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Sample records for oxygen isotope record

  1. 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.

  2. 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

  3. 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

  4. A record of ozone variability in South Pole Antarctic snow: Role of nitrate oxygen isotopes

    NASA Astrophysics Data System (ADS)

    McCabe, Justin R.; Thiemens, Mark H.; Savarino, Joel

    2007-06-01

    The information contained in polar nitrate has been an unresolved issue for over a decade. Here we demonstrate that atmospheric nitrate's oxygen isotopic composition (Δ17O-NO3) reflects stratospheric chemistry in winter and tropospheric chemistry in summer. Surface snow isotope mass balance indicates that nitrate oxygen isotopic composition is the result of a mixture of 25% stratospheric and 75% tropospheric origin. Analysis of trends in Δ17O-NO3 in a 6 m snow pit that provides a 26-year record reveals a strong 2.70-year cycle that anticorrelates (R = -0.77) with October-November-December column ozone. The potential mechanisms linking the records are either denitrification or increased boundary layer photochemical ozone production. We suggest that the latter is dominating the observed trend and find that surface ozone and Δ17O-NO3 correlate well before 1991 (R = 0.93). After 1991, however, the records show no significant relationship, indicating an altered oxidative environment consistent with current understanding of a highly oxidizing atmosphere at the South Pole. The disappearance of seasonal Δ17O-NO3 trends in the surface layer at depth remain unresolved and demand further investigation of how postdepositional processes affect nitrate's oxygen isotope composition. Overall, the findings of this study present a new paleoclimate technique to investigate Antarctic nitrate records that appear to reflect trends in stratospheric ozone depletion by recording tropospheric surface ozone variability.

  5. Oxygen Isotopes in Tree Rings: A 345 Year Record of Precipitation in Amazonia

    NASA Astrophysics Data System (ADS)

    Jenkins, H. S.; Baker, P. A.; Evans, M. N.

    2008-12-01

    The Amazon basin is one of the world's key centers of atmospheric convection and acts as an engine for global hydrologic circulation. Despite its importance, a paucity of high resolution climate data exists for this region, in large part due to a poor instrumental record. The oxygen isotopic measurement of meteoric water has been used extensively to reconstruct past temperatures derived from ice cores, corals, and tree rings but is only recently recognized as a precipitation proxy in the tropics. Here we present a continuous, highly resolved (intra-annual), 345 year oxygen isotopic record from the Madre de Dios department in Southeastern Peru. Using tropical hardwood species Dipteryx micrantha, we present oxygen (and carbon) isotopic data from digested tree ring cellulose. We also present some of the first intra-annual (early wood versus late wood) isotopic data on this old growth tropical species. We demonstrate the utility of Amazon tropical tree rings to accurately record rainfall. We also identify that this meteoric water was delivered to the region via the South American Low-level Jet (SALLJ), which develops over the Atlantic and is the major water source during the South American Summer Monsoon.

  6. Tree-ring Oxygen Isotope Records of Climate Modes Influencing North Atlantic Tropical Cyclone Activity

    NASA Astrophysics Data System (ADS)

    Mora, C. I.; Miller, D. L.; Grissino-Mayer, H. D.; Kocis, W. N.; Lewis, D. B.

    2006-12-01

    The relatively short instrumental record hinders our ability to discern the linkages between low frequency modes of climate variability and tropical cyclone activity and to differentiate natural versus anthropogenic components of these trends. The development of biological proxies for tropical cyclone activity and climate provides a basis for evaluation of these linkages over much longer time frames. The oxygen isotope composition of tree-ring cellulose, sampled at high resolution (seasonal or better), provides a new proxy for tropical cyclone activity that preserves a concurrent isotope time series reflecting the influence of climate variability. This proxy archive potentially extends many centuries beyond the instrumental and historical (documentary) record of climate and tropical cyclone activity. Isotope time series for longleaf pines (Pinus palustris Mill.) in southern Georgia and South Carolina preserve distinct tropical cyclone histories, yet similar, long term trends in cellulose δ 18O compositions. The isotope time series correlate to various climate modes proposed to impact hurricane formation and frequency. Tree-ring cellulose δ 18O values at the Georgia study site show a significant negative correlation with AMO indices from 1875 to about 1950, and a weaker, positive correlation from about 1965 to 1990. The "crossover" parallels a change in the predominant ontogeny of North Atlantic tropical cyclones from tropical-only to baroclinically-enhanced hurricanes. The intervening 1950s is marked by greater correspondence to ENSO indices. Reduced seasonality in the isotope record (i.e., the difference between earlywood and latewood δ 18O values) corresponds to warm phases of the PDO. An isotope series for 1580 to 1650 suggests little tropical cyclone activity coinciding with a period (1560-1625) of severe drought in the African Sahel. Although preliminary, these results suggest that tree-ring oxygen isotope compositions are sensitive to changes in climate

  7. Paired oxygen isotope records reveal modern North American atmospheric dynamics during the Holocene.

    PubMed

    Liu, Zhongfang; Yoshimura, Kei; Bowen, Gabriel J; Buenning, Nikolaus H; Risi, Camille; Welker, Jeffrey M; Yuan, Fasong

    2014-04-16

    The Pacific North American (PNA) teleconnection has a strong influence on North American climate. Instrumental records and century-scale reconstructions indicate an accelerating tendency towards the positive PNA state since the mid-1850s, but much less is known about long-term PNA variability. Here we reconstruct PNA-like climate variability during the mid- and late Holocene using paired oxygen isotope records from two regions in North America with robust, anticorrelated isotopic response to the modern PNA. We identify mean states of more negative and positive PNA-like climate during the mid- and late Holocene, respectively. Superimposed on the secular change between states is a robust, quasi-200-year oscillation, which we associate with the de Vries solar cycle. These findings suggest the persistence of PNA-like climate variability throughout the mid- and late Holocene, provide evidence for modulation of PNA over multiple timescales and may help researchers de-convolve PNA pattern variation from other factors reflected in palaeorecords.

  8. 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

  9. Coordinated Oxygen Isotopic and Petrologic Studies of CAIs Record Varying Composition of Protosolar Gas

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

    High-resolution O-isotopic zoning profiles obtained by NanoSIMS indicate a progressive and cyclic record of exchange between CAIs and distinct nebular gases. Numerical models are used to constrain conditions and duration of these exchange events.

  10. Oxygen Isotopes in Meteorites

    NASA Astrophysics Data System (ADS)

    Clayton, R. N.

    2003-12-01

    types of stellar sources, corresponding to the r-process, s-process, and p-process. Presolar silicon carbide grains, extracted from primitive meteorites, contain molybdenum that has been subject to s-process neutron capture in red-giant stars, resulting in large enrichments of isotopes at masses 95, 96, 97, 98, and severe depletions (up to 100%) of isotopes at masses 92 and 94 (p-process) and 100 (r-process) (Nicolussi et al., 1998). Complementary patterns have been found in whole-rock samples of several meteorites, with >1,000-fold smaller amplitude, suggesting the preservation of a small fraction of the initial isotopic heterogeneity ( Yin et al., 2002; Dauphas et al., 2002). Oxygen is another element for which primordial isotopic heterogeneity might be preserved. This is discussed further below.It would be highly desirable to have samples of oxygen-rich mineral grains that have formed in stellar atmospheres and have recorded the nucleosynthetic processes in individual stars. Similar samples are already available for carbon-rich grains, in the form of SiC and graphite, primarily from asymptotic giant branch (AGB) stars and supernovae (Anders and Zinner, 1993). These presolar grains have provided a wealth of detailed information concerning nucleosynthesis of carbon, nitrogen, silicon, calcium, titanium, and heavier elements (see Chapter 1.02). It is thought that such carbon-rich minerals should form only in environments with C/O>1, as in the late stages of AGB evolution, or in carbon-rich layers of supernovae. By analogy, one would expect to form oxide and silicate minerals in environments with C/O<1, as is common for most stars. Indeed there is evidence in infrared spectra for the formation of Al2O3 (corundum) and silicates, such as olivine (Speck et al., 2000) around evolved oxygen-rich stars. However, searches for such grains in meteorites have yielded only a very small population of corundum grains, a few grains of spinel and hibonite, and no silicates ( Nittler et

  11. 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

  12. Oxygen isotopes in tree rings record variation in precipitation δ(18)O and amount effects in the south of Mexico.

    PubMed

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

    2013-12-01

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

  13. 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

  14. Oxygen Isotope Variations at the Margin of a CAI Records Circulation Within the Solar Nebula

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

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

    PubMed

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

    2011-03-04

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

  16. Does Oxygen Isotopic Heterogeneity in Refractory Inclusions and Their Wark-Lovering Rims Record Nebular Repressing?

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

    Large systematic variations in O-isotopic compositions found within individual mineral layers of rims surrounding Ca-, Al-rich inclusions (CAIs) and at the margins of some CAIs imply formation from distinct environments [e.g., 1-3]. The O-isotope compositions of many CAIs preserve a record of the Solar nebula gas believed to initially be O-16-rich (delta O-17 less than or equal to -25%0) [4-5]. Data from a recent study of the compact Type A Allende CAI, A37, preserve a diffusion profile in the outermost 70 micrometers of the inclusion and show greater than 25%0 variations in delta O-17 within its 100 micrometer-thick Wark-Lovering rim (WL-rim) [3]. This and comparable heterogeneity measured in several other CAIs have been explained by isotopic mixing between the O-16-rich Solar reservoir and a second O-16-poor reservoir (probably nebular gas) with a planetary-like isotopic composition, e.g., [1,2,3,6]. However, there is mineralogical and isotopic evidence from the interiors of CAIs, in particular those from Allende, for parent body alteration. At issue is how to distinguish the record of secondary reprocessing in the nebula from that which occurred on the parent body. We have undertaken the task to study a range of CAI types with varying mineralogies, in part, to address this problem.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    The Ordovician Period was characterized by several major events, including a prolonged 'super greenhouse' during the Early Ordovician, the 'Great Ordovician Biodiversification Event (GOBE)' of the Middle and early Late Ordovician, and the Hirnantian ice age and mass extinction of the latest Ordovician (Webby et al., 2004, The Great Ordovician Biodiversification Event, Columbia University Press). The cause of the rapid diversification of marine invertebrates during the GOBE is not clear, however, and several scenarios have been proposed including widespread development of shallow cratonic seas, strong magmatic and tectonic activity, and climate moderation. In order to investigate relationships between climate change and marine ecosystem evolution during the Ordovician, we measured the oxygen isotopic composition of single coniform conodonts using a Cameca secondary ion mass spectrometer. Our δ18O profile shows a shift at the Early/Middle Ordovician transition that is indicative of a rapid 6 to 8 °C cooling. This cooling event marks the termination of the Early Ordovician 'super greenhouse' and may have established cooler tropical seawater temperatures that were more favorable for invertebrate animals, setting the stage for the GOBE. Additional cooling episodes occurred during the early Sandbian, early Katian, and Hirnantian, the last culminating in a short-lived (<1-Myr) end-Ordovician ice age. The much cooler conditions that prevailed at that time may have been an important factor in the end-Ordovician mass extinction. Our results differ from those of Trotter et al. (2008, 'Did cooling oceans trigger Ordovician biodiversification? Evidence from conodont thermometry,' Science 321:550-554). Instead of a slow, protracted cooling through the Early and Middle Ordovician, our high-resolution record shows that cooling occurred in several discrete steps, with the largest step being at the Early/Middle Ordovician transition.

  18. Coordinated Oxygen Isotopic and Petrologic Studies of CAIS Record Varying Composition of Protosolar

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

    Ca-, Al-rich inclusions (CAIs) record the O-isotope composition of Solar nebular gas from which they grew [1]. High spatial resolution O-isotope measurements afforded by ion microprobe analysis across the rims and margin of CAIs reveal systematic variations in (Delta)O-17 and suggest formation from a diversity of nebular environments [2-4]. This heterogeneity has been explained by isotopic mixing between the O-16-rich Solar reservoir [6] and a second O-16-poor reservoir (probably nebular gas) with a "planetary-like" isotopic composition [e.g., 1, 6-7], but the mechanism and location(s) where these events occur within the protoplanetary disk remain uncertain. The orientation of large and systematic variations in (Delta)O-17 reported by [3] for a compact Type A CAI from the Efremovka reduced CV3 chondrite differs dramatically from reports by [4] of a similar CAI, A37 from the Allende oxidized CV3 chondrite. Both studies conclude that CAIs were exposed to distinct, nebular O-isotope reservoirs, implying the transfer of CAIs among different settings within the protoplanetary disk [4]. To test this hypothesis further and the extent of intra-CAI O-isotopic variation, a pristine compact Type A CAI, Ef-1 from Efremovka, and a Type B2 CAI, TS4 from Allende were studied. Our new results are equally intriguing because, collectively, O-isotopic zoning patterns in the CAIs indicate a progressive and cyclic record. The results imply that CAIs were commonly exposed to multiple environments of distinct gas during their formation. Numerical models help constrain conditions and duration of these events.

  19. Resolving seasonality in tropical trees: multi-decade, high-resolution oxygen and carbon isotope records from Indonesia and Thailand

    NASA Astrophysics Data System (ADS)

    Poussart, Pascale F.; Evans, Michael N.; Schrag, Daniel P.

    2004-02-01

    Dendrochronological techniques have found limited applications in the tropics because of invisible or indistinct banding in wood. The seasonal cycles of rainfall and relative humidity in these regions, while not sufficient to produce distinct visible rings, may still generate seasonal signals in the oxygen isotopic composition of tree cellulose which can be used for climate reconstruction and chronology. We explore this approach using trees from Indonesia and Thailand, from three different families. Multi-decade δ 18O records from Javanese cross-dated teak rings and bomb radiocarbon-dated Suar wood lacking visible rings demonstrate the reproducibility of the signal between trees grown at the same locality as well as from wider geographical regions. These results confirm predictions that the trees oxygen isotopic signatures reflect an external climatic forcing. High-resolution δ 18O records reveal large seasonal cycles: up to 4‰ for Javanese Suar samples and up to 18‰ for a Thai Podocarpus sample. We show that the six δ 18O and δ 13C cycles measured on a Podocarpus match the number of growth years for the period spanning the time of wounding and cutting of the wedge section. This result demonstrates that the isotopic cycles found in this tree with indistinct annual rings are indeed seasonal and could be used for chronology. We present evidence that stable isotope chronologies of tropical trees also contain insights in tropical tree physiology and growth dynamics.

  20. Mo isotope record of shales points to deep ocean oxygenation in the early Paleoproterozoic

    NASA Astrophysics Data System (ADS)

    Asael, Dan; Scott, Clint; Rouxel, Olivier; Poulton, Simon; Lyons, Timothy; Javaux, Emmanuelle; Bekker, Andrey

    2014-05-01

    Two steps in Earth's surface oxidation lie at either end of the Proterozoic Eon. The first step, known as the Great Oxidation Event (GOE), occurred at ca. 2.32 Ga (1), when atmospheric oxygen first exceeded 0.001% of present atmospheric levels (2). The second step, occurred at ca. 0.58 Ga, resulting in the pervasive oxygenation of the deep oceans, a feature that persisted through most of the Phanerozoic (3). The conventional model envisions two progressive and unidirectional increases in free oxygen. However, recent studies have challenged this simplistic view of the GOE (4, 5). A dramatic increase and decline in Earth oxidation state between 2.3 and 2.0 Ga is now well supported (6-9) and raises the question of how well-oxygenated the Earth surface was in the immediate aftermath of the GOE. In order to constrain the response of the deep oceans to the GOE, we present a study of Mo isotope composition and Mo concentration from three key early Paleoproterozoic black shale units with ages ranging from 2.32 to 2.06 Ga. Our results suggest high and unstable surface oxygen levels at 2.32 Ga, leading to an abrupt increase in Mo supply to the still globally anoxic ocean, and producing extreme seawater Mo isotopic enrichments in these black shales. We thus infer a period of significant Mo isotopic Rayleigh effects and non-steady state behaviour of the Mo oceanic system at the beginning of the GOE. Between 2.2-2.1 Ga, we observe smaller Mo isotopic variations and estimate the δ98Mo of seawater to be 1.42 ± 0.27 ‰W conclude that oxygen levels must have stabilized at a relatively high level and that the deep oceans were oxygenated for the first time in Earth's history. By ca. 2.06 Ga, immediately after the Lomagundi Event, the Mo isotopic composition decreased dramatically to δ98MoSW = 0.80 ± 0.21 o reflecting the end of deep ocean oxygenation and the return of largely anoxic deep oceans. References: [1] A. Bekker et al., 2004, Nature 427, 117-20. [2] A. Pavlov and J

  1. Wavelet analysis of oxygen isotope and paleotemperature records from NGRIP Ice Core

    NASA Astrophysics Data System (ADS)

    Wysokinski, A.; Kobylinski, Z.

    The recent completion of drilling of ice core at the North Greenland NGRIP has allowed the studies of climate back to 123000 years before the present That high resolution oxygen 18 isotopic composition data with 100 yrs sampling averages are investigated by means of wavelet transform and wavelet coherence methods Torrence and Compo 1996 and Grinsted et al 2004 The obtained wavelet spectrum indicates that the stronger variability of the oxygen 18 content are related to cooler glacial seasons when clear oscillations in data occur with the periods of about 1 5 - 4 ky Such oscillations were significant at the 95 confidence level in the time intervals 10-12 ky 34-36 5 ky and 72-76 ky back in time The warmer interglacial times are much more quiet and the climate is more stable then The implications of the results are discussed The results are compared with similar studies in which other advanced spectral methods were used

  2. Magma reservoir dynamics at Toba caldera, Indonesia, recorded by oxygen isotope zoning in quartz

    PubMed Central

    Budd, David A.; Troll, Valentin R.; Deegan, Frances M.; Jolis, Ester M.; Smith, Victoria C.; Whitehouse, Martin J.; Harris, Chris; Freda, Carmela; Hilton, David R.; Halldórsson, Sæmundur A.; Bindeman, Ilya N.

    2017-01-01

    Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ18O values. Overall, Toba quartz crystals exhibit comparatively high δ18O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ18O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum ∆core−rim = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ18O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ18O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems. PMID:28120860

  3. Magma reservoir dynamics at Toba caldera, Indonesia, recorded by oxygen isotope zoning in quartz

    NASA Astrophysics Data System (ADS)

    Budd, David A.; Troll, Valentin R.; Deegan, Frances M.; Jolis, Ester M.; Smith, Victoria C.; Whitehouse, Martin J.; Harris, Chris; Freda, Carmela; Hilton, David R.; Halldórsson, Sæmundur A.; Bindeman, Ilya N.

    2017-01-01

    Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ18O values. Overall, Toba quartz crystals exhibit comparatively high δ18O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ18O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum ∆core‑rim = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ18O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ18O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems.

  4. Magma reservoir dynamics at Toba caldera, Indonesia, recorded by oxygen isotope zoning in quartz.

    PubMed

    Budd, David A; Troll, Valentin R; Deegan, Frances M; Jolis, Ester M; Smith, Victoria C; Whitehouse, Martin J; Harris, Chris; Freda, Carmela; Hilton, David R; Halldórsson, Sæmundur A; Bindeman, Ilya N

    2017-01-25

    Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ(18)O values. Overall, Toba quartz crystals exhibit comparatively high δ(18)O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ(18)O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum ∆core-rim = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ(18)O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ(18)O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems.

  5. A High-resolution Detrital and Oxygen Isotope Record from Flemish Pass, Labrador Sea

    NASA Astrophysics Data System (ADS)

    deJesus, E.; Hoffman, J. S.; Clark, P. U.; Mix, A. C.

    2014-12-01

    High-resolution records of deglacial paleoceanographic change along the Labrador shelf are scarce. However, they are required in order to characterize and understand possible ice-ocean interactions involving the eastern sector of the Laurentide Ice Sheet (LIS). We have generated a high-resolution stable isotope and detrital stratigraphic record for core HU2001043-008 (990m, 48° N, 45° W) from Flemish Pass, Labrador Sea, to better understand the role of LIS ice-rafting events in abrupt climate changes during the last glaciation. Samples at two-centimeter resolution were disaggregated, washed, and picked for Neogloboquandrina pachyderma (sinistral) for stable isotope and radiocarbon analysis. The δ18O signal in foraminiferal calcite allows us to examine surface-ocean changes that may indicate an influx of freshwater, which may or may not be related to an LIS ice-rafting event. Our results will help in developing a better understanding of the source of LIS ice-rafting events, precursory indicators of the events, and how these events are associated with changes in deep-water formation in the Labrador Sea.

  6. Oxygen isotope record of the 1997-1998 El Niño in Peruvian sea catfish (Galeichthys peruvianus) otoliths

    NASA Astrophysics Data System (ADS)

    Andrus, C. Fred T.; Crowe, Douglas E.; Romanek, Christopher S.

    2002-12-01

    Sagittal otoliths of the Peruvian sea catfish Galeichthys peruvianus were collected from the north coast of Peru during and after the 1997-1998 El Niño. The otoliths were analyzed via laser microprobe and micromilling techniques for oxygen isotope composition through ontogeny to document their use as an El Niño-Southern Oscillation (ENSO) proxy. Results were compared to theoretical calculations for the δ18O of otolith aragonite using measured sea surface temperatures (SST) and δ18O values for local seawater assuming equilibrium oxygen isotope fractionation was achieved. All otoliths recorded the 1997-1998 El Niño event as well as seasonal temperature variations. These ENSO events were recorded in otolith aragonite as significant negative excursions in δ18O that reflected the increased temperature of local marine waters. The combined otolith data were used to create a 10-year SST record, including ENSO events and local seasonal temperature variation, validating the use of otolith δ18O as a temperature proxy.

  7. Stable oxygen and hydrogen isotope analyses of bowhead whale baleen as biochemical recorders of migration and arctic environmental change

    NASA Astrophysics Data System (ADS)

    deHart, Pieter A. P.; Picco, Candace M.

    2015-06-01

    An analysis of the stable isotopes of oxygen (δ18O) and hydrogen (δD) was used to examine the linkage between sea ice concentration and the migration of western arctic bowhead whales (Balaena mysticetus; WABW). We compared δ18O and δD variability along the length of WABW baleen with isotopic values of zooplankton prey from different WABW habitat, with published δ13C and δ15N data, and with historical sea ice records. Zooplankton signatures varied widely (δ18O = -13‰-56‰; δD = -220‰ to -75‰), with regional separation between winter (Bering Sea) and summer (eastern Beaufort Sea) habitats of WABW observable in δD. The δ18O and δD of WABW varied significantly along the length of baleen (δ18O = 8-18‰; δD = -180 to -80‰), confirming seasonal migration and reflecting distinct regional dietary variation in isotopes. WABW migration appears to have varied concomitant with temporal sea ice concentration (SIC) changes; in years with high SIC, the difference in δD of WABW baleen between seasonal habitats was significantly greater than low SIC periods. This work shows that SIC is not only a determinant of habitat accessibility for WABW, but baleen may also be a record of historical SIC and Arctic climate.

  8. A cryptic record of magma mixing in diorites revealed by high-precision SIMS oxygen isotope analysis of zircons

    NASA Astrophysics Data System (ADS)

    Appleby, S. K.; Graham, C. M.; Gillespie, M. R.; Hinton, R. W.; Oliver, G. J. H.; EIMF

    2008-05-01

    High-precision in-situ ion microprobe (SIMS) oxygen isotope analysis of zircons from two diorite intrusions associated with the late Caledonian Lochnagar pluton in Scotland has revealed large differences in the degree of heterogeneity in zircon δ18O between the diorites. Zircon crystals from the Cul nan Gad diorite (CnG) show a unimodal distribution of oxygen isotope values ( δ18O = 6.0 ± 0.6‰ (2 σ)) and no or only minor grain-scale variation. Those from the Allt Darrarie diorite (AD1) show a large range in δ18O and an apparent bimodal distribution with modes of 6.6 ± 0.4‰ and 7.3 ± 0.4‰. Variations of up to 1.2‰ occur between and within grains; both an increase and decrease in δ18O with zircon growth has been observed. The δ18O composition of growing zircon can only change if open-system processes affect the magma composition, i.e. if material of contrasting δ18O composition is added to the magma. The variability in AD1 is interpreted to represent a cryptic record of magma mixing. A 'deep crustal hot zone' is a likely site for generation of the dioritic magmas which developed by mixing of residual melts and crustal partial melts or by melting of mafic lower crustal rocks. The overall small number of zircons with mantle-like δ18O values (5.3 ± 0.6‰ (2 σ)) in the Lochnagar diorites is largely the product of crustal differentiation rather than crustal growth. The δ18O of quartz from the CnG and AD1 diorites shows only minor variation (CnG: 10.9 ± 0.5‰ (2 σ), AD1: 11.7 ± 0.6‰ (2 σ)) within single populations, with no evidence of mixing. Quartz-zircon isotopic disequilibrium is consistent with later crystallisation of quartz from late magmatic fluids, and in case of the AD1 diorite after the inferred magma mixing from a homogenised, higher δ18O melt. High-precision SIMS oxygen isotope analysis of zircon provides a new approach to identifying and resolving previously undetected early-stage magma mixing and constraining the compositions

  9. The oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Brown, B. Alex

    The properties of the oxygen isotopes provide diverse examples of progress made in experiments and theory. This chain of isotopes has been studied from beyond the proton drip line in 12O to beyond the neutron drip line in 25,26O. This short survey starts with the microscopic G matrix approach for 18O of Kuo and Brown in the 1960’s and shows how theory has evolved. The nuclear structure around the doubly-magic nucleus 24O is particularly simple in terms of the nuclear shell model. The nuclear structure around the doubly-magic nucleus 16O exhibits the coexistence of single-particle and collective structure.

