C. 18O-depleted plutonic rocks necessarily produced during hydrothermal circulation were later removed as a result of tectonism. Submarine weathering and later burial metamorphism at the base of the Great Valley sequence cannot by itself have produced the zonation of hydrothermal minerals and the corresponding variations in oxygen isotope compositions. The pervasive zeolite and prehnite-pumpellyite facies mineral assemblages found in the Del Puerto ophiolite may reflect its origin near an island arc rather than deep ocean spreading center. ?? 1984.

  14. Oxygen isotope values of precipitation and the thermal climate in Europe during the middle to late Weichselian ice age

    NASA Astrophysics Data System (ADS)

    Arppe, L.; Karhu, J. A.

    2010-05-01

    The oxygen isotope compositions of 28 mammoth tooth enamel samples from Estonia, Latvia, Lithuania, Poland and Denmark provide new quantitative records of the middle to late Weichselian climate in northern Europe. The new δ18O data was combined with records of oxygen isotope values from earlier investigations on European mammoth tooth enamel and palaeogroundwaters to study the spatial patterns and temporal variations in the oxygen isotope composition of precipitation and the thermal climate over much of Europe. The reconstructed geographical distribution of δ18O in precipitation during 52-24 ka reflects the progressive isotopic depletion of air masses moving northeast, consistent with a westerly source of moisture for the entire region, and a circulation pattern similar to that of the present-day. Regional long-term average δ18O w values were 0.6-4.1‰ lower than at present, the largest changes recorded for the currently maritime influenced southern Sweden and the Baltic region. The application of regionally varied δ/ T-slopes, estimated from palaeogroundwater data and modern correlations, yield reasonable estimates of glacial surface temperatures in Europe and imply 2-9 °C lower long-term mean annual surface temperatures during the glacial period.

  15. A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water—USGS50 Lake Kyoga Water

    USGS Publications Warehouse

    Coplen, Tyler B.; Wassenaar, Leonard I; Mukwaya, Christine; Qi, Haiping; Lorenz, Jennifer M.

    2015-01-01

    This isotopic reference material, designated as USGS50, is intended as one of two reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer, of use especially for isotope-hydrology laboratories analyzing freshwater samples from equatorial and tropical regions.

  16. Sulfur and oxygen isotope tracing in zero valent iron based In situ remediation system for metal contaminants.

    PubMed

    Kumar, Naresh; Millot, Romain; Battaglia-Brunet, Fabienne; Négrel, Philippe; Diels, Ludo; Rose, Jérôme; Bastiaens, Leen

    2013-01-01

    In the present study, controlled laboratory column experiments were conducted to understand the biogeochemical changes during the microbial sulfate reduction. Sulfur and oxygen isotopes of sulfate were followed during sulfate reduction in zero valent iron incubated flow through columns at a constant temperature of 20±1°C for 90 d. Sulfur isotope signatures show considerable variation during biological sulfate reduction in our columns in comparison to abiotic columns where no changes were observed. The magnitude of the enrichment in δ(34)S values ranged from 9.4‰ to 10.3‰ compared to initial value of 2.3‰, having total fractionation δS between biotic and abiotic columns as much as 6.1‰. Sulfur isotope fractionation was directly proportional to the sulfate reduction rates in the columns. Oxygen isotopes in this experiment seem less sensitive to microbial activities and more likely to be influenced by isotopic exchange with ambient water. A linear relationship is observed between δ(34)S and δ(18)O in biotic conditions and we also highlight a good relationship between δ(34)S and sulfate reduction rate in biotic columns.

  17. Variability in magnesium, carbon and oxygen isotope compositions, and trace element contents of brachiopod shells: implications for paleoceanographic studies

    NASA Astrophysics Data System (ADS)

    Rollion-Bard, Claire; Saulnier, Ségolène; Vigier, Nathalie; Schumacher, Aimryc; Chaussidon, Marc; Lécuyer, Christophe

    2016-04-01

    Magnesium content in the ocean is ≈ 1290 ppm and is one of the most abundant elements. It is involved in the carbon cycle via the dissolution and precipitation of carbonates, especially Mg-rich carbonates as dolomites. The Mg/Ca ratio of the ocean is believed to have changed through time. The causes of these variations, i.e. hydrothermal activity change or enhanced precipitation of dolomite, could be constrained using the magnesium isotope composition (δ26Mg) of carbonates. Brachiopods, as marine environmental proxies, have the advantage to occur worldwide in a depth range from intertidal to abyssal, and have been found in the geological record since the Cambrian. Moreover, as their shell is in low-Mg calcite, they are quite resistant to diagenetic processes. Here we report δ26Mg, δ18O, δ13C values along with trace element contents of one modern brachiopod specimen (Terebratalia transversa) and one fossil specimen (Terebratula scillae, 2.3 Ma). We combined δ26Mg values with oxygen and carbon isotope compositions and trace element contents to look for possible shell geochemical heterogeneities in order to investigate the processes that control the Mg isotope composition of brachiopod shells. We also evaluate the potential of brachiopods as a proxy of past seawater δ26Mg values. The two investigated brachiopod shells present the same range of δ26Mg variation (up to 2 ‰)). This variation cannot be ascribed to changes in environmental parameters, i.e. temperature or pH. As previously observed, the primary layer of calcite shows the largest degree of oxygen and carbon isotope disequilibrium relative to seawater. In contrast, the δ26Mg value of this layer is comparable to that of the secondary calcite layer value. In both T. scillae and T. transversa, negative trends are observable between magnesium isotopic compositions and oxygen and carbon isotopic compositions. These trends, combined to linear relationships between δ26Mg values and REE contents, are best

  18. A model predicting hydrogen and oxygen isotopes of mammalian hair at the landscape scale

    NASA Astrophysics Data System (ADS)

    Ehleringer, J.; Podlesak, D.; Cerling, T.; Chesson, L.; Bowen, G.

    2006-12-01

    A model has been developed to predict hydrogen and oxygen isotope ratios of keratin in hair of mammalian herbivores and omnivores, incorporating the influences of drinking water and dietary input. The isotopic composition of carbohydrates in food sources and the water in blood and tissues are predicted as intermediate components linking drinking water and dietary sources (environment) with hair (environmental recorder). This model is scaled to landscape and regional levels using geographic information system map predictions of the hydrogen and oxygen isotope ratios of drinking waters and anticipated hydrogen and oxygen isotope ratios of carbohydrate food sources. The model was tested using isotope ratios of human hair (an omnivore) from across the USA. We discuss the application of this model as a tool for providing spatially integrated information about the quality of primary productivity relevant to mammalian herbivores over time, through the effects of varying primary productivity on protein nitrogen balance of the herbivore.

  19. Stable H and O isotope variations reveal sources of recharge in Dhofar, Sultanate of Oman.

    PubMed

    Strauch, Gerhard; Al-Mashaikhi, Khalid S; Bawain, Abdullah; Knöller, Kay; Friesen, Jan; Müller, Thomas

    2014-01-01

    Due to the ability of stable water isotopes to characterize the origin of water and connected processes of groundwater recharge, we used the isotope variations of hydrogen and oxygen in different water sources for assessing the recharge process in the Dhofar region. δ(18)O and δ(2)H of precipitation, spring water, and groundwater cover a range from -10 to +2 and from -70 to +7 ‰ (vs Vienna Standard Mean Ocean Water), respectively, and correlate in a linear relationship close to the Global Meteoric Water Line. No obvious evaporation processes are detected. A clear signal of the recent precipitation is given by the annual monsoon. The monsoon signal is confirmed by several springs existing in the south at the foot of the Dhofar mountains and sources at Gogub above 450 m and Tawi Atir at 650 m above sea level. They occur here first in the form of water intercepted by trees as stemflow and throughflow. The isotope signature of groundwater in the Dhofar mountains reflects the climatic conditions at the time of recharge and the lithological features of the limestone matrix. To the north, the isotope patterns of the groundwater are continuously depleted from the monsoon signal along the outcropping aquifer D (Lower Umm Er Radhuma). Here, a more negative signature towards the wells in the Najd desert region was observed. Cyclone water that flooded wadis in the Dhofar region occasionally, as observed in November 2011, falls isotopically into the same range as we observed in the fossil groundwater. Taking into account the different sources of precipitation and groundwater and thus a clear distinction of the isotopic composition of the water sources, we conclude a recharge process divided into a southward and a northward component in the Dhofar region.

  20. Comparing Stable Water Isotope Variation in Atmospheric Moisture Observed over Coastal Water and Forests

    NASA Astrophysics Data System (ADS)

    Lai, C. T.; Rambo, J. P.; Welp, L. R.; Bible, K.; Hollinger, D. Y.

    2014-12-01

    Stable oxygen (δ18O) and hydrogen (δD) isotopologues of atmospheric moisture are strongly influenced by large-scale synoptic weather cycles, surface evapotranspiration and boundary layer mixing. Atmospheric water isotope variation has been shown to empirically relate to relative humidity (Rh) of near surface moisture, and to a less degree, air temperature. Continuous δ18O and δD measurements are becoming more available, providing new opportunities to investigate processes that control isotope variability. This study shows the comparison of δ18O and δD measured at a continental location and over coastal waters for 3 seasons (spring to fall, 2014). The surface moisture isotope measurements were made using two LGR spectroscopy water vapor isotope analyzers (Los Gatos Research Inc.), one operated in an old-growth coniferous forest at Wind River field station, WA (45.8205°N, 121.9519°W), and another sampling marine air over seawater at the Scripps Pier in San Diego, CA (32.8654°N, 117.2536°W), USA. Isotope variations were measured at 1Hz and data were reported as hourly averages with an overall accuracy of ±0.1‰ for δ18O, ±0.5‰ for δ2H. Day-to-day variations in δ18O and δD are shown strongly influenced by synoptic weather events at both locations. Boundary layer mixing between surface moisture and the dry air entrained from the free troposphere exerts a midday maximum and a consistent diel pattern in deuterium excess (dx). At the forest site, surface moisture also interacts with leaf water through transpiration during the day and re-equilibration at night. The latter occurs by retro-diffusion of atmospheric H2O molecules into leaf intercellular space, which becomes intensified as Rh increaes after nightfall, and continues until sunrise, to counter-balance the evaporative isotopic enrichment in leaf water on a daily basis. These vegetation effects lead to negative dx values consistently observed at nighttime in this continental location that were not

  1. Pressure control on iron isotope variations in MORBS determined by nuclear resonant vibrational spectroscopy

    NASA Astrophysics Data System (ADS)

    Roskosz, M.; Dauphas, N.; Alp, E. E.; Sio, C.; Bi, W.; Tissot, F.; Hu, M.; Zhao, J.; Bouhifd, M. A.; Medard, E.

    2013-12-01

    Isotopes distribution sheds light on interactions and dynamics of planetary reservoirs. During the last decade, significant Fe isotopes variations were measured in materials produced in high temperature environments such as planetary mantles. Because iron is a multivalent element, its isotopes could be good tracers of redox conditions during melting [e.g., 1]. However, reliable database of equilibrium fractionation factors between melts and igneous minerals such as olivine is critically lacking to interpret the rock record. Iron equilibrium fractionation factors can be derived from Nuclear Resonant Inelastic X-ray Scattering (NRIXS) experiments at a synchrotron facility [2, 3] through the determination of mean force constants. This method is insensitive to kinetic effects during mineral and glass synthesis, contrasting with conventional experimental approaches [4]. This technique was used on synthetic 57Fe-labelled olivine prepared in piston-cylinders and silicate glasses synthesized and quenched at different oxygen fugacities in a gas mixing furnace, in piston-cylinders and in multi-anvil apparatuses with and without dissolved water. Finally, in-situ diamond-anvil cell experiments were carried out on some of these high pressure glasses to document both configurational and elastic effects of the pressure applied to them. At a given Fe3+/Fe2+ ratio, the force constants of tholeitic to andesitic glasses are almost identical. For all samples, the force constant increases dramatically and linearly with Fe3+/Fetot. Dissolved water (up to a few wt%) does not affect significantly the force constant at a given redox state. Pressure shows clear configurational and elastic effects. Nonetheless, for mafic melts, redox effects seem to dominate. The olivine-melt and melt Fe2+-Fe3+ iron isotopic fractionations derived from NRIXS data can explain the heavy iron isotopic compositions measured in MORBS. This study provides a solid reference for interpreting Fe isotopic variations

  2. Carbon, Hydrogen, and Oxygen Isotope Ratios of Cellulose from Plants Having Intermediary Photosynthetic Modes 1

    PubMed Central

    Sternberg, Leonel O'Reilly; Deniro, Michael J.; Ting, Irwin P.

    1984-01-01

    Carbon and hydrogen isotope ratios of cellulose nitrate and oxygen isotope ratios of cellulose from species of greenhouse plants having different photosynthetic modes were determined. When hydrogen isotope ratios are plotted against carbon isotope ratios, four clusters of points are discernible, each representing different photosynthetic modes: C3 plants, C4 plants, CAM plants, and C3 plants that can shift to CAM or show the phenomenon referred to as CAM-cycling. The combination of oxygen and carbon isotope ratios does not distinguish among the different photosynthetic modes. Analysis of the carbon and hydrogen isotope ratios of cellulose nitrate should prove useful for screening different photosynthetic modes in field specimens that grew near one another. This method will be particularly useful for detection of plants which show CAM-cycling. PMID:16663360

  3. The oxygen isotopic composition of phosphate in Elkhorn Slough, California: A tracer for phosphate sources

    NASA Astrophysics Data System (ADS)

    McLaughlin, Karen; Cade-Menun, Barbara J.; Paytan, Adina

    2006-11-01

    Elkhorn Slough, a small seasonal estuary in central California, has been subjected to increased nutrient loading from agricultural and other non-point sources. However, because nutrients do not behave conservatively, tracing nutrient sources and cycling in ecosystems like Elkhorn Slough has been difficult to assess. This is particularly true of phosphorus (P), which has only one stable isotope and cannot be used as an isotopic tracer. However, isotopic fractionation of oxygen in phosphate at surface water temperatures only occurs as a result of enzyme-mediated, biochemical reactions. Thus, if phosphate demand is low relative to input and is not heavily cycled within the ecosystem, the δ18O of phosphate will reflect the isotopic composition of phosphate sources to the system. We utilized the δ18O of dissolved inorganic phosphate (DIP) within the main channel of the slough and nearby Moss Landing Harbor and the δ18O of reactive phosphate from sediment and soil samples collected within the watershed to understand phosphate sources and cycling within Elkhorn Slough. Trends in the δ18O of DIP were seasonally consistent with high values near the mouth reflecting oceanic phosphate (19.1‰-20.3‰), dropping to a minimum value near Hummingbird Island in the central slough (point source, 14.1‰-14.4‰), and increasing again near the head of the slough, reflecting fertilizer input (18.9‰-19.3‰). Reactive phosphate δ18O values extracted from sediments and soils in the watershed range from 10.6‰ in a drainage ditch to 22.3‰ in creek sediments near agriculture fields. The wide range in phosphate δ18O values reflects the variations in land use and application of different fertilizers in this agriculturally dominated landscape. These data suggest that phosphate δ18O can be an effective tool for identifying P sources and understanding phosphate dynamics in estuarine ecosystems.

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

    NASA Astrophysics Data System (ADS)

    Savarino, J.; Vicars, W. C.; Legrand, M.; Preunkert, S.; Jourdain, B.; Frey, M. M.; Kukui, A.; Caillon, N.; Gil Roca, J.

    2015-09-01

    Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrogen oxides (NO + NO2 = NOx). The unique and distinctive 17O-excess (Δ17O = δ17O - 0.52 × δ18O) of ozone, which is transferred to NOx via oxidation, is a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O-excess within the NOx cycle is critical in polar areas where there exists the possibility of extending atmospheric investigations to the glacial/interglacial time scale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C (East Antarctic plateau) during the austral summer of 2011/12. Nitrate isotope analysis has been here combined for the first time with key precursors involved in nitrate production (NOx, O3, OH, HO2, RO2, etc.) and direct observations of the transferrable Δ17O of surface ozone, which was measured at Dome C throughout 2012 using our recently developed analytical approach. Assuming that nitrate is mainly produced in Antarctica in summer through the OH + NO2 pathway and using concurrent measurements of OH and NO2, we calculated a Δ17O signature for nitrate in the order of (21-22 ± 3) ‰. These values are lower than the measured values that ranged between 27 and 31 ‰. This discrepancy between expected and observed Δ17O(NO3-) values suggests the existence of an unknown process that contributes significantly to the atmospheric nitrate budget over this east Antarctic region.

  5. Oxygen isotopes as a tracer of phosphate sources and cycling in aquatic systems (Invited)

    NASA Astrophysics Data System (ADS)

    Young, M. B.; Kendall, C.; Paytan, A.

    2013-12-01

    The oxygen isotopic composition of phosphate can provide valuable information about sources and processes affecting phosphorus as it moves through hydrologic systems. Applications of this technique in soil and water have become more common in recent years due to improvements in extraction methods and instrument capabilities, and studies in multiple aquatic environments have demonstrated that some phosphorus sources may have distinct isotopic compositions within a given system. Under normal environmental conditions, the oxygen-phosphorus bonds in dissolved inorganic phosphate (DIP) can only be broken by enzymatic activity. Biological cycling of DIP will bring the phosphate oxygen into a temperature-dependent equilibrium with the surrounding water, overprinting any existing isotopic source signals. However, studies conducted in a wide range of estuarine, freshwater, and groundwater systems have found that the phosphate oxygen is often out of biological equilibrium with the water, suggesting that it is common for at least a partial isotopic source signal to be retained in aquatic systems. Oxygen isotope analysis on various potential phosphate sources such as synthetic and organic fertilizers, animal waste, detergents, and septic/wastewater treatment plant effluents show that these sources span a wide range of isotopic compositions, and although there is considerable overlap between the source groups, sources may be isotopically distinct within a given study area. Recent soil studies have shown that isotopic analysis of phosphate oxygen is also useful for understanding microbial cycling across different phosphorus pools, and may provide insights into controls on phosphorus leaching. Combining stable isotope information from soil and water studies will greatly improve our understanding of complex phosphate cycling, and the increasing use of this isotopic technique across different environments will provide new information regarding anthropogenic phosphate inputs and

  6. Variation of Oxygen-to-Carbon Ratio in Oxyacetylene Flame

    SciTech Connect

    Saraf, Laxmikant V.; Bunch, Kyle J.; Engelhard, Mark H.; Gassman, Paul L.

    2008-09-03

    We present micro-structural and surface analysis of carbon soot using variation in C2H2 to O2 ratio in oxyacetylene flame torch. Preliminary analysis indicate that at higher oxygen content, formation of SiO2 nanotubes and amorphous-SiC like structure take place while at higher C2H2 flame content, we observe majority of amorphous carbon with an evidence of some amorphous sp3 hybridization.