  10. Carbon and Oxygen Isotope Records from Tridacna derasa Shells: Toward Establishing a Reliable Proxy for Sea Surface Environments

    PubMed Central

    Yamanashi, Junpei; Takayanagi, Hideko; Isaji, Ayaka; Asami, Ryuji

    2016-01-01

    We report the carbon (δ13C) and oxygen (δ18O) isotope records of three modern Tridacna derasa shells from Ishigaki-jima, southwestern Japan. The high-resolution δ13C profiles of samples from the inner shell layer on cross-sections fall within similar narrow ranges and display no regular variations or trends, such as an ontogenetic trend or abrupt short-term drops likely to be related to reproductive activity. This suggests that the calcification site of this species is not likely affected by photosynthetic CO2 uptake or CO2 incorporation during respiration. The δ18O profiles show distinct seasonal cycles. The intraspecific variability in the δ18O values is small in parts of the shell precipitated in the adult stage, but is not negligible in the juvenile and senescent stages. The differences in the monthly and seasonally resolved δ18O values among shells are less than 0.51‰ and 0.76‰, respectively. The shell δ18O values are nearly identical or close to the δ18O values for aragonite precipitated in oxygen isotope equilibrium with ambient seawater (δ18OEA). The largest differences between the shell δ18O and δ18OEA values calculated from the monthly and seasonally resolved data correspond to an overestimate of the seawater temperature by as much as 1.7°C and 2.3°C, respectively. However, these differences are smaller in the adult stage (<0.25‰) than in the other stages. This small difference allows an accurate reconstruction of the seawater temperature with an error of <1.1°C. Consequently, we recommend that multiple shell records be obtained because of the non-negligible intraspecific variations in their δ18O values. Growth banding, composed of alternating narrow white bands and wide light-grey bands, is discernible on cross-sections of the inner shell layer. The δ18Oshell data indicate that they were formed in winter and the other seasons, respectively. PMID:27327430

  11. 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

  12. 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

  13. Early Cenomanian "hot greenhouse" revealed by oxygen isotope record of exceptionally well-preserved foraminifera from Tanzania

    NASA Astrophysics Data System (ADS)

    Ando, Atsushi; Huber, Brian T.; MacLeod, Kenneth G.; Watkins, David K.

    2015-11-01

    The search into Earth's mid-Cretaceous greenhouse conditions has recently been stimulated by the Tanzania Drilling Project (TDP) which has recovered exceptionally well-preserved biogenic carbonates from subsurface pre-Neogene marine sediments in the eastern margin of central Africa. Published Tanzanian oxygen isotope records measured on exquisitely preserved foraminiferal tests, dating to as old as ~93 Ma, provided evidence for a Turonian "hot greenhouse" with very high and stable water-column temperatures. We have generated a comparable data set of exceptionally well-preserved foraminifera from a lower Cenomanian interval of TDP Site 24 spanning 99.9-95.9 Ma (planktonic foraminiferal Thalmanninella globotruncanoides Zone; nannofossil Corollithion kennedyi to Lithraphidites eccentricus Zones), thereby extending the age coverage of the Tanzanian foraminiferal δ18O record back by ~7 million years. Throughout the interval analyzed, the new foraminiferal δ18O data are consistently around -4.3‰ for surface-dwelling planktonic taxa and -1.9‰ for benthic Lenticulina spp., which translate to conservative paleotemperature estimates of >31°C at the surface and >17°C at the sea floor (upper bathyal depths). Considering the ~40°S Cenomanian paleolatitude of TDP Site 24, these estimates are higher than computer simulation results for accepted "normal" greenhouse conditions (those with up to 4X preindustrial pCO2 level) and suggest that the climate mode of the early Cenomanian was very similar to the Turonian hot greenhouse. Taking account of other comparable data sources from different regions, the hot greenhouse mode within the normal mid-Cretaceous greenhouse may have begun by the latest Albian, but the precise timing of the critical transition remains uncertain.

  14. Triple oxygen isotopes and clumped isotopes in modern vertebrate and dinosaur biominerals: Records of paleoecology, paleoaridity, and paleo-carbon-cycling

    NASA Astrophysics Data System (ADS)

    Hu, H.; Passey, B. H.; Lehmann, S. B.; Levin, N. E.; Montanari, S.; Chin, K.; Johnson, B. J.

    2015-12-01

    The parameter Δ17O describes the departure of δ17O from an expected equilibrium relationship with δ18O, which can be caused by factors such as evaporation of parent waters, and photochemical reactions among oxygen-bearing gases in stratosphere. Hence, the Δ17O of water records information about environmental aridity, and the Δ17O of atmospheric O2 is related to atmospheric concentrations of CO2 and O2, and gross primary productivity (GPP). Vertebrates incorporate Δ17O signals of input water (e.g. drinking water and free food water) and atmospheric O2 into body water through respiration, and biominerals forming in equilibrium with body water can preserve this signal over geological timescales. The preservation of fossil biominerals can be evaluated by clumped isotopes as they record the temperature of mineralization, be it primary mineralization in the living animal (at body temperature), or secondary mineralization during diagenesis. We can distinguish the alteration of samples from the deviation between observed clumped isotope temperatures and plausible body temperatures. Meanwhile, diagenesis tends to moderate Δ17O of biominerals towards Δ17O of meteoric waters, such that measured Δ17O values reflect the minimum anomaly in fossil samples. Thus, preservation of anomalous Δ17O indicates at least partial preservation of the original signal. We present Δ17O data from both modern vertebrate and fossil dinosaur biominerals. We use a 17O-enabled body water model to explore the influence of aridity and dietary ecology on animal Δ17O, and to predict the degree of dilution of the atmospheric O2 Δ17O signal by other sources of oxygen to the animal. We observe: 1) animals consuming more leaf water than drinking water are "evaporation sensitive" (ES) animals, and have lower Δ17O relative to "evaporation insensitive" animals in the same climates; 2) ES animals from arid climates have lower Δ17O values compared to ES animals from humid climates, which forms the

  15. Long-distance relationship between large-scale tropical SSTs and ice core-derived oxygen isotopic records in the Third Pole Region

    NASA Astrophysics Data System (ADS)

    Thompson, L. G.; Yao, T.; Mosley-Thompson, E. S.; Lin, P.

    2012-12-01

    The tropical hydrological cycle is a key factor coupling isotopic records from ice core, speleothem and lake records with tropical SSTs and the vertical amplification of temperature in the Tropics. Stable isotopic ratios, particularly of oxygen, preserved in glacier ice provide high resolution records of climate changes over long time periods. In polar ice sheets the isotopic signal is driven primarily by temperature while in low-latitudes it depends on a variety of hydrologic and thermal influences in the broad geographic region that supplies moisture to the mountain glaciers. The strong correlation between ice core-derived isotopic records throughout the low- and mid-latitudes and tropical SSTs likely reflects the dominance of tropical evaporation in the flux of water vapor to the atmosphere and provides a possible explanation for the large-scale isotopic links among low- and mid-latitude paleoclimate records. Many low- to mid-latitude ice fields provide continuous, annually-resolved proxy records of climatic and environmental variability recorded by many preserved and measurable parameters including oxygen and hydrogen isotopic ratios and net mass balance (accumulation). These records present an opportunity to examine the nature of climate variability in these regions in greater detail and to extract new information about long-distance relationships in the climate system. Understanding these relationships is essential for proper interpretation of the isotopic records archived in glaciers, lakes, speleothems and other paleo-archives in the Third Pole (TP) Region. Here we compare high resolution records from Dasuopu Glacier in the Himalaya, a speleothem record from Wanxiang Cave in Gansu Province on the TP and the annually resolved ice core records from the Quelccaya Ice Cap in the tropical Andes of South America. The purpose is to explore the role of long-distance processes in determining the isotopic composition of paleo archives on the TP. Running correlations

  16. Living on the edge: The oxygen isotope record of Eocene Basins at the margin of the Cenozoic North American plateau

    NASA Astrophysics Data System (ADS)

    Methner, Katharina; Mulch, Andreas; Chamberlain, Page

    2013-04-01

    Topography has a strong impact on atmospheric circulation and precipitation patterns and is a key element in reconstructing the dynamics of mountain building processes. The topographic evolution of the world's major orogens remains one of the most important questions when discussing the interactions among tectonics, climate, and Earth surface processes. Here, we focus on the spatial and temporal development of topography and relief in the western North American Cordillera and how changes in the topography may have affected precipitation patterns and vice versa. In this context, we sampled more than 20 sections in Eocene to Oligocene terrestrial (intermontane?) basins (Chumstick, Swauk, and Chuckanut) in western and central Washington (USA) to the W and E of the modern Cascades. Oxygen isotope analysis of pedogenic carbonate in these sections allows us to reconstruct the isotopic composition of ancient soilwater or groundwater, and ultimately precipitation. Oxygen isotope measurements of pedogenic concretions and calcic horizons interestingly yield uniformly low δ18O values of 10 to 13‰ SMOW despite the proximity of all sections to the Pacific moisture source. These extremely low oxygen isotope values can result from (1) highly 18O-depleted meteoric waters (soil- or groundwater), (2) burial diagenesis at moderate temperatures and interaction with 18O-depleted (ground)water, and (3) high burial temperatures and and exchange with basins brines. Vitrinite reflectance data and preservation of primary soil structures such as rootlets, root casts, burrows, or even preserved wood fragments clearly show that some of the low-d18O sections were not affected by high degrees of burial diagenesis. Thus, we believe that the primary isotopic signal of ancient soil- or groundwater is preserved at least in parts (if not in all) of these basins. Low δ18O values of pedogenic carbonate require highly 18O-depleted meteoric water, which in turn, would require high elevation either at

  17. Chronological study of oxygen isotope composition for the solar protoplanetary disk recorded in a fluffy Type A CAI from Vigarano

    NASA Astrophysics Data System (ADS)

    Kawasaki, Noriyuki; Itoh, Shoichi; Sakamoto, Naoya; Yurimoto, Hisayoshi

    2017-03-01

    Fluffy Type A Ca-Al-rich inclusions (CAIs) containing reversely zoned melilite crystals are suggested to be aggregates of direct condensates from solar nebular gas. We conducted an investigation of 26Al-26Mg systematics of a fluffy Type A CAI from Vigarano, named V2-01, with known oxygen isotopic distributions of reversely zoned melilite crystals; we also conducted oxygen isotope measurements of coexisting minerals. Two of six reversely zoned melilite crystals show continuous variations in magnesium isotopic composition, with δ25Mg decreasing along the inferred direction of crystal growth, which supports the idea that they originated through condensation. Petrography suggests that the constituent minerals of V2-01 formed in the following order: first spinel and fassaite enclosed by melilite, then reversely zoned melilite crystals, and spinel and diopside in the Wark-Lovering rim. The spinel enclosed by melilite has 16O-rich compositions (Δ17O ∼ -24‰) and on an Al-Mg evolutionary diagram plots along model isochron with an initial value of (26Al/27Al)0 = (5.6 ± 0.2) × 10-5. The fassaite enclosed by melilite crystals shows variable oxygen isotopic compositions (Δ17O ∼ -12‰ and -17‰) and plots on an isochron with (26Al/27Al)0 = (5.6 ± 0.2) × 10-5. The oxygen isotopic compositions of reversely zoned melilite showed continuous variations in Δ17O along the inferred direction of crystal growth, suggesting that surrounding nebular gas, during the formation of the reversely zoned melilite, changed from 16O-poor (Δ17O values larger than -10‰) to 16O-rich (Δ17O ∼ -25‰). The six reversely zoned melilite crystals show indistinguishable initial 26Al/27Al values with an average (26Al/27Al)0 of (4.7 ± 0.3) × 10-5, which is clearly distinguishable from the value of enclosed spinel and fassaite, indicating a younger formation age than the enclosed spinel and fassaite. The spinel and diopside from the Wark-Lovering rim show 16O-rich compositions (Δ17O

  18. Oxygen isotope heterogeneity of arc magma recorded in plagioclase from the 2010 Merapi eruption (Central Java, Indonesia)

    NASA Astrophysics Data System (ADS)

    Borisova, Anastassia Y.; Gurenko, Andrey A.; Martel, Caroline; Kouzmanov, Kalin; Cathala, Annick; Bohrson, Wendy A.; Pratomo, Indyo; Sumarti, Sri

    2016-10-01

    Chemical and isotopic compositions of magmatic crystals provide important information to distinguish between deep juvenile and crustal contributions. In this work, high-resolution multicollector secondary ion mass spectrometry data reveal strong variations of δ18O values in three plagioclase crystals (800-1700 μm) from two representative basaltic andesite samples of the 2010 Merapi eruption (Central Java, Indonesia). The δ18O values (from 4.6‰ to 7.9‰) are interpreted to reflect oxygen isotope heterogeneity in the melt composition during plagioclase growth. The lowest δ18O values (4.6-6.6‰) are found in anorthite-rich cores (An82-97), whereas higher δ18O values (5.7-7.9‰) are found in anorthite-poorer zones (An33-86), typically in crystal rims. Combining these new plagioclase δ18O data with δ18O of calc-silicate crustal xenoliths erupted between 1994 and 1998, the composition of glass inclusions hosted by the anorthite-rich plagioclase (An82-92), available experimental data, and the results of thermodynamic modeling using the Magma Chamber Simulator code, we conclude that the abundant anorthite-rich cores crystallized from a mantle-derived hydrous basaltic to basaltic trachyandesite melt that recharged a deeper (200-600 MPa) magma storage zone, whereas lower anorthite zones crystallized at shallower levels (100-200 MPa). The oxygen isotope variations in the plagioclase are explained by a two-stage model of interaction of the hydrous, mafic mantle-derived magma (1) with old crustal rocks depleted in 18O due to high temperature alteration that yielded the low δ18O values in the anorthite-rich cores at deep levels (13-20 km), and later (2) with 18O-enriched carbonate material that yielded the high δ18O values in anorthite-poorer zones at shallow levels (∼4.5-9 km). Thermodynamic modeling is consistent with ∼18 wt.% assimilation of crustal calc-silicate material at 925-950 °C and 100-200 MPa by the 2010 Merapi basaltic andesite magma prior to

  19. Discovery of Lower Pleistocene Shallow-marine Deposits on Mayaguana Island, Bahamas. Implications for Eustatic Sea-Level Curves Derived From Deep-Sea Oxygen-Isotope Records

    NASA Astrophysics Data System (ADS)

    Godefroid, F.; Kindler, P.; Chiaradia, M.; Hasler, C.; Samankassou, E.

    2008-12-01

    87Sr/86Sr-dated marine and beach sediments exposed along the north shore of Mayaguana Island (Bahamas) provide new estimates of the elevation of high sea stands during the Early Pleistocene that will contribute to better calibrate eustatic sea-level curves derived from deep-sea oxygen-isotope records. A newly investigated sea cliff located to the west of Mount Misery Point on the northern coast of Mayaguana, in the SE part of the Bahamian archipelago, includes two vertically stacked sequences of shallow-marine carbonates separated and capped by paleosols and eolianites. The lower unit, reaching up to 5.5 m above modern sea level, consists of coarse laminated calcarenites containing numerous mollusk and red-algal fragments, and large in-situ coral specimens (Diploria strigosa). The second unit, exposed between 7.3 and 10 m, includes bioturbated, coral-rich limestones, overlain by thinly bedded calcarenites characterized by an early generation of fibrous rim cement. 87Sr/86Sr ratios measured from these carbonates range from 0.709123 at the base of the section to 0.709142 at its top. The first unit can be interpreted as a peri-reefal facies deposited when relative sea level was at least 5.5 m above present. The second unit corresponds to one shallowing-upward sequence of subtidal and beach deposits generated when sea level was around 9 m above its actual stand. Sr-isotope ratios indicate that both units were formed during the Early Pleistocene, likely between 1.6 and 1.0 Ma BP. Comparison with existing oxygen-isotope records from deep- sea sediments suggests that the identified sea-level highstands could correspond to negative δ18O peaks estimated at 1.45 and 1.50 Ma BP. Based on the elevation of fossil reefs dating from the last interglacial (Marine Isotope Stage 5e) and the occurrence of Upper Miocene shallow-marine deposits close to modern sea level, Mayaguana can be considered as tectonically stable. The elevation values obtained for these Early Pleistocene

  20. A 16-ka oxygen-isotope record from Genggahai Lake on the northeastern Qinghai-Tibetan Plateau: Hydroclimatic evolution and changes in atmospheric circulation

    NASA Astrophysics Data System (ADS)

    Qiang, Mingrui; Song, Lei; Jin, Yanxiang; Li, Yuan; Liu, Li; Zhang, Jiawu; Zhao, Yan; Chen, Fahu

    2017-04-01

    Moisture source history and changes in atmospheric circulation are the most important attributes for portraying past climate changes and for estimating possible future trends. However, few climate records reflecting these attributes are available from the marginal zones of the Asian summer monsoon. Here, we present a record of the oxygen isotopic composition of authigenic carbonates (δ18Ocarb) of sequential sediments from Genggahai Lake in the northeastern Qinghai-Tibetan Plateau (QTP). Isotopic analyses were performed on the fine-grained carbonate fraction (<38 μm), mollusc shells, and stem encrustations from submerged plants. The stratigraphic variations of the δ18O record from the different carbonate components exhibit a remarkably similar pattern, probably reflecting the fact that δ18Ocarb variability was controlled primarily by changes in the oxygen isotopic composition of the lake water (δ18OLW). Disequilibrium effects and water temperature are precluded as major factors affecting the δ18Ocarb variations. Genggahai Lake is hydrologically open and characterized by a rapid discharge rate, as indicated by analysis of the hydrological setting of the lake system and by the observed significant positive correlation between δ18OLW and the oxygen isotopic composition of the inflowing water (δ18OI). Under such hydrological conditions, we argue that the isotopic signals of different moisture sources should be reflected in the carbonate isotopic composition. Furthermore, placing the δ18Ocarb record in the context of regional palaeoclimate archives, we found that the isotopic signals, particularly the negative shifts from the average values, cannot be interpreted consistently, despite a process of evaporative enrichment at the lake surface. During the early- to mid-Holocene, low δ18Ocarb values during 10.6-9.4 and 7.4-6.3 ka were associated with higher lake levels, and thus the record may have been significantly affected by a strengthened Asian summer monsoon

  1. Spatial and temporal oxygen isotope variability in northern Greenland - implications for a new climate record over the past millennium

    NASA Astrophysics Data System (ADS)

    Weißbach, S.; Wegner, A.; Opel, T.; Oerter, H.; Vinther, B. M.; Kipfstuhl, S.

    2016-02-01

    We present for the first time all 12 δ18O records obtained from ice cores drilled in the framework of the North Greenland Traverse (NGT) between 1993 and 1995 in northern Greenland. The cores cover an area of 680 km × 317 km, 10 % of the Greenland ice sheet. Depending on core length (100-175 m) and accumulation rate (90-200 kg m-2 a-1) the single records reflect an isotope-temperature history over the last 500-1100 years. Lowest δ18O mean values occur north of the summit and east of the main divide as a consequence of Greenland's topography. In general, ice cores drilled on the main ice divide show different results than those drilled east of the main ice divide that might be influenced by secondary regional moisture sources. A stack of all NGT records and the NGRIP record is presented with improved signal-to-noise ratio. Compared to single records, this stack represents the mean δ18O signal for northern Greenland that is interpreted as proxy for temperature. Our northern Greenland δ18O stack indicates distinctly enriched δ18O values during medieval times, about AD 1420 ± 20 and from AD 1870 onwards. The period between AD 1420 and AD 1850 has depleted δ18O values compared to the average for the entire millennium and represents the Little Ice Age. The δ18O values of the 20th century are comparable to the medieval period but are lower than that about AD 1420.

  2. A model-based test of accuracy of seawater oxygen isotope ratio record derived from a coral dual proxy method at southeastern Luzon Island, the Philippines

    NASA Astrophysics Data System (ADS)

    Liu, Gang; Kojima, Keitaro; Yoshimura, Kei; Okai, Takashi; Suzuki, Atsushi; Oki, Taikan; Siringan, Fernando P.; Yoneda, Minoru; Kawahata, Hodaka

    2013-06-01

    The oxygen isotope ratio in seawater (δ18Osw) is an important indicator of past hydroclimatic conditions in the tropics. In this study, we apply a dual proxy approach using δ18O and Sr/Ca in coral skeletons to estimate δ18Osw. Due to a lack of long-term continuous observational data for δ18Osw, a simplified one-dimensional box model of the ocean surface associated with historical surface atmospheric data is used for comparison with coral-derived δ18Osw record. The atmospheric data consist of the precipitation and evaporation values, together with their δ18O compositions from the global isotope reanalysis data. The model successfully reproduces a multidecadal time series for δ18Osw at southeastern Luzon Island, the Philippines, for the period 1979-2001 (r = 0.57, p < 0.01). The result suggests that the coral records are an accurate indicator of hydrological cycle changes at the site. A discrepancy between the reproduction and the coral record in the wet season (December-February) may be caused by seasonal variation in the depth of the mixed layer and upwelling, since these factors are not accounted for in the model. The reproduction is in good agreement with the coral records in the dry season (April-June), implying that δ18Osw estimated using the coral dual proxy method is more robust at this time of year.

  3. Evolution of Sulfur Isotopes and Oceanic Oxygenation Recorded in a Neoproterozoic Cap Carbonate From the Chaidam Block, China

    NASA Astrophysics Data System (ADS)

    Shen, B.; Xiao, S.; Kaufman, A.; Zhou, C.

    2006-12-01

    Neoproterozoic successions in the Chaidam Block, northwestern China, include the Hongtiegou Formation, which consists of a 20-meter thick, reddish diamictite with widespread dropstones and outsized clasts. The age of the Hongtiegou diamictite is unknown, but recent biostratigraphic correlations support a Neoproterozoic assignment. The glacial deposit is immediately overlain by a 5-meter thick carbonate of the basal Zhoujieshan Formation, which we interpret as a classic post-glacial cap carbonate. However, carbon isotope compositions of samples from this unit are near zero or slightly positive (up to ~ 2‰), which contrasts with the strongly negative (ca. -5‰) values recorded in the basal portions of most other post-glacial Neoproterozoic caps. Trace sulfate concentrations in samples of the carbonate are notably high, with an average of 366 ± 266 ppm. In the lower 2.5 meters of the Zhoujieshan cap (stage I) sulfur isotope compositions of both carbonate associated sulfate (CAS) and sulfides isolated from the same sample are indistinguishable from each other, and rise in concert by over 10% to values around +22‰. Above this level (stage II), 34S abundances of sulfides continue to increase to a peak of +27‰, but CAS values fall back to ~15‰. As a result isotopic differences between sulfides and sulfates are near zero in stage I and around 10% in stage II. The evolution of both systems in the lower half of the deposit suggests that seawater sulfate must have evolved to progressively heavier 34S compositions, and that sulfate in pore waters ¨C where sulfate reducing bacteria were active ¨C was quantitatively reduced to pyrite. This might result from the progressive distillation of sulfate from seawater by an enhanced rain of carbonate, in addition to bacterial reduction of sulfate, in the glacial aftermath. The anomalous isotope systematics of stage II are difficult to model, but might signal a new source and higher abundances of oceanic sulfate, based on

  4. Middle Pleistocene climate and habitat change at Zhoukoudian, China, from the carbon and oxygen isotopic record from herbivore tooth enamel

    NASA Astrophysics Data System (ADS)

    Gaboardi, Mabry; Deng, Tao; Wang, Yang

    2005-05-01

    The Pleistocene deposits at Zhoukoudian, often referred to as the "Peking Man" site, contain dental remains from a diverse group of herbivores, including Equus sanmeniensis, Cervus elaphus, Cervus nippon, Megaloceros pachyosteus, Sus lydekkeri, and Dicerorhinus choukoutienensis. The carbon and oxygen isotopic compositions of structural carbonate within the enamel of these teeth are used to reconstruct the paleodiet and paleoenvironment of the mammals. The δ13C values of enamel from Zhoukoudian range from -2.3‰ to -13.0‰, indicating that these mammals consumed between ˜25% and 100% C 3 plants. The presence of significant amounts of C 4 plants in the diets of some herbivore species indicates that at the onset of the Middle Pleistocene local habitats included mixed C 3/C 4 vegetation. By approximately 470,000 yr ago, C 3 plants dominated the diets of herbivores studied, suggesting that the abundance of C 4 flora had decreased in the area. For all deer analyzed in this study, the values of δ13C and δ18O decrease substantially from about 720,000 to 470,000 yr ago. This trend may be due to a strengthening of the winter monsoon during the Middle Pleistocene.