  7. Small Tails Tell Tall Tales – Intra-Individual Variation in the Stable Isotope Values of Fish Fin

    PubMed Central

    Hayden, Brian; Soto, David X.; Jardine, Tim D.; Graham, Brittany S.; Cunjak, Richard A.; Romakkaniemi, Atso; Linnansaari, Tommi

    2015-01-01

    Background Fish fin is a widely used, non-lethal sample material in studies using stable isotopes to assess the ecology of fishes. However, fish fin is composed of two distinct tissues (ray and membrane) which may have different stable isotope values and are not homogeneously distributed within a fin. As such, estimates of the stable isotope values of a fish may vary according to the section of fin sampled. Methods To assess the magnitude of this variation, we analysed carbon (δ13C), nitrogen (δ15N), hydrogen (δ2H) and oxygen (δ18O) stable isotopes of caudal fin from juvenile, riverine stages of Atlantic salmon (Salmo salar) and brown trout (Salmo trutta). Individual fins were sub-sectioned into tip, mid and base, of which a further subset were divided into ray and membrane. Findings Isotope variation between fin sections, evident in all four elements, was primarily related to differences between ray and membrane. Base sections were13C depleted relative to tip (~ 1 ‰) with equivalent variation evident between ray and membrane. A similar trend was evident in δ2H, though the degree of variation was far greater (~ 10 ‰). Base and ray sections were 18O enriched (~ 2 ‰) relative to tip and membrane, respectively. Ray and membrane sections displayed longitudinal variation in 15N mirroring that of composite fin (~ 1 ‰), indicating that variation in15N values was likely related to ontogenetic variation. Conclusions To account for the effects of intra-fin variability in stable isotope analyses we suggest that researchers sampling fish fin, in increasing priority, 1) also analyse muscle (or liver) tissue from a subsample of fish to calibrate their data, or 2) standardize sampling by selecting tissue only from the extreme tip of a fin, or 3) homogenize fins prior to analysis. PMID:26670464

  8. Contrasting behavior of oxygen and iron isotopes in banded iron formation revealed by in situ analysis

    NASA Astrophysics Data System (ADS)

    Beard, B.; Li, W.; Kita, N.; Valley, J. W.; Johnson, C.

    2012-12-01

    Banded iron formations (BIFs) record a period of dramatic secular change in Earth's geologic history, when abundant aqueous Fe(II) was removed from Archean and Proterozoic oceans by oxidation. BIFs are characterized by co-existing of quartz and iron minerals, including oxides and carbonates, and alternating iron-rich and iron-poor layers range from m to isotope ratios in minerals in BIFs provide valuable information about the origin of BIFs, as well as diagenetic and metamorphic effects that were superimposed on primary layering. We analyzed O and Fe isotope compositions of magnetite and hematite in BIFs from the 2.5 Ga Dales Gorge Member of the Brockman Iron Formation, Hamersley Group, Western Australia. Oxygen isotope ratios were measured by Secondary Ion Mass Spectrometry (SIMS), and Fe isotope ratios were measured by femtosecond Laser ablation Multi-Collector ICP-MS (fs-LA-MC-ICP-MS), with spatial resolutions of 15 mm (O) and 30-50 mm (Fe), and external precisions (2s) of +0.7 ‰ for δ18O and +0.2 ‰ for δ56Fe, respectively. Analysis of δ18O in iron oxides by SIMS employed special tuning with a 3kV primary beam to minimize orientation effects (Huberty et al. 2010 ). For hematite, δ18O values range from -7.1 ‰ to -0.6 ‰, with the majority of data clustering around -4.5 ‰, and δ56Fe values range from -0.50 ‰ to +1.53‰. Magnetite has a δ18O range of -5.6 ‰ to +5.6 ‰ and a δ56Fe range of -0.76 ‰ to +1.33 ‰. Notably, magnetite shows significant O isotope heterogeneity at a mineral grain scale, and the highest δ18O values were commonly measured from Si-rich (1-3 wt% SiO2) magnetite overgrowths or magnetite grains that have a recrystallization texture. In contrast, lowest δ18O values were measured from magnetite that contains less than 1 wt% SiO2. Individual magnetite grains can have up to 6 ‰ variation in δ18O values between low-Si core and Si-rich overgrowth. Iron

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

    PubMed

    Popa-Lisseanu, Ana G; Kramer-Schadt, Stephanie; Quetglas, Juan; Delgado-Huertas, Antonio; Kelm, Detlev H; Ibáñez, Carlos

    2015-01-01

    The stable carbon and nitrogen isotope composition of animal tissues is commonly used to trace wildlife diets and analyze food chains. Changes in an animal's isotopic values over time are generally assumed to indicate diet shifts or, less frequently, physiological changes. Although plant isotopic values are known to correlate with climatic seasonality, only a few studies restricted to aquatic environments have investigated whether temporal isotopic variation in consumers may also reflect environmental baselines through trophic propagation. We modeled the monthly variation in carbon and nitrogen isotope values in whole blood of four insectivorous bat species occupying different foraging niches in southern Spain. We found a common pattern of isotopic variation independent of feeding habits, with an overall change as large as or larger than one trophic step. Physiological changes related to reproduction or to fat deposition prior to hibernation had no effect on isotopic variation, but juvenile bats had higher δ13C and δ15N values than adults. Aridity was the factor that best explained isotopic variation: bat blood became enriched in both 13C and 15N after hotter and/or drier periods. Our study is the first to show that consumers in terrestrial ecosystems reflect seasonal environmental dynamics in their isotope values. We highlight the danger of misinterpreting stable isotope data when not accounting for seasonal isotopic baselines in food web studies. Understanding how environmental seasonality is integrated in animals' isotope values will be crucial for developing reliable methods to use stable isotopes as dietary tracers. PMID:25700080

  10. Herbivore tooth oxygen isotope compositions: Effects of diet and physiology

    SciTech Connect

    Kohn, M.J.; Valley, J.W.; Schoeninger, M.J.

    1996-10-01

    The applicability of rapid and precise laser probe analysis of tooth enamel for {delta}{sup 18}O has been verified, and the method has been applied to different modern herbivores in East Africa. Sampling and pretreatment procedures involve initial bleaching and grinding of enamel to <75 {mu}m, and elimination of adsorbed water and organic compounds with BrF{sub 5}. Typical analytical reproducibilities for 0.5-2 mg samples are {+-}0.08{per_thousand} ({+-} 1{sigma}). Chemical and spectroscopic characterization of pretreated but unanalyzed samples show no alteration compared to fresh enamel. Solid reaction products are nearly pure CaF{sub 2} with little evidence for residual O{sub 2}. Because laser probe fluorination extracts oxygen from all sites in the apatite structure (phosphate, structural carbonate, and hydroxyl), only unaltered tooth enamel ( >95% apatite) can be analyzed reliably. Different East African herbivores exhibit previously unsuspected compositional differences. Average enamel {delta}{sup 18}O values (V-SMOW) are approximately: 25{per_thousand} (goat). 27{per_thousand} (oryx), 28{per_thousand} (dikdik and zebra), 29{per_thousand} (topi), 30{per_thousand} (gerenuk), and 32{per_thousand} (gazelle). These compositions differ from generalized theoretical models, but are broadly consistent with expected isotope effects associated with differences in how much each animal (a) drinks, (b) eats C3 vs. C4 plants, and (c) pants vs. sweats. Consideration of diet, water turnover. and animal physiology will allow the most accurate interpretation of ancient teeth and targeting of environmentally-sensitive animals in paleoclimate studies. 66 refs., 2 figs., 2 tabs.

  11. Soil phosphate stable oxygen isotopes across rainfall and bedrock gradients.

    PubMed

    Angert, Alon; Weiner, Tal; Mazeh, Shunit; Sternberg, Marcelo

    2012-02-21

    The stable oxygen isotope compositions of soil phosphate (δ(18)O(p)) were suggested recently to be a tracer of phosphorus cycling in soils and plants. Here we present a survey of bioavailable (resin-extractable or resin-P) inorganic phosphate δ(18)O(p) across natural and experimental rainfall gradients, and across soil formed on sedimentary and igneous bedrock. In addition, we analyzed the soil HCl-extractable inorganic δ(18)O(p), which mainly represents calcium-bound inorganic phosphate. The resin-P values were in the range 14.5-21.2‰. A similar range, 15.6-21.3‰, was found for the HCl-extractable inorganic δ(18)O(p), with the exception of samples from a soil of igneous origin that show lower values, 8.2-10.9‰, which indicate that a large fraction of the inorganic phosphate in this soil is still in the form of a primary mineral. The available-P δ(18)O(p) values are considerably higher than the values we calculated for extracellular hydrolysis of organic phosphate, based on the known fractionation from lab experiments. However, these values are close to the values expected for enzymatic-mediated phosphate equilibration with soil-water. The possible processes that can explain this observation are (1) extracellular equilibration of the inorganic phosphate in the soil; (2) fractionations in the soil are different than the ones measured at the lab; (3) effect of fractionation during uptake; and (4) a flux of intercellular-equilibrated inorganic phosphate from the soil microbiota, which is considerably larger than the flux of hydrolyzed organic-P.

  12. Strontium isotopic variations of Neoproterozoic seawater: implications for crustal evolution.

    PubMed

    Asmerom, Y; Jacobsen, S B; Knoll, A H; Butterfield, N J; Swett, K

    1991-01-01

    We report high precision Sr isotopic data on carbonates from the Neoproterozoic Shaler Group, Victoria Island, Northwest Territories, Canada. Lithostratigraphic correlations with the relatively well-dated Mackenzie Mountains Supergroup constrain Shaler deposition to approximately 770-880 Ma, a range corroborated by 723 +/- 3 Ma lavas that disconformably overlie Shaler carbonates and by Late Riphean microfossils within the section. Samples with low 87Rb/86Sr ratios (<0.01) were selected for Sr isotopic analysis. Delta 18O, Mn, Ca, Mg, and Sr data were used to recognize altered samples. The altered samples are characterized by high Mn/Sr (> or = 2) and variable delta 18O; most are dolomites. The data indicate that between ca. 790-850 Ma the 87Sr/86Sr ratio of seawater varied between 0.70676 and 0.70561. The samples show smooth and systematic variation, with the lowest 87Sr/86Sr value of 0.70561 at ca. 830 Ma. The low 87Sr/86Sr ratio of carbonates from the lower parts of our section is similar to a value reported for one sample from the Adrar of Mauritania (approximately 900 Ma), West African Craton. Isotopic ratios from the upper part of the Shaler section are identical to values from the lower part of the Neoproterozoic Akademikerbreen Group, Spitsbergen. Although a paucity of absolute age determinations hinders attempts at the precise correlation of Neoproterozoic successions, it is possible to draw a broad outline of the Sr isotopic composition of seawater for this period. Indeed, the Sr isotope data themselves provide a stratigraphic tool of considerable potential. Data from this study and the literature are used to construct a curve of the 87Sr/86Sr ratio of Neoproterozoic seawater. The new data reported in this study substantially improve the isotopic record of Sr in seawater for the period 790-850 Ma. The Sr isotope composition of seawater reflects primarily the balance between continental Sr input through river input and mantle input via hydrothermal

  13. Strontium isotopic variations of Neoproterozoic seawater: implications for crustal evolution.

    PubMed

    Asmerom, Y; Jacobsen, S B; Knoll, A H; Butterfield, N J; Swett, K

    1991-01-01

    We report high precision Sr isotopic data on carbonates from the Neoproterozoic Shaler Group, Victoria Island, Northwest Territories, Canada. Lithostratigraphic correlations with the relatively well-dated Mackenzie Mountains Supergroup constrain Shaler deposition to approximately 770-880 Ma, a range corroborated by 723 +/- 3 Ma lavas that disconformably overlie Shaler carbonates and by Late Riphean microfossils within the section. Samples with low 87Rb/86Sr ratios (<0.01) were selected for Sr isotopic analysis. Delta 18O, Mn, Ca, Mg, and Sr data were used to recognize altered samples. The altered samples are characterized by high Mn/Sr (> or = 2) and variable delta 18O; most are dolomites. The data indicate that between ca. 790-850 Ma the 87Sr/86Sr ratio of seawater varied between 0.70676 and 0.70561. The samples show smooth and systematic variation, with the lowest 87Sr/86Sr value of 0.70561 at ca. 830 Ma. The low 87Sr/86Sr ratio of carbonates from the lower parts of our section is similar to a value reported for one sample from the Adrar of Mauritania (approximately 900 Ma), West African Craton. Isotopic ratios from the upper part of the Shaler section are identical to values from the lower part of the Neoproterozoic Akademikerbreen Group, Spitsbergen. Although a paucity of absolute age determinations hinders attempts at the precise correlation of Neoproterozoic successions, it is possible to draw a broad outline of the Sr isotopic composition of seawater for this period. Indeed, the Sr isotope data themselves provide a stratigraphic tool of considerable potential. Data from this study and the literature are used to construct a curve of the 87Sr/86Sr ratio of Neoproterozoic seawater. The new data reported in this study substantially improve the isotopic record of Sr in seawater for the period 790-850 Ma. The Sr isotope composition of seawater reflects primarily the balance between continental Sr input through river input and mantle input via hydrothermal

  14. Spatial and Temporal Trends in Stable Carbon and Oxygen Isotope Ratios of Juvenile Winter Flounder

    EPA Science Inventory

    Isotopic ratios of fish otoliths have been used in numerous studies as natural tags or markers to aid the study of connectivity among fish populations. We investigated the use of spatial and temporal changes in the stable carbon and oxygen isotope ratios of otoliths to different...

  15. Carbon and oxygen isotopes in apatite CO/sub 2/ and co-existing calcite

    SciTech Connect

    Kolodny, Y.; Kaplan, I. R.

    1981-04-01

    Carbon and oxygen isotopes were analyzed in carbonate apatite CO/sub 2/ and in co-existing calcite. Both C and O in apatite CO/sub 2/ are enriched in the respective light isotopes relative to calcite. These results confirm the proposition that carbonate is part of the apatite structure.

  16. Variations of the glacio-marine air mass front in West Greenland through water vapor isotopes

    NASA Astrophysics Data System (ADS)

    Kopec, B. G.; Lauder, A. M.; Posmentier, E. S.; Feng, X.

    2012-12-01

    While the isotopic distribution of precipitation has been widely used for research in hydrology, paleoclimatology, and ecology for decades, intensive isotopic studies of atmospheric water vapor has only recently been made possible by spectral-based technology. New instrumentation based on this technology opens up many opportunities to investigate short-term atmospheric dynamics involving the water cycle and moisture transport. We deployed a Los Gatos Water Vapor Isotope Analyzer (WVIA) at Kangerlussuaq, Greenland from July 21 to August 15, and measured the water vapor concentration and its isotopic ratios continuously at 10s intervals. A Danish Meteorological Institute site is located about 1 km from the site of the deployment, and meteorological data is collected at 30 min intervals. During the observation period, the vapor concentration of the ambient air ranges from 5608.4 to 11189.4 ppm; dD and d18O range from -254.5 to -177.7 ‰ and -34.2 to -23.2 ‰, respectively. The vapor content (dew point) and the isotopic ratios are both strongly controlled by the wind direction. The easterly winds are associated with dry, isotopically depleted air masses formed over the glacier, while westerly winds are associated with moist and isotopically enriched air masses from the marine/fjord surface. This region typically experiences katabatic winds off of the ice sheet to the east. However, during some afternoons, the wind shifts 180 degrees, blowing off the fjord to the west. This wind switch marks the onset of a sea breeze, and significant isotopic enrichment results. Enrichment in deuterium is up to 60 ‰ with a mean of 15‰, and oxygen-18 is enriched by 3‰ on average and up to 8 ‰. Other afternoons have no change in wind, and only small changes in humidity and vapor isotopic ratios. The humidity and isotopic variations suggest the local atmosphere circulation is dominated by relatively high-pressure systems above the cold glaciers and cool sea surface, and diurnal

  17. A summary of extremes of isotopic variations in extra-terrestrial materials

    NASA Astrophysics Data System (ADS)

    Shima, M.

    1986-04-01

    In this comprehensive review of current research on isotopic variations of elements in extraterrestrial materials, the variations were classified in terms of the major process involved in the modification of the iostopic composition of the element concerned. Maximum isotopic variations of each element were retrieved from publications which were available in Tokyo up to December 1985, and are presented in tabular form.

  18. Oxygen Isotope in Phosphate an Indicator of Phosphorous Cycling in the Ocean - Controls, and Applications

    NASA Astrophysics Data System (ADS)

    Paytan, A.; Roberts, K.; Defforey, D.; McLaughlin, K.; Lomas, M. W.; Church, M. J.; Mackey, K. R.

    2012-12-01

    In order to better constrain the parameters affecting oxygen isotope exchange between water and phosphate via biochemical reactions a set of culture experiments were conducted. Different species of phytoplankton were grown in seawater at various temperatures, light levels, and phosphate concentrations. The oxygen isotopic composition in the phosphate source, algal cells, and the isotopic composition oxygen in the dissolved inorganic phosphate (DIP) were measured. Results showing the effect of species, temperature, light and P availability on intracellular oxygen isotope exchange between phosphorus compounds and water will be presented. The effect of these parameters on the utility of the oxygen isotopic composition of phosphate as a tracer of phosphate utilization rate in the ocean will be discussed. This information is fundamental to any application of isotopic composition of oxygen of dissolved inorganic or organic phosphate to quantify the dynamics of phosphorus cycling in aquatic systems. The data will be utilized to investigate seasonal changes in phosphate sources and cycling in the open ocean and how these relate to phytoplankton abundance, hydrography, and nutrient concentrations.

  19. Oxygen isotope fractionation during N2O production by soil denitrification

    NASA Astrophysics Data System (ADS)

    Lewicka-Szczebak, Dominika; Dyckmans, Jens; Kaiser, Jan; Marca, Alina; Augustin, Jürgen; Well, Reinhard

    2016-02-01

    The isotopic composition of soil-derived N2O can help differentiate between N2O production pathways and estimate the fraction of N2O reduced to N2. Until now, δ18O of N2O has been rarely used in the interpretation of N2O isotopic signatures because of the rather complex oxygen isotope fractionations during N2O production by denitrification. The latter process involves nitrate reduction mediated through the following three enzymes: nitrate reductase (NAR), nitrite reductase (NIR) and nitric oxide reductase (NOR). Each step removes one oxygen atom as water (H2O), which gives rise to a branching isotope effect. Moreover, denitrification intermediates may partially or fully exchange oxygen isotopes with ambient water, which is associated with an exchange isotope effect. The main objective of this study was to decipher the mechanism of oxygen isotope fractionation during N2O production by soil denitrification and, in particular, to investigate the relationship between the extent of oxygen isotope exchange with soil water and the δ18O values of the produced N2O. In our soil incubation experiments Δ17O isotope tracing was applied for the first time to simultaneously determine the extent of oxygen isotope exchange and any associated oxygen isotope effect. We found that N2O formation in static anoxic incubation experiments was typically associated with oxygen isotope exchange close to 100 % and a stable difference between the 18O / 16O ratio of soil water and the N2O product of δ18O(N2O / H2O) = (17.5 ± 1.2) ‰. However, flow-through experiments gave lower oxygen isotope exchange down to 56 % and a higher δ18O(N2O / H2O) of up to 37 ‰. The extent of isotope exchange and δ18O(N2O / H2O) showed a significant correlation (R2 = 0.70, p < 0.00001). We hypothesize that this observation was due to the contribution of N2O from another production process, most probably fungal denitrification. An oxygen isotope fractionation model was used to test various scenarios with

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

    NASA Astrophysics Data System (ADS)

    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

  1. Oxygen isotope effects as probes of electron transfer mechanisms and structures of activated O2.

    PubMed

    Roth, Justine P

    2009-03-17

    Competitively determined oxygen ((18)O) isotope effects can be powerful probes of chemical and biological transformations involving molecular oxygen as well as superoxide and hydrogen peroxide. They play a complementary role to crystallography and spectroscopy in the study of activated oxygen intermediates by forging a link between electronic/vibrational structure and the bonding that occurs within ground and transition states along the reaction coordinate. Such analyses can be used to assess the plausibility of intermediates and their catalytic relevance in oxidative processes. This Account describes efforts to advance oxygen kinetic isotope effects ((18)O KIEs) and equilibrium isotope effects ((18)O EIEs) as mechanistic probes of reactive, oxygen-derived species. We focus primarily on transition metal mediated oxidations, outlining both advances over the past five years and current limitations of this approach. Computational methods are now being developed to probe transition states and the accompanying kinetic isotope effects. In particular, we describe the importance of using a full-frequency model to accurately predict the magnitudes as well as the temperature dependence of the isotope effects. Earlier studies have used a "cut-off model," which employs only a few isotopic vibrational modes, and such models tend to overestimate (18)O EIEs. Researchers in mechanistic biological inorganic chemistry would like to differentiate "inner-sphere" from "outer-sphere" reactivity of O(2), a designation that describes the extent of the bonding interaction between metal and oxygen in the transition state. Though this problem remains unsolved, we expect that this isotopic approach will help differentiate these processes. For example, comparisons of (18)O KIEs to (18)O EIEs provide benchmarks that allow us to calibrate computationally derived reaction coordinates. Once the physical origins of heavy atom isotope effects are better understood, researchers will be able to apply

  2. Oxygen isotope composition of diatoms as Late Holocene climate proxy at Two-Yurts Lake, Central Kamchatka, Russia

    NASA Astrophysics Data System (ADS)

    Meyer, Hanno; Chapligin, Bernhard; Hoff, Ulrike; Nazarova, Larisa; Diekmann, Bernhard

    2015-11-01

    Especially in combination with other proxies, the oxygen isotope composition of diatom silica (δ18Odiatom) from lake sediments is useful for interpreting past climate conditions. This paper presents the first oxygen isotope data of fossil diatoms from Kamchatka, Russia, derived from sediment cores from Two-Yurts Lake (TYL). For reconstructing Late Holocene climate change, palaeolimnological investigations also included diatom, pollen and chironomid analysis. The most recent diatom sample (δ18Odiatom = + 23.3‰) corresponds well with the present day isotopic composition of the TYL water (mean δ18O = - 14.8‰) displaying a reasonable isotope fractionation in the system silica-water. Nonetheless, the TYL δ18Odiatom record is mainly controlled by changes in the isotopic composition of the lake water. TYL is considered as a dynamic system triggered by differential environmental changes closely linked with lake-internal hydrological factors. The diatom silica isotope record displays large variations in δ18Odiatom from + 27.3‰ to + 23.3‰ from about ~ 4.5 kyr BP until today. A continuous depletion in δ18Odiatom of 4.0‰ is observed in the past 4.5 kyr, which is in good accordance with other hemispheric environmental changes (i.e. a summer insolation-driven Mid- to Late Holocene cooling). The overall cooling trend is superimposed by regional hydrological and atmospheric-oceanic changes. These are related to the interplay between Siberian High and Aleutian Low as well as to the ice dynamics in the Sea of Okhotsk. Additionally, combined δ18Odiatom and chironomid interpretations provide new information on changes related to meltwater input to lakes. Hence, this diatom isotope study provides further insight into hydrology and climate dynamics of this remote, rarely investigated area.