  5. Oxygen Isotopic Compositions of Fulgurites

    NASA Astrophysics Data System (ADS)

    Robert, F.; Javoy, M.

    1992-07-01

    Two occurrences of vitreous rocks (fulgurites) that have resulted from the fusion of Etnean lavas, have been ascribed to the result of lightning striking the basalts and melting fresh volcanic rocks [1]. Rapidly quenched melts appear as tubular cavities that preserve the path of the discharge. Glass droplets (D <= 500 micrometers) are always dispersed around the fused lava tube and show several petrographic similarities with chondrules found in ordinary chondrites (presence of melilite, radiating skeletal fassaite, etc). In this process, high temperatures (T>1800 K) have probably been reached during timescales <=10 sec. Because it has been suggested that lightning discharges may have played an important role in the formation of chondrules [2], we have analyzed the oxygen isotope compositions of these fulgurites (our experimental protocol is described elsewhere [3]). The glass (free from any contamination from the unmelted basalt) is 1.5o/oo depleted in ^18O relative to its measured initial isotopic composition (delta^18O = +5.6o/oo); most of the data define a mass-dependent fractionation relationship (i.e. delta^17O = 0.52 x delta^18O). Therefore the data clearly do not reproduce the oxygen isotope anomaly defined for meteorites, which has a slope of 1 in the diagram delta^17O versus delta^18O (i.e. delta^17O = 1.0 x delta^18O). Nevertheless, it should be noted that some glass samples scatter around this canonical value of 0.52 with minor departures from a purely mass-dependent fractionation. If these results are confirmed by additional determinations (now in progress) on the separated glassy droplets, the following conclusions can be proposed: 1) lightning discharges do not yield oxygen isotope anomalies similar to those measured in chondrules and 2) an isotope exchange between hot chondrules and their parent nebular gas--presumably "anomalous" in its oxygen isotopes-- seems difficult to achieve within the duration of the rapid cooling of the melt. This last point

  6. Sea surface temperatures in the central southern Indian Ocean over the period 1790 to 2007 inferred from two monthly resolved Sr/Ca and oxygen isotope records

    NASA Astrophysics Data System (ADS)

    Zinke, J.; Wassenburg, J.; Hardman, E.

    2009-04-01

    We obtained two monthly resolved Sr/Ca records from Rodrigues island (Mauritius) located in the trade wind belt of the central southern Indian Ocean. The longest core was obtained at a nearshore fringing reef and covers the period 1790-2005. This coral records surface air temperatures from the local weather station available from 1950 to the present. The most remarkable signal is a slight cooling after the 1950's. The second core was obtained from the open ocean and records a long-term warming trend between 1947 to 2007. The warming accelerated after the late 1970's in agreement with instrumental data. The oxygen isotope record is affected by salinity variations and shows a strong freshening trend after the late 1970's. The freshening trend is probably related to advection of low salinity waters with the South Equatorial Current and/or increased cyclonicity. We will discuss our results in light of interannual and decadal variability and present long-term seawater monitoring data.

  7. A 430 year record of hydroclimate variability for NE-Germany based on stable carbon and oxygen isotopes from pine and oak tree rings

    NASA Astrophysics Data System (ADS)

    Helle, Gerhard; Baschek, Heiko; Heinrich, Ingo; Navabzadeh, Nadia; Riedel, Frank; Wilmking, Martin; Heußner, Karl-Uwe

    2016-04-01

    European lowlands experience many direct and indirect influences of global warming, particularly related to the hydrological cycle which lately faces increasing flood and drought events. Although important for humans and the ecosystems in which they live, little is known about the long-term spatiotemporal hydrological changes in various European regions. Here we present the first 430-year stable carbon and oxygen chronologies from tree ring cellulose in lowland oak and pine trees (P. sylvestris, Q. petraea) for the region of NE-Germany and provide annually resolved high quality hydroclimatic reconstructions. When compared to ring width data isotope data can be used with only minor adjustments to their means (besides correction of short juvenile trends) and sample depths of 4-5 trees are normally enough for a significant expressed population signal being representative for a site. For this study more than 20 individual tree ring sub-samples for isotopic analyses were obtained from well replicated tree ring chronologies built using living trees as well as historical timber originating from four different lowland sites (50-90m asl.). By a calibration and verification approach we have evaluated the response to instrumental climate and trends of atmospheric partial pressure of CO2 (13C, only) data. While ring widths shows strong correlation to winter temperature, highly significant correlations with summer (JJA) hydroclimate conditions were found for both tree ring 13C and 18O. Strongest relationships were found with summer water vapour pressure deficit (13C and 18O) and Tmax (JJA). Although significant, relationships between 13C and climate data were found considerably weaker than climate/18O relations. On the other hand, the 13C record reveals high similarity with solar irradiance, whereas 18O does not. Based on this profound calibration the presentation will show and discuss annually resolved hydroclimatic variability of the region from our multi-centennial isotope

  8. Ordinary Chondrite Chondrules: Oxygen Isotope Variations

    NASA Astrophysics Data System (ADS)

    Metzler, K.; Pack, A.; Hezel, D. C.

    2017-02-01

    Chondrules in some H and LL chondrites show positive/negative correlations between size and oxygen isotopic composition. This indicates that they exchanged oxygen with different oxygen reservoirs and cannot stem from a common chondrule population.

  9. Analysis of the interdecadal variability of summer precipitation in central Japan using a reconstructed 106 year long oxygen isotope record from tree ring cellulose

    NASA Astrophysics Data System (ADS)

    Kurita, Naoyuki; Nakatsuka, Takeshi; Ohnishi, Keiko; Mitsutani, Takumi; Kumagai, Tomo'omi

    2016-10-01

    We present a unique proxy for reconstructing the interannual variability of summer precipitation associated with the quasi-stationary front (Baiu front) in central Japan. The rainfall from the Baiu front has a relatively lower oxygen isotopic composition than other types of nonfrontal precipitation. The variability in the oxygen isotopes in summer rainfall is closely related to the Baiu frontal activity. In this study we used a mechanistic tree ring isotope model to reconstruct a 106 year long oxygen isotopic composition of precipitation during the early rainy season (June) based on the oxygen isotopic compositions of the annual rings of Chamaecyparis obtusa Endl trees from central Japan. The year-to-year variations of the isotopes over the most recent 25 years are associated with several teleconnection patterns that often lead to the Baiu precipitation anomalies in central Japan (such as the Pacific-Japan (PJ) pattern, Silk Road pattern, and wave train pattern along the polar jet). Yet none of these external forcing mechanisms apply further back in time. From the 1950s to 1980s, the interannual isotopic variability is predominantly related to local factors such as anomalous intensification/weakening of the Bonin High. Before the 1950s, the variability of the oxygen isotopic composition of precipitation is mainly associated with a wave train pattern along the polar jet. The isotopic variability is predominantly linked to the PJ pattern, while the PJ index is correlated with El Niño-Southern Oscillation. These findings suggest that the teleconnection patterns influencing Baiu precipitation variability vary according to interdecadal time scales during the twentieth century.

  10. 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

  11. On the timing and forcing mechanisms of late Pleistocene glacial terminations: Insights from a new high-resolution benthic stable oxygen isotope record of the eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Konijnendijk, T. Y. M.; Ziegler, M.; Lourens, L. J.

    2015-12-01

    Benthic oxygen isotope records of deep marine sedimentary archives have yielded a wealth of information regarding ice sheet dynamics and climate change during the Pleistocene. However, since they often lack independent age control, these records are generally bound by a fixed phase relationship between orbital forcing and the climate response, e.g. ice volume changes. We present the first long (∼1.2 Ma) benthic oxygen isotope record from the eastern Mediterranean, based on ODP Sites 967 and 968, which clearly reflects the behavior of global climate on a glacial-interglacial scale throughout the late Pleistocene time period. The age model for our record is based on tuning the elemental ratio of titanium versus aluminum (Ti/Al) against insolation. The Ti/Al record is dominated by the precession-related changes in northern African climate, i.e. monsoonal forcing, and hence largely independent of glacial-interglacial variability. We found the largest offset between our chronology and that of the widely applied, open ocean stacked record LR04 (Lisiecki and Raymo, 2005) for TVII (∼624 ka), which occurred ∼9 kyr earlier according to our estimates, though in agreement with the AICC2012 δDice chronology of EPICA Dome C (Bazin et al., 2013). Spectral cross-correlation analysis between our benthic δ18O record and 65°N summer insolation reveals significant amounts of power in the obliquity and precession range, with an average lag of 5.5 ± 0.8 kyr for obliquity, and 6.0 ± 1.0 kyr for precession. In addition, our results show that the obliquity-related time lag was smaller (3.0 ± 3.3 kyr) prior to ∼900 ka than after (5.7 ± 1.1 kyr), suggesting that on average the glacial response time to obliquity forcing increased during the mid-Pleistocene transition, much later than assumed by Lisiecki and Raymo (2005). Finally, we found that almost all glacial terminations have a consistent phase relationship of ∼45 ± 45° with respect to the precession and obliquity

  12. 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.

  13. Triple oxygen isotope variations in sedimentary rocks

    NASA Astrophysics Data System (ADS)

    Levin, Naomi E.; Raub, Timothy D.; Dauphas, Nicolas; Eiler, John M.

    2014-08-01

    Relatively large (⩾0.2‰) 17O anomalies in the geologic record have been used to recognize atmospheric processes such as photochemical reactions and to trace changes in the partial pressures of O2 and CO2 in Earth’s atmosphere through time. However, recent oxygen isotope measurements of terrestrial rocks, minerals and waters also reveal common, smaller (but statistically significant) deviations from a single mass-dependent fractionation line. These subtle anomalies have been explained through differences in mass-dependent isotopic fractionations for various equilibrium and kinetic mechanisms. Here we present triple oxygen isotope data on sedimentary silica and oxides, including Archean and Phanerozoic cherts, and iron formations. The distribution of data reflects the mass fractionation laws of low-temperature precipitation reactions during growth of authigenic minerals, variation in Δ17O of the waters from which sedimentary minerals precipitate, and equilibrium exchange after initial authigenic formation. We use these results to illustrate the potential for small, mass-dependent variations in Δ17O values of sedimentary rocks to provide constraints on the environmental and climatic conditions in which they formed.

  14. Oxygen isotopes in deep-sea spherules

    NASA Technical Reports Server (NTRS)

    Clayton, Robert N.; Mayeda, Toshiko K.; Brownlee, Donald E.

    1986-01-01

    Oxygen isotopic compositions have been measured on several size fractions of deep-sea spherules of extraterrestrial origin. The silicate spherules have an isotopic composition unlike that of any known macrometeorite. Their pre-terrestrial compositions may have been similar to those of C3 chondrites or the anhydrous component of C2 chondrites, the latter being preferred on chemical grounds. Metallic particles oxidize in the upper atmosphere, and sample a region for which no previous oxygen isotope data exist. This part of the atmosphere, above about 100 km, is apparently strongly enriched in the heavy isotopes of oxygen.

  15. Lake oxygen isotopes as recorders of North American Rocky Mountain hydroclimate: Holocene patterns and variability at multi-decadal to millennial time scales

    USGS Publications Warehouse

    Anderson, Lesleigh; Max Berkelhammer,; Barron, John A.; Steinman, Byron A.; Finney, Bruce P.; Abbott, Mark B.

    2016-01-01

    Lake sediment oxygen isotope records (calcium carbonate-δ18O) in the western North American Cordillera developed during the past decade provide substantial evidence of Pacific ocean–atmosphere forcing of hydroclimatic variability during the Holocene. Here we present an overview of 18 lake sediment δ18O records along with a new compilation of lake water δ18O and δ2H that are used to characterize lake sediment sensitivity to precipitation-δ18O in contrast to fractionation by evaporation. Of the 18 records, 14 have substantial sensitivity to evaporation. Two records reflect precipitation-δ18O since the middle Holocene, Jellybean and Bison Lakes, and are geographically positioned in the northern and southern regions of the study area. Their comparative analysis indicates a sequence of time-varying north–south precipitation-δ18O patterns that is evidence for a highly non-stationary influence by Pacific ocean–atmosphere processes on the hydroclimate of western North America. These observations are discussed within the context of previous research on North Pacific precipitation-δ18O based on empirical and modeling methods. The Jellybean and Bison Lake records indicate that a prominent precipitation-δ18O dipole (enriched-north and depleted-south) was sustained between ~ 3.5 and 1.5 ka, which contrasts with earlier Holocene patterns, and appears to indicate the onset of a dominant tropical control on North Pacific ocean–atmosphere dynamics. This remains the state of the system today. Higher frequency reversals of the north–south precipitation-δ18O dipole between ~ 2.5 and 1.5 ka, and during the Medieval Climate Anomaly and the Little Ice Age, also suggest more varieties of Pacific ocean–atmosphere modes than a single Pacific Decadal Oscillation (PDO) type analogue. Results indicate that further investigation of precipitation-δ18O patterns on short (observational) and long (Holocene) time scales is needed to improve our understanding of the

  16. Lake oxygen isotopes as recorders of North American Rocky Mountain hydroclimate: Holocene patterns and variability at multi-decadal to millennial time scales

    NASA Astrophysics Data System (ADS)

    Anderson, Lesleigh; Berkelhammer, Max; Barron, John A.; Steinman, Byron A.; Finney, Bruce P.; Abbott, Mark B.

    2016-02-01

    Lake sediment oxygen isotope records (calcium carbonate-δ18O) in the western North American Cordillera developed during the past decade provide substantial evidence of Pacific ocean-atmosphere forcing of hydroclimatic variability during the Holocene. Here we present an overview of 18 lake sediment δ18O records along with a new compilation of lake water δ18O and δ2H that are used to characterize lake sediment sensitivity to precipitation-δ18O in contrast to fractionation by evaporation. Of the 18 records, 14 have substantial sensitivity to evaporation. Two records reflect precipitation-δ18O since the middle Holocene, Jellybean and Bison Lakes, and are geographically positioned in the northern and southern regions of the study area. Their comparative analysis indicates a sequence of time-varying north-south precipitation-δ18O patterns that is evidence for a highly non-stationary influence by Pacific ocean-atmosphere processes on the hydroclimate of western North America. These observations are discussed within the context of previous research on North Pacific precipitation-δ18O based on empirical and modeling methods. The Jellybean and Bison Lake records indicate that a prominent precipitation-δ18O dipole (enriched-north and depleted-south) was sustained between ~ 3.5 and 1.5 ka, which contrasts with earlier Holocene patterns, and appears to indicate the onset of a dominant tropical control on North Pacific ocean-atmosphere dynamics. This remains the state of the system today. Higher frequency reversals of the north-south precipitation-δ18O dipole between ~ 2.5 and 1.5 ka, and during the Medieval Climate Anomaly and the Little Ice Age, also suggest more varieties of Pacific ocean-atmosphere modes than a single Pacific Decadal Oscillation (PDO) type analogue. Results indicate that further investigation of precipitation-δ18O patterns on short (observational) and long (Holocene) time scales is needed to improve our understanding of the processes that drive

  17. On the Timing and Forcing Mechanisms of Late Pleistocene Glacial Terminations: Insights from a New High-Resolution Benthic Stable Oxygen Isotope Record of the Eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Lourens, L. J.; Konijnendijk, T.; Ziegler, M.

    2015-12-01

    We present the first long (~1.2 Ma) benthic oxygen isotope record from the eastern Mediterranean, based on ODP Sites 967 and 968, which clearly reflects the behavior of global climate on a glacial-interglacial scale. The age model for our record is based on tuning the elemental ratio of titanium versus aluminum (Ti/Al) against insolation. The Ti/Al record is dominated by the precession-related changes in northern African climate, i.e. monsoonal forcing, and hence largely independent of glacial-interglacial variability. We found the largest offset between our chronology and that of the widely applied, open ocean stacked record LR04 (Lisiecki and Raymo, 2005) for TVII (~624 ka), which occurred ~9 kyr earlier according to our estimates, though in agreement with the AICC2012 δDice chronology of EPICA Dome C (Bazin et al., 2013). Spectral cross-correlation analysis between our benthic δ18O record and 65°N summer insolation reveals significant amounts of power in the obliquity and precession range, with an average lag of 5.5±0.8 kyr for obliquity, and 6.0±1.0 kyr for precession. In addition, our results show that the obliquity-related time lag was smaller (3.0±3.3 kyr) prior to ~900 ka than after (5.7±1.1 kyr), suggesting that on average the glacial response time to obliquity forcing increased during the mid-Pleistocene transition, much later than assumed by Lisiecki and Raymo (2005). Finally, we found that almost all glacial terminations have a consistent phase relationship of ~45±45 degrees with respect to the precession and obliquity-driven increases in 65°N summer insolation, consistent with the general consensus that both obliquity and precession are important for deglaciation during the Late Pleistocene. Exceptions are glacial terminations TIIIb, T36 and potentially T32 (and TVII T24 and T34), which show this consistent phase relationship only with precession (only with obliquity). Our findings point towards an early (>1200 ka) onset of the Mid Pleistocene

  18. A deglacial and Holocene record of climate variability in south-central Alaska from stable oxygen isotopes and plant macrofossils in peat

    USGS Publications Warehouse

    Jones, Miriam C.; Wooller, Matthew J.; Peteet, Dorothy M.

    2014-01-01

    We used stable oxygen isotopes derived from bulk peat (δ18OTOM), in conjunction with plant macrofossils and previously published carbon accumulation records, in a ∼14,500 cal yr BP peat core (HT Fen) from the Kenai lowlands in south-central Alaska to reconstruct the climate history of the area. We find that patterns are broadly consistent with those from lacustrine records across the region, and agree with the interpretation that major shifts in δ18OTOM values indicate changes in strength and position of the Aleutian Low (AL), a semi-permanent low-pressure cell that delivers winter moisture to the region. We find decreased strength or a more westerly position of the AL (relatively higher δ18OTOM values) during the Bølling-Allerød, Holocene Thermal Maximum (HTM), and late Holocene, which also correspond to warmer climate regimes. These intervals coincide with greater peat preservation and enhanced carbon (C) accumulation rates at the HT Fen and with peatland expansion across Alaska. The HTM in particular may have experienced greater summer precipitation as a result of an enhanced Pacific subtropical high, a pattern consistent with modern δ18O values for summer precipitation. The combined warm summer temperatures and greater summer precipitation helped promote the observed rapid peat accumulation. A strengthened AL (relatively lower δ18OTOM values) is most evident during the Younger Dryas, Neoglaciation, and the Little Ice Age, consistent with lower peat preservation and C accumulation at the HT Fen, suggesting less precipitation reaches the leeward side of the Kenai Mountains during periods of enhanced AL strength. The peatlands on the Kenai Peninsula thrive when the AL is weak and the contribution of summer precipitation is higher, highlighting the importance of precipitation seasonality in promoting peat accumulation. This study demonstrates that δ18OTOM values in peat can be applied toward understand large-scale shifts in atmospheric circulation

  19. Oxygen stable isotope ratios from British oak tree-rings provide a strong and consistent record of past changes in summer rainfall

    NASA Astrophysics Data System (ADS)

    Young, Giles H. F.; Loader, Neil J.; McCarroll, Danny; Bale, Roderick J.; Demmler, Joanne C.; Miles, Daniel; Nayling, Nigel T.; Rinne, Katja T.; Robertson, Iain; Watts, Camilla; Whitney, Matthew

    2015-12-01

    United Kingdom (UK) summers dominated by anti-cyclonic circulation patterns are characterised by clear skies, warm temperatures, low precipitation totals, low air humidity and more enriched oxygen isotope ratios (δ18O) in precipitation. Such conditions usually result in relatively more positive (enriched) oxygen isotope ratios in tree leaf sugars and ultimately in the tree-ring cellulose formed in that year, the converse being true in cooler, wet summers dominated by westerly air flow and cyclonic conditions. There should therefore be a strong link between tree-ring δ18O and the amount of summer precipitation. Stable oxygen isotope ratios from the latewood cellulose of 40 oak trees sampled at eight locations across Great Britain produce a mean δ18O chronology that correlates strongly and significantly with summer indices of total shear vorticity, surface air pressure, and the amount of summer precipitation across the England and Wales region of the United Kingdom. The isotope-based rainfall signal is stronger and much more stable over time than reconstructions based upon oak ring widths. Using recently developed methods that are precise, efficient and highly cost-effective it is possible to measure both carbon (δ13C) and oxygen (δ18O) isotope ratios simultaneously from the same tree-ring cellulose. In our study region, these two measurements from multiple trees can be used to reconstruct summer temperature (δ13C) and summer precipitation (δ18O) with sufficient independence to allow the evolution of these climate parameters to be reconstructed with high levels of confidence. The existence of long, well-replicated oak tree-ring chronologies across the British Isles mean that it should now be possible to reconstruct both summer temperature and precipitation over many centuries and potentially millennia.

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

    NASA Astrophysics Data System (ADS)

    Hesselbo, S. P.; Korte, C.

    2010-12-01

    The Jurassic comprises some 55 million years of Earth history. However, within the Jurassic, only one major environmental change (hyperthermal) event is really well known - the Early Toarcian Oceanic Anoxic Event (OAE) at ~183 Ma - and until very recently the extent to which the accompanying environmental changes were global has been strongly debated. Nevertheless, partly as a result of the international effort to define Global Stratotype Sections and Points (GSSPs), much more is now being discovered about environmental changes taking place at and around the other Jurassic Age (Stage) boundaries, to the extent that meaningful comparisons between these events can begin to be made. Here we present new carbon and oxygen isotope data from mollusks (bivalves and belemnites) and brachiopods collected through the marine Early Jurassic succession of NE England, including the Sinemurian-Plienbachian boundary GSSP. All materials have been screened by chemical analysis and scanning electron microscopy to check for diagenetic alteration. Analysis of carbon isotopes from marine calcite is supplemented by analysis of carbon-isotope values from fossil wood collected through the same section. It is demonstrated that both long-term and short-term carbon-isotope shifts from the UK Early Jurassic represent global changes in carbon cycle balances. The Sinemurian-Pliensbachian boundary event is an event of global significance and shows several similarities to the Toarcian OAE (relative sea-level change, carbon-isotope signature), but also some significant contrasts (oxygen-isotope based paleotemperatures which provide no evidence for warming). Significant contrast in oxygen- and carbon-isotope co-variation also occurs on a long timescale. There appear to be two modes in the co-variation of carbon and oxygen isotopes through this time interval: mode 1 shows positive correlation and may be explained by conventional sources and sinks for carbon-dioxide; mode 2, representing negative

  1. OXYGEN ISOTOPIC COMPOSITIONS OF SOLAR CORUNDUM GRAINS

    SciTech Connect

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

    2009-11-20

    .0), Bishunpur (LL3.1), Roosevelt County 075 (H3.2)) and unmetamorphosed carbonaceous chondrites (Orgueil (CI1), Murray (CM2), and Alan Hills A77307 (CO3.0)) measured with a Cameca ims-1280 ion microprobe. All corundum grains, except two, are {sup 16}O-rich (DELTA{sup 17}O = -22.7 per mille +- 8.5 per mille, 2sigma), and compositionally similar to the mineralogically pristine CAIs from the CR carbonaceous chondrites (-23.3 per mille +- 1.9 per mille, 2sigma), and solar wind returned by the Genesis spacecraft (-27 per mille +- 6 per mille, 2sigma). One corundum grain is highly {sup 17}O-enriched (delta{sup 17}O approx +60 per mille, delta{sup 18}O approx -40 per mille) and is probably of the presolar origin; the origin of another {sup 17}O-rich grain (delta{sup 17}O approx -15 per mille , delta{sup 18}O approx -35 per mille) is unclear. We conclude that the {sup 16}O-rich corundum grains in the acid-resistant residues from unequilibrated ordinary and unmetamorphosed carbonaceous chondrites recorded initial oxygen isotopic composition of the solar nebula, and, hence, of the Sun. Our inferred oxygen isotopic composition of the Sun is inconsistent with the more extreme {sup 16}O-rich value (DELTA{sup 17}O approx -35 per mille) proposed by Gounelle et al. on the basis of two extremely {sup 16}O-rich CAIs from the CH/CB-like chondrite Isheyevo and with the {sup 16}O-poor value observed as a component of the solar wind implanted into the metallic particles in lunar soil (Ireland et al.).

  2. A continuous 250,000 yr record of oxygen and carbon isotopes in ostracode and bulk-sediment carbonate from Bear Lake, Utah-Idaho

    USGS Publications Warehouse

    Bright, Jordon; Kaufman, D.S.; Forester, R.M.; Dean, W.E.

    2006-01-01

    Oxygen and carbon isotopes from a continuous, 120-m-long, carbonate-rich core from Bear Lake, Utah-Idaho, document dramatic fluctuations in the hydrologic budget of the lake over the last 250,000 yr. Isotopic analyses of bulk sediment samples capture millennial-scale variability. Ostracode calcite was analyzed from 78 levels, mainly from the upper half of the core where valves are better preserved, to compare the isotopic value of purely endogenic carbonate with the bulk sediment, which comprises both endogenic and detrital components. The long core exhibits three relatively brief intervals with abundant endogenic aragonite (50??10%) and enriched ??18O and ??13C. These intervals are interpreted as warm/dry periods when the lake retracted into a topographically closed basin. We correlate these intervals with the interglacial periods of marine oxygen-isotope stages 1, 5e, and 7a, consistent with the presently available geochronological control. During most of the time represented by the core, the lake was fresher than the modern lake, as evidenced by depleted ??18O and ??13C in bulk-sediment carbonate. ?? 2006 Elsevier Ltd. All rights reserved.

  3. A Deglacial and Holocene Record of Climate Variability in South-Central Alaska from Stable Oxygen Isotopes and Plant Macrofossils in Peat

    NASA Technical Reports Server (NTRS)

    Jones, Miriam C.; Wooller, Matthew; Peteet, Dorothy M.

    2014-01-01

    We used stable oxygen isotopes derived from bulk peat (delta-O-18(sub TOM) in conjunction with plant macrofossils and previously published carbon accumulation records, in a approximately14,500 cal yr BP peat core (HT Fen) from the Kenai lowlands in south-central Alaska to reconstruct the climate history of the area. We find that patterns are broadly consistent with those from lacustrine records across the region, and agree with the interpretation that major shifts in delta-O-18(sub TOM) values indicate changes in strength and position of the Aleutian Low (AL), a semi-permanent low-pressure cell that delivers winter moisture to the region. We find decreased strength or a more westerly position of the AL (relatively higher delta-O-18(sub TOM) values) during the Bolling-Allerod, Holocene Thermal Maximum (HTM), and late Holocene, which also correspond to warmer climate regimes. These intervals coincide with greater peat preservation and enhanced carbon (C) accumulation rates at the HT Fen and with peatland expansion across Alaska. The HTM in particular may have experienced greater summer precipitation as a result of an enhanced Pacific subtropical high, a pattern consistent with modern delta-O-18 values for summer precipitation. The combined warm summer temperatures and greater summer precipitation helped promote the observed rapid peat accumulation. A strengthened AL (relatively lower delta-O-18(sub TOM) values) is most evident during the Younger Dryas, Neoglaciation, and the Little Ice Age, consistent with lower peat preservation and C accumulation at the HT Fen, suggesting less precipitation reaches the leeward side of the Kenai Mountains during periods of enhanced AL strength. The peatlands on the Kenai Peninsula thrive when the AL is weak and the contribution of summer precipitation is higher, highlighting the importance of precipitation seasonality in promoting peat accumulation. This study demonstrates that delta-O-18(sub TOM) values in peat can be applied

  4. 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

  5. Oxygen isotope perspective on crustal evolution on early Earth: A record of Precambrian shales with emphasis on Paleoproterozoic glaciations and Great Oxygenation Event

    NASA Astrophysics Data System (ADS)

    Bindeman, I. N.; Bekker, A.; Zakharov, D. O.

    2016-03-01

    We present stable isotope and chemical data for 206 Precambrian bulk shale and tillite samples that were collected mostly from drillholes on all continents and span the age range from 0.5 to 3.5 Ga with a dense coverage for 2.5-2.2 Ga time interval when Earth experienced four Snowball Earth glaciations and the irreversible rise in atmospheric O2. We observe significant, downward shift of several ‰ and a smaller range of δ18 O values (7 to 9‰) in shales that are associated with the Paleoproterozoic and, potentially, Neoproterozoic glaciations. The Paleoproterozoic samples consist of more than 50% mica minerals and have equal or higher chemical index of alteration than overlying and underlying formations and thus underwent equal or greater degrees of chemical weathering. Their pervasively low δ18 O and δD (down to - 85 ‰) values provide strong evidence of alteration and diagenesis in contact with ultra-low δ18 O glacial meltwaters in lacustrine, deltaic or periglacial lake (sikussak-type) environments associated with the Paleoproterozoic glaciations. The δDsilicate values for the rest of Precambrian shales range from -75 to - 50 ‰ and are comparable to those for Phanerozoic and Archean shales. Likewise, these samples have similar ranges in δ13Corg values (-23 to - 33 ‰ PDB) and Corg content (0.0 to 10 wt%) to Phanerozoic shales. Precambrian shales have a large range of δ18 O values comparable to that of the Phanerozoic shales in each age group and formation, suggesting similar variability in the provenance and intensity of chemical weathering, except for the earliest 3.3-3.5 Ga Archean shales, which have consistently lower δ18 O values. Moreover, Paleoproterozoic shales that bracket in age the Great Oxidation Event (GOE) overlap in δ18 O values. Absence of a step-wise increase in δ18 O and δD values suggests that despite the first-order change in the composition of the atmosphere, weathering cycle was not dramatically affected by the GOE at ∼2

  6. The oxygen isotope evolution of parent body aqueous solutions as recorded by multiple carbonate generations in the Lonewolf Nunataks 94101 CM2 carbonaceous chondrite

    NASA Astrophysics Data System (ADS)

    Lee, M. R.; Sofe, M. R.; Lindgren, P.; Starkey, N. A.; Franchi, I. A.

    2013-11-01

    The CM2 carbonaceous chondrite LON 94101 contains aragonite and two generations of calcite that provide snapshots of the chemical and isotopic evolution of aqueous solutions during parent body alteration. Aragonite was the first carbonate to crystallize. It is rare, heterogeneously distributed within the meteorite matrix, and its mean oxygen isotope values are δ18O 39.9 ± 0.6‰, Δ17O -0.3 ± 1.0‰ (1σ). Calcite precipitated soon afterwards, and following a fall in solution Mg/Ca ratios, to produce small equant grains with a mean oxygen isotope value of δ18O 37.5 ± 0.7‰, Δ17O 1.4 ± 1.1‰ (1σ). These grains were partially or completely replaced by serpentine and tochilinite prior to precipitation of the second generation of calcite, which occluded an open fracture to form a millimetre-sized vein, and replaced anhydrous silicates within chondrules and the matrix. The vein calcite has a mean composition of δ18O 18.4 ± 0.3‰, Δ17O -0.5 ± 0.5‰ (1σ). Petrographic and isotopic results therefore reveal two discrete episodes of mineralisation that produced calcite generations with contrasting δ18O, and mean Δ17O values. The aragonite and equant calcite crystallized over a relatively brief period early in the aqueous alteration history of the parent body, and from static fluids that were evolving chemically in response to mineral dissolution and precipitation. The second calcite generation crystallized from solutions of a lower Δ17O, and a lower δ18O and/or higher temperature. As two generations of calcite whose petrographic characteristics and oxygen isotopic compositions are similar to those in LON 94101 occur in at least one other CM2, multiphase carbonate mineralisation could be the typical outcome of the sequence of chemical reactions during parent body aqueous alteration. It is equally possible however that the second generation of calcite formed in response to an event such as impact fracturing and concomitant fluid mobilisation that affected

  7. The stable oxygen and carbon isotopic record from a coral growing in Florida Bay: a 160 year record of climatic and anthropogenic influence

    USGS Publications Warehouse

    Swart, Peter K.; Healy, Genevieve F.; Dodge, Richard E.; Kramer, Philip; Hudson, J. Harold; Halley, Robert B.; Robblee, Michael B.

    1996-01-01

    A 160 year record of skeletal δ13C and δ18O was examined in a specimen of the coral Solenastrea bournonigrowing in Florida Bay. Variations in the δ18O of the skeleton can be correlated to changes in salinity while changes in the δ13C reflect cycling of organic material within the Bay. Based on the correlation between salinity and skeletal δ18O, we have concluded that there has been no long term increase in salinity in this area of Florida Bay over the past 160 years. Using salinity correlations between the various basins obtained from instrumental data, we have been able to extend our interpretations to other parts of Florida Bay reaching similar conclusions. In contrast to current ideas which have focused on changes in Florida Bay water quality over the past 20-yr history of the Bay as causative in its decline, we have determined that changes in water quality in this basin were already set in motion between 1905 and 1912 by the construction of the Florida East Coast Railway from Miami to Key West. The construction of the railway resulted in the restriction of the exchange of water between the Florida reef tract and the Gulf of Mexico causing Florida Bay to become more eutrophic. Evidence of this process is observed in the sudden shift to relatively lower δ13C values coincident with railway construction. Natural events also appear to have influenced the water in the Bay. Between 1912 and 1948 frequent hurricanes had the effect of increasing exchange of water between the Bay and reef tract and removing large quantities of organic rich sediments. However, since 1948 the number of hurricanes affecting the area has decreased and the products of the oxidation of organic material have been increasingly retained within the basin promoting the initiation of eutrophic conditions.

  8. 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.

  9. Distinguishing Biotic from Abiotic Phosphate Oxygen Isotopic Signatures

    NASA Astrophysics Data System (ADS)

    Blake, R.; Moyer, C.; Colman, A.; Liang, Y.; Dogru, D.

    2006-05-01

    On earth, phosphate has a strong biological oxygen isotope signature due to its concentration and intense cycling by living organisms as an essential nutrient. Phosphate does not undergo oxygen isotope exchange with water at low temperature without enzymatic catalysis, making the oxygen isotope ratio (18O/16O) of phosphate, δ18OP, an attractive biosignature in the search for early and extraterrestrial life. Recent laboratory and field studies have demonstrated that the δ18OP value of dissolved inorganic phosphate (PO4) records specific microbial activity and enzymatic reaction pathways in both laboratory cultures and natural waters/sediments (Blake et al., 2005; Colman et al 2005; Liang and Blake, 2005). Phosphate oxygen isotope biosignatures may be distinguished from abiotic signatures by: (1) evaluating the degree of temperature-dependent PO4-water oxygen isotope exchange in aqueous systems and deviation from equilibrium; and (2) evolution from an abiotic P reservoir signature towards a biotic P reservoir signature. Important abiotic processes potentially affecting phosphate δ18OP values include dissolution/precipitation, adsorption/desorption, recrystallization of PO4 mineral phases, diagenesis and metamorphism. For most of these processes, the recording, retention and alteration of δ18OP biosignatures have not been evaluated. Deep-sea hydrothermal vent fields are an ideal system in which to study the preservation and alteration of δ18OP biosignatures, as well as potential look-alikes produced by heat-promoted PO4 -water oxygen isotope exchange. Results from recent studies of δ18OP biosignatures in hydrothermal deposits near 9 and 21 degrees N. EPR and at Loihi seamount will be presented.

  10. Tree-ring isotope records of tropical cyclone activity.

    PubMed

    Miller, Dana L; Mora, Claudia I; Grissino-Mayer, Henri D; Mock, Cary J; Uhle, Maria E; Sharp, Zachary

    2006-09-26

    The destruction wrought by North Atlantic hurricanes in 2004 and 2005 dramatically emphasizes the need for better understanding of tropical cyclone activity apart from the records provided by meteorological data and historical documentation. We present a 220-year record of oxygen isotope values of alpha-cellulose in longleaf pine tree rings that preserves anomalously low isotope values in the latewood portion of the ring in years corresponding with known 19th and 20th century landfalling/near-coastal tropical storms and hurricanes. Our results suggest the potential for a tree-ring oxygen isotope proxy record of tropical cyclone occurrence extending back many centuries based on remnant pine wood from protected areas in the southeastern U.S.

  11. A 1000-year record of dry conditions in the eastern Canadian prairies reconstructed from oxygen and carbon isotope measurements on Lake Winnipeg sediment organics

    USGS Publications Warehouse

    Buhay, W.M.; Simpson, S.; Thorleifson, H.; Lewis, M.; King, J.; Telka, A.; Wilkinson, Philip M.; Babb, J.; Timsic, S.; Bailey, D.

    2009-01-01

    A short sediment core (162 cm), covering the period AD 920-1999, was sampled from the south basin of Lake Winnipeg for a suite of multi-proxy analyses leading towards a detailed characterisation of the recent millennial lake environment and hydroclimate of southern Manitoba, Canada. Information on the frequency and duration of major dry periods in southern Manitoba, in light of the changes that are likely to occur as a result of an increasingly warming atmosphere, is of specific interest in this study. Intervals of relatively enriched lake sediment cellulose oxygen isotope values (??18Ocellulose) were found to occur from AD 1180 to 1230 (error range: AD 1104-1231 to 1160-1280), 1610-1640 (error range: AD 1571-1634 to 1603-1662), 1670-1720 (error range: AD 1643-1697 to 1692-1738) and 1750-1780 (error range: AD 1724-1766 to 1756-1794). Regional water balance, inferred from calculated Lake Winnipeg water oxygen isotope values (??18Oinf-lw), suggest that the ratio of lake evaporation to catchment input may have been 25-40% higher during these isotopically distinct periods. Associated with the enriched d??18Ocellulose intervals are some depleted carbon isotope values associated with more abundantly preserved sediment organic matter (d??13COM). These suggest reduced microbial oxidation of terrestrially derived organic matter and/or subdued lake productivity during periods of minimised input of nutrients from the catchment area. With reference to other corroborating evidence, it is suggested that the AD 1180-1230, 1610-1640, 1670-1720 and 1750-1780 intervals represent four distinctly drier periods (droughts) in southern Manitoba, Canada. Additionally, lower-magnitude and duration dry periods may have also occurred from 1320 to 1340 (error range: AD 1257-1363), 1530-1540 (error range: AD 1490-1565 to 1498-1572) and 1570-1580 (error range: AD 1531-1599 to 1539-1606). ?? 2009 John Wiley & Sons, Ltd.

  12. The deep sea oxygen isotopic record: Significance for tertiary global ice volume history, with emphasis on the latest Miocene/early Pliocene

    SciTech Connect

    Prentice, M.L.

    1988-01-01

    Planktonic and benthic isotopic records as well as carbonate sedimentation records extending from 6.1 to 4.1 Ma for eastern South Atlantic Holes 526A and 525B are presented. These data suggest ice volume variations about a constant mean sufficient to drive sea level between 10 m and 75 m below present. Isotopic records at the deeper (2500 m) site have been enriched by up to 0.5% by dissolution. Carbonate accumulation rates at both sites quadrupled at 4.6 Ma primarily because of increased production and, secondarily, decreased dissolution. The second part presents a Cenozoic-long composite {delta}{sup 18}O curve for tropical shallow-dwelling planktonic foraminifers and the benthic foraminifer Cibicides at 2-4 km depths. Surface {delta}{sup 18}O gradients between various low-and-mid latitude sites reflect: (1) widespread SST stability through the Cenozoic and (2) significant change in Tasman Sea SST through the Tertiary. Assuming average SST for tropical non-upwelling areas was constant, the planktonic composite suggest that global ice volume for the last 40 my has not been significantly less than today. Residual benthic {delta}{sup 18}O reflect relatively warm and saline deep water until the early Miocene after which time deep water progressively cooled. The third part presents {delta}{sup 18}O for Recent Orbulina universa from 44 core-tops distributed through the Atlantic and Indian Oceans. The purpose was to test the hypothesis that Orbulina calcifies at constant temperature and so records only ice volume changes. Orbulina commonly calcifies at intermediate depths over a wide range of temperatures salinities, and densities. These physical factors are not the primary controls on the spatial and vertical distribution of Orbulina.

  13. Oxygen isotope ratios in eclogites from kimberlites.

    PubMed

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

    1971-06-04

    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.

  14. 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.

  15. 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.

  16. A 200,000-Year Record of Change in Oxygen Isotope Composition of Sulfate in a Saline Sediment Core, Death Valley, California

    NASA Astrophysics Data System (ADS)

    Yang, Wenbo; Krouse, H. Roy; Spencer, Ronald J.; Lowenstein, Tim K.; Hutcheon, Ian E.; Ku, Teh-Lung; Li, Jianren; Roberts, Sheila M.; Brown, Christopher B.

    1999-03-01

    δ 18O values of sulfate minerals from a 186-m core (past 200,000 years) in Death Valley varied from +9 to +23‰ (V-SMOW). Sulfates that accumulated in the past ephemeral saline lake, salt pans, and mud flats have relatively low δ 18O values similar to those of present-day local inflows. Sulfates that accumulated during two perennial lake intervals, however, have higher δ 18O values, reflecting changes in temperature, lake water levels, and/or sulfur redox reactions. Over the same time interval, the δ 18O record for sulfate had excursions that bear similarities to those found for carbonate in the Death Valley core, marine carbonate (SPECMAP), and polar ice in the Summit ice core, Greenland. The δ 18O record differed considerably from the records reported for carbonate at Owens Lake and Devils Hole, which probably relates to different water sources. Death Valley, Owens Lake, and Devils Hole are responding to the same climatic changes but manifesting them differently. In Death Valley sediments, the isotopic composition of sulfate may have potential as an indicator of paleoenvironmental changes.

  17. Defining uncertainty and error in planktic foraminiferal oxygen isotope measurements

    NASA Astrophysics Data System (ADS)

    Fraass, A. J.; Lowery, C. M.

    2017-02-01

    Foraminifera are the backbone of paleoceanography. Planktic foraminifera are one of the leading tools for reconstructing water column structure. However, there are unconstrained variables when dealing with uncertainty in the reproducibility of oxygen isotope measurements. This study presents the first results from a simple model of foraminiferal calcification (Foraminiferal Isotope Reproducibility Model; FIRM), designed to estimate uncertainty in oxygen isotope measurements. FIRM uses parameters including location, depth habitat, season, number of individuals included in measurement, diagenesis, misidentification, size variation, and vital effects to produce synthetic isotope data in a manner reflecting natural processes. Reproducibility is then tested using Monte Carlo simulations. Importantly, this is not an attempt to fully model the entire complicated process of foraminiferal calcification; instead, we are trying to include only enough parameters to estimate the uncertainty in foraminiferal δ18O records. Two well-constrained empirical data sets are simulated successfully, demonstrating the validity of our model. The results from a series of experiments with the model show that reproducibility is not only largely controlled by the number of individuals in each measurement but also strongly a function of local oceanography if the number of individuals is held constant. Parameters like diagenesis or misidentification have an impact on both the precision and the accuracy of the data. FIRM is a tool to estimate isotopic uncertainty values and to explore the impact of myriad factors on the fidelity of paleoceanographic records, particularly for the Holocene.

  18. Oxygen isotope variation in stony-iron meteorites.

    PubMed

    Greenwood, R C; Franchi, I A; Jambon, A; Barrat, J A; Burbine, T H

    2006-09-22

    Asteroidal material, delivered to Earth as meteorites, preserves a record of the earliest stages of planetary formation. High-precision oxygen isotope analyses for the two major groups of stony-iron meteorites (main-group pallasites and mesosiderites) demonstrate that each group is from a distinct asteroidal source. Mesosiderites are isotopically identical to the howardite-eucrite-diogenite clan and, like them, are probably derived from the asteroid 4 Vesta. Main-group pallasites represent intermixed core-mantle material from a single disrupted asteroid and have no known equivalents among the basaltic meteorites. The stony-iron meteorites demonstrate that intense asteroidal deformation accompanied planetary accretion in the early Solar System.

  19. 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.

  20. Very high-frequency and seasonal cave atmosphere PCO 2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

    NASA Astrophysics Data System (ADS)

    Baldini, James U. L.; McDermott, Frank; Hoffmann, Dirk L.; Richards, David A.; Clipson, Nicholas

    2008-07-01

    Cave air PCO 2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO 2 production, resulting in high summer PCO 2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO 2 degassing rates from drip water, by considering both the seasonal and high-frequency cave air PCO 2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h - 1 ) and minima in late June/early July (0.033 μm h - 1 ). For well-mixed 'diffuse flow' cave drips such as those that feed CC-Bil, high summer cave air PCO 2 depresses summer calcite deposition, while low winter PCO 2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ18O, integrated annual stalagmite calcite δ18O is unaffected; however, seasonality in cave air PCO 2 may influence non-conservative geochemical climate proxies (e.g., δ13C, Sr/Ca). Stalagmites fed by 'seasonal' drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air PCO 2 may increase relative to cave air PCO 2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ18O records towards isotopically heavier summer drip water δ18O values, resulting in elevated calcite δ18O values compared to the 'equilibrium' values predicted by calcite-water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air PCO 2 variability and the resulting intra

  1. 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

  2. Stable isotope analyses of palaeo-pollen records

    NASA Astrophysics Data System (ADS)

    Hemming, D.; Loader, N.

    2002-12-01

    Pollen stratigraphy is one of the most widely used tools for studying climate and vegetation dynamics over global and multi-millennial scales. Since the isotopic compositions of photosynthates that are used to form the pollen structure reflect environmental conditions during the time of pollen formation, the stable carbon, oxygen and hydrogen isotopic compositions (δ13C, δ18O and δ{}D) of the pollen grains may reflect this environmental information. Although there are many preliminary tests and methodological problems to overcome before we can fully utilise palaeo-pollen records, it is the general goal of our research to use pollen isotope records together with conventional palynological analyses to provide additional, independent spatial and temporal palaeo-environmental information and to provide new data on terrestrial ecosystem dynamics, including the timing of environmental changes, phase relationships of vegetation responses and regional and temporal variations in δ13C, Δ13C, δ18O and δ{}D. These isotopic records will facilitate in the modelling of palaeo-environments. By separating and analysing different pollen species, including C3 and C4, we also aim to assess species-specific climatic responses. We present results describing some recent investigations concerning the nature of the isotopic signal contained within pollen, the methodological developments we have made to measure the pollen isotopic composition and the future challenges that must be overcome before this potentially powerful quantitative terrestrial palaeo-archive can be fully and correctly utilised.

  3. 1.8 billion years of fluid-crust interaction: A zircon oxygen isotope record for the lower crust, western Churchill Province, Canadian Shield

    NASA Astrophysics Data System (ADS)

    Petts, Duane C.; Moser, Desmond E.; Longstaffe, Frederick J.; Davis, William J.; Stern, Richard A.

    2014-04-01

    The western Churchill Province of the Canadian Shield experienced a prolonged and complex formation history (ca. 4.04 to 1.70 Ga), with evidence for multiple episodes of orogenesis and regional magmatic activity. Here we report on the oxygen isotopic compositions of garnet and zircon recovered from lower crustal xenoliths, which have U-Pb ages between ca. 3.5 and 1.7 Ga. Overall, zircon from four metabasite xenoliths from the Rankin Inlet sample suite have δ18O values ranging from + 5.5 to + 8.6‰. Zircon from three metatonalite/anorthosite xenoliths and five metabasite xenoliths from the Repulse Bay sample suite have δ18O values of + 5.6 to + 8.3‰. High δ18O values (> + 6.0‰) for the oldest igneous zircon cores (ca. 3.5 Ga and 3.0-2.6 Ga) indicate that their metatonalite/anorthosite protolith magmas were generated from, or had assimilated, supracrustal rocks that interacted previously with surface-derived fluids. Igneous zircon cores (ca. 2.9-2.6 Ga) from one metabasite xenolith have δ18O values of + 5.6 to + 6.4‰, which suggests a formation from a mantle-derived basaltic/gabbroic magma. Metamorphic zircon cores (ca. 2.0-1.9 Ga) from one metabasite xenolith commonly have δ18O values between + 6.0 and + 6.3‰, which is indicative of a basalt/gabbro protolith and localized reworking of the lower crust caused by regional-scale plate convergence. The wide range of δ18O values (+ 5.5 to + 8.3‰) for ca. 1.75-1.70 Ga metamorphic zircon rims (identified in all xenoliths) indicates regional transient heating and reworking of mantle- and supracrustal-derived crust, induced by magmatic underplating along the crust-mantle boundary.

  4. 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.

  5. 100,000-year-long terrestrial record of millennial-scale linkage between eastern North American mid-latitude paleovegetation shifts and Greenland ice-core oxygen isotope trends

    NASA Astrophysics Data System (ADS)

    Litwin, Ronald J.; Smoot, Joseph P.; Pavich, Milan J.; Markewich, Helaine W.; Brook, George; Durika, Nancy J.