  3. Fe and Si isotope variations at Cedar Butte volcano; insight into magmatic differentiation

    NASA Astrophysics Data System (ADS)

    Zambardi, Thomas; Lundstrom, Craig C.; Li, Xiaoxiao; McCurry, Michael

    2014-11-01

    This study presents the stable isotopic variations of both Si and Fe recorded in a single well-characterized magmatic suite from Cedar Butte volcano (ID, USA), as well as a sill with progressive compositional change within Finland granophyre (Duluth Complex, MN, USA). Both isotopic systems show a significant enrichment in heavy isotopes in the more differentiated materials, in agreement with previous studies. In addition, the Finland granophyre sill shows a strong dependence between the isotopic composition and the sampling depth, suggesting the isotopic compositions follow a temperature gradient in which the cold part systematically enriches in heavy isotopes. From these results it appears that at Cedar Butte, neither crystal fractionation, nor crustal contamination, nor late stage fluid exsolution can likely explain the isotopic variations we observe for both Fe and Si. We rather attribute these isotopic fractionations to a thermal migration process involving a top-down sill injection during which the isotopic distribution mostly follows a vertical temperature gradient.

  4. O-18/O-16 and Si-30/Si-28 studies of some Apollo 15, 16, and 17 samples. [oxygen and silicon isotope ratios

    NASA Technical Reports Server (NTRS)

    Taylor, H. P., Jr.; Epstein, S.

    1973-01-01

    A study of lunar rock samples from eight sites on the near side of the moon showed oxygen isotope abundance variations much smaller than those in meteorites and earth material. The grain-surface coatings of the lunar fines were found to be generally depleted in oxygen relative to silicon. The lunar soils, on the other hand, were somewhat richer in both O18 and Si30 than the lunar crystalline rock.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

    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 sacculifer and Neogloboquadrina dutertrei were carried out from the Ocean Drilling Program Site 723A in the western Arabian Sea to unravel the seasonal changes for the last 22 kyr. δ18O values of single shells of G. sacculifer range from of 0.54 to 2.09‰ at various depths in the core which cover a time span of the last 22 kyr. Maximum inter-shell δ18O variability and high standard deviation is noticed from 20 to 10 kyr, whereas from 10 kyr onwards the inter shell δ18O variability decreased. The individual contribution of sea surface temperature (SST) and sea surface salinity (SSS) on the inter shell δ18O values of G. sacculifer were quantified. Maximum seasonal SST between 20 and 14 ka was caused due to weak summer monsoon upwelling and strong cold winter arid continental winds. Maximum SSS differences between 18 and 10 ka is attributed to the increase of net evaporation minus precipitation due to the shift of ITCZ further south. Overall, winter dominated SST signal in Greenland would be responsible to make a teleconnection between Indian monsoon and Greenland temperature. Thus the present study has wider implications in understanding wether the forcing mechanisms of tropical monsoon climate lies in high latitudes or in the tropics.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  9. Theoretical and Experimental Approaches to Understanding the Anomalous Distribution of Oxygen Isotopes in the Solar System

    NASA Astrophysics Data System (ADS)

    Dominguez, Gerardo; Christensen, Elizabeth; Boyer, Charisa; Park, Manesseh; Benitez, Ezra; Nunn, Morgan; Thiemens, Mark H.; Jackson, Terri

    2016-06-01

    Decades of careful laboratory analysis of primitive meteorites have revealed an intriguing and unexplained pattern in the distribution of oxygen isotopes in the solar system. With the recent analysis of solar wind oxygen by NASA’s Genesis mission, it appears that the Sun has a distinct oxygen isotopic composition from the terrestrial planets, asteroids, and comets. These differences cannot be explained by mass-dependent diffusion and require a physical-chemical mechanism or mechanisms that separate oxygen isotopes in a non-mass dependent manner.Several hypothesis have been proposed to explain the anomalous distribution. Photochemical self-shielding of CO may explain the anomalous distribution, however, this mechanism has key weaknesses including the requirement of a very fine tuned timescale to explain the isotopic differences between the Sun and bulk of the terrestrial planets. Recently, attention has been directed at understanding specific chemical reactions that occur on interstellar dust grains due to their similarities with non-equilibrium photochemical reactions believed to be responsible for the mass-independent isotopic fractionation patterns observed in Earth’s atmosphere. A specific focus has been directed towards understanding the formation of H2O because some of its precursor (HO2, and O3) are well-known to acquire mass-independent isotopic signatures when formed in the gas-phase.In this presentation, I describe a series of laboratory astrophysical experiments whose goal is to understand the distribution of oxygen isotopes in the solar system and perhaps, by extension, the distribution in other planetary systems. Preliminary results for the isotopic composition of O3 formed at 5K will be presented as well as the first, to our knowledge, measurements of the isotopic composition of H2O (18O/16O, 17O/16O, D/H) formed at 32K. We find that H2O formed in the astrophysical conditions we simulated acquired an anomalous isotopic composition with a triple-oxygen

  10. A Delayed Noeproterozoic Oceanic Oxygenation: Evidence from the Mo Isotope of the Cryogenian Datangpo Formation

    NASA Astrophysics Data System (ADS)

    Cheng, M.; Li, C.; Algeo, T. J.; Zhou, L.; Liu, X. D.; Feng, L. J.

    2015-12-01

    The onset of the Neoproterozoic oxygenation event (NOE) is usually considered to be at 750-800Ma, which was supposed to have triggered the subsequent oxygenation of the earth's atmosphere-ocean system, thus removing the barrier for the emergence and rapid diversification of animals. However, the subsequent oceanic redox responses in the Cryogenian are poorly constrained. Here, we conducted an integrated Fe-S-C-Mo biogeochemical study on black shales of the Cryogenian Datangpo Formation (~660Ma, Nanhua Basin, South China). Iron speciation data indicate that these black shales were deposited under euxinic water conditions. Co-variation between Mo and TOC suggests an increasing isolation of the basin from open ocean during the deposition of the black shales. Correspondingly, the Datangpo black shales show higher δ98Mo values (+0.97‰ to +1.12‰) for the lower part (0-10m) and lower δ98Mo values (+0.44‰ to +0.53‰) for the upper part (10-20m) consistent with a global scale seawater δ98Mo recorded in the lower part but only a basin scale seawater δ98Mo recorded in the upper part. Accordingly, we estimate the seawater Mo isotope closed to +1.1‰ at ~660 Ma, which suggests substantial oceanic anoxia compared to modern oceans (+2.3‰). The seawater δ98Mo reconstructed by the Datangpo black shales is exactly the same to previously reported seawater δ98Mo at ~750 Ma and ~640 Ma, indicating a continuous oceanic anoxia throughout the Cryogenian although widespread oceanic oxygenation was suggested for the subsequent Ediacaran by multiple geochemical records. Thus, in light of previous studies, our findings indicate a delayed oceanic oxygenation relative to the onset of NOE, which may help to explain the first presence of metazoa in Cryogenian but rapid diversification occurred in Ediacaran.

  11. Making an honest measurement scale out of the oxygen isotope delta-values.

    PubMed

    Gat, Joel R; DeBievre, Paul

    2002-01-01

    The differential measurement of the abundance of oxygen isotopes based on reference materials, such as VSMOW for the case of water, was used because the precision of the absolute mass-spectrometric determination of the abundance fell short of the differences to be measured. Since then these measurements have been much improved, so that a calibration scheme of the oxygen isotope abundance in water, carbonates, silica, phosphates, sulfates, nitrates and organic materials is suggested, based on an accredited primary standard of oxygen in air and using standard fluorination and O(2) to CO(2) conversion techniques. PMID:12442297

  12. Oxygen isotope systematics of gem corundum deposits in Madagascar: relevance for their geological origin

    NASA Astrophysics Data System (ADS)

    Giuliani, Gaston; Fallick, Anthony; Rakotondrazafy, Michel; Ohnenstetter, Daniel; Andriamamonjy, Alfred; Ralantoarison, Théogène; Rakotosamizanany, Saholy; Razanatseheno, Marie; Offant, Yohann; Garnier, Virginie; Dunaigre, Christian; Schwarz, Dietmar; Mercier, Alain; Ratrimo, Voahangy; Ralison, Bruno

    2007-02-01

    comparison with oxygen isotope data obtained on gem corundum from Eastern Africa, India, and Sri Lanka is presented. Giant placer deposits from Sri Lanka, Madagascar, and Tanzania have a large variety of colored sapphires and rubies with a large variation in δ18O due to mingling of corundum of different origin: mafic and ultramafic rocks for ruby, desilicated pegmatites for blue sapphire, syenite for yellow, green, and blue sapphire, and skarn in marbles for blue sapphire.

  13. Oxygen isotopic transport and exchange during fluid flow: One-dimensional models and applications

    SciTech Connect

    Bowman, J.R. ); Willett, S.D. ); Cook, S.J. Environ Corp., Houston, TX )

    1994-01-01

    In this work the authors investigate the consequences of fluid flow and fluid-rock interaction to the isotopic evolution of fluids and rock with one-dimensional transport models of fluid flow and oxygen isotope exchange. Transport models dealing with stable isotopes are well established in recent geochemical literature. The authors extend previous treatments by presenting the derivation of both analytical and numerical solutions to the transport equations incorporating simultaneously advection, diffusion and hydrodynamic dispersion, and kinetics of isotopic exchange. The increased generality of numerical solutions allows the incorporation of other effects which control the spatial patterns of [delta][sup 18]O values developed in rocks and fluids including multiple reactive species and temperature gradients. The authors discuss the effects of flow parameters, conditions of isotopic exchange, and temperature gradients on the spatial patterns of isotopic shifts produced in rock sequences subjected to fluid flow, and on conventionally calculated W/R ratios for these rock sequences. Finally, the authors examine the implications of oxygen isotope transport for two natural systems where isotopic shifts or gradients could be interpreted in terms of unidirectional fluid infiltration. Solutions of one-dimensional transport equations including the mechanisms of advection, diffusion, hydrodynamic dispersion, and non-equilibrium exchange between water and rock indicate that the time-space evolution of oxygen isotopic compositions of rock and infiltrating fluid is dependent on (1) the rate of fluid infiltration, (2) the diffusive and dispersive properties of the rock matrix, (3) the rate of isotopic exchange, and (4) the rock-water mass oxygen ratio in a unit volume of water-saturated, porous rock. 56 refs., 18 figs., 2 tabs.

  14. Fidelity of Stable Oxygen Isotope Ratios as Environmental Recorders Using Multiple Coral Cores From Coastal Kenya

    NASA Astrophysics Data System (ADS)

    Naish, T.; Carter, B.; Abbott, S.; Field, B.; Zhu, H.; Wilson, G.; Alloway, B.; Edwards, S.; Pillans, B.; Barker, A.; Niessen, F.; Maslen, G.; Beu, A.; Fleitmann, D.; Dunbar, R. B.; Mucciarone, D. A.

    2004-12-01

    0.80) reveal that sample- and site-specific effects do not sufficiently bias \\delta18O such that regional climate signals cannot be discerned from any of the 5 sites. Furthermore, correlation of all individual oxygen isotope time series with instrumental monthly SST yields r values between -0.70 and -0.75, demonstrating that fluctuations in \\delta18O primarily reflect variations in SST. Although correlation coefficients between \\delta18O and instrumental monthly SST are higher using either single-site composite \\delta18O time series, such as for Malindi (r = -0.76), or a multisite, multi-core composite (r = -0.81), these correlation coefficients are only slightly higher than those for individual coral \\delta18O time series. We conclude that in this case, the cost of developing replicate coral delta18O time series from individual sites may not be warranted in terms of a marginal gain in signal-to-noise ratio. Our work suggests that a 300 year long, near-monthly \\delta18O record from a single coral head from Malindi, can be used with confidence for environmental reconstructions in the western equatorial Indian Ocean.

  15. Oxygen and iron isotope constraints on near-surface fractionation effects and the composition of lunar mare basalt source regions

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Spicuzza, Michael J.; Craddock, Paul R.; Day, James M. D.; Valley, John W.; Dauphas, Nicolas; Taylor, Lawrence A.

    2010-11-01

    Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ 18O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO 2, Al 2O 3). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ 56Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions. The δ 18O and δ 56Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ 56Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ 18O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ 18O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions

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

    NASA Astrophysics Data System (ADS)

    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

  17. Strontium, Lead, and Oxygen Isotopic Signatures of Mid-Miocene Silicic Volcanism in Eastern Oregon

    NASA Astrophysics Data System (ADS)

    Hess, Emily Nancy

    Widespread, mid-Miocene rhyolite volcanism of eastern Oregon that are coeval or slightly postdate flood basalts of the Columbia River Basalt Province allows for mapping crustal domains using radiogenic and stable isotopes. Rhyolites are thought to be derived in large part by partial melting of the crust and thus yield direct information on the composition of the crust. Silicic volcanism is expressed in the form of numerous domes and tuffs exposed over a wide area (~300 km in N-S dimension and ~200 km in E-W dimension) west of the presumed craton boundary, which runs parallel but mostly east of the Oregon-Idaho state border as delineated by geophysical characteristics and isotopic transitions, including the 87Sr/86Sri =0.7060 line (MSL) and 87Sr/86Sri =0.7040 line (CSL). 87Sr/86Sri of twenty-seven silicic units are variable and some are high. Sr isotopic ratios are inconsistent with the location of the traditional MSL and CSL boundaries. A primary control on the 87Sr/86Sri isotope variations may reflect changes in the crustal make-up of Paleozoic accreted terranes of a particular area rather than arising from a westward-dipping decollement that moved cratonic lithosphere below accreted terranes in eastern Oregon. A secondary control on observed isotopic ratios may be related to the amount and composition of basalt involved in the generation of rhyolites. This could lead to higher or lower 87Sr/86Sri relative to the surrounding crust because de facto coeval mafic magmas of the Columbia River Basalt Group have a wide range of Sr isotopic signatures. While Pb isotope data is incomplete for all samples of this study, the available data indicate a significant range in Pb isotopes. Yet, data of individual regions tend to plot close to one another relative to the entire data distribution. Comparison of samples from this study in a more regional view indicates the samples generally fall within the previously defined lead isotope boundaries of the main-phase Columbia River

  18. Oxygen and strontium isotopic studies of basaltic lavas from the Snake River plain, Idaho

    USGS Publications Warehouse

    Leeman, William P.; Whelan, Joseph F.

    1983-01-01

    The Snake Creek-Williams Canyon pluton of the southern Snake Range crops out over an area of about 30 km2, about 60 km southeast of Ely, Nev. This Jurassic intrusion displays large and systematic chemical and mineralogical zonation over a horizontal distance of 5 km. Major-element variations compare closely with Dalyls average andesite-dacite-rhyolite over an SiO2 range of 63 to 76 percent. For various reasons it was originally thought that assimilation played a dominant role in development of the Snake Creek-Williams Canyon pluton. However, based on modeling of more recently obtained trace element and isotopic data, we have concluded that the zonation is the result of in-situ fractional crystallization, with little assimilation at the level of crystallization. This report summarizes data available for each of the mineral species present in the zoned intrusion. Special attention has been paid to trends We present oxygen and strontium isotopic data for olivine tholeiites, evolved (that is, differentiated and (or) contaminated) lavas, rhyolites, and crustal- derived xenoliths from the Snake River Plain. These data show that the olivine tholeiites are fairly uniform in d80 (5.1 to 6.2) and 87Sr/86Sr (0.7056 to 0.7076) and reveal no correlation between these ratios. The tholeiites are considered representative of mantle-derived magmas that have not interacted significantly with crustal material or meteoric water. The evolved lavas display a wider range in d 80 (5.6 to 7.6) and 87Sr/86Sr (0.708 to 0.717) with positive correlations between these ratios in some suites but not in others. Crustal xenoliths have high and variable 8?Sr/86Sr (0.715 to 0.830) and d80 values that vary widely (6.7 to 9.2) and are a few permil greater than d80 values of the Snake River basalts. Thus, isotopic data for the evolved lavas are permissive of small degrees of contamination by crustal rocks similar to the most d80-depleted xenoliths. The d80 enrichments in some evolved lavas also are

  19. Oxygen isotopes and hydroclimatic change in the Yukon Flats National Wildlife Refuge, northeast Alaska (Invited)

    NASA Astrophysics Data System (ADS)

    Anderson, L.; Finney, B. P.; Guldager, N.; Rover, J. A.; Shapley, M.; van Sistine, D. R.

    2010-12-01

    The Yukon Flats is the region surrounding the confluence of the Porcupine, Sheenjek, Christian, Chandalar, and Yukon Rivers including approximately 20,000 lakes. It is a diverse boreal mosaic landscape (~23,000 km2) that provides spring and summer habitat for over 150 bird species. The climate of the area is continental with severe winter temperatures and warm summers. High effective moisture deficits relative to most boreal environments lead to the unique occurrence of evaporite mineral deposits as well as the highest incidence of naturally occurring wildfires in Alaska. Lake levels are dynamic, and frequently localized, because of subdued topography, varying lake ages and surficial geologic substrates, permafrost extent, and corresponding surface and groundwater flow paths. To better understand the relationships between climate and hydro-environmental change, we are sampling oxygen isotope ratios spatially and temporally. Here we present preliminary GIS-spatial analyses from 108 water bodies and a late Holocene sediment oxygen isotope record from Twelve Mile Lake. We find that the first-order wetland water chemistry relation is with geographic location and hydrologic linkages. A 1.45-m sediment core from 8.8-m water depth was retrieved from Twelve Mile Lake because lake-water δ18O values indicate that evaporation dominates the lake’s hydrologic balance and because it is sufficiently alkaline to generate bioinduced endogenic carbonate sedimentation. The sediment δ18O trends during the last millennia have decade-to-century scale temporal resolution and similarities with paleoclimatic trends documented by other lakes in interior regions of Alaska and the Yukon Territory. Results from these preliminary studies reinforce that 1) wetland and lake sensitivity to climate-induced changes in hydrology varies spatially in the Yukon Flats because of dynamic hydrogeographic factors, and 2) recent hydro-environmental changes are better evaluated within a long-term context

  20. Astronomical Oxygen Isotopic Evidence for Supernova Enrichment of the Solar System Birth Environment

    NASA Astrophysics Data System (ADS)

    Young, Edward; Gounelle, M.; Smith, R. L.; Morris, M. R.; Pontoppidan, K. M.

    2010-01-01

    Ratios among [C16O], [C17O] and [C18O] from young stellar objects (YSOs) obtained by high-resolution infrared spectroscopy (CRIRES, NIRSPEC) suggest that the solar system is indeed unusual in its 18O/17O compared with the present-day Galaxy at a variety of scales of observation. Galactic chemical evolution (GCE) models suggest that 18O/17O is independent of time. A nearly constant Galactic 18O/17O with time is indicated by existing data showing a systematic variation in oxygen isotopologue ratios with distance from the Galactic center. In this context, we show that the disparity between present-day Galactic and solar 18O/17O is explained if the solar system was born in an environment enriched by type II supernovae from low-mass progenitors. Enrichment by ejecta from exploding B stars (not O stars) on the order of 1 % by mass can account for the enhancement in 18O/17O of the birth environment of the solar system compared with normal Galactic values. Analysis of the stochastic nature of star formation utilizing a well-known mass generation function shows that the parental molecular cloud complex that produced the solar system was proximal to a cluster composed of order 500 stars. Larger clusters produce SNe II with oxygen isotope ratios that are inconsistent with enhancement in 18O/17O. This cluster predated the solar system by approximately 10 to 30 Myrs. Enrichment by B star ejecta explains not only the anomalous 18O/17O of the solar system but also its anomalous Si isotopic composition and the former presence of extinct 60Fe.

  1. Temporal variations of the anomalous oxygen component, 1977 - 1984

    NASA Technical Reports Server (NTRS)

    Mason, G. M.; Klecker, B.; Galvin, A. B.; Hovestadt, D.; Ipavich, F. M.

    1985-01-01

    A survey is of the long term temporal variations of 6.6 to 12 MeV/nucleon anomalous oxygen at 1 AU covering the period 1977 to 1984. This time interval included the recent solar maximum, with the recovery at neutron monitor energies beginning in 1982. During this time interval, 6.6 to 12 MeV/nucleon 0 fluxes decreased by at least a factor of 50, and indeed remained below the instrumental detection threshold after 1979. By late 1984, neutron monitors had recovered to roughly 1979 levels from the 1982 solar maximum, and anomalous O still remained below the detection threshold.

  2. Stable isotope analysis of molecular oxygen from silicates and oxides using CO2 laser extraction

    NASA Technical Reports Server (NTRS)

    Perry, Eugene

    1996-01-01

    A laser-excited system for determination of the oxygen isotope composition of small quantities of silicate and oxide minerals was constructed and tested at JSC. This device is the first reported to use a commercially available helium cryostat to transfer and purify oxygen gas quantitatively within the system. The system uses oxygen gas instead of the conventional CO2 for mass spectrometer analyses. This modification of technique permits determination of all three stable oxygen isotopes, an essential requirement for oxygen isotope analysis of meteoritic material. Tests of the system included analysis of standard silicate materials NBS 28 and UWMG2 garnet, six SNC meteorites, and inclusions and chondrules from the Allende meteorite. Calibration with terrestrial standards was excellent. Meteorite values are close to published values and show no evidence of terrestrial oxygen contamination. The one limitation observed is that, in some runs on fine-grained SNC matrix material, sample results were affected by other samples in the sample holder within the reaction chamber. This reemphasizes the need for special precautions in dealing with fine-grained, reactive samples. Performance of the JSC instrument compares favorably with that of any other instrument currently producing published oxygen isotope data.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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 (δ(18)Ocalc and δ(13)Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ(18)Ocalc 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 (18)O relative to (16)O 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 δ(18)Ocalc value of eggshell calcite to the δ(18)Ow 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 δ(13)Ccalc and δ(18)Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ(13)Ccalc and high δ(18)Ocalc 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.

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

    PubMed

    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 (δ(18)Ocalc and δ(13)Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ(18)Ocalc 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 (18)O relative to (16)O 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 δ(18)Ocalc value of eggshell calcite to the δ(18)Ow 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 δ(13)Ccalc and δ(18)Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ(13)Ccalc and high δ(18)Ocalc 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. PMID:27639729

  6. Oxygen and carbon isotopic composition of limestones and dolomites, bikini and eniwetok atolls.

    PubMed

    Gross, M G; Tracey, J I

    1966-03-01

    Aragonitic, unconsolidated sediments from the borings on the Eniwetok and Bikini atolls are isotopically identical with unaltered skeletal fragments, whereas the recrystallized limestones exhibit isotopic variations resulting from alteration in meteoric waters during periods of emergence. Dolomites and associated calcites are enriched in O(18), perhaps because of interaction with hypersaline brines.

  7. Distinguishing phosphate from fertilizers and wastewater treatment plant effluents in Western Canada using oxygen isotope measurements

    NASA Astrophysics Data System (ADS)

    Fau, Veronique; Nightingale, Michael; Tamburini, Frederica; Mayer, Bernhard

    2014-05-01

    The successful application of oxygen isotope ratios as a tracer for phosphate in aquatic ecosystems requires that different sources of phosphate are isotopically distinct. The objective of this study was to determine whether the oxygen isotope ratios of phosphate from fertilizers and effluents from wastewater treatment plants in Western Canada are isotopically distinct. Therefore, we carried out oxygen isotope analyses on phosphate in effluent from five different wastewater treatment plants (WWTP) in the Bow River watershed of Alberta, Canada. Samples were collected directly from the final effluent (post-UV) in Banff and Canmore upstream of Calgary, and from effluents of Calgary's WWTPs at Bonnybrook, Fish Creek and Pine Creek. We also carried out oxygen isotope analyses on a variety of phosphate-containing fertilizers that are widely used in Western Canada. Historically, most of the phosphate contained in manufactured fertilizers sold in Alberta came from two distinct deposits: 1) a weathered Pliocene igneous carbonatite located in eastern Canada, and 2) the Permian Phosphoria Formation in the western USA. Phosphate (PO43-) contained in the water or the fertilizer was concentrated and quantitatively converted to pure silver phosphate (Ag3PO4). The silver phosphate was then reduced with carbon in an oxygen free environment using a TC/EA pyrolysis reactor linked to a mass spectrometer where 18O/16O ratios of CO were measured in continuous flow mode. Preparation of samples for δ18OPO4 analyses was conducted using the Magnesium Induced Coprecipitation (MAGIC) method. Expected oxygen isotope ratios for phosphate in equilibrium with water (δ18Oeq) were calculated using the Longinelli and Nuti equation: T (° C) = 111.4 - 4.3 (δ18Oeq - δ18Owater). Measured δ18O values of phosphate for fertilizer samples varied from 8 to 25 oÈ®n average, fertilizer samples of sedimentary origin had higher δ18O values (15.8) than those of igneous origin (11.5). Phosphate isotopic

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    (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 ∆17O as function of log Mb. Predicted and measured data agree within the uncertainty of the model and the measurements, respectively. Small mammals with their high specific metabolic rate show the greatest portion of oxygen from air O2 in their body water and in their bones and teeth. With this approach, ∆17O of air O2 can be determined with an uncertainty in the range of 0.05-0.1‰. This is more precise than what can be obtained from analyses of terrigene sulfate. With well-preserved fossil material, it may be possible to determine ∆17O of air O2 beyond the time limit of ice core data. The high precision of our approach may allow identifying variations in ∆17O of air O2 between glacial and interglacial periods. With mammal material, we will construct a ∆17O-profile of tropospheric O2 back to the Palaeogene. Using the same approach with reptile apatite, we expect to be able to extend the database beyond the Cretaceous/Palaeogene boundary. Correct interpretation of ∆17O of biogenic apatite, however, requires knowledge of the metabolic parameters for the analyzed groups as well as the β-values for all isotope fractionation processes involved. [1] Luz B. et al. (1999) Nature, 400, 547-550. [2] Pack A. et al. (2007) Rapid Communications in Mass Spectrometry, 21, 3721-3728. [3] Rumble D. et al. (2007) Geochimica et Cosmochimica Acta, 71, 3592-3600. [4] Bao H

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

    NASA Technical Reports Server (NTRS)

    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.

  10. Toward forward modeling for paleoclimatic proxy signal calibration: A case study with oxygen isotopic composition of tropical woods

    NASA Astrophysics Data System (ADS)

    Evans, M. N.

    2007-07-01

    A forward model of the oxygen isotopic composition (δ18O) of wood cellulose is parameterized for time series prediction in tropical environments and driven with meteorological data observed at La Selva Biological Research Station, Costa Rica, for 1985-2001. Monthly-resolution model results correlate modestly (r = 0.34, p < 0.05) with observed isotopic data, with higher correlation (r = 0.45, p < 0.01) over the earliest 10 years of comparison and nonsignificant correlation over the most recent 6 years of record. Analysis of model output for La Selva suggests that isotopic variations are strongly controlled by rainfall amount. The model simulates an analogous but stronger than observed negative isotopic anomaly associated with positive July-September rainfall anomalies during El Niño-Southern Oscillation (ENSO) warm phase event years. Simulated tree isotope data for the global tropics suggest that a network of well-replicated data series from selected locations may resolve the large-scale precipitation anomaly pattern associated with ENSO.

  11. Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

    SciTech Connect

    Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid; Jackson, Teresa L.; Thiemens, Mark H.

    2012-01-03

    Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasing synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.

  12. High Precision Oxygen Three Isotope Analysis of Wild-2 Particles and Anhydrous Chondritic Interplanetary Dust Particles

    NASA Technical Reports Server (NTRS)

    Nakashima, D.; Ushikubo, T.; Zolensky, Michael E.; Weisberg, M. K.; Joswiak, D. J.; Brownlee, D. E.; Matrajt, G.; Kita, N. T.

    2011-01-01

    One of the most important discoveries from comet Wild-2 samples was observation of crystalline silicate particles that resemble chondrules and CAIs in carbonaceous chondrites. Previous oxygen isotope analyses of crystalline silicate terminal particles showed heterogeneous oxygen isotope ratios with delta(sup 18)O to approx. delta(sup 17)O down to -50% in the CAI-like particle Inti, a relict olivine grain in Gozen-sama, and an olivine particle. However, many Wild-2 particles as well as ferromagnesian silicates in anhydrous interplanetary dust particles (IDPs) showed Delta(sup 17)O values that cluster around -2%. In carbonaceous chondrites, chondrules seem to show two major isotope reservoirs with Delta(sup 17)O values at -5% and -2%. It was suggested that the Delta(sup 17)O = -2% is the common oxygen isotope reservoir for carbonaceous chondrite chondrules and cometary dust, from the outer asteroid belt to the Kuiper belt region. However, a larger dataset with high precision isotope analyses (+/-1-2%) is still needed to resolve the similarities or distinctions among Wild-2 particles, IDPs and chondrules in meteorites. We have made signifi-cant efforts to establish routine analyses of small particles (< or =10micronsm) at 1-2% precision using IMS-1280 at WiscSIMS laboratory. Here we report new results of high precision oxygen isotope analyses of Wild-2 particles and anhydrous chondritic IDPs, and discuss the relationship between the cometary dust and carbonaceous chondrite chondrules.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Ni biogeochemical cycle through geological time: insights from Ni isotope variations in modern and ancient marine metallifereous deposits

    NASA Astrophysics Data System (ADS)

    Gueguen, B.; Rouxel, O.; Ponzevera, E.; Sorensen, J. V.; Toner, B.; Bekker, A.

    2011-12-01

    Studies of isotopic composition of transition metals such as Fe, Cu, Zn, and Mo as biogeochemical tracers became popular recently. Since Ni is ubiquitous in marine metallifereous deposits and its concentration in water column is coupled to that of nutrients, it has a potential as a biogeochemical tracer. Isotopic analyses were performed on a Neptune MC-ICP-MS using a double-spike correction method for instrumental mass bias. Deep-sea ferromanganese crusts have been used to establish a record of seawater over the last 60 Myr. Our results show that Fe-Mn crusts from both Atlantic and Pacific oceans are systematically enriched in heavy isotopes relative to Bulk Silicate Earth with δ60/58Ni values ranging from 0.30 to 1.80% (2se = 0.04%). In contrast, Iron Formations (IF) with ages ranging from 3.8 to 0.7 Gyr display a wider range of values with a striking negative Ni isotope excursion down to -2.46% (2se = 0.03%) in Neoproterozoic IF. Although correlation between Ni isotope compositions, Ni concentrations and BIFs ages seems to be lacking, several Ni isotope excursions to either positive or negative Ni isotope values are notable prior to 2.4 Gyr. Methanogens were likely abundant in Precambrian water column until they retreated to pore waters and local environments once the oceans were oxygenated after the Great Oxidation Event (GOE). They preferentially uptake light Ni isotopes leaving isotopically heavier Ni in oceans. Our Ni isotope record of Precambrian IF does not show a unidirectional change across the GOE implying that Ni isotope composition of the Archean oceans was not dominated by this metabolism. Preliminary Ni adsorption experiments on Fe-Mn oxy-hydroxides show a maximum fractionation factor between the mineral phase and aqueous solution of -1.00% (2se = 0.03%). Hence, isotopic variations in Fe-Mn crusts and IF cannot be simply explained by adsorption processes, but require changes in composition of either Ni sources (local or global) to seawater (e

  15. Oxygen Isotopes in Bivalve Shells Record Hydrological Changes in the Siberian Land-Shelf Connection on Annual Timescales

    NASA Astrophysics Data System (ADS)

    Mueller-Lupp, T.; Bauch, H. A.; Erlenkeuser, H.

    2002-12-01

    It is now widely accepted that changes in surface ocean hydrology at northern high latitudes is a major forcing mechanism that can strongly perturbate a particular climate mode. Given the variability on subdecadal and on centennial to millennial timescales, the dispersal and fate of arctic riverine water discharge and its role on the ice regime as well as on surface water properties are central issues in the understanding of Holocene climate change in the arctic marginal seas, the Arctic Ocean, and beyond. Oxygen isotope profiles from living and fossil bivalves were investigated in order to trace modern and past hydrographical changes in the strongly coupled land-shelf system of the Laptev Sea. Detailed oxygen isotope measurements were executed on the shells along their axis of maximum growth and provide an isotopic record of hydrological and environmental changes for the lifespan of the individual bivalves. The oxygen isotopic records exhibit amplitude cycles interpreted as recording annual cycles. Based on the well-known relationship between the carbonate δ18O, temperature and the isotopic composition of water, it is possible to relate phases of more negative (lighter) δ18O values indicating summer and more positive (heavier) δ18O values indicating the winter season. The main forcing factor of the δ18O variations is the variability of the isotopic composition of the bottom water. Measurements of δ18O in surface and bottom waters of the Laptev Sea show a linear relation of salinity and water δ18O with a coefficient of 0.50 \\permil salinity-1 and document the mixing of freshwater and seawater. The δ18O cycles from growing profiles of the living bivalves indicate a correspondence to seasonal hydrographic changes and can be compared with runoff data and circulation patterns in the Laptev Sea. Given the seasonal cycles in living bivalves, oxygen isotope profiles of fossil, radiocarbon-dated, and well-preserved bivalve shells from sediment cores are used to

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    Most olivine relict grains in cosmic spherules selected for the present study are pristine and have not been disturbed during their atmospheric entry, thereby preserving their chemical, mineralogical and isotopic compositions. In order to understand the origin of the particles, oxygen isotope compositions of relict olivine grains in twelve cosmic spherules collected from deep sea sediments of the Indian Ocean were studied using secondary ion mass spectrometry. Most of the data lie close to the CCAM (Carbonaceous Chondrite Anhydrous Mineral) line, with Δ17O ranging from -5‰ to 0‰. The data overlap oxygen isotopic compositions of chondrules from carbonaceous chondrites such as CV, CK, CR and CM, which suggests that chondrules from carbonaceous chondrites are the source of relict grains in cosmic spherules. Chemical compositions of olivine in cosmic spherules are also very similar to chondrule olivine from carbonaceous chondrites. Several olivine relict grains in three cosmic spherules are 16O-rich (Δ17O -21.9‰ to -18.7‰), similar to oxygen isotopic compositions observed in calcium aluminum 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 grains from two cosmic spherules have δ18O values >+20‰, which could be interpreted as mixing with stratospheric oxygen during atmospheric entry.

  17. Stable isotopic variation in tropical forest plants for applications in primatology.

    PubMed

    Blumenthal, Scott A; Rothman, Jessica M; Chritz, Kendra L; Cerling, Thure E

    2016-10-01

    Stable isotope analysis is a promising tool for investigating primate ecology although nuanced ecological applications remain challenging, in part due to the complex nature of isotopic variability in plant-animal systems. The aim of this study is to investigate sources of carbon and nitrogen isotopic variation at the base of primate food webs that reflect aspects of primate ecology. The majority of primates inhabit tropical forest ecosystems, which are dominated by C3 vegetation. We used stable isotope ratios in plants from Kibale National Park, Uganda, a well-studied closed-canopy tropical forest, to investigate sources of isotopic variation among C3 plants related to canopy stratification, leaf age, and plant part. Unpredictably, our results demonstrate that vertical stratification within the canopy does not explain carbon or nitrogen isotopic variation in leaves. Leaf age can be a significant source of isotopic variation, although the direction and magnitude of this difference is not consistent across tree species. Some plant parts are clearly differentiated in carbon and nitrogen isotopic composition, particularly leaves compared to non-photosynthetic parts such as reproductive parts and woody stem parts. Overall, variation in the isotopic composition of floral communities, plant species, and plant parts demonstrates that stable isotope studies must include analysis of local plant species and parts consumed by the primates under study from within the study area. Am. J. Primatol. 78:1041-1054, 2016. © 2015 Wiley Periodicals, Inc.

  18. Oxygen isotope constraints on the origin of island arc granitoids

    NASA Astrophysics Data System (ADS)

    Perez, R. J.; Cavosie, A. J.; Valley, J. W.