    2013-09-01

    We document frequent, rapid, strong, millennial-scale paleovegetation shifts throughout the late Pleistocene, within a 100,000+ yr interval (~ 115-15 ka) of terrestrial sediments from the mid-Atlantic Region (MAR) of North America. High-resolution analyses of fossil pollen from one core locality revealed a continuously shifting sequence of thermally dependent forest assemblages, ranging between two endmembers: subtropical oak-tupelo-bald cypress-gum forest and high boreal spruce-pine forest. Sedimentary textural evidence indicates fluvial, paludal, and loess deposition, and paleosol formation, representing sequential freshwater to subaerial environments in which this record was deposited. Its total age-depth model, based on radiocarbon and optically stimulated luminescence ages, ranges from terrestrial oxygen isotope stages (OIS) 6 to 1. The particular core sub-interval presented here is correlative in trend and timing to that portion of the oxygen isotope sequence common among several Greenland ice cores: interstades GI2 to GI24 (≈ OIS2-5 d). This site thus provides the first evidence for an essentially complete series of 'Dansgaard-Oeschger' climate events in the MAR. These data reveal that the ~ 100,000 yr preceding the Late Glacial and Holocene in the MAR of North America were characterized by frequently and dynamically changing climate states, and by vegetation shifts that closely tracked the Greenland paleoclimate sequence.

  6. The Oxygen Isotopic Composition of the Sun

    NASA Astrophysics Data System (ADS)

    McKeegan, K. D.; Kallio, A.; Heber, V. S.; Jarzebinski, G.; Mao, P.; Coath, C.; Kunihiro, T.; Wiens, R. C.; Judith, A.; Burnett, D. S.

    2010-12-01

    An accurate and precise determination of the oxygen isotopic composition of the Sun is the highest priority scientific goal of the Genesis Mission [1] as such data would provide a baseline from which one could interpret the oxygen isotopic anomalies found at all spatial scales in inner solar system materials. We have measured oxygen isotope compositions of implanted solar wind in 40 spots along a radial traverse of the Genesis SiC target sample 60001 by depth profiling with the UCLA MegaSIMS [2]. Mass-dependent fractionation induced by the solar wind concentrator [3] ion optics was corrected by comparison of the concentrator 22Ne/20Ne with that measured in a bulk solar wind target (diamond-like carbon on Si, [4]). The solar wind captured at L1 has an isotopic composition of (δ18O, δ17O) ≈ (-99, -79)‰, a value which is far removed from the terrestrial mass fractionation line. Profiles from the central portion of the target, where solar concentrations are highest and background corrections minimal, yield a mean Δ17O = -28.3 ± 1.8 ‰ indicating that the Earth and other planetary materials from the inner solar system are highly depleted in 16O relative to the solar wind. A mass-dependent fractionation of ~ -20%/amu in the acceleration of solar wind is required if we hypothesize that the photospheric oxygen isotope value, which represents the bulk starting composition of the solar system, is on the 16O-mixing line characteristic of refractory phase in primitive meteorites [5]. With this assumption, our preferred value for the bulk solar oxygen isotope composition is δ18O ≈ δ17O ≈ -57‰. A mechanism is required to fractionate oxygen isotopes in a non-mass-dependent manner to deplete 16O by ~6 to 7% in the rocky materials of the solar nebula. As oxygen is the third most abundant element in the solar system, and the most abundant in the terrestrial planets, this mechanism must operate on a large scale. Isotope-selective photochemistry, for example as in

  7. Devils Hole paleotemperatures and implications for oxygen isotope equilibrium fractionation

    NASA Astrophysics Data System (ADS)

    Kluge, Tobias; Affek, Hagit P.; Dublyansky, Yuri; Spötl, Christoph

    2014-08-01

    Subaqueous calcite in Devils Hole, Nevada, was growing continuously from slightly super-saturated groundwater, providing a 570 kyr-long δO18 paleoclimate record. Due to its very slow growth it has been assumed to have grown under conditions of isotopic equilibrium. However, its Holocene δO18 value is 1.5‰ higher than predicted by laboratory-precipitation-based oxygen isotope thermometer calibrations. The suggestion that Devils Hole calcite anchors the isotope thermometer to more 18O-enriched values has stirred a debate as to which paleothermometer calibration is relevant for paleoclimate and casts doubt on the validity of δO18-based paleotemperatures. We used clumped isotopes to test the assumptions of the Devils Hole alternative 18O-thermometer. Carbonate clumped isotopes are a temperature proxy that measures the abundance of 13Csbnd 18O bonds in CaCO3. This proxy is independent of the water composition and therefore gives independent estimates of temperatures when calcite forms at thermodynamic and isotopic equilibrium. We find that Devils Hole water paleotemperatures were constant at 30.6±2.6 °C between 27 and 180 ka, similarly to the modern groundwater temperature of 32.8-34.3 °C. The proximity of the Devils Hole clumped isotope data to values expected based on modern groundwater temperatures supports the notion that Devils Hole calcite grew under equilibrium conditions. Therefore, the commonly used laboratory-based δO18-temperature calibrations should be reconsidered. The constant water temperature over the glacial-interglacial cycles indicates that the long Devils Hole δO18 record reflects only variations in the groundwater δO18 values and as such, represents a valuable archive of paleoclimate and isotope paleohydrology.

  8. 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.

  9. Paleoclimate Reconstruction at Lamanai, Belize Using Oxygen-Isotope Tropical Dendrochronology

    NASA Astrophysics Data System (ADS)

    Prentice, A.; Webb, E. A.; White, C. D.; Graham, E.

    2009-05-01

    Tropical dendrochronology can be complicated because many trees growing in these areas lack distinct visible annual rings. However, the oxygen-isotope composition of wood growing in tropical regions can provide a record of seasonal fluctuations in the amount of precipitation even when visible rings are absent. Variations in the oxygen-isotope compositions of cellulose as the trees grow can be related to the relative timing of wet and dry seasons and used to identify periods of drought. In this study, the oxygen-isotope composition was determined for cellulose extracted from living trees at the site of Lamanai, Belize to assess the variation in oxygen-isotope values that result from heterogeneity within individual tree rings and seasonal fluctuations in amount of precipitation. In temperate regions, the latewood rings that form during periods of reduced growth are traditionally selected for oxygen-isotope analysis of cellulose because their oxygen-isotope compositions are more directly influenced by climate and precipitation during the growing season. However, in tropical isotope dendrochronology, when visible rings are present, detailed sampling of both the light coloured earlywood and the denser latewood is required. At Lamanai, a seasonal signal was evident in the oxygen- isotope composition of the cellulose when tree rings were sectioned in very small increments (approximately every mm), sub-sampling both earlywood and latewood. However, the visible rings did not always correspond with minimum or maximum oxygen-isotope values. As a result, the amplitude of the oxygen-isotope signal obtained by considering only latewood samples is smaller than that obtained from fine-increment sampling. Hence, the oxygen-isotope values of latewood samples alone did not provide accurate data for climate reconstruction. Multiple series of latewood samples extracted from different cross-sections of the same tree did not consistently show the same trends in oxygen isotope values

  10. Deconvolving the Carbon Isotope Record

    NASA Astrophysics Data System (ADS)

    Cramer, B. S.

    2003-12-01

    The evolution of the whole-ocean δ 13C value, under an assumption of steady state with respect to mass, can be modeled as: \\[ {d \\over dt}\\delta_\\Sigma(t)+{\\delta_\\Sigma(t) \\over \\tau_C}={1 \\over \\tau_C}\\delta_F(t) \\] where δ Σ is the whole-ocean δ 13C value, τ C is the residence time of carbon and a net instantaneous δ 13C forcing function is defined: \\[ \\delta_F=\\delta_i-f_{carb}\\Delta_{carb}-\\(1-f_{carb}\\)\\Delta_{org} \\] where δ i is the δ 13C value of carbon input (e.g. weathering and volcanism), fcarb is the fraction of carbon removed through burial of carbonates as opposed to organic carbon, and Δ carb and Δ org are the differences between δ Σ and δ 13C values for buried carbonate and organic carbon. The solution to this differential equation is: \\[ \\delta_\\Sigma\\(t\\)={1 \\over \\tau_C}\\int_0^t{{\\delta_F\\(t^\\prime\\)}e^{\\(-{t-t^\\prime \\over \\tau_C}\\)}dt^\\prime} \\] which can be expressed as a convolution \\[ \\delta_\\Sigma\\(t\\)={1 \\over \\tau_C} {{\\delta_F\\(t^\\prime\\)} \\otimes e^{\\(-{t-t^\\prime \\over \\tau_C}\\)}} \\] revealing that the evolution of the whole ocean δ 13C value is determined by the instantaneous δ 13C forcing (δ F) subjected to a causal (i.e. phase-shifting) low-pass filter whose frequency response is dependent only on the carbon residence time. One consequence of this observation is that variance in δ 13C records should be concentrated at wavelengths >0.1 m.y., thereby explaining the persistent appearance of cyclicity dependent on orbital eccentricity ( ˜0.1~and ˜0.4 m.y.~periods) in δ 13C records. I demonstrate that an assumption of non-linear forcing of fcarb by orbitally-forced variations in insolation can explain most of the structure of high-resolution δ 13C records throughout the Cenozoic. A second consequence is that τ C and δ F should be separable by numerical manipulation of δ 13C records. Two applications are 1) estimation of the residence time of carbon at

  11. 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.

  12. Cyclostratigraphy and eccentricity tuning of the early Oligocene through early Miocene (30.1-17.1 Ma): Cibicides mundulus stable oxygen and carbon isotope records from Walvis Ridge Site 1264

    NASA Astrophysics Data System (ADS)

    Liebrand, Diederik; Beddow, Helen M.; Lourens, Lucas J.; Pälike, Heiko; Raffi, Isabella; Bohaty, Steven M.; Hilgen, Frederik J.; Saes, Mischa J. M.; Wilson, Paul A.; van Dijk, Arnold E.; Hodell, David A.; Kroon, Dick; Huck, Claire E.; Batenburg, Sietske J.

    2016-09-01

    Few astronomically calibrated high-resolution (≤5 kyr) climate records exist that span the Oligocene-Miocene time interval. Notably, available proxy records show responses varying in amplitude at frequencies related to astronomical forcing, and the main pacemakers of global change on astronomical time-scales remain debated. Here we present newly generated X-ray fluorescence core scanning and benthic foraminiferal stable oxygen and carbon isotope records from Ocean Drilling Program Site 1264 (Walvis Ridge, southeastern Atlantic Ocean). Complemented by data from nearby Site 1265, the Site 1264 benthic stable isotope records span a continuous ∼13-Myr interval of the Oligo-Miocene (30.1-17.1 Ma) at high resolution (∼3.0 kyr). Spectral analyses in the stratigraphic depth domain indicate that the largest amplitude variability of all proxy records is associated with periods of ∼ 3.4 m and ∼ 0.9 m, which correspond to 405- and ∼110-kyr eccentricity, using a magnetobiostratigraphic age model. Maxima in CaCO3 content, δ18O and δ13C are interpreted to coincide with ∼110 kyr eccentricity minima. The strong expression of these cycles in combination with the weakness of the precession- and obliquity-related signals allow construction of an astronomical age model that is solely based on tuning the CaCO3 content to the nominal (La2011_ecc3L) eccentricity solution. Very long-period eccentricity maxima (∼2.4-Myr) are marked by recurrent episodes of high-amplitude ∼110-kyr δ18O cycles at Walvis Ridge, indicating greater sensitivity of the climate/cryosphere system to short eccentricity modulation of climatic precession. In contrast, the responses of the global (high-latitude) climate system, cryosphere, and carbon cycle to the 405-kyr cycle, as expressed in benthic δ18O and especially δ13C signals, are more pronounced during ∼2.4-Myr minima. The relationship between the recurrent episodes of high-amplitude ∼110-kyr δ18O cycles and the ∼1.2-Myr amplitude

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. The origin of hydrous, high-δ18O voluminous volcanism: diverse oxygen isotope values and high magmatic water contents within the volcanic record of Klyuchevskoy volcano, Kamchatka, Russia

    NASA Astrophysics Data System (ADS)

    Auer, Sara; Bindeman, Ilya; Wallace, Paul; Ponomareva, Vera; Portnyagin, Maxim

    2009-02-01

    Klyuchevskoy volcano, in Kamchatka’s subduction zone, is one of the most active arc volcanoes in the world and contains some of the highest δ18O values for olivines and basalts. We present an oxygen isotope and melt inclusion study of olivine phenocrysts in conjunction with major and trace element analyses of 14C- and tephrochronologically-dated tephra layers and lavas spanning the eruptive history of Klyuchevskoy. Whole-rock and groundmass analyses of tephra layers and lava samples demonstrate that both high-Mg (7-12.5 wt% MgO) and high-Al (17-19 wt% Al2O3, 3-6.5 wt% MgO) basalt and basaltic andesite erupted coevally from the central vent and flank cones. Individual and bulk olivine δ18O range from normal MORB values of 5.1‰ to values as high as 7.6‰. Likewise, tephra and lava matrix glass have high-δ18O values of 5.8-8.1‰. High-Al basalts dominate volumetrically in Klyuchevskoy’s volcanic record and are mostly high in δ18O. High-δ18O olivines and more normal-δ18O olivines occur in both high-Mg and high-Al samples. Most olivines in either high-Al or high-Mg basalts are not in oxygen isotopic equilibrium with their host glasses, and Δ18Oolivine-glass values are out of equilibrium by up to 1.5‰. Olivines are also out of Fe-Mg equilibrium with the host glasses, but to a lesser extent. Water concentrations in olivine-hosted melt inclusions from five tephra samples range from 0.4 to 7.1 wt%. Melt inclusion CO2 concentrations vary from below detection (<50 ppm) to 1,900 ppm. These values indicate depths of crystallization up to ~17 km (5 kbar). The variable H2O and CO2 concentrations likely reflect crystallization of olivine and entrapment of inclusions in ascending and degassing magma. Oxygen isotope and Fe-Mg disequilibria together with melt inclusion data indicate that olivine was mixed and recycled between high-Al and high-Mg basaltic melts and cumulates, and Fe-Mg and δ18O re-equilibration processes were incomplete. Major and trace elements in

  19. Climate and human impacts on vegetation changes in central Guizhou, China: Carbon and oxygen isotopic records in a stalagmite from Yelang Cave

    NASA Astrophysics Data System (ADS)

    Lee, T.; Liu, Z.; Li, H.; Shen, C.

    2009-12-01

    High-resolution δ18O and δ13C records of a 13.5-cm long stalagmite from Yelang Cave, 60 km west of Guiyang in the southwestern China, have been established by 750 measurements. With low U (10~40 ppb) and Th (0.01~0.367 ppb), four ICP-MS 230Th/U dates indicate that the upper 5.5 cm part is younger than 1000 years, with clear calcite deposition. Below 6 cm depth where the age suddenly changed from late Holocene to late Pleistocene, the stalagmite shows the deposition alternating between white-pure calcite layers and dark-dirty carbonate layers. The dating samples below 6 cm depth have low U contents (26~41 ppb) but high Th concentrations (10~22 ppb) showing 230Th/U dates ranging from 11 ka to 25 ka with large uncertainties. Based on current chronologies, the δ18O and δ13C records exhibit different features in the late Holocene and late Pleistocene. During the past 1000 yrs (0~5.5 cm), the δ18O ranges from -12.0‰ to -9.0‰ (PDB), containing many 10-100 yrs variations with Δδ18O >1‰. The δ13C during this period varies between -7.4‰ and -1.9‰, showing no correlation with the δ18O. Prior to 10.7 ka (below 6 cm), the δ18O and δ13C strongly co-varied, indicating climatic control on the surface vegetation with wet climates (lighter δ18O) resulting in better vegetation (lighter δ13C). The δ13C during the past 1000 yrs had three long-term increasing trends and a sharp decreasing trend, reflecting human impacts on the surface vegetation. The δ13C increased from about -6‰ at ca. AD 1370 to -3.2‰ around AD 1580, illustrating the first deforestation caused by human activity due to large immigration in Ming Dynasty to the region. The δ13C fluctuated between -4.5‰ and -3.0‰ from AD 1580 to AD 1740, then increased to -2.0‰ around AD 1770 with an opposite δ18O trend. This second deforestation event might be caused a strong immigration in early Qing Dynasty due to mining demand. Karst desertification occurred in the area reflected by heavy δ13C

  20. Oxygen isotopic compositions of chondrules in Allende and ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Clayton, R. N.; Mayeda, T. K.; Hutcheon, I. D.; Molini-Velsko, C.; Onuma, N.; Ikeda, Y.; Olsen, E. J.

    1983-01-01

    The ferromagnesian chondrules in Allende follow a trend in the oxygen three-isotope plot that diverges significantly from the 16-O mixing line defined by light and dark inclusions and the matrix of the meteorite. The trend probably results from isotopic exchange with an external gaseous reservoir during the process of chondrule formation sometime after the establishment of the isotopic compositions of the inclusions and matrix. The Allende chondrules approach, but do not reach, the isotopic compositions of chondrules in unequilibrated ordinary chondrites, implying exchange with a similar ambient gas, but isotopically different solid precursors for the two types of meteorite.

  1. Argon isotopes as recorders of magmatic processes

    NASA Astrophysics Data System (ADS)

    Layer, P. W.; Gardner, J. E.; Mora Chaparro, J. C.; Arce, J. L.

    2003-12-01

    Argon isotopic ratios vary enough between different reservoirs (atmosphere, crust, mantle) and diffuse fast enough through most minerals at magmatic temperatures (700-1200 C) to make them ideal for looking at magma chamber dynamics. Indeed, diffusion is sufficiently fast to allow short time scales to be deciphered, setting argon apart from many other isotopic methods. A mineral's ability to retain "excess" argon (40Ar/36Ar ratios greater than the atmospheric value and apparent ages older than the known eruption age) during post-eruption cooling is key to Ar studies. Previous work shows that both phenocrysts (crystallizing in the magma chamber; e.g. Mt St. Helens; Layer and Gardner, 2001) and xenocrysts (introduced into the magma chamber; e.g Toba; Gardner et al., 2002) preserve excess argon, which enables magma chamber processes to be deciphered through the variable diffusion rates between crystal phases. Single crystal 40Ar/39Ar step-heating of biotite from the 10.5 ka eruption of Nevado de Toluca volcano, Mexico indicates that they are xenocrystic and resided for only a short (< 1 year) time in the magma before it erupted. The biotite has reaction rims of hornblende, orthopyroxene and plagioclase, and failed to grow experimentally at pressure-temperature conditions of the magma, confirming the xenocrystic nature of this phase. Single-step fusion of plagioclase phenocrysts from eruptions of El Chichon volcano, Mexico, shows evidence of excess (mantle) argon, whereas hornblende from the same eruptions contains little or none. In this case, faster diffusion of Ar in plagioclase than in hornblende allow plagioclase to incorporate excess argon during magma recharge; hornblende does not. Combining such results with other isotopic systems may in fact better determine magma chamber processes. At El Chichon, Sr isotopes suggest magma recharges ocurred (Tepley et al., 2000), whereas the argon isotopes suggest such pulses occurred just before each eruption. The fast and

  2. 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

  3. 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.

  4. Oxygen Isotopes and Geothermometry of Secondary Minerals in CR Chondrites

    NASA Astrophysics Data System (ADS)

    Jilly, C. E.; Huss, G. R.; Nagashima, K.; Schrader, D. L.

    2014-09-01

    We report oxygen isotopes measured from secondary calcite and magnetite in QUE 99177, a weakly altered CR chondrite, and discuss implications for temperature and fluid chemistry during aqueous alteration on the CR parent body.

  5. 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

  6. 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.

  7. 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.

  8. Stalagmite stable isotope record of recent tropical cyclone events

    NASA Astrophysics Data System (ADS)

    Benoit Frappier, Amy; Sahagian, Dork; Carpenter, Scott J.; González, Luis A.; Frappier, Brian R.

    2007-02-01

    We present a 23 yr stalagmite record (1977 2000) of oxygen isotope variation, associated with 11 tropical cyclones (TCs), from Actun Tunichil Muknal cave in central Belize. High-resolution microsampling yielded a record of monthly to weekly temporal resolution that contains abrupt decreases (negative excursions) in calcite δ18O values that correspond with recent TC rain events nearby. A logistic discriminant model reliably identified TC proxy signals using the measurable parameters δ18O and δ13C values, and single point changes in δ18O value. The logistic model correctly identified 80% of excursions as TC events and incorrectly classified only 1 of nearly 1200 nonstorm sampling points. In addition to enabling high-resolution TC frequency reconstruction, this geologic proxy also provides information about the intensity of individual TCs. A multiple regression predicted TC intensity (R2 = 0.465, p = 0.034) using sampling frequency and excursion amplitude. Consistent with previous low-resolution studies, we found that the decadal average δ18O value was lower during the 1990s when several TCs produced rainfall in the area, but higher during the 1980s when only one TC struck. Longer, accurately dated, high-resolution speleothem stable isotope records may be a useful new tool for paleotempestology, to clarify associations between highly variable TC activity and the dynamic range of Quaternary climate.

  9. Oxygen isotope fractionation between aragonite and seawater: Developing a novel kinetic oxygen isotope fractionation model

    NASA Astrophysics Data System (ADS)

    Wang, Zhengrong; Gaetani, Glenn; Liu, Chao; Cohen, Anne

    2013-09-01

    Oxygen isotope fractionation factors between aragonite and seawater are studied at T = 25-55 °C and pH = 7.4-8.1 in a set of 'free-drift' precipitation experiments with various CO2-degassing rates (0-75 cc/min). The measured fractionation factors correlate weakly with degassing rate, but strongly with temperature in the following form (R2 = 0.998): 1000lnα=22.5(±0.5)(103/T)-46.1(±1.6) where α is the fractionation factor and T is the temperature in Kelvin. Along with results from previous studies, these experiments help calibrate two extreme cases of a new kinetic model - extremely fast (e.g., during spontaneous precipitation) and slow aragonite precipitation processes (e.g., during slow 'free-drift' precipitation experiments) - at pH >7.5, T = 0-55 °C and salinity = ˜5-39.6‰. The model assumes little isotopic fractionation between DIC species and aragonite during their attachment and detachment on aragonite surfaces at low temperatures and the δ18O value of aragonite equals the average δ18O value of all contributing DIC species. During the fast precipitation of aragonite, the contribution of each DIC species to the δ18O value of aragonite is proportional to its concentration, whereas in a slow precipitation process when the system reaches a steady state, the contribution is determined by both its concentration and a modifying factor. Although the physical meaning of this modifying factor depends on the method of derivation and other assumptions made, three different derivations based on precipitation/dissolution kinetics, isotope exchange reactions, and isotope disequilibrium among DIC species all lead to the same formulation. At pH >7.5, the natural logarithm of the modifying factor (k) for adjusting the contribution of the bicarbonate ion relative to the carbonate ion is calibrated, using experimental data covering a range of temperature, salinity, pH, and precipitation rate, as follows: lnk=(2.22±0.08)×(pH-pH)+{(846±78)·S-(40.3±2.1)×103}/{RT

  10. 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

    about 8-10‰ below 500° C, 5-6‰ between 500-700° C, and 8-10‰ above 700° C. CI and oxygen isotopic compositions of carbonate and phosphate are not well correlated. Only modest CI changes are recorded from 25-675° C, compared with much larger changes in oxygen isotopic composition, especially above 300° C. On average, original isotopic compositions are largely preserved for both phosphate (+/-1‰ ) and carbonate (+/-2‰ ) oxygen at <300° C. At higher temperatures, however, both phosphate and carbonate oxygen in the bioapatite are systematically depleted of oxygen-18 relative to original values.

  11. 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

  12. Improved Quaternary North Atlantic stratigraphy using relative paleointensity (RPI), oxygen isotopes, and magnetic excursions (Invited)

    NASA Astrophysics Data System (ADS)

    Channell, J. E.

    2013-12-01

    Improving the resolution of Quaternary marine stratigraphy is one of the major challenges in paleoceanography. IODP Expedition 303/306, and ODP Legs 162 and 172, have yielded multiple high-resolution records (mean sedimentation rates in the 7-20 cm/kyr range) of relative paleointensity (RPI) that are accompanied by oxygen isotope data and extend through much of the Quaternary. Tandem fit of RPI and oxygen isotope data to calibrated templates (LR04 and PISO), using the Match protocol, yields largely consistent stratigraphies, implying that both RPI and oxygen isotope data are dominated by regional/global signals. Based on the recent geomagnetic field, RPI can be expected to be a global signal (i.e. dominated by the axial dipole field) when recorded at sedimentation rates less than several decimeters/kyr. Magnetic susceptibility, on the other hand, is a local/regional lithologic signal, and therefore less useful for long-distance correlation. Magnetic excursions are directional phenomena and, when adequately recorded, are manifest as paired reversals in which the virtual geomagnetic poles (VGPs) reach high latitudes in the opposite hemisphere, and they occupy minima in RPI records. Reversed VGPs imply that excursions are attributable to the main axial dipole, and therefore provide global stratigraphy. The so-called Iceland Basin excursion is recorded at many IODP/ODP sites and lies at the MIS 6/7 boundary at ~188 ka, with a duration of 2-3 kyr. Other excursions in the Brunhes chron are less commonly recorded because their duration (perhaps <~1 kyr) requires sedimentation rates >20 cm/kyr to be adequately recorded. On the other hand, several excursions within the Matuyama Chron are more commonly recorded in North Atlantic drift sediments due to relatively elevated durations. With some notable exceptions (e.g. Iberian Margin), high quality RPI records from North Atlantic sediments, together with magnetic excursions, can be used in tandem with oxygen isotope data to

  13. 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

  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 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.