    2007-12-01

    Granitic intrusions in island arcs constitute additions of juvenile crust from oceanic environs that ultimately get accreted to continents. The genesis of island arc granitoids is thus important to studies of the growth of oceanic and continental crust. Puerto Rico (USA) is a composite island arc terrane that preserves a record of plutonism from 85 Ma to 38 Ma (Cavosie et al., 2007 AGU). Mid-crustal granitoid plutons are exposed (~1 to 500 km2), but their origins are unknown, as no suspected parental magmas associated with the plutons (e.g., gabbro) are exposed. This study uses petrography, WR major elements, and oxygen isotopes of WR and zircon from granitoids and xenoliths to place better constraints on the origin of granitoid in the Greater Antilles island arc. WR δ18O analyses were made with laser fluorination by IRMS at the Univ. of Wisconsin (uncertainties = 0.10 to 0.20‰, 2sd). The main plutons (Caguas, Rio Blanco, San Lorenzo, Utuado, Vieques) yield primitive δ18O(WR) values, ranging from 6.24 to 7.72‰ over a range of wt.% SiO2= 58.03 to 66.54. Smaller stocks (<20 km2) yield higher δ18O(WR) values, ranging from 7.47 to 10.27‰. Qualitative petrographic analysis reveals that granitoids with δ18O(WR) >~7.5‰ are partially to pervasively altered. Zircon preserves magmatic δ18O and is used here to quantitatively evaluate the measured δ18O(WR) values. If δ18O(Zrc) and wt.% SiO2 are known, a comparison of measured vs. predicted δ18O(WR) can be made (Valley et al., 2005, CMP). The measured δ18O(WR) values record variable amounts of alteration, ranging from virtually undetectable, to WR δ18O elevations of ~4‰, indicative of low-T subsolidus alteration. The Δ18O (WR-Zrc) values using calculated δ18O(WR) yield the following fractionations: -1.57 to 1.00‰ for granodiorites (wt.% SiO2=66 to 57); -0.85‰ for diorite (wt.% SiO2=55); and -0.56‰ for the only gabbro analyzed (wt.% SiO2=50). Mafic xenoliths (53-57 wt.% SiO2) from 4 granitoids yield

  19. Oxygen isotope biogeochemistry of phosphate in brackish marginal seas: I. The Black Sea

    NASA Astrophysics Data System (ADS)

    Isensee, Kirsten; Hille, Sven; Dellwig, Olaf; Blake, Ruth; Böttcher, Michael E.

    2010-05-01

    Phosphorus (P) is an important limiting nutrient for primary production in aquatic ecosystems. Therefore, it is important to understand the sources and biogeochemical cycling of different P species. Biotic and abiotic processes, like the uptake and metabolism of inorganic and organic P compounds, enzymatic regeneration of P, redox controlled sorption and release of phosphates and precipitation of apatite or other P containing solids can alter the isotopic composition of oxygen in dissolved and particulate phosphorus matter. The Black Sea is known as the world's largest permanently modern euxinic basin - the Type System for anoxia in Earth's history. Strong gradients for dissolved species are observed across the redoxcline and a zonation of the biogeochemical processes occurs along the stratified water column and further within the sediments. Oxygen isotope analyses of phosphate were carried out as a additional tool to allow the evaluation of biotic and abiotic influences on the P cycle. We analyzed for the first time, the oxygen isotope composition of DIP (d18OP) in the water column of the Black Sea and compared the results to inorganic P extracted from laminated brackish and limnic sediments. Samples were recovered during two cruises (M51/4, M72/5) of the research vessel RV METEOR. Besides hydrographical and physical parameters, particulate P and Fe, as well as dissolved constituents, like DIP, O2 and H2S, were analyzed for water column samples. Oxygen isotope compositions of phosphate were measured after conversion to silver phosphate, and then results were compared with published values for oxygen isotope compositions of water. In addition, oxygen isotope compositions of inorganic phosphate bound to laminated brackish (MUC sample) and bioturbated (formerly limnic) sediments were determined. We found an increase in δ18OP from the redoxcline down to the deep anoxic waters. The isotope values even exceed the calculated equilibrium composition. The increase in d18

  20. Comparison of oxygen isotope values from bulk lake sediment and ostracod valves

    NASA Astrophysics Data System (ADS)

    Teng, J.; Blisniuk, P.

    2012-12-01

    The oxygen isotope composition of the water in a lake is largely controlled by the isotopic composition of precipitation in the lake's catchment area, which is, in turn, controlled by a variety of geographic and climatic factors. Accordingly, the potential to reconstruct past isotopic compositions of lake water using authigenic minerals formed in isotopic equilibrium with the lake water makes lake sediments a promising target for paleoclimate reconstructions. Several different materials can be utilized to reconstruct the oxygen isotope composition of paleo-lake water. These include biogenic carbonates, such as shells of macrofossils (e.g., clams and snails), microfossils, (e.g., ostracods) and chemically precipitated carbonates in bulk lake sediment. To evaluate the suitability of different materials for the reconstruction of oxygen isotope values of past precipitation, we compared the oxygen isotope values of bulk lake sediments and ostracod microfossils that were extracted from an 800 meters thick sequence of sediments in the Zada Basin, southwestern Tibet. The sediment was wet-sieved for grain size separation, and the <63 um size fraction was used for the analysis of the bulk lake sediment. The ostracod microfossils were typically separated from the 125-500 um size fraction. Ostracod valves were cleaned using deionized water and ultrasound. When this did not successfully clean them, we used a brush under a microscope. Preliminary results of our work yielded oxygen isotope values of -2 to -22 permil for bulk lake sediment and a narrower range of -4 to -15 permil for ostracod valves (relative to PDB). In some stratigraphic levels, the oxygen isotope values differed by as much as 10 permil. These differences are significantly higher than offsets of several permil which are commonly observed as the result of species specific vital effects during biogenic calcite precipitation. A plausible explanation for this is that the lake sediment contains a significant portion

  1. Search for Nucleosynthetic Cadmium Isotope Variations in Bulk Carbonaceous Chondrites

    NASA Astrophysics Data System (ADS)

    Toth, E. R.; Schönbächler, M.; Friebel, M.; Fehr, M. A.

    2016-08-01

    New high-precision Cd isotope data will be presented for bulk carbonaceous chondrites, such as Allende and Murchison. Volatile element isotope anomalies and their potential nucleosynthetic sources will be discussed.

  2. Chemostratigraphies of carbon, oxygen and strontium isotopes and oxygen contents across the Precambrian-Cambrian boundary

    NASA Astrophysics Data System (ADS)

    Komiya, T.; Sawaki, Y.; Ishikawa, T.

    2007-12-01

    The Precambrian-Cambrian (PC-C) boundary is one of the most important intervals for evolution of life. However, the scarcity of well-preserved outcrops through the boundary makes it ambiguous to decode change of the surface environment and biological evolution. In south China, strata through the PC-C boundary are continuously exposed and contain many fossils, suitable for study of environmental and biological change. In addition, we conducted excavations at four sites of Three Gorge area to obtain continuous and fresh samples. We measured the delta13C, delta18O and 87Sr/86Sr values of the drill core samples and REE compositions of fresh carbonate rocks, respectively. We identified two positive and two negative isotope excursions of delta13Ccarb within this interval: a moderate increase from 0 to +2 permil and a subsequent dramatic drop to -7 permil at the PC-C boundary, and a continuous increase to +5 permil at the upper part of the Nemakit-Daldynian (ND) stage and the subsequent sharp decrease to -9 permil just below the basal Tommotian unconformity, respectively. The continuous pattern of the delta13C shift is irrespective of lithotype and is comparable to fragmented records of other sections within and outside of the Yangtze Platform, indicating that the profile represents global change of seawater chemistry. A chemostratigraphy of 87Sr/86Sr ratios of the drilled samples also displays a smooth curve and its large positive anomaly just below the PC-C boundary. The estimate of oxygen content of seawater from REE composition of carbonate minerals shows significant decreases around PC-C and ND-Tommotian boundaries, respectively. The combination of chemostratigraphies of delta13C, 87Sr/86Sr and pO2 indicates that the 87Sr/86Sr excursions preceded the delta13C negative excursion at PC-C boundary, and suggests that global regression or formation of the Gondwana supercontinent, evident in increase of influx of continental materials, caused biological depression together

  3. Atmospheric Oxygen Variation Over the Last 100 Million Years

    NASA Astrophysics Data System (ADS)

    Watson, A. J.; Mills, B.; Daines, S. J.; Lenton, T. M.; Belcher, C.

    2014-12-01

    There is no agreement over how atmospheric oxygen has varied over recent Earth history. Our knowledge of past O2 concentrations relies on biogeochemical modelling, constrained by geochemical data and proxies. There are however few direct indicators of oxygen concentrations, though the presence of fossil charcoal indicates that levels have not strayed outside the "fire window", say below 16% or above 35%, during the last hundred million years. Different model predictions encompass both decreasing and increasing trends over this period however. These predictions are sensitive to weathering of continental rocks, which provide a sink for O2, but also a supply of phosphorus and sediment to the ocean, both of which increase carbon burial and thereby provide an oxygen source. Here we update our COPSE model with a more detailed treatment than hitherto, incorporating new input data, seafloor weathering processes, and different compositions and weatherability of granites and basalts. Our model suggests a broadly declining O2 trend over the late Mesozoic to present. An alternative forcing uses the phosphorus deposition curve of Follmi (1995), which is constructed from P measurements in ocean cores, and indicates P fluxes to the oceans that have varied over time by two orders of magnitude. Used to drive the model this also results in a declining long-term trend for atmospheric O2 over the last hundred million years, but with dramatic shorter-term variations superposed on the trend. These however stay (just) within the "fire window" for oxygen concentrations, and can be tentatively related to the evolution of fire adaptations in plants.

  4. Oxygen and Sulfur Isotope Composition of Dissolved Sulfate in Interstitial Waters of the Great Australian Bight, ODP Leg 182.

    NASA Astrophysics Data System (ADS)

    Bernasconi, S. M.; Böttcher, M. E.; Wormann, U. G.

    2005-12-01

    We measured the sulfur and oxygen isotope composition of dissolved sulfides and sulfate at ODP Sites 1129, 1130, 1131 and 1132 in the Great Australian Bight (GAB). At all Sites, a saline brine is present in the subsurface as indicated by increasing chloride concentrations with depth to reach contents up to 3 times seawater. Sulfate also increases with depth but the concentrations are reduced by intense microbial sulfate reduction. The sulfur isotope fractionation between coexisting dissolved sulfate and sulfide is very large and reaches up to 70 ‰ at all studied Sites. Due to the high sulfide concentrations and the lack of a significant source of oxidants we consider that the large sulfur isotope fractionations are induced by sulfate reducing bacteria alone without a significant contribution of elemental sulfur disproportionation and sulfide oxidation processes. The oxygen isotope composition of dissolved sulfate reaches maximum values of approximately +27 ‰ vs. VSMOW at all sites, close to the equilibrium isotope fractionation between sulfate and water. The oxygen isotope composition of dissolved sulfate positively correlates with the sulfur isotope fractionation between sulfate and sulfide. These oxygen isotope data thus support the hypothesis that that the high sulfur isotope fractionation are related to a single step fractionation by sulfate reducing bacteria and do not involve significant sulfide oxidation reactions and/or elemental sulfur disproportionation. Sulfide oxidation processes would lead to a lowering of the oxygen isotope composition of residual sulfate. Elemental sulfur disproportionation has been shown to increase the oxygen isotope composition of sulfate but to a smaller extent than that that observed in the GAB. The patterns of the oxygen isotope increase with progressive sulfate reduction indicate a predominant influence of isotope exchange rather than a kinetic isotope fractionation controlling the oxygen isotope composition of sulfate

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

    PubMed Central

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

    2013-01-01

    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 ∆17O 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 ∆17O = 3.3‰, OEI = 11 and ∆17O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that ∆17O 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. PMID:23447567

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

    PubMed

    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. PMID:23447567

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

    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 ∆17O 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 ∆17O = 3.3‰, OEI = 11 and ∆17O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that ∆17O 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.

  9. Hydrogen and oxygen isotope exchange reactions between clay minerals and water

    USGS Publications Warehouse

    O'Neil, J.R.; Kharaka, Y.K.

    1976-01-01

    The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

  10. Coupled variations in helium isotopes and fluid chemistry: Shoshone Geyser Basin, Yellowstone National Park

    SciTech Connect

    Hearn, E.H.; Kennedy, B.M. ); Truesdell, A.H. )

    1990-11-01

    Early studies of {sup 3}He/{sup 4}He variations in geothermal systems have generally attributed these fluctuations to either differences in the source of the magmatic {sup 3}He-rich helium or to local differences in the deep flux of magmatic {sup 3}He-rich helium. Kennedy et al, however, show that near-surface processes such as boiling and dilution may also drastically affect {sup 3}He/{sup 4}He ratios of geothermal vapors. Helium isotope ratios were determined for several hot springs at Shoshone Geyser Basin of Yellowstone National Park for this study, along with other noble gas data. Stable isotope data and water and gas chemistry data for each spring were also compiled. The water chemistry indicates that there is one deep, hot thermal water in the area which is mixing with dilute meteoric water that has entered the system at depth. Spring HCO{sub 3}{sup {minus}} concentrations correlate with {sup 3}He/{sup 4}He values, as in nearby Lower Geyser Basin. This correlation is attributed to variable amounts of deep dilution of thermal waters with a relatively cool water that inhibits boiling at depth, thus preventing the loss of CO{sub 2} and magmatic He in the most diluted samples. Oxygen and hydrogen isotope data also support a boiling and dilution model, but to produce the observed fractionations, the boiling event would have to be extensive, with steam loss at the surface, whereas the boiling that affected the helium isotope ratios was probably a small scale event with steam loss at depth. It is possible that deep boiling occurred in the basin and that small amounts of steam escaped along fractures at about 500 m below the surface while all subsequently produced steam was lost near or at the surface.

  11. Coupled variations in helium isotopes and fluid chemistry: Shoshone Geyser Basin, Yellowstone National Park

    USGS Publications Warehouse

    Hearn, E.H.; Kennedy, B.M.; Truesdell, A.H.

    1990-01-01

    Early studies of 3He/4He variations in geothermal systems have generally attributed these fluctuations to either differences in the source of the magmatic 3He-rich helium or to local differences in the deep flux of magmatic 3He-rich helium. Kennedy et al. (1987), however, show that near-surface processes such as boiling and dilution may also drastically affect 3He 4He ratios of geothermal vapors. Helium isotope ratios were determined for several hot springs at Shoshone Geyser Basin of Yellowstone National Park for this study, along with other noble gas data. Stable isotope data and water and gas chemistry data for each spring were also compiled. The water chemistry indicates that there is one deep, hot thermal water in the area which is mixing with dilute meteoric water that has entered the system at depth. Spring HCO3- concentrations correlate with 3He 4He values, as in nearby Lower Geyser Basin. This correlation is attributed to variable amounts of deep dilution of thermal waters with a relatively cool water that inhibits boiling at depth, thus preventing the loss of CO2 (and therefore HCO3-) and magmatic He in the most diluted samples. Oxygen and hydrogen isotope data also support a boiling and dilution model, but to produce the observed fractionations, the boiling event would have to be extensive, with steam loss at the surface, whereas the boiling that affected the helium isotope ratios was probably a small scale event with steam loss at depth. It is possible that deep boiling occurred in the basin and that small amounts of steam escaped along fractures at about 500 m below the surface while all subsequently produced steam was lost near or at the surface. ?? 1990.

  12. Can isotopic variations in structural water of gypsum reveal paleoclimatic changes?

    NASA Astrophysics Data System (ADS)

    Gatti, E.; Bustos, D.; Coleman, M. L.

    2015-12-01

    Water of crystallization in gypsum can be used as paleo-environmental proxy to study large scale climatic variability in arid areas. This is because changes in the isotopic composition of water of crystallization are due to isotopic variations in the mother brine from which the mineral precipitated, and the brine isotopic composition is linked to evaporation processes and humidity. This is particularly important when the salts are the only traces left of the original water, i.e. in modern arid areas. This study aims to prove that the 2-D/18-O compositions of the water of crystallization extracted from successive precipitates or even different growth zones of natural gypsum (CaSO4·H2O) can reconstruct the evaporation history and paleo-humidity of the source water basin. The method was tested in a laboratory experiment that evaporated CaSO4 brines under controlled temperature and humidity conditions. The brine was left to evaporate for five days at two different humidities (45 and 75 RH%); subsequently, brines and precipitated gypsum were sampled at 24 hour intervals. In this way we simulated zoned growth of gypsum. The samples were then analyzed for oxygen and hydrogen isotopic composition using a Thermo Scientific TC/EA with modified column, coupled to a MAT 253 Thermo Finnigan mass spectrometer at JPL. If preliminary results validate the novel hypothesis that changes in mineral composition can reveal details of paleo-environmental conditions the theory will be tested on natural gypsum collected from selected areas in White Sands National Monument, New Mexico. The study is currently ongoing but the full dataset will be presented at the conference.

  13. Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater

    NASA Astrophysics Data System (ADS)

    Hermoso, Michaël; Horner, Tristan J.; Minoletti, Fabrice; Rickaby, Rosalind E. M.

    2014-09-01

    In this study, we show that there are independent controls of 18O/16O and 13C/12C fractionation in coccolithophore and dinoflagellate calcite due to the contrasting kinetics of each isotope system. We demonstrate that the direction and magnitude of the oxygen isotope fractionation with respect to equilibrium is related to the balance between calcification rate and the replenishment of the internal pool of dissolved inorganic carbon (DIC). As such, in fast growing cells, such as those of Emiliania huxleyi and Gephyrocapsa oceanica (forming the so-called “heavy group”), calcification of the internal carbon pool occurs faster than complete isotopic re-adjustment of the internal DIC pool with H2O molecules. Hence, coccoliths reflect the heavy oxygen isotope signature of the CO2 overprinting the whole DIC pool. Conversely, in large and slow growing cells, such as Coccolithus pelagicus ssp. braarudii, complete re-equilibration is achieved due to limited influx of CO2 leading to coccoliths that are precipitated in conditions close to isotopic equilibrium (“equilibrium group”). Species exhibiting the most negative oxygen isotope composition, such as Calcidiscus leptoporus (“light group”), precipitate coccolith under increased pH in the coccolith vesicle, as previously documented by the “carbonate ion effect”. We suggest that, for the carbon isotope system, any observed deviation from isotopic equilibrium is only “apparent”, as the carbon isotopic composition in coccolith calcite is controlled by a Rayleigh fractionation originating from preferential incorporation of 12C into organic matter. Therefore, species with low PIC/POC ratios as E. huxleyi and G. oceanica are shifted towards positive carbon isotope values as a result of predominant carbon fixation into the organic matter. By contrast, cells with higher PIC/POC as C. braarudii and C. leptoporus maintain, to some extent, the original negative isotopic composition of the CO2. The calcareous

  14. Deep drilling at the Siljan Ring impact structure: oxygen-isotope geochemistry of granite

    USGS Publications Warehouse

    Komor, S.C.; Valley, J.W.

    1990-01-01

    The Siljan Ring is a 362-Ma-old impact structure formed in 1700-Ma-old I-type granites. A 6.8-km-deep borehole provides a vertical profile through granites and isolated horizontal diabase sills. Fluid-inclusion thermometry, and oxygen-isotope compositions of vein quartz, granite, diabase, impact melt, and pseudotachylite, reveal a complex history of fluid activity in the Siljan Ring, much of which can be related to the meteorite impact. In granites from the deep borehole, ??18O values of matrix quartz increase with depth from near 8.0 at the surface to 9.5??? at 5760 m depth. In contrast, feldspar ??18O values decrease with depth from near 10 at the surface to 7.1??? at 5760 m, forming a pattern opposite to the one defined by quartz isotopic compositions. Values of ??18O for surface granites outside the impact structure are distinct from those in near-surface samples from the deep borehole. In the deep borehole, feldspar coloration varies from brick-red at the surface to white at 5760 m, and the abundances of crack-healing calcite and other secondary minerals decrease over the same interval. Superimposed on the overall decrease in alteration intensity with depth are localized fracture zones at 4662, 5415, and 6044 m depth that contain altered granites, and which provided pathways for deep penetration of surface water. The antithetic variation of quartz and feldspar ??18O values, which can be correlated with mineralogical evidence of alteration, provides evidence for interaction between rocks and impact-heated fluids (100-300?? C) in the upper 2 km of the pluton. Penetration of water to depths below 2 km was restricted by a general decrease in impact-fracturing with depth, and by a 60-m-thick diabase sill at 1500 m depth that may have been an aquitard. At depths below 4 km in the pluton, where water/rock ratios were low, oxygen isotopic compositions preserve evidence for limited high-temperature (>500?? C) exchange between alkali feldspar and fluids. The high

  15. Carbon, hydrogen, and oxygen isotope studies of the regional metamorphic complex at Naxos, Greece

    USGS Publications Warehouse

    Rye, R.O.; Schuiling, R.D.; Rye, D.M.; Jansen, J.B.H.

    1976-01-01

    At Naxos, Greece, a migmatite dome is surrounded by schists and marbles of decreasing metamorphic grade. Sillimanite, kyanite, biotite, chlorite, and glaucophane zones are recognized at successively greater distances from the migmatite dome. Quartz-muscovite and quartz-biotite oxygen isotope and mineralogie temperatures range from 350 to 700??C. The metamorphic complex can be divided into multiple schist-rich (including migmatites) and marblerich zones. The ??18O values of silicate minerals in migmatite and schist units and quartz segregations in the schist-rich zones decrease with increase in metamorphic grades. The calculated ??18OH2O values of the metamorphic fluids in the schist-rich zones decrease from about 15??? in the lower grades to an average of about 8.5??? in the migmatite. The ??D values of OH-minerals (muscovite, biotite, chlorite, and glaucophane) in the schist-rich zones also decrease with increase in grade. The calculated ??DH2O values for the metamorphic fluid decrease from -5??? in the glaucophane zone to an average of about -70??? in the migmatite. The ??D values of water in fluid inclusions in quartz segregations in the higher grade rocks are consistent with this trend. The??18O values of silicate minerals and quartz segregations in marble-rich zones are usually very large and were controlled by exchange with the adjacent marbles. The ??D values of the OH minerals in some marble-rich zones may reflect the value of water contained in the rocks prior to metamorphism. Detailed data on 20 marble units show systematic variations of ??18O values which depend upon metamorphic grade. Below the 540??C isograd very steep ??18O gradients at the margins and large ??18O values in the interior of the marbles indicate that oxygen isotope exchange with the adjacent schist units was usually limited to the margins of the marbles with more exchange occurring in the stratigraphic bottom than in the top margins. Above the 540??C isograd lower ??18O values occur in

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

    NASA Astrophysics Data System (ADS)

    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.

  17. The abiotic disproportionation of sulfur dioxide (SO2) produces sulfate with an oxygen isotope signature close to the isotope composition of seawater sulfate

    NASA Astrophysics Data System (ADS)

    Müller, Inigo A.; Brunner, Benjamin; Max, Thomas; Breuer, Christian; Reeves, Eoghan P.; Thal, Janis; Bernasconi, Stefano M.; Bach, Wolfgang

    2013-04-01

    Whereas the sulfur isotope effects during the abiotic disproportionation of SO2 were thoroughly investigated in the last years, data on the oxygen isotope signature of produced sulfate is scarce. To fill in this gap in knowledge, we performed laboratory experiments which simulated the abiotic SO2 disproportionation at temperatures ranging from 150°C to 320°C. In our experiments SO2 disproportionated rapidly into sulfate and elemental sulfur. The oxygen isotope fractionation between produced sulfate and water is in the range of the observed oxygen isotope offset between seawater sulfate and seawater. The isotope fractionations observed for the experiments is likely composed of an initial kinetic oxygen isotope fractionation, which is rapidly overprinted by equilibrium oxygen isotope between sulfate and water (reaching completion probably within a time frame of ½ to 1 hour. Our observations raise the questions if disproportionation of magmatic SO2 in submarine hydrothermal vent systems is an important control for today's seawater sulfate isotope composition, and if so, if marine hydrothermal SO2 disproportiantion shaped the oxygen isotope signature of marine sulfate over geological times.

  18. Microbial cycling, oxidative weathering, and the triple oxygen isotope consequences for marine sulfate

    NASA Astrophysics Data System (ADS)

    Johnston, D. T.; Cowie, B.; Turchyn, A. V.; Antler, G.; Gill, B. C.; Berelson, W.

    2015-12-01

    Microorganisms are responsible for most geochemical sulfur cycling in the ocean. On both modern and geological time scales, stable isotope ratios often serve as a mechanism to track conspicuous or coupled microbial processes, which in turn inform burial fluxes. The most common example of this approach is the use of sulfur isotopes in sulfate and sulfide (both aqueous and in mineral form) to track everything from rates of microbial processes through to the presence/absence of certain metabolic processes in a given environment. The use of oxygen isotope ratios in sulfate has developed in a similar fashion, providing complementary information to that of sulfur isotopes. Through our current work, we will extend the application of oxygen isotopes to include the trace stable oxygen isotope, 17O. These data are facilitated by a new laser F2 fluorination technique running at Harvard, and accompanied by the calibration of a suite of common sulfate standards. At first blush, 16O - 17O - 18O systematics should carry mass-dependent microbial fractionations with process-specific mass laws that are resolvable at the level of our analytical precision. We look to calibrate these biogeochemical effects through the integrated picture captured in marine pore water sulfate profiles, where the 18O/16O is known to evolve. In compliment, riverine sulfate (the sulfate input to the ocean) is an oxidative weathering product and is posited to carry a memory effect of tropospheric O2. Interestingly, the 17O/16O of that O2 carries a mass-independent signal reflecting the balance between stratospheric reactions and Earth surface biospheric fluxes. Through this presentation, we look to calibrate the controls on the balance between biospheric and atmospheric contributions to the marine sulfate reservoir. This is enabled by a series of isotope mass-balance models and with the ultimate goal of developing the geological triple oxygen isotope records of sulfate as a new environmental proxy for paleo

  19. Oxygen and Nitrogen Isotopes in the Sun and Solar Nebula

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.

    2014-12-01

    The record of light stable isotope signatures in early solar system materials provides key constraints on the formation environment, mixing processes, and loss processes that influenced the solar nebula. Considering first the Sun, the NASA Genesis mission showed that the solar wind has a 17O depletion that is slightly more negative than the isotopically lightest CAIs (McKeegan et al. 2011), but still only yields an inferred photospheric (and bulk) solar O isotope composition. Recent reanalysis of astronomical measurement of O isotopes from infrared CO lines (Ayres et al. 2013) argues for a similarity in d18O for the directly observed photosphere and the inferred photosphere from Genesis, in contrast to the wildly divergent astronomical values previously reported. The accuracy of the Ayres et al. results are limited by the accuracy of the IR oscillator strength models; I will report on the impact of new oscillator strength models for CO. Turning to the CAIs, the Genesis O isotope results are consistent with CO self-shielding as the mechanism for producing the CAI mixing line from a mixture of photo-produced H2O (17O-enriched) and solar-like initial material (Clayton 2002; Lyons and Young 2005). Two other mechanisms have been proposed: 17O enrichment from 1) high temperature SiO reactions with OH (Chakraborty et al. 2013), and 2) transfer from low temperature O3 formation on dust. I will critique both of these suggested mechanisms. Finally, N isotope ratios, which span a range in d15N values from ~-400 permil for the Sun (Marty et al. 2011) and solar nebula, to +1000s permil for hotspots in CB chondrites, are influenced by low temperature ion-molecule reactions, and potentially by photoprocesses. Heays et al. (2014) have shown that N2 photolysis can produce very large 15N enrichments in product HCN in a static protoplanetary disk. I will present similar calculations for a turbulently mixed disk. Implications for cometary isotopic composition will be presented.

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

    NASA Astrophysics Data System (ADS)

    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

  1. Oxygen isotope records of Holocene climate variability in the Pacific Northwest

    NASA Astrophysics Data System (ADS)

    Steinman, Byron A.; Pompeani, David P.; Abbott, Mark B.; Ortiz, Joseph D.; Stansell, Nathan D.; Finkenbinder, Matthew S.; Mihindukulasooriya, Lorita N.; Hillman, Aubrey L.

    2016-06-01

    Oxygen isotope (δ18O) measurements of authigenic carbonate from Cleland Lake (southeastern British Columbia), Paradise Lake (central British Columbia), and Lime Lake (eastern Washington) provide a ∼9000 year Holocene record of precipitation-evaporation balance variations in the Pacific Northwest. Both Cleland Lake and Paradise Lake are small, surficially closed-basin systems with no active inflows or outflows. Lime Lake is surficially open with a seasonally active overflow. Water isotope values from Cleland and Paradise plot along the local evaporation line, indicating that precipitation-evaporation balance is a strong influence on lake hydrology. In contrast, Lime Lake water isotope values plot on the local meteoric water line, signifying minimal influence by evaporation. To infer past hydrologic balance variations at a high temporal resolution, we sampled the Cleland, Paradise, and Lime Lake sediment cores at 1-60 mm intervals (∼3-33 years per sample on average) and measured the isotopic composition of fine-grained (<63 μm) authigenic CaCO3 in each sample. Negative δ18O values, which indicate wetter conditions in closed-basin lakes, occur in Cleland Lake sediment from 7600 to 2200 years before present (yr BP), and are followed by more positive δ18O values, which suggest drier conditions, after 2200 yr BP. Highly negative δ18O values in the Cleland Lake record centered on ∼2400 yr BP suggest that lake levels were high (and that the lake may have been overflowing) at this time as a result of a substantially wetter climate. Similarly, Paradise Lake sediment δ18O values are relatively low from 7600 to 4000 yr BP and increase from ∼4000 to 3000 yr BP and from ∼2000 yr BP to present, indicating that climate became drier from the middle through the late Holocene. The δ18O record from Lime Lake, which principally reflects changes in the isotopic composition of precipitation, exhibits less variability than the closed-basin lake records and follows a

  2. Uranium and molybdenum isotope evidence for an episode of widespread ocean oxygenation during the late Ediacaran Period

    NASA Astrophysics Data System (ADS)

    Kendall, Brian; Komiya, Tsuyoshi; Lyons, Timothy W.; Bates, Steve M.; Gordon, Gwyneth W.; Romaniello, Stephen J.; Jiang, Ganqing; Creaser, Robert A.; Xiao, Shuhai; McFadden, Kathleen; Sawaki, Yusuke; Tahata, Miyuki; Shu, Degan; Han, Jian; Li, Yong; Chu, Xuelei; Anbar, Ariel D.

    2015-05-01

    : (1) inadequate dissolved sulfide for quantitative thiomolybdate formation and capture of a seawater-like δ98Mo signature in sediments or (2) delivery of isotopically light Mo to sediments via a particulate Fe-Mn oxyhydroxide shuttle. A compilation of Mo isotope data from euxinic ORM suggests that there were transient episodes of extensive ocean oxygenation that break up intervals of less oxygenated oceans during late Neoproterozoic and early Paleozoic time. Hence, Member IV does not capture irreversible deep ocean oxygenation. Instead, complex ocean redox variations likely marked the transition from O2-deficient Proterozoic oceans to widely oxygenated later Phanerozoic oceans.

  3. Ground Based Observation of Isotopic Oxygen in the Martian Atmosphere Using Infrared Heterodyne Spectroscopy

    NASA Technical Reports Server (NTRS)

    Smith, R. L.; Kostiuk, T.; Livengood, T. A.; Fast, K. E.; Hewagama, T.; Delgado, J. D.; Sonnabend, G.

    2010-01-01

    Infrared heterodyne spectra of isotopic CO2 in the Martian atmosphere were obtained using the Goddard Heterodyne Instrument for Planetary Wind and Composition, HIPWAC, which was interfaced with the 3-meter telescope at the NASA Infrared Telescope Facility- Spectra were colle cted at a resolution of lambda/delta lambda=10(exp 7). Absorption fea tures of the CO2 isotopologues have been identified from which isotop ic ratios of oxygen have been determined. The isotopic ratios O-17/O -16 and O-18/O-16 in the Martian atmosphere can be related to Martian atmospheric evolution and can be compared to isotopic ratios of oxyg en in the Earth's atmosphere. Isotopic carbon and oxygen are importa nt constraints on any theory for the erosion of the Martian primordia l atmosphere and the interaction between the atmosphere and surface o r subsurface chemical reservoirs. This investigation explored the pr esent abundance of the stable isotopes of oxygen in Mars' atmospheric carbon dioxide by measuring rovibrational line absorption in isotop ic species of CO2 using groundbased infrared heterodyne spectroscopy in the vicinity of the 9.6 micron and 10.6 micron CO2 lasing bands. T he target transitions during this observation were O-18 C-12 O-16 as well as O-178 C-12 O-16 and O-16 C-113 O-16 at higher resolving power of lambda/delta lambda=10(exp 7) and with high signal-to-noise ratio (longer integration time) in order to fully characterize the absorpt ion line profiles. The fully-resolved lineshape of both the strong n ormal-isotope and the weak isotopic CO2 lines were measured simultane ously in a single spectrum.

  4. Impact of Tibetan Plateau uplift on Asian climate and stable oxygen isotopes in precipitation

    NASA Astrophysics Data System (ADS)

    Botsyun, Svetlana; Sepulchre, Pierre; Risi, Camille; Donnadieu, Yannick

    2016-04-01

    Surface elevation provides crucial information for understanding both geodynamic mechanisms of Earth's interior and influence of mountains growth on climate. Stable oxygen isotopes paleoaltimetry is considered to be a very efficient technic for reconstruction of the elevation history of mountains belts, including Tibetan Plateau and the Himalayas. This method relies on the difference between δ18O of paleo-precipitation reconstructed using the natural archives, and modern measured values for the point of interest. However, stable-isotope paleoaltimetry is potentially hampered by the fact that the presumed constancy of altitude-δ18O relationships through time might not be valid and climate changes affects δ18O in precipitation. We use the isotope-equipped atmospheric general circulation model LMDZ-iso for modeling Asia climate variations and associated δ18O in precipitation linked with Himalayas and Tibetan Plateau uplift. Experiments with reduced height over the Tibetan Plateau and the Himalayas have been designed. For the purpose of understanding where and how simulated complex climatic changes linked with the growth of mountains affect δ18O in precipitation we develop a theoretical expression for the precipitation composition. Our results show that modifying Tibetan Plateau height alters large-scale atmospheric dynamics including monsoon circulation and subsidence and associated climate variables, namely temperature, precipitation, relative humidity and cloud cover. In turn, δ18O signal decomposition results show that the isotopic signature of rainfall is very sensitive to climate changes related with the growth of the Himalayas and Tibetan Plateau, notably changes in relative humidity and precipitation amount. Topography appears to be the main controlling factor for only 40{%} of the sites where previous paleoelevation studies have been performed. Change of moisture sources linked with Asian topography uplift is shown to be not sufficient to yield a strong

  5. Genetic relations among basic lavas and ultramafic nodules: Evidence from oxygen isotope compositions

    USGS Publications Warehouse

    Kyser, T.K.; O'Neil, J.R.; Carmichael, I.S.E.

    1982-01-01

    ??18O values of unaltered basic lavas range from 4.9 to 8.3 but different types of basalts are usually restricted to narrow and distinct ranges of isotopic composition. The average ??18O values for Hawaiian tholeiites, mid-ocean ridge tholeiites, and alkali basalts are 5.4, 5.7, and 6.2 permil, respectively. Potassic lavas and andesites tend to be more 18O rich with ??18O values between 6.0 and 8.0 permil. The differences among the oxygen isotopic compositions of most of these lavas can be attributed to partial melting of isotopically distinct sources. The oxygen isotope compositions of the sources may be a function of prior melting events which produce 18O-depleted partial melts and 18O-enriched residues as a consequence of relatively large isotopic fractionations that exist at high temperatures. It is proposed that lavas with relatively low ??18O values are derived from primitive, 18O-depleted sources whereas 18O-rich basalts are produced from refractory sources that have already produced partial melts. High temperature fractionations among silicate liquids and coexisting minerals can be used in conjunction with the oxygen isotope compositions of ultramafic nodules to place constraints on the genetic relations between some nodules and different types of basic lavas. ?? 1982 Springer-Verlag.

  6. Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

    USGS Publications Warehouse

    Qi, Haiping; Lorenz, Jennifer M.; Coplen, Tyler B.; Tarbox, Lauren V.; Mayer, Bernhard; Taylor, Steve

    2014-01-01

    RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

  7. Geologic implications of the oxygen isotope profile of the Toa Baja drill hole, Puerto Rico

    SciTech Connect

    Smith, B.M. )

    1991-03-01

    The whole-rock O-isotopic compositions of volcanic and volcaniclastic samples from the Toa Baja drill hole demonstrate that low-temperature (< 200C) processes have strongly enriched the island arc materials in {sup 18}O. Subsequent to eruption, processes such as subaerial weathering, alteration during transport and deposition in volcaniclastic aprons, submarine weathering, burial diagenesis, and prograde regional metamorphism through the beginning of the prehnite-pumpellyite facies have raised average whole-rock {delta}{sup 18}O values by {approximately}4% for basalt and andesite lava flows, and by {approximately}8% for volcaniclastic sandstones. These O-isotopic disturbances were probably caused by oxygen exchange with regionally circulating seawater under rather high-water/rock conditions. The processes associated with ageing' of volcanic and volcaniclastic materials in the oceanic environment are probably more important to the global budgets of the oxygen isotopes than has been assumed in the past. Integration of these results into global models for the oxygen isotopes awaits analysis of more varied oceanic terranes, to determine the generality of the O-isotopic conclusions proferred here, and to more carefully evaluate the relative sizes of volcanic, volcaniclastic, and oceanic oxygen reservoirs and their variabilities in time.

  8. Enhancement of ferromagnetism by oxygen isotope substitution in strontium ruthenate SrRuO3

    NASA Astrophysics Data System (ADS)

    Kawanaka, Hirofumi; Aiura, Yoshihiro; Hasebe, Takayuki; Yokoyama, Makoto; Masui, Takahiko; Nishihara, Yoshikazu; Yanagisawa, Takashi

    2016-10-01

    The oxygen isotope effect of the ferromagnetic transition in itinerant ferromagnet strontium ruthenate SrRuO3 with a Curie temperature Tc of 160 K is studied. We observed for the first time a shift of ∆Tc ~ 1 K by oxygen isotope substitution of 16O → 18O in SrRuO3 by precise measurements of DC and AC magnetizations. The results surprisingly lead to the noteworthy inverse isotope effect with negative coefficient α = ‑∂ lnTc/∂ lnM. The Raman spectra indicate that the main vibration frequency of 16O at 363 cm‑1 shifts to 341 cm‑1 following oxygen isotope substitution 18O. This shift is remarkably consistent with the Debye frequency being proportional to ∝ 1√M where M is the mass of an oxygen atom. The positive isotope shift of ∆Tc can be understood by taking account of the electron-phonon interaction.