  16. Methane isotope records from Antarctic firn air

    NASA Astrophysics Data System (ADS)

    Sowers, T. A.; Battle, M.

    2007-12-01

    and isotopic) to accumulate deeper in the firn relative to the lighter gases. We use δ15N of N2 measurements to identify the depth of the convective zone and to correct for gravitational settling. We developed a physically based air transport model to account for the diffusive properties of the firn that allows us to test various historical records spanning the 20th century in a forward modeling exercise. Preliminary results suggest atmospheric δ13C and δ D values near the start of the 20th century were 1.8‰ and 11‰ lower than present day values, respectively. The increasing isotope trends throughout the last century are primarily the result of increased CH4 emissions with elevated isotope signatures (e.g. fossil fuel and biomass burning).

  17. 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.

  18. 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

  19. Oxygen isotope composition of mafic magmas at Vesuvius

    NASA Astrophysics Data System (ADS)

    Dallai, L.; Cioni, R.; Boschi, C.; D'Oriano, C.

    2009-12-01

    The oxygen isotope composition of olivine and clinopyroxene from four plinian (AD 79 Pompeii, 3960 BP Avellino), subplinian (AD 472 Pollena) and violent strombolian (Middle Age activity) eruptions were measured to constrain the nature and evolution of the primary magmas of the last 4000 years of Mt. Vesuvius activity. A large set of mm-sized crystals was accurately separated from selected juvenile material of the four eruptions. Crystals were analyzed for their major and trace element compositions (EPMA, Laser Ablation ICP-MS), and for 18O/16O ratios. As oxygen isotope composition of uncontaminated mantle rocks on world-wide scale is well constrained (δ18Oolivine = 5.2 ± 0.3; δ18Ocpx = 5.6 ± 0.3 ‰), the measured values can be conveniently used to monitor the effects of assimilation/contamination of crustal rocks in the evolution of the primary magmas. Instead, typically uncontaminated mantle values are hardly recovered in Italian Quaternary magmas, mostly due to the widespread occurrence of crustal contamination of the primary magmas during their ascent to the surface (e.g. Alban Hills, Ernici Mts., and Aeolian Islands). Low δ18O values have been measured in olivine from Pompeii eruption (δ18Oolivine = 5.54 ± 0.03‰), whereas higher O-compositions are recorded in mafic minerals from pumices or scoria of the other three eruptions. Measured olivine and clinopyroxene share quite homogeneous chemical compositions (Olivine Fo 85-90 ; Diopside En 45-48, respectively), and represent phases crystallized in near primary mafic magmas, as also constrained by their trace element compositions. Data on melt inclusions hosted in crystals of these compositions have been largely collected in the past demonstrating that they crystallized from mafic melt, basaltic to tephritic in composition. Published data on volatile content of these melt inclusions reveal the coexistence of dissolved water and carbon dioxide, and a minimum trapping pressure around 200-300 MPa, suggesting

  20. Linking the Fe-, Mo-, and Cr isotope records with the multiple S isotope record of Archean sedimentary rocks

    NASA Astrophysics Data System (ADS)

    Ohmoto, H.; Watanabe, Y.

    2011-12-01

    Researchers have interpreted the isotopic data of redox sensitive elements (e.g., Fe, Mo and Cr) in Archean- and Proterozoic-aged sedimentary rocks within a framework of an atmospheric O2 evolution model that relied on an interpretation of the multiple sulfur isotopic record of sedimentary rocks. The current paradigm is that the anomalous isotopic fractionations of sulfur (AIF-S, or MIF-S) in sedimentary rocks were created by the UV photolysis of volcanic SO2 in an O2-poor (i.e., pO2 < 1 ppm) atmosphere, and that the rise of atmospheric pO2 to > 1 ppm occurred at ~2.45 Ga. However, this paradigm has recently encountered the following serious problems: (1) UV photolysis of SO2 by a broad-band UV lamp, which simulates the UV spectra of the sun light, produced the δ34S-Δ33S values for the S0 and SO4 that are significantly different from >90% of data on natural samples. (2) Many Archean-age sedimentary rocks do not exhibit AIF-S signatures. (3) Strong AIF-S signatures are typically found in organic C- and pyrite rich Archean-age black shales that were altered by submarine hydrothermal fluids during the early diagenetic stage of the rocks. (4) H2S, rather than SO2, was probably the dominant S-bearing volcanic gas on an anoxic Earth. Yet, UV photolysis of H2S does not generate AIF-S. (5) Some post-2.0 Ga natural samples were found to possess strong AIF-S signatures, such as sulfates in air pollutants that were produced by coal burning in an oxygen-rich atmosphere. Lasaga et al. (2008) demonstrated theoretically that chemisorption reactions between some solid surfaces and S-bearing aqueous (or gaseous) species, such as between organic matter and aqueous sulfate, may generate AIF-S. Watanabe et al. (2009; in prep.) demonstrated experimentally that reactions between simple amino acid crystals and sulfate under hydrothermal conditions produced AIF-S signatures that matched with more than 90% of data on natural samples. These studies, as well as the observed correlations

  1. Oxygen isotope variability within Nautilus shell growth bands

    DOE PAGES

    Linzmeier, Benjamin J.; Kozdon, Reinhard; Peters, Shanan E.; ...

    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

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

    PubMed

    Kaneko, Masanori; Poulson, Simon R

    2012-04-17

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

  3. Oxygen isotope fractionation between analcime and water - An experimental study

    NASA Technical Reports Server (NTRS)

    Karlsson, Haraldur R.; Clayton, Robert N.

    1990-01-01

    The oxygen isotope fractionation between analcime and water is studied to test the feasibility of using zeolites as low-temperature thermometers. The fractionation of oxygen isotopes between natural analcime and water is determined at 300, 350, and 400 C, and at fluid pressures ranging from 1.5 to 5.0 kbar. Also, isotope ratios for the analcime framework, the channel water, and bulk water are obtained. The results suggest that the channel water is depleted in O-18 relative to bulk water by a constant value of about 5 percent, nearly independent of temperature. The analcime-water fractionation curve is presented, showing that the exchange has little effect on grain morphology and does not involve recrystallization. The exchange is faster than any other observed for a silicate. The exchange rates suggest that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. It is concluded that calibrated zeolites may be excellent low-temperature oxygen isotope geothermometers.

  4. On the mean oxygen isotope composition of the Solar System

    NASA Astrophysics Data System (ADS)

    Ozima, M.; Podosek, F. A.; Higuchi, T.; Yin, Q.-Z.; Yamada, A.

    2007-02-01

    Since the first discovery of extraordinary oxygen isotope compositions in carbonaceous meteorites by Clayton et al. [Clayton, R.N., Grossman, L., Mayeda, T.K., 1973. Science 182, 485-488], numerous studies have been done to explain the unusual mass-independent isotope fractionation, but the problem is still unresolved to this day. Clayton's latest interpretation [Clayton, R.N., 2002. Nature 415, 860-861] sheds new light on the problem, and possible hypotheses now seem to be fairly well defined. A key issue is to resolve whether the oxygen isotopes in the Solar System represented by the Sun (solar oxygen) are the same as oxygen isotopes in planetary objects such as bulk meteorites, Mars, Earth, and Moon, or whether the solar oxygen is more similar to the lightest oxygen isotopes observed in CAIs (Calcium Aluminum-rich Inclusions) in primitive meteorites. Here, we examined the problem using oxygen isotope analytical data of about 400 bulk meteorite samples of various classes or types (data compiled by K. Lodders). We used in our discussion exclusively the parameter Δ 17O, a direct measure of the degree of mass-independent isotope fractionation of oxygen isotopes. When Δ 17O is arranged according to a characteristic size of their host planetary object, it shows a systematic trend: (1) Δ 17O values scatter around zero; (2) the scatter from the mean (Δ 17O=0) decreases with increasing representative size of the respective host planetary object. This systematic trend is easily understood on the basis of a hierarchical scenario of planetary formation, that is, larger planetary objects have formed by progressive accretion of planetesimals by random sampling over a wide spectrum of proto-solar materials. If this progressive random sampling of planetesimals were the essential process of planetary formation, the isotopic composition of planetary oxygen should approach that of the solar oxygen. To test this random sampling hypothesis, we applied a multiscale, multistep

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

    NASA Astrophysics Data System (ADS)

    Helliker, B.

    2007-12-01

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

  6. Tooth enamel maturation reequilibrates oxygen isotope compositions and supports simple sampling methods

    NASA Astrophysics Data System (ADS)

    Trayler, Robin B.; Kohn, Matthew J.

    2017-02-01

    Oxygen isotope and major element zoning patterns of several disparate ungulate teeth were collected to evaluate the timing and geometry of enamel formation, records of isotope zoning, and tooth enamel sampling strategies. Isotopic zoning in mammalian tooth enamel encodes a sub-annual time series of isotopic variation of an animal's body water composition, with a damping factor that depends on the specifics of how enamel mineralizes. Enamel formation comprises two stages: precipitation of appositional enamel with a high CO3:PO4 ratio, followed by precipitation of maturational enamel with a lower CO3:PO4. If appositional and maturational enamel both contribute to isotope compositions (but with different CO3:PO4), and if isotope compositions vary seasonally, paired δ18O values from CO3 and PO4 profiles should show a spatial separation. CO3 isotope patterns should be shifted earlier seasonally than PO4 isotope patterns. Such paired profiles for new and published data show no resolvable shifts, i.e. CO3 and PO4 δ18O profiles show coincident maxima and minima. This coincidence suggests that enamel maturation reequilibrates appositional isotope compositions. If enamel maturation establishes enamel isotope compositions, the geometry of maturation, not apposition, should be considered when devising sampling protocols. X-ray maps of Ca zoning show that the majority of enamel (inner and middle layers) mineralizes heavily at a high angle to the external tooth surface and the enamel-dentine junction over length scales of 2-4 mm, while the outer enamel surface mineralizes more slowly. These data suggest that isotopic sampling strategies should parallel maturational geometry and focus on interior enamel to improve data fidelity. The magnitude of isotopic damping is also smaller than implied in previous studies, so tooth enamel zoning more closely reflects original body water isotopic variations than previously assumed.

  7. 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.

  8. Controls, variation, and a record of climate change in detailed stable isotope record in a single bryozoan skeleton

    NASA Astrophysics Data System (ADS)

    Smith, Abigail M.; Key, Marcus M., Jr.

    2004-03-01

    The long-lived (about 20 yr) bryozoan Adeonellopsis sp. from Doubtful Sound, New Zealand, precipitates aragonite in isotopic equilibrium with seawater, exerting no metabolic or kinetic effects. Oxygen isotope ratios (δ 18O) in 61 subsamples (along three branches of a single unaltered colony) range from -0.09 to +0.68‰ PDB (mean = +0.36‰ PDB). Carbon isotope ratios (δ 13C) range from +0.84 to +2.18‰ PDB (mean = +1.69‰ PDB). Typical of cool-water carbonates, δ 18O-derived water temperatures range from 14.2 to 17.5 °C. Adeonellopsis has a minimum temperature growth threshold of 14 °C, recording only a partial record of environmental variation. By correlating seawater temperatures derived from δ 18O with the Southern Oscillation Index, however, we were able to detect major events such as the 1983 El Niño. Interannual climatic variation can be recorded in skeletal carbonate isotopes. The range of within-colony isotopic variability found in this study (0.77‰ in δ 18O and 1.34 in δ 13C) means that among-colony variation must be treated cautiously. Temperate bryozoan isotopes have been tested in less than 2% of described extant species — this highly variable phylum is not yet fully understood.

  9. 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

  10. 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.

  11. 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

  12. Exploring the oxygen isotope fingerprint of Dansgaard-Oeschger variability and Heinrich events

    NASA Astrophysics Data System (ADS)

    Bagniewski, Witold; Meissner, Katrin J.; Menviel, Laurie

    2017-03-01

    We present the first transient simulations of Marine Isotope Stage 3 (MIS 3) performed with an oxygen isotope-enabled climate model. Our simulations span several Dansgaard-Oeschger cycles and three Heinrich stadials and are directly compared with oxygen isotope records from 13 sediment and 2 ice cores. Our results are consistent with a 30-50% weakening of the Atlantic Meridional Overturning Circulation during Dansgaard-Oeschger stadials and a complete shutdown during Heinrich stadials. We find that the simulated δ18 O anomalies differ significantly between Heinrich stadials and non-Heinrich stadials. This difference is mainly due to different responses in ocean circulation, and therefore climate, impacting oceanic δ18 O, while the volume of 18O-depleted meltwater plays a secondary role.

  13. 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.

  14. Determining the oxygen isotope composition of evapotranspiration with eddy covariance

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The oxygen isotope componsition of evapotranspiration (dF) represents an important tracer in the study of biosphere-atmosphere interactions, hydrology, paleoclimate, and carbon cycling. Here we demonstrate direct measurement of dF based on eddy covariance (EC) and tunable diode laser (EC-TDL) techni...

  15. 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.

  16. Atmospheric odd oxygen production due to the photodissociation of ordinary and isotopic molecular oxygen

    NASA Technical Reports Server (NTRS)

    Omidvar, K.; Frederick, J. E.

    1987-01-01

    Line-by-line calculations are performed to determine the contributions of the Schumann-Runge bands of ordinary and isotopic oxygen to the photodissociation of these molecules at different altitudes. The contributions to the dissociation rates of the satellite lines and of the first and higher vibrational states of the initial molecular states are found to be insignificant. At 70 km, (O-16)(O-18) is found to produce 10 times as much odd oxygen as would be produced if the isotope did not have selective absorption, and 6 percent of the odd oxygen produced is due to this isotope. It is noted that the excess odd oxygen produced is not enough to explain the excess quantity of ozone observed in the atmosphere, which cannot be accounted for in photochemical models. Comparison with previous results is made.

  17. 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.

  18. 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.

  19. 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

    dinoflagellate Thoracosphaera heimii exhibits different behaviour for both isotopic systems, in particular with respect to its very negative carbon isotope composition, owing to coeval intra and extracellular biomineralisation in this group. In this study, we also investigate the sensitivity of 18O/16O fractionation to varying ambient oxygen isotope composition of the medium for inorganic, coccolithophore, and dinoflagellate calcite precipitated under controlled laboratory conditions. The varying responses of different taxa to increased oxygen isotope composition of the growth medium may point to a potential bias in sea surface temperature reconstructions that are based on the oxygen isotopic compositions of sedimentary calcite, especially during times of changing seawater oxygen isotopic composition. Overall, this study represents an important step towards establishing a mechanistic understanding of the “vital effect” in coccolith and dinoflagellate calcite, and provides valuable information for interpreting the geochemistry of the calcareous nannofossils in the sedimentary record, at both monospecific and interspecies levels.

  20. Investigations of the oxidation capacities of polar atmospheres with multiple oxygen isotopes

    NASA Astrophysics Data System (ADS)

    McCabe, Justin R.

    contains results and interpretations of nitrate oxygen isotopes from South Pole, Antarctica measured in aerosol and surface snow during 2004 and a 6-meter snow pit that provides a record 1977 to 2003. The isotope measurements from South Pole are compared to instrumental measurements of October-November-December column ozone, October-November-December UV, annual surface ozone, the quasi-biennial oscillation, and solar variability. A summary of related work on the oxygen and sulfur isotopic composition of volcanic sulfate from the Masaya volcano in Nicaragua is presented in the appendix along with measurements of ion chemistry used to establish a chronology in the South Pole snow pit. The nitrogen cycle has been drastically altered by human influence; however the sources of nitrogen to the Antarctic are expected to be relatively unaffected by human activity and may provide a means of establishing natural variability of nitrogen sources. Unfortunately, two significant problems exist. One, the sources to Antarctica are quite uncertain, and two, the records are difficult to interpret as a result of post-depositional effects in the ice. Through the use of multiple oxygen isotopes, the present work provides new insights into Antarctic nitrate records. The results suggest that greater knowledge of the influence of post-depositional effects (volatilization, photochemistry and diffusion) emerges from multiple oxygen isotope measurements in aerosol, surface snow and firn nitrate. The seasonal variation in winter stratospheric and summer tropospheric values of oxygen isotopes in Antarctic nitrate aerosol is preserved in surface snow. Evidence of stratospheric nitrate in snow at the South Pole suggests the potential for a proxy of ozone hole variability and solar variability; however, the location and meteorology of the South Pole create a site best suited for understanding boundary layer oxidation conditions across the Antarctic plateau. Changes in these conditions are driven by

  1. 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

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

    PubMed

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

    2007-03-06

    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.

  3. 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.

  4. Oxygen isotopes in spinels from Antarctic micrometeorites

    NASA Astrophysics Data System (ADS)

    Kurat, G.; Hoppe, P.; Walter, J.; Engrand, C.; Maurette, M.

    1994-07-01

    Spinel-rich inclusions were found in a large unmelted micrometeorite (MM) from Antarctica. This particle (MM92/15-23) consists of a fine-grained matrix of dehydrated former phyllosilicates that enclose a few small olivines, one large chromite, and several spinel-rich inclusions. The latter form elongated to rounded bodies up to 35 microns in length and consist of a spinel core enveloped by a Fe-rich silicate phase that probably is a (dehydrated?) phyllosilicate -- too small to be analyzed with the electron microprobe. A few very small perovskite grains are enclosed within the spinel. The chemical composition of the spinel is that of a Mg-Al spinel. On top of the Fe-rich silicate envelopes there is a discontinuous rim of aluminous Ca-rich pyroxene with a fairly high FeO content. The trace-element content is determined by secondary ion mass spectrometry (SIMS) of these inclusions resembles that of group II CAIs. Meanwhile we have found a second Antartic micrometeorite containing a few spinel grains. This spinel is associated with some tiny ilmenite grains and embedded in the foamy melt matrix of scoriaceous micrometeorite particle MM94/1-28. The chemical composition of the spinel is that of a Mg-Al-spinel containing small amounts of FeO (0.6 wt%), but no Cr2O3. We have successfully analyzed the O isotopic composition of two spinels from MM92/15-23 and one from MM94/1-28. The most common matter accreting onto the Earth today and represented by unmelted and partially melted micrometeorites consists of a matter similar, but not identical, to CM carbonaceous chondrites. The presence of spinel-rich Ca-Al rich inclusions (CAIs) with trace-element contents and O isotopic compositions of group II inclusions provides an additional support of that view.

  5. Clumped-Isotope Thermometry and Oxygen Isotope Systematics in Speleothem Calcite From a Near Cave-Entrance Environment

    NASA Astrophysics Data System (ADS)

    Carlson, P. E.; Banner, J.; Breecker, D.; Affek, H. P.

    2015-12-01

    Speleothems that grow in well-ventilated zones of caves have not been widely used in paleoclimate studies, yet may provide paleotemperature records. These zones are characterized by low CO2 concentrations year-round and, in temperate climates, large seasonal temperature fluctuations. They are typically avoided for paleoclimate reconstruction due to concerns about kinetic isotope effects (KIE). However, speleothems in general seem to be sensitive to KIE, even in non-ventilated areas and can nonetheless provide useful paleoclimate records. At Westcave Preserve (Westcave), a shallow, well-ventilated cave in central Texas, we have found seasonal temperature differences recorded in both the oxygen isotope and clumped isotope compositions of speleothem calcite grown on glass-plate substrates harvested from active drips. Although growth rates in this cave are relatively rapid, speleothem analogs in Westcave are growing near oxygen-isotopic equilibrium with their drip waters (between the calibrations of Kim and O'Neil, 1997 and Coplen, 2007). We have tested the compatibility of the Zaarur et al. (2013) clumped isotope bulk solution thermometer calibration to glass-substrate calcite in the cave collected during various months. This technique can provide absolute temperatures, but is sensitive to kinetic isotope effects, often significantly overestimating growth temperatures of speleothems. When this thermometer was applied to calcite collected from near where the plates were impacted by drip water, it overestimated measured temperatures by 7.7 ± 4.3°C, showing moderate KIE. When applied to calcite away from the drip impact, it overestimated temperatures by 18.7 ± 4.2°C, showing KIE increasing away from the drip. Measured monthly average temperatures in the cave ranged seasonally between 8 and 28°C, and daily temperatures vary significantly. At Westcave, calcite growth rates increase with temperature, and the calcite may therefore preferentially record warmer daily or

  6. 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.

  7. Local and regional oscillations of carbon and oxygen isotopes in terestrial carbonates

    NASA Astrophysics Data System (ADS)

    Skipitytė, Raminta; Stančikaitė, Miglė

    2014-05-01

    Stable isotope ratios of carbon and oxygen in sediment carbonates are used as a tool to identify climatic changes in the past [1], [2]. Carbon is more related to humidity whereas oxygen is thought to respond the temperature [2]. Nevertheless number of questions about local, regional and global scale impacts to these records is left. In this research work carbon and oxygen isotope ratios in lacustrine carbonates are used to identify palaeoenvironmental dynamics of different locations. Samples of lacutrine carbonates were obtained from 8 sequences of different sites in Lithuania (4), Poland (1), Belarus (1) and Kaliningrad (1). Every sequence was divided into 2 cm intervals. The study showed differences in average carbon and oxygen isotope ratios between Lithuania and other countries (Poland, Belarus and Kaliningrad). Carbon and oxygen isotope ratios in 4 sites in Lithuania are: ¯U la δ13C -4.72± 2.11, o and δ18O -9.46± 1.9, o ; Zervynos δ13C -4.79± 1.82, o and δ18O -9.57± 1.69, o ; Rudnia δ13C -4.94± 7.53, o and δ18O -9.3± 3.92, o ; Pauliai δ13C -4.15± 0.67, o and δ18O -9.94± 1.07, o : In other countries: Poland δ13C -1.07± 1.94, o and δ18O -7.69± 0.95, o ; Belarus δ13C 0.97± 1.94, o and δ18O -7.61± 1.42, o ; Kaliningrad δ13C -1.14± 1.43, o and δ18O -6.51± 1.00, o : Average stable carbon and oxygen isotope values from four sites in Lithuania were -4.65 o for carbon and -9.51 o for oxygen. Despite homogeneity of average isotope signals in these four sites there are relatively large oscillations of isotopic values in Rudnia and relatively small in Pauliai. These oscillations could be related to local characteristics of particular place such as environmental conditions, water balance, input of terrigenous materials into basin, etc. Total amount of CaCO3 could also play a significant role in reconstructing palaeoenvironment from stable isotopes and creating isomaps. The comparison of isotope records from different locations could enable to

  8. The magnesium isotope record of cave carbonate archives

    NASA Astrophysics Data System (ADS)

    Riechelmann, S.; Buhl, D.; Schröder-Ritzrau, A.; Riechelmann, D. F. C.; Richter, D. K.; Vonhof, H. B.; Wassenburg, J. A.; Geske, A.; Spötl, C.; Immenhauser, A.

    2012-05-01

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

  9. Dehydroxylation and diagenetic variations in diatom oxygen isotope values

    NASA Astrophysics Data System (ADS)

    Dodd, Justin P.; Wiedenheft, Wilson; Schwartz, Joshua M.

    2017-02-01

    Numerous studies have documented changes in the dissolution and reactivity of biogenic silica as it is transferred from the water column to sediment archives; here we present the first experimental data that demonstrate a physical mechanism by which the oxygen isotope (δ18Osil) values of biogenic silica (diatoms) are altered during early diagenesis. The δ18Osil value of diatom silica cultured at 19.3 °C was +31.9‰ ± 0.2‰ (n = 6); the same silica experimentally aged in an artificial seawater media at near silica saturation at 85 °C had an average δ18Osil value of +27.1‰ ± 0.6‰ (n = 20). The most significant change in the δ18Osil value was coincident with an initial reduction in the total silanol abundance, indicating that the timing of dehydroxylation reactions in natural sedimentary environments is associated with diagenetic changes in the recorded δ18Osil values. The rate of change in the experimental aging environment at 85 °C was rapid, with significant changes in both silanol abundance and δ18Osil values. Additionally, the silica-water fractionation relationship recorded by the experimentally-aged samples approaches the equilibrium quartz-water fractionation factor. The linear rate law was used to estimate the timing of these changes in low temperature environments; the initial and most significant change in silica reactivity and δ18Osil values is likely to occur on the order of 10's of years at 4 °C. Published silica-water fractionation factors for sedimentary diatoms most likely represent a combination of growth and diagenetic environments, and the δ18O value of diagenetic water needs to be addressed when using δ18Osil values to reconstruct paleoceanographic and paleoenvironmental conditions.

  10. 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

    was likely responsible for the return of lighter, seawater-like Fe isotope compositions in pyrite. Our pyrite Fe isotope profile thus records increased oxygenation in the Nanhua Basin between the Sturtian and Marinoan glaciations. The increased oxygenation of Nanhua Basin seawater deduced from pyrite Fe isotopes could have resulted from either local or global controls. Further work will be needed to determine whether this increasing oxygenation extended to the global scale.

  11. 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.

  12. 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.

  13. 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

  14. Understanding oxygen isotope environmental signals in tree ring sequences from New York State

    NASA Astrophysics Data System (ADS)

    Anderson, W. W.; Kirby, M. E.; Griggs, C.; Patterson, W. P.; Brasseur, J. M.; Mullins, H. T.; Burnett, A. W.

    2008-12-01

    The development of proxy climate records and analyses that allow for investigation and comparison of widespread regions will enhance the global understanding of past climate change through better correlations of significant events among different locations. Trees with a global distribution ranging from the tropics to the subarctic are an ideal medium from which to develop high-resolution isotopic records equivalent to those from varved lake sequences. However, in order to interpret the isotope record in the tree rings, proper calibration sites must be selected and studied. Here we present the results of a constructed calibration data set of oxygen isotopes in tree rings (1942 to 2003 A.D.) from four different locations, ranging from western, south central, central and southeastern New York State. Species studied for this project include eastern hemlock, eastern white pine, white spruce and tuliptree. The data set indicates that there is a clear regional signal in the oxygen isotope data, which indicates different precipitation sources areas for the four sites; these data have a total range of 25 to 33 V-SMOW. It is anticipated that this calibration data set will be used to calibrate older time-series spanning the Holocene from NE USA.

  15. Oxygen-isotope exchange rates for three isostructural polyoxometalate ions.

    PubMed

    Villa, Eric M; Ohlin, C André; Casey, William H

    2010-04-14

    We compare oxygen-isotope exchange rates for all structural oxygens in three polyoxoniobate ions that differ by systematic metal substitutions of Ti(IV) --> Nb(V). The [H(x)Nb(10)O(28)]((6-x)-), [H(x)TiNb(9)O(28)]((7-x)-), and [H(x)Ti(2)Nb(8)O(28)]((8-x)-) ions are all isostructural yet have different Brønsted properties. Rates for sites within a particular molecule in the series differ by at least approximately 10(4), but the relative reactivities of the oxygen sites rank in nearly the same relative order for all ions in the series. Within a single ion, most structural oxygens exhibit rates of isotopic exchange that vary similarly with pH, indicating that each structure responds as a whole to changes in pH. Across the series of molecules, however, the pH dependencies for isotope exchanges and dissociation are distinctly different, reflecting different contributions from proton- or base-enhanced pathways. The proton-enhanced pathway for isotope exchange dominates at most pH conditions for the [H(x)Ti(2)Nb(8)O(28)]((8-x)-) ion, but the base-enhanced pathways are increasingly important for the [H(x)TiNb(9)O(28)]((7-x)-) and [H(x)Nb(10)O(28)]((6-x)-) structures at higher pH. The local effect of Ti(IV) substitution could be assessed by comparing rates for structurally similar oxygens on each side of the [H(x)TiNb(9)O(28)]((7-x)-) ion and is surprisingly small. Interestingly, these nanometer-size structures seem to manifest the same general averaged amphoteric chemistry that is familiar for other reactions affecting oxides in water, including interface dissolution by proton- and hydroxyl-enhanced pathways.

  16. 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.

  17. Extreme oxygen isotope ratios in the early Solar System.

    PubMed

    Aléon, Jérôme; Robert, François; Duprat, Jean; Derenne, Sylvie

    2005-09-15

    The origins of the building blocks of the Solar System can be studied using the isotopic composition of early planetary and meteoritic material. Oxygen isotopes in planetary materials show variations at the per cent level that are not related to the mass of the isotopes; rather, they result from the mixture of components having different nucleosynthetic or chemical origins. Isotopic variations reaching orders of magnitude in minute meteoritic grains are usually attributed to stellar nucleosynthesis before the birth of the Solar System, whereby different grains were contributed by different stars. Here we report the discovery of abundant silica-rich grains embedded in meteoritic organic matter, having the most extreme 18O/16O and 17O/16O ratios observed (both approximately 10(-1)) together with a solar silicon isotopic composition. Both O and Si isotopes indicate a single nucleosynthetic process. These compositions can be accounted for by one of two processes: a single exotic evolved star seeding the young Solar System, or irradiation of the circumsolar gas by high energy particles accelerated during an active phase of the young Sun. We favour the latter interpretation, because the observed compositions are usually not expected from nucleosynthetic processes in evolved stars, whereas they are predicted by the selective trapping of irradiation products.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  19. Chromium Isotopes in Carbonate Rocks: New Insights into Proterozoic Atmospheric Oxygenation

    NASA Astrophysics Data System (ADS)

    Kah, L. C.; Gilleaudeau, G. J.; Frei, R.; Kaufman, A. J.; Azmy, K.; Bartley, J. K.; Chernyavskiy, P.; Knoll, A. H.

    2015-12-01

    There has been a long-standing debate in geobiology about the role that Earth's oxygenation played in the evolution of complex life. Temporal linkages exist between the Great Oxidation Event (GOE) and the evolution of eukaryotes, as well as Neoproterozoic rise in oxygen and the diversification of metazoans. Further advances have been hampered, however, by the lack of direct proxies that mark specific levels of atmospheric pO2 in the geologic past. Chromium (Cr) isotopes show promise in this regard because the oxidation of Cr during terrestrial weathering—which results in isotopic fractionation—is dependent on a specific threshold of atmospheric pO2 (0.1-1% of the present atmospheric level [PAL]). This threshold value broadly coincides with recent estimates of the oxygen requirements of early animals. Here we report new Cr-isotope data from four late Mesoproterozoic carbonate-dominated successions. Samples were collected from the Turukhansk Uplift (Siberia), the El Mreiti Group (Mauritania), the Vazante Group (Brazil), and the Angmaat Formation (Canada). We emphasize the application of Cr-isotopes to carbonate rocks because the broad temporal range of this lithology in the geologic record provides an opportunity to significantly expand our understanding of Proterozoic oxygenation on shorter time scales. Our data indicate that pO2 levels required to support early animals were attained long before Neoproterozoic metazoan diversification, although the large degree of isotopic heterogeneity in our dataset may indicate that pO2 > 0.1-1% PAL was only a transient phenomenon in the Mesoproterozoic. This study demonstrates the utility of Cr-isotopes as an atmospheric redox proxy in carbonate rocks and helps inform future avenues of research on Proterozoic pO2 thresholds.

  20. Biological oxygen productivity during the last 60,000 years from triple oxygen isotope measurements

    NASA Astrophysics Data System (ADS)

    Blunier, Thomas; Barnett, Bruce; Bender, Michael L.; Hendricks, Melissa B.

    2002-07-01

    The oxygen isotope signature of atmospheric O2 is linked to the isotopic signature of seawater (H2O) through photosynthesis and respiration. Fractionation during these processes is mass dependent, affecting δ17O about half as much as δ18O. An ``anomalous'' fractionation process, which changes δ17O and δ18O of O2 about equally, takes place during isotope exchange between O2 and CO2 in the stratosphere. The relative rates of biologic O2 production and stratospheric processing determine the relationship between δ17O and δ18O of O2 in the atmosphere. Variations of this relationship thus allow us to estimate changes in the rate of mass-dependent O2 production by photosynthesis versus the rate of O2-CO2 exchange in the stratosphere with about equal fractionations of δ17O and δ18O. In this study we reconstruct total oxygen productivity for the last glacial, the last glacial termination, and the early Holocene from the triple isotope composition of atmospheric oxygen trapped in ice cores. With a box model we estimate that total biogenic productivity was only ~76-83% of today for the glacial and was probably lower than today during the glacial-interglacial transition and the early Holocene. Depending on how reduced the oxygen flux from the land biosphere was during the glacial, the oxygen flux from the glacial ocean biosphere was 88-140% of its present value.

  1. The magnesium isotope record of cave carbonate archives

    NASA Astrophysics Data System (ADS)

    Riechelmann, S.; Buhl, D.; Schröder-Ritzrau, A.; Riechelmann, D. F. C.; Richter, D. K.; Vonhof, H. B.; Wassenburg, J. A.; Geske, A.; Spötl, C.; Immenhauser, A.

    2012-11-01

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

  2. Iron isotope fractionation and the oxygen fugacity of the mantle.

    PubMed

    Williams, Helen M; McCammon, Catherine A; Peslier, Anne H; Halliday, Alex N; Teutsch, Nadya; Levasseur, Sylvain; Burg, Jean-Pierre

    2004-06-11

    The oxygen fugacity of the mantle exerts a fundamental influence on mantle melting, volatile speciation, and the development of the atmosphere. However, its evolution through time is poorly understood. Changes in mantle oxidation state should be reflected in the Fe3+/Fe2+ of mantle minerals, and hence in stable iron isotope fractionation. Here it is shown that there are substantial (1.7 per mil) systematic variations in the iron isotope compositions (delta57/54Fe) of mantle spinels. Spinel delta57/54Fe values correlate with relative oxygen fugacity, Fe3+/sigmaFe, and chromium number, and provide a proxy of changes in mantle oxidation state, melting, and volatile recycling.

  3. 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

  4. Oxygen isotopic disequilibrium in coccolith carbonate from phytoplankton blooms

    NASA Astrophysics Data System (ADS)

    Paull, Charles K.; Balch, William M.

    1994-01-01

    Particulate carbonate was concentrated with a flow centrifuge out of the waters from a coccolithophore bloom in the Gulf of Maine for δ 18O CaCO 3 measurement. The particulate samples were composed of diverse organic materials, but most samples were observed to be dominated by Emiliana huxleyi CaCO 3. The oxygen isotopic fractionation associated with these E. huxleyi populations were determined by comparing oxygen isotope ratios in coccoliths with those of anbient waters at the time of collection. The observed isotopic fractionations were large (up to 2.8%), but did not match well with the expected values based on previous laboratory experiments. The temperatures calculated from the isotopic values of surface samples averaged 7.4°C cooler than the waters from which this carbonate was collected. These discrepancies may indicate that the coccoliths were precipatated in cooler water 10-20 m below the surface waters were they were captured, or that the waters had warmed since the coccoliths grew.

  5. 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.

  6. 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

  7. Hydrogen and oxygen isotope ratios in body water and hair: modeling isotope dynamics in nonhuman primates.

    PubMed

    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

    2012-07-01

    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water ((2)H/(1)H, (18)O/(16)O expressed as δ(2) H and δ(18)O). 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 δ(2)H and δ(18)O values of body water and a second model to predict the δ(2)H and δ(18)O 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 δ(2)H and δ(18)O 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 δ(2)H and δ(18)O values of gut water and the (18)O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (α(ow)). 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 α(ow) 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.

  8. Recent variability in the hydrological cycle of tropical Asia from oxygen isotopes of tree cellulose

    NASA Astrophysics Data System (ADS)

    Zhu, Mengfan

    This dissertation investigates hydrological variability within tropical Asia over the past several few centuries as reflected in the stable oxygen isotope composition of atmospheric moisture. High-resolution water isotope records are developed from trees collected from northern Thailand, southern Cambodia, and eastern part of the Tibetan Plateau. These records are examined to assess whether and how the 20th century is unique in terms of the hydrological conditions in tropical Asia under the influences of both monsoon and ENSO with the observed temperature changes. In northern Thailand, the oxygen isotopic composition (δ 18O) of tree cellulose samples of Pinus kesiya from a montane forest has been analyzed in subannual resolution for the past 80 years. The cellulose δ18O values exhibit a distinctive annual cycle with an amplitude of up to 12 ‰, which is interpreted to reflect primarily the seasonal cycle of precipitation δ18 O. The cellulose δ18O annual mean values correlate significantly with the amount of summer monsoon precipitation over the India subcontinent, corroborating recent studies that suggest the so-called "isotope amount effect" in the tropical precipitation δ18O reflects the hydrological processes of the upstream or the moisture source regions instead of the rainfall amount at the local site. No obvious trend in the summer monsoon precipitation is detected from the cellulose δ 18O record. However, the record does suggest a temporal weakening relationship between the Indian Monsoon and ENSO over the 20th century. The annual maxima in the cellulose δ18O values are representative of the moisture balance during the winter dry season, and possibly document a decreasing trend in the isotopically-distinct fog water input during the dry season because of the warming in the 20th century. Isotope chronologies of Pinus merkusii from a coastal lowland forest in Cambodia have been generated to investigate hydrological variability over the Indo

  9. Oxygen and carbon isotopic systematics of aragonite speleothems and water in Furong Cave, Chongqing, China

    NASA Astrophysics Data System (ADS)

    Li, Ting-Yong; Shen, Chuan-Chou; Li, Hong-Chun; Li, Jun-Yun; Chiang, Hong-Wei; Song, Sheng-Rong; Yuan, Dao-Xian; Lin, Chris D.-J.; Gao, Pan; Zhou, Liping; Wang, Jian-Li; Ye, Ming-Yang; Tang, Liang-Liang; Xie, Shi-You

    2011-08-01

    To understand oxygen and carbon stable isotopic characteristics of aragonite stalagmites and evaluate their applicability to paleoclimate, the isotopic compositions of active and fossil aragonite speleothems and water samples from an in situ multi-year (October 2005-July 2010) monitoring program in Furong Cave located in Chongqing of China have been examined. The observations during October 2005-June 2007 show that the meteoric water is well mixed in the overlying 300-500-m bedrock aquifer, reflected by relatively constant δ 18O, ±0.11-0.14‰ (1 σ), of drip waters in the cave, which represents the annual status of rainfall water. Active cave aragonite speleothems are at oxygen isotopic equilibrium with drip water and their δ 18O values capture the surface-water oxygen isotopic signal. Aragonite-to-calcite transformation since the last glaciation is not noticeable in Furong stalagmites. Our multi-year field experiment approves that aragonite stalagmite δ 18O records in this cave are suitable for paleoclimate reconstruction. With high U, 0.5-7.2 ppm, and low Th, 20-1270 ppt, the Furong aragonite stalagmites provide very precise chronology (as good as ±20s yrs (2 σ)) of the climatic variations since the last deglaciation. The synchroneity of Chinese stalagmite δ 18O records at the transition into the Bølling-Allerød (t-BA) and the Younger Dryas from Furong, Hulu and Dongge Caves supports the fidelity of the reconstructed East Asian monsoon evolution. However, the Furong record shows that the cold Older Dryas (OD) occurred at 14.0 thousand years ago, agreeing with Greenland ice core δ 18O records but ˜200 yrs younger than that in the Hulu record. The OD age discrepancy between Chinese caves can be attributable to different regionally climatic/environmental conditions or chronological uncertainty of stalagmite proxy records, which is limited by changes in growth rate and subsampling intervals in absolute dating. Seasonal dissolved inorganic carbon δ 13C

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

    PubMed

    Yurimoto, H; Ito, M; Nagasawa, H

    1998-12-04

    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

    1998-12-04

    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. 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

  13. Interpreting the Ca isotope record of marine biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Sime, Neil G.; De La Rocha, Christina L.; Tipper, Edward T.; Tripati, Aradhna; Galy, Albert; Bickle, Michael J.

    2007-08-01

    An 18 million year record of the Ca isotopic composition (δ 44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. δ 44/42Ca in this record averages +0.37 ± 0.05 (1 σ SD) and ranges from +0.21‰ to +0.52‰. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25‰ lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their δ 44/42Ca (i.e., by 0.06 ± 0.06‰ ( n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in δ 44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (δ 44/42Ca w) and for isotope fractionation associated with the production of carbonate sediments (Δ sed) results in unrealistically large variations in the total mass of Ca 2+ in the oceans over the Neogene. Alternatively, variations of ±0.05‰ in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in δ 44/42Ca w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in Δ sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in δ 44/42Ca w and Δ sed have been established, modeling the Ca 2+ content

  14. Pore fluid constraints on the temperature and oxygen isotopic composition of the glacial ocean

    SciTech Connect

    Schrag, D.P.; Hampt, G.; Murray, D.W.

    1996-06-28

    Pore fluids from the upper 60 meters of sediment 3000 meters below the surface of the tropical Atlantic indicate that the oxygen isotopic composition ({delta}{sup 18}O) of seawater at this site during the last glacial maximum was 0.8 {plus_minus} 0.1 per mil higher than it is today. Combined with the {delta}{sup 18}O change in benthic foraminifera from this region, the elevated ratio indicates that the temperature of deep water in the tropical Atlantic Ocean was 4{degree}C colder during the last glacial maximum. Extrapolation from this site to a global average suggests that the ice volume contribution to the change in {delta}{sup 18}O of foraminifera is 1.0 per mil, which partially reconciles the foraminiferal oxygen isotope record of tropical sea surface temperatures with estimates from Barbados corals and terrestrial climate proxies. 25 refs., 3 figs.

  15. Does the Shuram δ13C excursion record Ediacaran oxygenation?

    NASA Astrophysics Data System (ADS)

    Husson, J. M.; Maloof, A. C.; Schoene, B.; Higgins, J. A.

    2013-12-01

    The most negative carbon isotope excursion in Earth history is found in carbonate rocks of the Ediacaran Period (635-542 Ma). Known colloquially as the the 'Shuram' excursion, workers have long noted its tantalizing, broad concordance with the rise of abundant macro-scale fossils in the rock record, variously interpreted as animals, giant protists, macro-algae and lichen, and known as the 'Ediacaran Biota.' Thus, the Shuram excursion has been interpreted by many in the context of a dramatically changing redox state of the Ediacaran oceans - e.g., a result of methane cycling in a low O2 atmosphere, the final destruction of a large pool of recalcitrant dissolved organic carbon (DOC), and the step-wise oxidation of the Ediacaran oceans. More recently, diagenetic interpretations of the Shuram excursion - e.g. sedimentary in-growth of very δ13C depleted authigenic carbonates, meteoric alteration of Ediacaran carbonates, late-stage burial diagenesis - have challenged the various Ediacaran redox models. A rigorous geologic context is required to discriminate between these explanatory models, and determine whether the Shuram excursion can be used to evaluate terminal Neoproterozoic oxygenation. Here, we present chemo-stratigraphic data (δ13C, δ18O, δ44/42Ca and redox sensitive trace element abundances) from 12 measured sections of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia that require a syn-depositional age for the extraordinary range of δ13C values (-12 to +4‰) observed in the formation. In some locations, the Wonoka Fm. is ~700 meters (m) of mixed shelf limestones and siliclastics that record the full 16 ‰ δ13C excursion in a remarkably consistent fashion across 100s of square kilometers of basin area. Fabric-altering diagenesis, where present, occurs at the sub-meter vertical scale, only results in sub-permil offsets in δ13C and cannot be used to explain the full δ13C excursion. In other places, the Wonoka Fm. is host to deep (1 km

  16. Biological Oxygen Productivity Over The Last Glacial Termination From Triple Oxygen Isotope Measurements

    NASA Astrophysics Data System (ADS)

    Blunier, T.; Bender, M. L.; Hendricks, M. B.

    The atmospheric oxygen isotope signature of O2 is linked to the oxygen signature of seawater through photosynthesis and respiration. Fractionation during these pro- cesses is mass dependent affecting 17O about half as much as 18O. A mass indepen- dent fractionation process takes place during isotope exchange between O2 and CO2 in the stratosphere (Thiemens, 1999; Luz et al., 1999). The magnitude of the mass- independent anomaly in the triple isotope composition of O2 depends on relative rates of biological O2 cycling and photochemical reactions in the stratosphere. Variations of this anomaly thus allows us to estimate changes of mass dependent O2 production by photosynthesis versus mass independent O2-CO2 exchange in the stratosphere. We reconstruct total oxygen productivity for the past from 17O and 18O measure- ments of O2 trapped in ice cores. With a box model we estimate that the total biogenic productivity was only 76-83 % of today for the glacial and was probably still lower than today during the glacial-interglacial transition and the early Holocene. In principle we can calculate the oxygen flux from the ocean biosphere if we know the oxygen flux from the land biosphere. Calculated ocean production is very sensitive to the estimate of land biosphere production. The latter term remains uncertain, however, and we can presently only constrain glacial ocean production to 88 to 140 % of the present value.

  17. 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

  18. Assessment of the clumped isotope composition of fossil bone carbonate as a recorder of subsurface temperatures

    NASA Astrophysics Data System (ADS)

    Suarez, Marina B.; Passey, Benjamin H.

    2014-09-01

    Bone is susceptible to early diagenesis, and its carbon and oxygen isotopic compositions have been suggested to reflect conditions in the soil environment and shallow subsurface during fossilization. This implies open-system recrystallization involving mass exchange of carbon and oxygen among bioapatite, soil water, and DIC. Such recrystallization would also redistribute isotopic clumping (including 13C-18O bonds), leading to the possibility that the carbonate clumped isotope compositions of fossil bone record ground temperature during early diagenesis. We assess this possibility by studying Quaternary mammalian fossil bone from subtropical to polar latitudes: if recrystallization is early and pervasive, clumped isotope derived temperatures, T(Δ47), should closely mirror latitudinal gradients in ground temperature. Excluding results from a mummified specimen yielding T(Δ47) = 38 °C (that is, indistinguishable from mammalian body temperature), we find that T(Δ47) values are intermediate between mammalian body temperature and ground temperature, suggesting partial recrystallization of bone carbonate. XRD analyses show that the nature and extent of diagenesis varies among the samples and does not relate in a straightforward manner to T(Δ47). No clear correlation exists between T(Δ47) and mean annual temperature or mean warm season temperature. Furthermore, bone tends to retain the 18O-enriched signature of body water, suggesting incomplete oxygen isotope exchange with meteoric waters. Incomplete carbon and oxygen isotope exchange between bone carbonate and soil waters is also indicated for a set of late Miocene bone-enamel pairs from a sequence of stacked paleosols in northern China. Analysis of bone as old as Early Cretaceous shows that bone carbonate is susceptible to later diagenesis at elevated burial temperatures, although T(Δ47) does not closely conform to maximum burial temperature, again suggesting partial recrystallization, or recrystallization during

  19. Interpreting the Marine Calcium Isotope Record: Influence of Reef Builders

    NASA Astrophysics Data System (ADS)

    Boehm, F.; Eisenhauer, A.; Farkas, J.; Kiessling, W.; Veizer, J.; Wallmann, K.

    2008-12-01

    The calcium isotopic composition of seawater as recorded in brachiopod shells varied substantially during the Paleozoic (Farkas et al. 2007, Geochim. Cosmochim. Acta, 71, 5117-5134). The most prominent feature of the record is an excursion to higher 44Ca/40Ca values that started during the Early Carboniferous and lasted until the Permian. The shift occurred shortly after the transition from a calcite-sea to an aragonite-sea (Sandberg 1983, Nature 305, 19-22; Stanley and Hardie 1998, Pal3, 144, 3-19). It therefore has been interpreted to reflect a change in the average calcium isotope fractionation of carbonates produced in the oceans. Aragonite is depleted by about 0.6 permil in 44Ca/40Ca compared to calcite (Gussone et al. 2005, Geochim. Cosmochim. Acta, 69, 4485-4494). Consequently a transient shift from calcite dominated to an aragonite dominated calcium carbonate sedimentation could have caused the observed 0.5 permil isotope shift. We compare the marine calcium isotope record with a new compilation of the Phanerozoic trends in the skeletal mineralogy of marine invertebrates (Kiessling et al. 2008, Nature Geoscience, 1, 527-530). The compilation is based on data collected in the PaleoReef database and the Paleobiology Database, which include information on Phanerozoic reef complexes and taxonomic collection data of Phanerozoic biota, respectively. We find a strong positive correlation between the calcium isotope ratios and the abundance of aragonitic reef builders from the Silurian until the Permian at a sample resolution of about 10 million years. The two records, however, diverge in the Triassic, when reefs were dominated by aragonite but the calcium isotope values remained at a relatively low level. We also find a good correlation between calcium isotopes and the proportion of aragonite in the general record of Phanerozoic biota. However, in this case the records start to diverge already in the latest Carboniferous. The observations suggest that the

  20. Isotopic study of oxygen diffusion in oxide coatings

    NASA Technical Reports Server (NTRS)

    Gulino, Daniel A.; Kren, Lawrence A.; Dever, Therese M.