  9. Enhancement of ferromagnetism by oxygen isotope substitution in strontium ruthenate SrRuO3

    PubMed Central

    Kawanaka, Hirofumi; Aiura, Yoshihiro; Hasebe, Takayuki; Yokoyama, Makoto; Masui, Takahiko; Nishihara, Yoshikazu; Yanagisawa, Takashi

    2016-01-01

    The oxygen isotope effect of the ferromagnetic transition in itinerant ferromagnet strontium ruthenate SrRuO3 with a Curie temperature Tc of 160 K is studied. We observed for the first time a shift of ∆Tc ~ 1 K by oxygen isotope substitution of 16O → 18O in SrRuO3 by precise measurements of DC and AC magnetizations. The results surprisingly lead to the noteworthy inverse isotope effect with negative coefficient α = −∂ lnTc/∂ lnM. The Raman spectra indicate that the main vibration frequency of 16O at 363 cm−1 shifts to 341 cm−1 following oxygen isotope substitution 18O. This shift is remarkably consistent with the Debye frequency being proportional to ∝ 1√M where M is the mass of an oxygen atom. The positive isotope shift of ∆Tc can be understood by taking account of the electron-phonon interaction. PMID:27739475

  10. Recrystallization-induced oxygen isotope changes in inclusion-hosted water of speleothems - paleoclimatological implications

    NASA Astrophysics Data System (ADS)

    Demény, Attila; Czuppon, György; Leél-Őssy, Szabolcs; Németh, Péter; Szabó, Máté; Tóth, Mária; Németh, Tibor

    2016-04-01

    Stable hydrogen and oxygen isotope data of water trapped in fluid inclusions were collected for recently forming stalagmites and flowstones in order to determine how dripwater compositions are reflected and preserved in the inclusion water compositions. The samples were collected from different cave sites (with temperatures around 10 ± 1 °C) from the central and north-eastern parts of Hungary. Hydrogen isotope compositions were found to reflect dripwater values, whereas the oxygen isotope data were increasingly shifted from the local dripwater compositions with the time elapsed after deposition. The δ18O data are correlated with X-Ray diffraction full width at half maximum values (related to crystal domain size and lattice strain), suggesting that the oxygen isotope shift is related to recrystallization of calcite. Transmission electron microscope analyses detected the presence of nanocrystalline (<50 nm) calcite, whose crystallization to coarser-grained calcite crystals (>200 nm) may have induced re-equilibration between the carbonate and the trapped inclusion water. Additional data indicated that amorphous calcium carbonate (ACC) may have formed as a precursor of nanocrystalline calcite. ACC-calcite transformation followed by Ostwald ripening process provides an explanation for unexpectedly low oxygen isotope compositions in the inclusion water, especially in cold caves where carbonate may form first as an amorphous phase. This research was supported by the National Office for Research and Technology of Hungary (GVOP-3.2.1-2004-04-0235/3.0), the Hungarian Scientific Research Fund (OTKA CK 80661 and OTKA NK 101664).

  11. Oxygen isotopes in tree rings show good coherence between species and sites in Bolivia

    NASA Astrophysics Data System (ADS)

    Baker, Jessica C. A.; Hunt, Sarah F. P.; Clerici, Santiago J.; Newton, Robert J.; Bottrell, Simon H.; Leng, Melanie J.; Heaton, Timothy H. E.; Helle, Gerhard; Argollo, Jaime; Gloor, Manuel; Brienen, Roel J. W.

    2015-10-01

    A tree ring oxygen isotope (δ18OTR) chronology developed from one species (Cedrela odorata) growing in a single site has been shown to be a sensitive proxy for rainfall over the Amazon Basin, thus allowing reconstructions of precipitation in a region where meteorological records are short and scarce. Although these results suggest that there should be large-scale (> 100 km) spatial coherence of δ18OTR records in the Amazon, this has not been tested. Furthermore, it is of interest to investigate whether other, possibly longer-lived, species similarly record interannual variation of Amazon precipitation, and can be used to develop climate sensitive isotope chronologies. In this study, we measured δ18O in tree rings from seven lowland and one highland tree species from Bolivia. We found that cross-dating with δ18OTR gave more accurate tree ring dates than using ring width. Our "isotope cross-dating approach" is confirmed with radiocarbon "bomb-peak" dates, and has the potential to greatly facilitate development of δ18OTR records in the tropics, identify dating errors, and check annual ring formation in tropical trees. Six of the seven lowland species correlated significantly with C. odorata, showing that variation in δ18OTR has a coherent imprint across very different species, most likely arising from a dominant influence of source water δ18O on δ18OTR. In addition we show that δ18OTR series cohere over large distances, within and between species. Comparison of two C. odorata δ18OTR chronologies from sites several hundreds of kilometres apart showed a very strong correlation (r = 0.80, p < 0.001, 1901-2001), and a significant (but weaker) relationship was found between lowland C. odorata trees and a Polylepis tarapacana tree growing in the distant Altiplano (r = 0.39, p < 0.01, 1931-2001). This large-scale coherence of δ18OTR records is probably triggered by a strong spatial coherence in precipitation δ18O due to large-scale controls. These results

  12. Seasonal Variation in Stable Carbon and Nitrogen Isotope Values of Bats Reflect Environmental Baselines

    PubMed Central

    Popa-Lisseanu, Ana G.; Kramer-Schadt, Stephanie; Quetglas, Juan; Delgado-Huertas, Antonio; Kelm, Detlev H.; Ibáñez, Carlos

    2015-01-01

    The stable carbon and nitrogen isotope composition of animal tissues is commonly used to trace wildlife diets and analyze food chains. Changes in an animal’s isotopic values over time are generally assumed to indicate diet shifts or, less frequently, physiological changes. Although plant isotopic values are known to correlate with climatic seasonality, only a few studies restricted to aquatic environments have investigated whether temporal isotopic varia-tion in consumers may also reflect environmental baselines through trophic propagation. We modeled the monthly variation in carbon and nitrogen isotope values in whole blood of four insectivorous bat species occupying different foraging niches in southern Spain. We found a common pattern of isotopic variation independent of feeding habits, with an overall change as large as or larger than one trophic step. Physiological changes related to reproduction or to fat deposition prior to hibernation had no effect on isotopic variation, but juvenile bats had higher δ13C and δ15N values than adults. Aridity was the factor that best explained isotopic variation: bat blood became enriched in both 13C and 15N after hotter and/or drier periods. Our study is the first to show that consumers in terrestrial ecosystems reflect seasonal environmental dynamics in their isotope values. We highlight the danger of misinterpreting stable isotope data when not accounting for seasonal isotopic baselines in food web studies. Understanding how environmental seasonality is inte-grated in animals’ isotope values will be crucial for developing reliable methods to use stable isotopes as dietary tracers. PMID:25700080

  13. Oxygen isotopic evidence for vigorous mixing during the Moon-forming giant impact.

    PubMed

    Young, Edward D; Kohl, Issaku E; Warren, Paul H; Rubie, David C; Jacobson, Seth A; Morbidelli, Alessandro

    2016-01-29

    Earth and the Moon are shown here to have indistinguishable oxygen isotope ratios, with a difference in Δ'(17)O of -1 ± 5 parts per million (2 standard error). On the basis of these data and our new planet formation simulations that include a realistic model for primordial oxygen isotopic reservoirs, our results favor vigorous mixing during the giant impact and therefore a high-energy, high-angular-momentum impact. The results indicate that the late veneer impactors had an average Δ'(17)O within approximately 1 per mil of the terrestrial value, limiting possible sources for this late addition of mass to the Earth-Moon system.

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

    NASA Technical Reports Server (NTRS)

    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.

  15. Ultrafiltration by a compacted clay membrane-I. Oxygen and hydrogen isotopic fractionation

    USGS Publications Warehouse

    Coplen, T.B.; Hanshaw, B.B.

    1973-01-01

    Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01 N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disc compacted to a porosity of 35 per cent by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5%. and in O18 by 0.8%. relative to the residual solution. No additional isotopic fractionation due to a salt filtering mechanism was observed at NaCl concentrations up to 0.01 N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. ?? 1973.

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  17. Changes in Oxygen Isotopes Composition of Precipitation over Tibetan Plateau during Cenozoic

    NASA Astrophysics Data System (ADS)

    Botsyun, S.; Sepulchre, P.; Donnadieu, Y.; Risi, C. M.; Fluteau, F.

    2014-12-01

    Despite the increasing role of the stable oxygen isotopes measurements for reconstructing mountains belts paleoelevation, some issues remain that lead to a large uncertainty in paleoelevation estimationes. Among them, the use of modern isotopic lapse rate with no account of climate change linked to lower topography can lead to misinterpretation of uplift rates. In this study, we use the atmospheric general circulation model LMDZ-iso to simulate changes in isotopic composition of precipitation due to uplift of the Himalayas and Tibetan plateau. Various scenarios of TP growth have been applied together with Paleocene, Eocene, Oligocene and Miocene boundary conditions. Our simulations allow us to estimate the magnitude of precipitation, temperature and wind field changes related to the spatial and temporal evolution of the Tibetan Plateau and Himalayas. Such changes affected the isotopic composition of precipitation during the Cenozoic.We investigate the impact of these changes on the isotopic lapse rate and the implications for paleoelevation estimates.

  18. Intracellular phosphorous compounds and the reversibility of dissimilatory sulfate reduction: what do we learn from oxygen isotopes?

    NASA Astrophysics Data System (ADS)

    Brunner, B.

    2012-12-01

    Dissimilatory sulfate reduction (DSR) leads to an overprint of the oxygen isotope composition of sulfate by the oxygen isotope composition of water. This overprint is assumed to occur via cell-internally formed sulfuroxy intermediates in the sulfate reduction pathway. Unlike sulfate, the sulfuroxy intermediates can readily exchange oxygen isotopes with water. Subsequent to the oxygen isotope exchange, these intermediates, e.g. sulfite, are re-oxidized by reversible enzymatic reactions to sulfate, incorporating the oxygen used for the re-oxidation of the sulfur intermediates. Consequently, the rate and expression of DSR-mediated oxygen isotope exchange between sulfate and water depends not only on the oxygen isotope exchange between sulfuroxy intermediates and water, but also on cell-internal forward and backward reactions. The latter are the very same processes that control the extent of sulfur isotope fractionation expressed by DSR. In the stepwise reduction of sulfate to sulfide, intracellular phosphorous compounds are pivotal for the conversion of intracellular sulfate to sulfite. Because of thermodynamics, the concentration of thereby produced intracellular phosphorous compounds affects the reversibility of this reduction step and thereby impacts the oxygen isotope composition of sulfate. Consequently, there should be a link between cell-internal management of phosphorous pools and the expression of sulfur and oxygen isotope effects. The measurement of multiple sulfur isotope fractionation has successfully been applied to obtain information on the reversibility of individual enzymatically catalyzed steps in DSR. Similarly, also the oxygen isotope signature of sulfate reveals information on the reversibility of DSR. High reversibility (i.e. large isotope effects) is generally assumed to be tied to low energy availability. This raises the question if and how cell-internal management of phosphorous pools could be tied to survival strategies under energy limitation.

  19. Multiple stable oxygen isotopic studies of atmospheric sulfate: A new quantitative way to understand sulfate formation processes in the atmosphere

    NASA Astrophysics Data System (ADS)

    Lee, Charles Chi-Woo

    2000-11-01

    Sulfate is an important trace species in the Earth's atmosphere because of its roles in numerous atmospheric processes. In addition to its inherent light-scattering properties, sulfate can serve as cloud condensation nucleus (CCN), affecting cloud formation as well as microphysical properties of clouds. Consequently, atmospheric sulfate species influence the global radiative energy balance. Sulfate is known to increase acidity of rainwater with negative consequences in both natural and urban environments. In addition, aerosol sulfate (<=2.5 μm) is respirable and poses a threat to human health as a potential carrier of toxic pollutants through the respiratory tract. Despite intense investigative effort, uncertainty regarding the relative significance of gas and aqueous phase oxidation pathways still remains. Acquisition of such information is important because the lifetime and transport of S(IV) species and sulfate aerosols are influenced by the oxidative pathways. In addition, sulfate formation processes affect the aerosol size distribution, which ultimately influences radiative properties of atmospheric aerosols. Therefore, the budgetary information of the sulfur cycle, as well as the radiative effects of sulfate on global climate variation, can be attained from better quantitative understanding of in situ sulfate formation processes in the atmosphere. Multiple stable oxygen isotopic studies of atmospheric sulfate are presented as a new tool to better comprehend the atmospheric sulfate formation processes. Coupled with isotopic studies, 35S radioactivity measurements have been utilized to assess contribution of sulfate from high altitude air masses. Atmospheric sulfate (aerosols and rainwater) samples have been collected from diverse environments. Laboratory experiments of gas and aqueous phase S(IV) oxidation by various oxidants, as well as biomass burning experiments, have also been conducted. The main isotopic results from these studies are as follows: (1

  20. Kinetic isotope effect in CO2 degassing: Insight from clumped and oxygen isotopes in laboratory precipitation experiments

    NASA Astrophysics Data System (ADS)

    Affek, Hagit P.; Zaarur, Shikma

    2014-10-01

    Laboratory precipitation experiments provide the basis for the common calibration of both the oxygen isotope and the clumped isotope thermometers. These focus on CaCO3 crystals that form deep in the bulk of the solution, often by the bubbling of N2(g) through a saturated Ca(HCO3)2 solution, following the classic experiments on McCrea (1950). Here we examine oxygen and clumped isotopes in CaCO3 that was precipitated at the surface of a solution that undergoes passive CO2 degassing. This CaCO3 is affected by enhanced disequilibrium that is associated with degassing, and has therefore higher δ18O and lower Δ47 values than those of the accepted thermometer calibrations. These offsets from the common thermometers calibrations increase with decreasing temperature for Δ47 but decrease with decreasing temperature for δ18O. The Δ47-δ18O co-variance is therefore strongly temperature dependent, in contrast to theoretical predictions. This suggests an influence of additional fractionation in fast growing minerals, between DIC and calcite, that affects δ18O and counteracts some of the degassing related enrichment. This effect seems not to influence Δ47. The physical setup of CaCO3 minerals growing at the solution surface is analogous to the degassing and precipitation processes that occur in stalagmites, such that these laboratory experiments may help shed light on the isotopic disequilibrium that is observed in speleothems.

  1. Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

    USGS Publications Warehouse

    Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C.

    2010-01-01

    Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

  2. Controls on soil oxygen variation across aquatic-terrestrial interfaces

    NASA Astrophysics Data System (ADS)

    Loecke, T.; Burgin, A. J.

    2013-12-01

    Soil oxygen (O2) is a fundamental control on terrestrial biogeochemical cycles including processes producing and consuming greenhouse gases (GHG), yet it is rarely measured. Instead, soil O2 is assumed to be proportional to soil moisture and physical soil properties. For example, soil O2 is often inferred from a 25-year old steady-state diffusion model; however, few data exist to test this model in stochastic systems. The variability of soil O2 may be particularly important to GHG emissions from aquatic-terrestrial interface zones because of the convergence of variable hydrology and rapid biogeochemical processing. Our objective is to gain a better understanding of soil O2 variation and its role in controlling GHG emissions across aquatic-terrestrial interface zones. Specifically, we hypothesize that in aquatic-terrestrial interface ecosystems, soil moisture predicts O2 concentration under stable conditions where diffusion dominates, but fails under dynamic conditions (e.g., water table fluctuations or precipitation) due to advective flux during soil drainage and lags in biological O2 consumption. Furthermore, we hypothesize that GHG emissions will correspond to variation in soil O2. Twenty-four near-continuous (hourly readings) soil O2 and moisture sensors were installed across an aquatic-terrestrial interface zone of a constructed wetland in April 2012. Drought conditions (2012) resulted in minimal soil O2 variation. Despite dry conditions a diurnal pattern of lower soil O2 during the day was observed. When precipitation increased in September (due to the remnants of Hurricane Isaac), soil O2 variation increased substantially with 20 of the 24 sensors recording soil O2 concentrations below 5%. The relationship between soil moisture and soil O2 was non-linear during periods of soil drainage and precipitation. A rapid (change of 10% over <24 hours) increase in soil O2 occurs at ~ 40% water filled soil volume during soil drainage. This rapid increase appears related

  3. Multiple oxygen and sulfur isotope compositions of atmospheric sulfate in Baton Rouge, LA, USA

    NASA Astrophysics Data System (ADS)

    Jenkins, Kathryn A.; Bao, Huiming

    Secondary atmospheric sulfates (SAS) is the ultimate oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. Their presence in the atmosphere as aqueous or solid phases contributes to acid rain and climate change, thus, understanding SAS formation pathways is pertinent. There has been extensive measurement of δ34S values for SAS, which mainly aimed at source identification. Relatively fewer oxygen isotope compositions ( δ18O, Δ 17O), which are most useful for resolving competing oxidation pathways, were available, however. This study represents the first effort to characterize the Δ 17O, δ18O, and δ34S simultaneously for SAS in a tropospheric air shed. We measured a total of 20 samples collected in Baton Rouge (LA, USA) during a 600-day period. The isotope compositions for atmospheric sulfate range from +0.25‰ to +1.43‰ for Δ 17O, +11.8‰ to +19.3‰ for δ18O, and -1.4‰ to +3.8‰ for δ34S. No apparent correlation is found among Δ 17O, δ18O, or δ34S values. The Δ 17O has no seasonal variation and its values are consistent with an oxidation pathway dominated by aqueous H 2O 2. The δ18O and δ34S are within the range of those observed in other sites around the world and are not characteristic for Baton Rouge. Despite the huge variability in atmospheric condition among mid-latitude sites, the long-term average Δ 17O value for SAS appears to fall within a fairly narrow range from +0.6‰ to +0.8‰, which is ˜1‰ to 2‰ lower than those in polar sites.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  5. Oxygen Isotope Systematics of Chondrules from the Least Equilibrated H Chondrite

    NASA Technical Reports Server (NTRS)

    Kita, N. T.; Kimura, M.; Ushikubo, T.; Valley, J. W.; Nyquist, L. E.

    2008-01-01

    Oxygen isotope compositions of bulk chondrules and their mineral separates in type 3 ordinary chondrites (UOC) show several % variability in the oxygen three isotope diagram with slope of approx.0.7 [1]. In contrast, ion microprobe analyses of olivine and pyroxene phenocrysts in ferromagnesian chondrules from LL 3.0-3.1 chondrites show mass dependent isotopic fractionation as large as 5% among type I (FeO-poor) chondrules, while type II (FeO-rich) chondrules show a narrow range (less than or equal to 1%) of compositions [2]. The .Delta(exp 17)O (=delta(exp 17)O-0.52xdelta(exp 18)O) values of olivine and pyroxene in these chondrules show a peak at approx.0.7% that are systematically lower than those of bulk chondrule analyses as well as the bulk LL chondrites [2]. Further analyses of glass in Semarkona chondrules show .17O values as high as +5% with highly fractionated d18O (max +18%), implying O-16-poor glass in chondrules were altered as a result of hydration in the parent body at low temperature [3]. Thus, chondrules in LL3.0-3.1 chondrites do not provide any direct evidence of oxygen isotope exchange between solid precursor and O-16-depleted gas during chondrule melting events. To compare the difference and/or similarity between chondrules from LL and H chondrites, we initiated systematic investigations of oxygen isotopes in chondrules from Yamato 793408 (H3.2), one of the least equilibrated H chondrite [4]. In our preliminary study of 4 chondrules, we reported distinct oxygen isotope ratios from dusty olivine and refractory forsterite (RF) grains compared to their host chondrules and confirmed their relict origins [5].

  6. The oxygen isotopic composition of captured solar wind: first results from the Genesis mission

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.; Coath, C. D.; Heber, V.; Jarzebinski, G.; Kallio, A.; Kunihiro, T.; Mao, P. H.; Burnett, D.

    2008-12-01

    Oxygen is the major constituent of rocky planets and the third most abundant element comprising the Sun, yet the solar oxygen isotopic composition has remained essentially unknown. One reason is that the usual appeal to primitive meteorites does not work because oxygen is isotopically distinct in all different classes of meteorites. The cause of this premier "isotopic anomaly" (first discovered in 1973) has been variously ascribed to nucleosynthetic input, e.g. from a nearby supernova, or to exotic isotope-selective chemistry in the solar nebula, e.g. based on molecular symmetry or UV photolysis. Knowledge of the average starting composition of the solar system, which is preserved in the Sun, would provide a baseline from which one could interpret the oxygen isotopic compositions of planetary materials. To this end, NASA flew the Genesis Mission to capture samples of the solar wind (SW) in ultra-pure target materials and return them to Earth for laboratory analysis. At UCLA, we have designed and constructed a hybrid secondary ion and accelerator mass spectrometer (SIMS/AMS), called the "MegaSIMS", specifically to tackle the unique analytical challenges posed by the Genesis samples: dilute elemental concentrations, limited sample material, and close proximity of likely surface contamination to the implanted solar wind ions. Three years after the crash- landing of the sample return capsule in the Utah desert, we have succeeded in making oxygen isotopic measurements on SW captured in a SiC target from the Genesis SW concentrator. Our preliminary data indicate that the Sun is enriched in 16O by at least 5% relative to Earth and meteorites. Implications for planetary science will be discussed.

  7. Oxygen Isotope Signatures of Water Masses and Planktonic Carbonate Shells of Southeastern Brazil

    NASA Astrophysics Data System (ADS)

    Venancio, I. M.; Belem, A. L.; Albuquerque, A.; Azevedo, A. G.; Barbosa, C. F.; Capilla, R.; Water Hunters

    2011-12-01

    The continental shelf of southeastern Brazil around Cabo Frio is an important region connecting the Campos and Santos basin, two main oil producing areas, characterized by the occurrence of three main water masses: the (1) warm surface Tropical Water (TW) with temperature ranging between 24-28°C and salinities higher then 36.8, carried by the Brazil Current; overlaying (2) the cooler South Atlantic Central Water (SACW) with temperatures below 18°C; and (3) Coastal Water (CW) which results from mixing of shelf waters with continental drainage showing low salinity values (<34). Eddy-induced and wind-driven upwelling zones can be found during specific meteorological and oceanographic conditions, when SACW can be found at the surface and TW far away from the coast. Oxygen isotopic ratio (δ18O) can be used as a proxy when the transfer rate between water and planktonic carbonate shells can be coupled to these oceanographic conditions. In this study water samples from different water masses and conditions as well as living species of planktonic foraminifera and pteropods were collected using plankton tows for analyses of oxygen isotope composition. We established ranges of oxygen isotope ratio values together with hydrographic data for the different water masses present in the region. First range between 1.0 and 0.75 was characterized as TW; second range with values below 0.75 and higher than 0.6 showed CW and mixing zones; and values below 0.6 indicated the SACW. These ranges are related to those found in literature and well correlated to the oceanographic conditions found in the region. Isotope records of both foraminifera and pteropods shells showed distinct patterns for the different water masses where they were sampled, due to inter-specific oxygen isotope transfer function. This study demonstrates the use of combined water and planktonic carbonate shells oxygen isotope analysis for generating more reliable paleo-oceanographic proxies to use in marine sediment

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

    NASA Astrophysics Data System (ADS)

    Yde, Jacob C.; Knudsen, Niels T.; Steffensen, Jørgen P.; Carrivick, Jonathan L.; Hasholt, Bent; Ingeman-Nielsen, Thomas; Kronborg, Christian; Larsen, Nicolaj K.; Mernild, Sebastian H.; Oerter, Hans; Roberts, David H.; Russell, Andrew J.

    2016-03-01

    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 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. A hydrograph separation analysis revealed that the ice melt component constituted 82 ± 5 % of the total run-off and dominated the observed variations during peak flow in August 2004. The snowmelt component peaked between 10:00 and 13:00 local time, reflecting the long travel time and an inefficient distributed subglacial drainage network in the upper part of the glacier. At the Kuannersuit Glacier river on the island Qeqertarsuaq in west Greenland, the δ18O characteristics were examined after the major 1995-1998 glacier surge event. The mean annual δ18O was -19.47 ± 0.55 ‰. Despite large spatial variations in the δ18O values of glacier ice on the newly formed glacier tongue, there were no diurnal oscillations in the bulk meltwater emanating from the glacier in the post-surge years. This is likely a consequence of a tortuous subglacial drainage system consisting of linked cavities, which formed during the surge 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 to obtain important information on water sources and the subglacial drainage system structure that is highly desired for understanding glacier hydrology.

  9. Individual variation of isotopic niches in grazing and browsing desert ungulates.

    PubMed

    Lehmann, D; Mfune, J K E; Gewers, E; Brain, C; Voigt, C C

    2015-09-01

    Ungulates often adjust their diet when food availability varies over time. However, it is poorly understood when and to what extent individuals change their diet and, if they do so, if all individuals of a population occupy distinct or similar dietary niches. In the arid Namibian Kunene Region, we studied temporal variations of individual niches in grazing gemsbok (Oryx gazella gazella) and predominantly browsing springbok (Antidorcas marsupialis). We used variation in stable C and N isotope ratios of tail hair increments as proxies to estimate individual isotopic dietary niches and their temporal plasticity. Isotopic dietary niches of populations of the two species were mutually exclusive, but similar in breadth. Isotopic niche breadth of gemsbok was better explained by within-individual variation than by between-individual variation of stable isotope ratios, indicating that gemsbok individuals were facultative specialists in using isotopically distinct local food resources. In contrast, inter- and intra-individual variations contributed similarly to the isotopic niche breadth of the springbok population, suggesting a higher degree of individual isotopic segregation in a more generalist ungulate. In both species, between-individual variation was neither explained by changes in plant primary productivity, sex, geographical position nor by group size. Within species, individual dietary niches overlapped partially, suggesting that both populations included individuals with distinct isotopic dietary niches. Our study provides the first evidence for isotopic dietary niche segregation in individuals of two distinct desert ungulates. Similar, yet isotopically distinct dietary niches of individuals may facilitate partitioning of food resources and thus individual survival in desert ecosystems.

  10. Individual variation of isotopic niches in grazing and browsing desert ungulates.

    PubMed

    Lehmann, D; Mfune, J K E; Gewers, E; Brain, C; Voigt, C C

    2015-09-01

    Ungulates often adjust their diet when food availability varies over time. However, it is poorly understood when and to what extent individuals change their diet and, if they do so, if all individuals of a population occupy distinct or similar dietary niches. In the arid Namibian Kunene Region, we studied temporal variations of individual niches in grazing gemsbok (Oryx gazella gazella) and predominantly browsing springbok (Antidorcas marsupialis). We used variation in stable C and N isotope ratios of tail hair increments as proxies to estimate individual isotopic dietary niches and their temporal plasticity. Isotopic dietary niches of populations of the two species were mutually exclusive, but similar in breadth. Isotopic niche breadth of gemsbok was better explained by within-individual variation than by between-individual variation of stable isotope ratios, indicating that gemsbok individuals were facultative specialists in using isotopically distinct local food resources. In contrast, inter- and intra-individual variations contributed similarly to the isotopic niche breadth of the springbok population, suggesting a higher degree of individual isotopic segregation in a more generalist ungulate. In both species, between-individual variation was neither explained by changes in plant primary productivity, sex, geographical position nor by group size. Within species, individual dietary niches overlapped partially, suggesting that both populations included individuals with distinct isotopic dietary niches. Our study provides the first evidence for isotopic dietary niche segregation in individuals of two distinct desert ungulates. Similar, yet isotopically distinct dietary niches of individuals may facilitate partitioning of food resources and thus individual survival in desert ecosystems. PMID:25953117

  11. Nitrogen cycling in shallow low-oxygen coastal waters off Peru from nitrite and nitrate nitrogen and oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Hu, Happy; Bourbonnais, Annie; Larkum, Jennifer; Bange, Hermann W.; Altabet, Mark A.

    2016-03-01

    O2 deficient zones (ODZs) of the world's oceans are important locations for microbial dissimilatory nitrate (NO3-) reduction and subsequent loss of combined nitrogen (N) to biogenic N2 gas. ODZs are generally coupled to regions of high productivity leading to high rates of N-loss as found in the coastal upwelling region off Peru. Stable N and O isotope ratios can be used as natural tracers of ODZ N-cycling because of distinct kinetic isotope effects associated with microbially mediated N-cycle transformations. Here we present NO3- and nitrite (NO2-) stable isotope data from the nearshore upwelling region off Callao, Peru. Subsurface oxygen was generally depleted below about 30 m depth with concentrations less than 10 µM, while NO2- concentrations were high, ranging from 6 to 10 µM, and NO3- was in places strongly depleted to near 0 µM. We observed for the first time a positive linear relationship between NO2-δ15N and δ18O at our coastal stations, analogous to that of NO3- N and O isotopes during NO3- uptake and dissimilatory reduction. This relationship is likely the result of rapid NO2- turnover due to higher organic matter flux in these coastal upwelling waters. No such relationship was observed at offshore stations where slower turnover of NO2- facilitates dominance of isotope exchange with water. We also evaluate the overall isotope fractionation effect for N-loss in this system using several approaches that vary in their underlying assumptions. While there are differences in apparent fractionation factor (ɛ) for N-loss as calculated from the δ15N of NO3-, dissolved inorganic N, or biogenic N2, values for ɛ are generally much lower than previously reported, reaching as low as 6.5 ‰. A possible explanation is the influence of sedimentary N-loss at our inshore stations which incurs highly suppressed isotope fractionation.

  12. High resolution Early Jurassic (Sinemurian-Early Pliensbachian) isotope variation, Dorset UK

    NASA Astrophysics Data System (ADS)

    Price, Gregory; Baker, Sarah; VanDeVelde, Justin; Clemence, Marie-Emilie

    2016-04-01

    We present a high-resolution carbon and oxygen isotope record for the Early Jurassic based on well-preserved marine molluscs (belemnites) from Dorset, UK. Our new data show a number of carbon isotope excursions, starting with the Sinemurian-Pliensbachian boundary Event followed by lesser negative excursions showing in the Polymorphous, Jamesoni and Masseanum-Valdani Subzones. The recognition of the Sinemurian-Pliensbachian boundary Event in this study and elsewhere suggests that observed carbon-isotope trends are likely to represent a supra regional or global perturbation of the carbon cycle. A prominent positive carbon isotope event is also seen within the Pliensbachian Ibex Zone. This event is also clearly evident in the data from belemnites from Spain, but rather puzzlingly not within carbon isotope records derived from bulk carbonate from Portugal. This carbon isotope excursion is not, however, coincident with inferred peak temperatures. The oxygen isotope and Mg/Ca data allows the determination of 2 pronounced Pliensbachian cool events within the Taylori and Brevispina Subzones. From the low point in the Brevispina Subzone, oxygen isotopes become more negative coupled with an increase in Mg/Ca values culminating in an Early Pliensbachian thermal maximum during the Davoei Zone. Taken with existing data it appears that the Pliensbachian is characterised by 2 major warmings, firstly within the Davoei Zone followed by warming beginning in the latest Pliensbachian and peaking in the Early Toarcian.

  13. Evaluation of Community Respiratory Mechanisms With Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Luz, B.; Barkan, E.

    Oxygen uptake in the surface waters of oceans and lakes takes place by ordinary dark respiration as well as by cyanide resistant respiration in both dark and light conditions, and by photorespiration and Mehler reaction that occur only during illumination. Thus in order to study the overall discrimination in aquatic systems it is necessary to eval- uate its effects in both light and dark conditions and to separate the effect of photo- synthetic production of oxygen. Such separation is possible if gross rates of oxygen production and consumption are known. We have estimated these rates from in situ incubation experiments and from the natural distribution of O-16, O-17, O-18 and the ratio of dissolved oxygen/argon. We have studied the respiration mechanisms in L. Kinneret, in the Atlantic Ocean near Bermuda and in the Southern Ocean. The over- all respiratory fractionation, which represents both light and dark consumption, was greater than the fractionation found in dark incubations of surface waters. We suggest that the only mechanism that can explain the strong overall fractionation is significant O2 uptake by cyanide resistant respiration in illuminated plankton. Our study shows that cyanide resistant respiration, which is known to strongly fractionate against O-18, is widespread in aquatic systems.

  14. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia.

    PubMed

    Baur, M E; Hayes, J M; Studley, S A; Walter, M R

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron. PMID:11539027

  15. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

    NASA Technical Reports Server (NTRS)

    Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

  16. Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from CR2 carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Makide, Kentaro; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.; Hutcheon, Ian D.; Bischoff, Addi

    2009-09-01

    canonical ( 26Al/ 27Al) 0, it may have experienced multistage formation from precursors with nonsolar magnesium-isotope composition and recorded evolution of oxygen-isotope composition in the early solar nebula over 0.9+2.2-0.7 My. Eight of the 166 CR2 CAIs identified are associated with chondrule materials, indicating that they experienced late-stage, incomplete melting during chondrule formation. Three of these CAIs show large variations in oxygen-isotope compositions (Δ 17O ranges from -23.5‰ to -1.7‰), suggesting dilution by 16O-depleted chondrule material and possibly exchange with an 16O-poor (Δ 17O > -5‰) nebular gas. The low inferred ( 26Al/ 27Al) 0 ratios of these CAIs (<0.7 × 10 -5) indicate melting >2 My after crystallization of CAIs with the canonical ( 26Al/ 27Al) 0 and suggest evolution of the oxygen-isotope composition of the inner solar nebula on a similar or a shorter timescale. Because CAIs in CR2 and CV chondrites appear to have originated in a similarly 16O-rich reservoir and only a small number of CR2 and CV CAIs were affected by chondrule melting events in an 16O-poor gaseous reservoir, the commonly observed oxygen-isotope heterogeneity in CAIs from metamorphosed CV chondrites is most likely due to fluid-solid isotope exchange on the CV asteroidal body rather than gas-melt exchange. This conclusion does not preclude that some CV CAIs experienced oxygen-isotope exchange during remelting, instead it implies that such remelting is unlikely to be the dominant process responsible for oxygen-isotope heterogeneity in CV CAIs. The mineralogy, oxygen and magnesium-isotope compositions of CAIs in CR2 chondrites are different from those in the metal-rich, CH and CB carbonaceous chondrites, providing no justification for grouping CR, CH and CB chondrites into the CR clan.

  17. ODP Site 1063 (Bermuda Rise) revisited: Oxygen isotopes, excursions and paleointensity in the Brunhes Chron

    NASA Astrophysics Data System (ADS)

    Channell, J. E.; Hodell, D. A.

    2011-12-01

    An age model for the Brunhes Chron for Ocean Drilling Program (ODP) Site 1063 (Bermuda Rise) is based on the tandem correlation of oxygen isotope and relative paleointensity data to calibrated reference templates. Four intervals in the Brunhes Chron where component inclinations are negative, for both u-channel samples and discrete samples, are correlated to the following magnetic excursions with Site 1063 ages in brackets: Laschamp (41 ka), Blake (116 ka), Iceland Basin (190 ka), Pringle Falls (239 ka). These ages are consistent with current age estimates for these excursion, other than for "Pringle Falls" which has an apparent age older than current estimates by ~20-30 kyrs. For each of these excursions, virtual geomagnetic poles (VGPs) reach high southerly latitudes implying paired polarity reversals in a brief time span (<2 kyr in each case) that is several times shorter than the observed duration of long-lived polarity transitions at mid-latitudes. Several intervals of low component inclinations, that are low and negative in one case, are observed both in u-channel and discrete samples at ~318 ka (MIS 9), ~413 ka (MIS 11) and in the 500-600 ka interval (MIS14-15). These may constitute inadequately recorded excursions, or high amplitude secular variation.

  18. ODP Site 1063 (Bermuda Rise) revisited: Oxygen isotopes, excursions and paleointensity in the Brunhes Chron

    NASA Astrophysics Data System (ADS)

    Channell, J. E. T.; Hodell, D. A.; Curtis, J. H.

    2012-02-01

    An age model for the Brunhes Chron of Ocean Drilling Program (ODP) Site 1063 (Bermuda Rise) is constructed by tandem correlation of oxygen isotope and relative paleointensity data to calibrated reference templates. Four intervals in the Brunhes Chron where paleomagnetic inclinations are negative for both u-channel samples and discrete samples are correlated to the following magnetic excursions with Site 1063 ages in brackets: Laschamp (41 ka), Blake (116 ka), Iceland Basin (190 ka), Pringle Falls (239 ka). These ages are consistent with current age estimates for three of these excursions, but not for "Pringle Falls" which has an apparent age older than a recently published estimate by ˜28 kyr. For each of these excursions (termed Category 1 excursions), virtual geomagnetic poles (VGPs) reach high southerly latitudes implying paired polarity reversals of the Earth's main dipole field, that apparently occurred in a brief time span (<2 kyr in each case), several times shorter than the apparent duration of regular polarity transitions. In addition, several intervals of low paleomagnetic inclination (low and negative in one case) are observed both in u-channel and discrete samples at ˜318 ka (MIS 9), ˜412 ka (MIS 11) and in the 500-600 ka interval (MIS 14-15). These "Category 2" excursions may constitute inadequately recorded (Category 1) excursions, or high amplitude secular variation.

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

    NASA Technical Reports Server (NTRS)

    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,

  20. Stabel Carbon and Oxygen Isotope Ratios of Otoliths from Juvenile and Adult Winter Flounder

    EPA Science Inventory

    This study was designed to determine if stable carbon (13C) and oxygen (18O) isotope ratios in otoliths could be used to differentiate the locations that serve as important nursery areas for winter flounder along the Rhode Island, USA coastline. In recent years the populations ...

  1. Stable Carbon and Oxygen Isotope Ratios of Otoliths Differentiate Winter Flounder (Pseudopleuonectes americanus) Habitats

    EPA Science Inventory

    Stable carbon (13C) and oxygen (18O) isotope ratios were measured in otoliths of juvenile winter flounder (Pseudopleuronectes americanus) collected from 18 nursery areas along the coast of Rhode Island, USA. Samples were obtained during June and July of 2002 from locations tha...

  2. The Oxygen Isotopic Case for Supernova Enrichment of the Solar System Birth Environment

    NASA Astrophysics Data System (ADS)

    Young, E. D.; Pontoppidan, K. M.; Smith, R. L.; Morris, M. R.; Gounelle, M.

    2010-03-01

    New oxygen isotope ratios for young stellar objects establish the disparity between solar system and galactic 18O/17O. We present evidence that the best explanation for this disparity is enrichment of the solar birth environment by exploding B stars.

  3. The Influence of pH on the Oxygen Isotope Composition of Calcium Carbonate

    NASA Astrophysics Data System (ADS)

    Hunt, J. D.; Watkins, J. M.; Ryerson, F. J.; DePaolo, D. J.

    2013-12-01

    Oxygen isotope fractionation between calcium carbonate and water is temperature-dependent and can therefore be used as a paleothermometer. Although oxygen isotope fractionation is expected from principles of equilibrium isotopic partitioning, the temperature-dependence remains uncertain because other factors, such as slow exchange between dissolved inorganic carbon (DIC) species and water, can obscure the temperature signal. Oxygen isotopic equilibrium between aqueous solution and calcium carbonate includes two distinct equilibria: equilibrium of the DIC species in solution (i.e., CO2(aq), H2CO3, HCO3-, and CO32-) with water, and equilibrium between the dissolved inorganic carbon with the precipitated carbonate. To isolate kinetic isotope effects that arise at the mineral-solution interface, isotopic equilibrium among DIC species must be maintained. This can be accomplished by dissolving the enzyme carbonic anhydrase (C