    1989-01-01

    Diffusion of oxygen in thin films of silicon dioxide was studied using oxygen isotopically enriched in oxygen of atomic mass 18 (O-18). This subject is of interest because thin films of dielectrics such as SiO2 are proposed for use as a protective coatings for solar mirrors in low Earth orbit, which is a strongly oxidizing environment. Films of this material were prepared with a direct current magnetron using reactive sputtering techniques. To produce (O-18)- enriched SiO2, a standard 3.5-in.-diameter silicon wafer was reactively sputtered using (O-18)-enriched (95 percent) oxygen as the plasma feed gas. The films were characterized using Rutherford backscattering and Secondary Ion Mass Spectrometer (SIMS) to establish stoichiometry and purity. Subsequently, the films were exposed to an air-derived oxygen plasma in a standard laboratory plasma reactor for durations of up to 10 hr. The concentration ratio of O-16 as a function of depth was determined using SIMS profiling and compared to a baseline, nonplasma exposed sample. A value for the diffusivity of oxygen near the surface of these films was obtained and found to be about 10(-15)sq cm/sec.

  1. Oxygen isotope fractionation of dissolved oxygen during reduction by ferrous iron

    NASA Astrophysics Data System (ADS)

    Oba, Yasuhiro; Poulson, Simon R.

    2009-01-01

    The oxygen isotope fractionation factor of dissolved oxygen gas has been measured during inorganic reduction by aqueous FeSO 4 at 10-54 °C under neutral (pH 7) and acidic (pH 2) conditions, with Fe(II) concentrations ranging up to 0.67 mol L -1, in order to better understand the geochemical behavior of oxygen in ferrous iron-rich groundwater and acidic mine pit lakes. The rate of oxygen reduction increased with increasing temperature and increasing Fe(II) concentration, with the pseudo-first-order rate constant k ranging from 2.3 to 82.9 × 10 -6 s -1 under neutral conditions and 2.1 to 37.4 × 10 -7 s -1 under acidic conditions. The activation energy of oxygen reduction was 30.9 ± 6.6 kJ mol -1 and 49.7 ± 13.0 kJ mol -1 under neutral and acidic conditions, respectively. Oxygen isotope enrichment factors ( ɛ) become smaller with increasing temperature, increasing ferrous iron concentration, and increasing reaction rate under acidic conditions, with ɛ values ranging from -4.5‰ to -11.6‰. Under neutral conditions, ɛ does not show any systematic trends vs. temperature or ferrous iron concentration, with ɛ values ranging from -7.3 to -10.3‰. Characterization of the oxygen isotope fractionation factor associated with O 2 reduction by Fe(II) will have application to elucidating the process or processes responsible for oxygen consumption in environments such as groundwater and acidic mine pit lakes, where a number of possible processes (e.g. biological respiration, reduction by reduced species) may have taken place.

  2. Sulfur isotope fractionation in modern euxinic systems: Implications for paleoenvironmental reconstructions of paired sulfate-sulfide isotope records

    NASA Astrophysics Data System (ADS)

    Gomes, Maya L.; Hurtgen, Matthew T.

    2015-05-01

    The sulfur (S) isotope difference between sulfates and sulfides preserved in sedimentary rocks (Δ34S) has been utilized to reconstruct ancient marine sulfate levels with implications for oxygenation of the Earth surface and biogeochemical cycling. S isotope data from modern, low-sulfate euxinic systems illustrate that preserved Δ34S values are positively correlated with sulfate concentration. However, absolute constraints on the range of low-sulfate levels over which preserved Δ34S values vary with sulfate concentration remain poorly constrained. Here, we present a compilation of S isotope data for modern euxinic systems demonstrating that preserved Δ34S values increase with sulfate concentration at low sulfate levels and approach values that are similar to in situ S isotope fractionation values from microbial sulfate reduction at high sulfate levels. We compare these results to a closed system model of S isotope cycling in a euxinic ocean in order to evaluate when the size of the sulfate reservoir is sufficiently small that Rayleigh fractionation affects the preservation of S isotope signatures. We conclude that the reservoir effect places constraints on Δ34S values deposited in euxinic settings at sulfate concentrations <5 mM. Thus, over this range, Δ34S values can be used to evaluate ancient sulfate levels. At higher sulfate levels (>10 mM), Δ34S values are similar to the kinetic isotope fractionation due to microbial sulfate reduction and therefore provide information about biological and environmental controls on sulfate reduction rates and location of pyrite formation. The results of this compilation provide an improved model for the use of Δ34S records to evaluate paleoenvironmental conditions in euxinic depositional environments.

  3. Oxygen isotopic ratios in intermediate-mass red giants

    NASA Astrophysics Data System (ADS)

    Lebzelter, T.; Straniero, O.; Hinkle, K. H.; Nowotny, W.; Aringer, B.

    2015-06-01

    Context. The abundances of the three main isotopes of oxygen are altered in the course of the CNO-cycle. When the first dredge-up mixes the burning products to the surface, the nucleosynthesis processes can be probed by measuring oxygen isotopic ratios. Aims: By measuring 16O/17O and 16O/18O in red giants of known mass we compare the isotope ratios with predictions from stellar and galactic evolution modelling. Methods: Oxygen isotopic ratios were derived from the K-band spectra of six red giants. The sample red giants are open cluster members with known masses of between 1.8 and 4.5 M⊙. The abundance determination employs synthetic spectra calculated with the COMARCS code. The effect of uncertainties in the nuclear reaction rates, the mixing length, and of a change in the initial abundance of the oxygen isotopes was determined by a set of nucleosynthesis and mixing models using the FUNS code. Results: The observed 16O/17O ratios are in good agreement with the model results, even if the measured values do not present clear evidence of a variation with the stellar mass. The observed 16O/18O ratios are clearly lower than the predictions from our reference model. Variations in nuclear reaction rates and mixing length parameter both have only a very weak effect on the predicted values. The 12C/13C ratios of the K giants studied implies the absence of extra-mixing in these objects. Conclusions: A comparison with galactic chemical evolution models indicates that the 16O/18O abundance ratio underwent a faster decrease than predicted. To explain the observed ratios, the most likely scenario is a higher initial 18O abundance combined with a lower initial 16O abundance. Comparing the measured 18O/17O ratio with the corresponding value for the interstellar medium points towards an initial enhancement of 17O as well. Limitations imposed by the observations prevent this from being a conclusive result.

  4. 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.

  5. Isotope fractionation during oxidation of tetravalent uranium by dissolved oxygen

    NASA Astrophysics Data System (ADS)

    Wang, Xiangli; Johnson, Thomas M.; Lundstrom, Craig C.

    2015-02-01

    We conducted laboratory experiments to investigate isotopic fractionations during oxidation of tetravalent uranium, U(IV), by dissolved oxygen. In hydrochloric acid media with the U(IV) dissolved, the δ238U value of the remaining U(IV) increased as the extent of oxidation increased. The δ238U value of the product U(VI) paralleled, but was offset to 1.1 ± 0.2‰ lower than the remaining U(IV). In contrast, oxidation of solid U(IV) by dissolved oxygen in 20 mM NaHCO3 solution at pH = 9.4 caused only a weak fractionation (∼0.1‰ to 0.3‰), with δ238U being higher in the dissolved U(VI) relative to the solid U(IV). We suggest that isotope fractionation during oxidation of solid U(IV) is inhibited by a "rind effect", where the surface layer of the solid U(IV) must be completely oxidized before the next layer is exposed to oxidant. The necessity of complete conversion of each layer results in minimal isotopic effect. The weak shift in δ238U of U(VI) is attributed to adsorption of part of the product U(VI) to the solid U(IV) surfaces.

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

    PubMed

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

    2007-01-02

    The isotopic composition of long-lived trace molecules provides a window into atmospheric transport and chemistry. Carbon dioxide is a particularly powerful tracer, because its abundance remains >100 parts per million by volume (ppmv) in the mesosphere. Here, we successfully reproduce the isotopic composition of CO(2) in the middle atmosphere, which has not been previously reported. The mass-independent fractionation of oxygen in CO(2) can be satisfactorily explained by the exchange reaction with O((1)D). In the stratosphere, the major source of O((1)D) is O(3) photolysis. Higher in the mesosphere, we discover that the photolysis of (16)O(17)O and (16)O(18)O by solar Lyman-alpha radiation yields O((1)D) 10-100 times more enriched in (17)O and (18)O than that from ozone photodissociation at lower altitudes. This latter source of heavy O((1)D) has not been considered in atmospheric simulations, yet it may potentially affect the "anomalous" oxygen signature in tropospheric CO(2) that should reflect the gross carbon fluxes between the atmosphere and terrestrial biosphere. Additional laboratory and atmospheric measurements are therefore proposed to test our model and validate the use of CO(2) isotopic fractionation as a tracer of atmospheric chemical and dynamical processes.

  7. Palaeoclimate signal recorded by stable isotopes in cave ice: a modeling approach

    NASA Astrophysics Data System (ADS)

    Perşoiu, A.; Bojar, A.-V.

    2012-04-01

    Ice accumulations in caves preserve a large variety of geochemical information as candidate proxies for both past climate and environmental changes, one of the most significant being the stable isotopic composition of the ice. A series of recent studies have targeted oxygen and hydrogen stable isotopes in cave ice as proxies for past air temperatures, but the results are far from being as straightforward as they are in high latitude and altitude glaciers and ice caps. The main problems emerging from these studies are related to the mechanisms of cave ice formation (i.e., freezing of water) and post-formation processes (melting and refreezing), which both alter the original isotopic signal in water. Different methods have been put forward to solve these issues and a fair understanding of the present-day link between stable isotopes in precipitation and cave ice exists now. However, the main issues still lays unsolved: 1) is it possible to extend this link to older ice and thus reconstruct past changes in air temperature?; 2) to what extent are ice dynamics processes modifying the original climatic signal and 3) what is the best method to be used in extracting a climatic signal from stable isotopes in cave ice? To respond to these questions, we have conducted a modeling experiment, in which a theoretical cave ice stable isotope record was constructed using present-day observations on stable isotope behavior in cave ice and ice dynamics, and different methods (presently used for both polar and cave glaciers), were used to reconstruct the original, known, isotopic values. Our results show that it is possible to remove the effects of ice melting and refreezing on stable isotope composition of cave ice, and thus reconstruct the original isotopic signal, and further the climatic one.

  8. Crustal evolution reflected in seawater Sr and Nd isotope records

    NASA Astrophysics Data System (ADS)

    Peucker-Ehrenbrink, B.

    2013-12-01

    Radiogenic isotope ratios record time-integrated parent-daughter ratios, and are thus sensitive to chemical composition and time. The oceans recieve the integrated runoff from the continental surface and preserve these signals in marine sedimentary records. Radiogenic isotope records of seawater and marine sediments have been reconstructed over the past five decades for many of the radiogenic isotope systems. For some systems (Sr) excellent records do exist that integrate seawater signals for the entire ocean. In contrast, globally averaged records of radiogenic isotopes with short marine residence times (Nd, Pb) are much more difficult to establish. Here, I attempt to link long-term (Phanerozoic) records of marine radiogenic isotope systems to records of the evolution of the continental surface that interacts with the hydrologic cycle. For the present we can show that the dissolved and particulate loads from the continents integrate different portions of the continental surface (Peucker-Ehrenbrink et al., 2010, G-cubed 11, doi: 10.1029/2009GC002869). For instance, the areas generating the dissolved load are characterized by significantly older bedrock (~400 Myr) than those generating the particulate load (~320 Myr). The fact that both are younger than the mean bedrock age of the non-glaciated, exorheic portion of the continental surface (~450 Myr) reflects the disproportionate role active margins, high-standing ocean island, and weathering and erosion of young sedimentary strata play in exporting dissolved matter and sedimnent to the oceans. Using present-day systematics as a guide, I argue that the first-order trough-like shape of the Phanerozoic marine Sr isotope record reflects the rejuvenation of the continental surface involved in exporting Sr to the ocean from the early Phanerozoic to the mid Jurassic that is followed by an 'aging' that continues into the Quaternary. This long-term evolution of the continental surface is mirrored by a similar - though more

  9. 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.

  10. Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation.

    PubMed

    Bao, Huiming; Lyons, J R; Zhou, Chuanming

    2008-05-22

    Understanding the composition of the atmosphere over geological time is critical to understanding the history of the Earth system, as the atmosphere is closely linked to the lithosphere, hydrosphere and biosphere. Although much of the history of the lithosphere and hydrosphere is contained in rock and mineral records, corresponding information about the atmosphere is scarce and elusive owing to the lack of direct records. Geologists have used sedimentary minerals, fossils and geochemical models to place constraints on the concentrations of carbon dioxide, oxygen or methane in the past. Here we show that the triple oxygen isotope composition of sulphate from ancient evaporites and barites shows variable negative oxygen-17 isotope anomalies over the past 750 million years. We propose that these anomalies track those of atmospheric oxygen and in turn reflect the partial pressure of carbon dioxide (P(CO2)) in the past through a photochemical reaction network linking stratospheric ozone to carbon dioxide and to oxygen. Our results suggest that P(CO2) was much higher in the early Cambrian than in younger eras, agreeing with previous modelling results. We also find that the (17)O isotope anomalies of barites from Marinoan (approximately 635 million years ago) cap carbonates display a distinct negative spike (around -0.70 per thousand), suggesting that by the time barite was precipitating in the immediate aftermath of a Neoproterozoic global glaciation, the P(CO2) was at its highest level in the past 750 million years. Our finding is consistent with the 'snowball Earth' hypothesis and/or a massive methane release after the Marinoan glaciation.

  11. 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.

  12. Isotopic records in CM hibonites: Implications for timescales of mixing of isotope reservoirs in the solar nebula

    NASA Astrophysics Data System (ADS)

    Liu, Ming-Chang; McKeegan, Kevin D.; Goswami, Jitendra N.; Marhas, Kuljeet K.; Sahijpal, Sandeep; Ireland, Trevor R.; Davis, Andrew M.

    2009-09-01

    The magnesium isotopic compositions of 26 hibonite-bearing inclusions from the CM chondrite Murchison, as well as isotopic measurements on a subset of these samples for oxygen, titanium, and lithium-beryllium-boron are reported along with oxygen isotopic data for an additional 13 hibonites that were previously investigated for other isotope systems (magnesium, potassium, calcium, and titanium) and rare earth element concentrations. Magnesium isotopic compositions divide CM hibonites into two distinct populations which correlate perfectly with their mineralogy and morphology, as previously discovered by Ireland [Ireland T. R. (1988) Correlated morphological, chemical, and isotopic characteristics of hibonites from the Murchison carbonaceous chondrite. Geochim. Cosmochim. Acta52, 2827-2839]: Spinel-HIBonite spherules (SHIBs) bear evidence of in situ26Al decay, whereas PLAty-Crystals (PLACs) and Blue AGgregates (BAGs) either lack resolvable 26Mg-excesses or exhibit 26Mg deficits by up to ˜4‰. High precision, multiple collector SIMS analyses show that 6 of 7 SHIBs investigated fall on a single correlation line implying 26Al/ 27Al = (4.5 ± 0.2) × 10 -5 at the time of isotopic closure, consistent with the "canonical" 26Al abundance characteristic of internal isochrons in many calcium-aluminum-rich inclusions (CAIs). One SHIB sample exhibits Δ 26Mg ∗ consistent with a "supracanonical" 26Al/ 27Al ratio of (6.4 ± 0.5) × 10 -5. The PLAC hibonites contain highly anomalous titanium isotopic compositions, with δ 50Ti values ranging from -80‰ to almost +200‰, whereas SHIBs generally lack large Ti isotopic anomalies. Eight out of 11 26Al-free PLAC hibonite grains record 10B/ 11B excesses that correlate with Be/B; the inferred initial 10Be/ 9Be ratio of (5.1 ± 1.4) × 10 -4 is lower than the best-constrained 10Be/ 9Be of (8.8 ± 0.6) × 10 -4 in a CV CAI. The data demonstrate that 10Be cannot be used as a relative chronometer for these objects and that most of the

  13. Oxygen isotope constraints on the alteration temperatures of CM chondrites

    NASA Astrophysics Data System (ADS)

    Verdier-Paoletti, Maximilien J.; Marrocchi, Yves; Avice, Guillaume; Roskosz, Mathieu; Gurenko, Andrey; Gounelle, Matthieu

    2017-01-01

    We report a systematic oxygen isotopic survey of Ca-carbonates in nine different CM chondrites characterized by different degrees of alteration, from the least altered known to date (Paris, 2.7-2.8) to the most altered (ALH 88045, CM1). Our data define a continuous trend that crosses the Terrestrial Fractionation Line (TFL), with a general relationship that is indistinguishable within errors from the trend defined by both matrix phyllosilicates and bulk O-isotopic compositions of CM chondrites. This bulk-matrix-carbonate (BMC) trend does not correspond to a mass-dependent fractionation (i.e., slope 0.52) as it would be expected during fluid circulation along a temperature gradient. It is instead a direct proxy of the degree of O-isotopic equilibration between 17,18O-rich fluids and 16O-rich anhydrous minerals. Our O-isotopic survey revealed that, for a given CM, no carbonate is in O-isotopic equilibrium with its respective surrounding matrix. This precludes direct calculation of the temperature of carbonate precipitation. However, the O-isotopic compositions of alteration water in different CMs (inferred from isotopic mass-balance calculation and direct measurements) define another trend (CMW for CM Water), parallel to BMC but with a different intercept. The distance between the BMC and CMW trends is directly related to the temperature of CM alteration and corresponds to average carbonates and serpentine formation temperatures of 110 °C and 75 °C, respectively. However, carbonate O-isotopic variations around the BMC trend indicate that they formed at various temperatures ranging between 50 and 300 °C, with 50% of the carbonates studied here showing precipitation temperature higher than 100 °C. The average Δ17O and the average carbonate precipitation temperature per chondrite are correlated, revealing that all CMs underwent similar maximum temperature peaks, but that altered CMs experienced protracted carbonate precipitation event(s) at lower temperatures than

  14. 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.

  15. An Archean Terrestrial Fractionation Line for Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Rumble, D.; Blake, R. E.; Bao, H.; Bowring, S.; Komiya, T.; Rosing, M.; Ueno, Y.

    2008-12-01

    The Terrestrial Fractionation Line (TFL) for oxygen isotopes is defined by 17O/16O and 18O/16O analyses of meteoric waters, seawater, sedimentary, metamorphic, and igneous rocks and constituent minerals. Interlaboratory measurements of the slope of the TFL on a plot of d18O vs. d17O revealed eclogitic garnets with a slope of 0.526 and hydrothermal quartz of 0.524 from rocks younger than 0.8 Ga (Giga years before present). New measurements show Archean metamorphic rocks and minerals from Barberton, (3.2 Ga, S. Africa), Isua (3.8 Ga, Greenland), and Acasta (4.0 Ga, Canada) have a slope of 0.524 +/- 0.002 (95% confidence, MSWD = 0.66). Analysis of Ag3PO4 prepared from apatite mineral separates from Isua meta-sediments gives a slope of 0.509 +/- 0.022 (95% confidence, MSWD = 0.59). Taken at face value, steeper slopes on a d17O vs. d18O diagram indicate an approach towards isotope exchange equilibrium. Lower slopes are expected when isotope fractionation is kinetically controlled. The lower slope of 0.509 for Isua apatite suggests that the formation of orthophosphate was kinetically controlled. Kinetic fractionations are known to occur during catalysis of reactions by enzymes secreted by microbes. Enzymatic catalysis confers an advantage on organisms because energy-producing reactions may be induced to occur at lower temperature conditions more accessible to the organism. May it be definitively concluded that enzymatic catalysis was responsible for the measured 0.509 slope? No, abiotic kinetic fractionation cannot be disproven with existing data. The preparation of Ag3PO4 from apatite may have introduced kinetic fractionation as an analytical artifact. Conclusions fully supported by the data suggest: (1) Mixing accompanying the violent birth of the Earth- Moon system had already succeeded in establishing Earth's current oxygen isotope composition by 4.0 Ga; and (2) No trace of an episode of late heavy meteorite bombardment remains in the oxygen isotope compositions of

  16. Climatic forcing of carbon-oxygen isotopic covariance in temperate-region marl lakes

    NASA Technical Reports Server (NTRS)

    Drummond, C. N.; Patterson, W. P.; Walker, J. C.

    1995-01-01

    Carbon and oxygen stable isotopic compositions of lacustrine carbonate from a southeastern Michigan marl lake display linear covariance over a range of 4.0% Peedee belemnite (PDB) in oxygen and 3.9% (PDB) in carbon. Mechanisms of delta 13 C-delta 18 O coupling conventionally attributed to lake closure in arid-region basins are inapplicable to hydrologically open lake systems. Thus, an alternative explanation of isotopic covariance in temperate region dimictic marl lakes is required. We propose that isotopic covariance is a direct record of change in regional climate. In short-residence-time temperate-region lake basins, summer meteoric precipitation is enriched in 18O relative to winter values, and summer organic productivity enriches epilimnic dissolved inorganic carbon in 13C. Thus, climate change toward longer summers and/or shorter winters could result in greater proportions of warm-month meteoric precipitation, longer durations of warm-month productivity, and net long-term enrichment in carbonate 18O and 13C. Isotopic covariance observed in the Michigan marl lake cores is interpreted to reflect postglacial warming from 10 to 3 ka followed by cooler mean annual temperature, a shift toward greater proportions of seasonal summer precipitation, a shortening of the winter season, or some combination of these three factors.

  17. Do foraminifera accurately record seawater neodymium isotope composition?

    NASA Astrophysics Data System (ADS)

    Scrivner, Adam; Skinner, Luke; Vance, Derek

    2010-05-01

    Palaeoclimate studies involving the reconstruction of past Atlantic meridional overturning circulation increasingly employ isotopes of neodymium (Nd), measured on a variety of sample media (Frank, 2002). In the open ocean, Nd isotopes are a conservative tracer of water mass mixing and are unaffected by biological and low-temperature fractionation processes (Piepgras and Wasserburg, 1987; Lacan and Jeandel, 2005). For decades, benthic foraminifera have been widely utilised in stable isotope and geochemical studies, but have only recently begun to be exploited as a widely distributed, high-resolution Nd isotope archive (Klevenz et al., 2008), potentially circumventing the difficulties associated with other methods used to recover past deep-water Nd isotopes (Klevenz et al., 2008; Rutberg et al., 2000; Tachikawa et al., 2004). Thus far, a single pilot study (Klevenz et al., 2008) has indicated that core-top sedimentary benthic foraminifera record a Nd isotope composition in agreement with the nearest available bottom seawater data, and has suggested that this archive is potentially useful on both millennial and million-year timescales. Here we present seawater and proximal core-top foraminifer Nd isotope data for samples recovered during the 2008 "RETRO" cruise of the Marion Dufresne. The foraminifer samples comprise a depth-transect spanning 3000m of the water column in the Angola Basin and permit a direct comparison between high-resolution water column and core-top foraminiferal Nd isotope data. We use these data to assess the reliability of both planktonic and benthic foraminifera as recorders of water column neodymium isotope composition. Frank, M., 2002. Radiogenic isotopes: Tracers of past ocean circulation and erosional input, Rev. Geophys., 40 (1), 1001, doi:10.1029/2000RG000094. Klevenz, V., Vance, D., Schmidt, D.N., and Mezger, K., 2008. Neodymium isotopes in benthic foraminifera: Core-top systematics and a down-core record from the Neogene south Atlantic

  18. 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.

  19. Unlocking the ice house: Oligocene-Miocene oxygen isotopes, eustasy, and margin erosion

    SciTech Connect

    Miller, K.G. Columbia Univ., Palisades, NY ); Wright, J.D.; Fairbanks, R.G. )

    1991-04-10

    Benthic foraminiferal {delta}{sup 18}O records place limits on the history of glaciation, suggesting the presence of ice sheets at least intermittently since the earliest Oligocene. The best indicator of ice growth is a coeval increase in global benthic and western equatorial planktonic {delta}{sup 18}O records. Although planktonic isotope records from the western equatorial regions are limited, subtropical planktonic foraminifera may also record such ice volume changes. It is difficult to apply these established principles to the Cenozoic {delta}{sup 18}O record because of the lack of adequate data and problems in stratigraphic correlations that obscure isotope events. The authors improved Oligocene to Miocene correlations of {delta}{sup 18}O records and erected eight oxygen isotope zones (Oi1-Oi2, Mi1-Mi6). Benthic foraminiferal {delta}{sup 18}O increases which can be linked with {delta}{sup 18}O increases in subtropical planktonic foraminifera and with intervals of glacial sedimentation on or near Antarctica. These new correlations of middle Miocene benthic and western equatorial planktonic {delta}{sup 18}O records show remarkable agreement in timing and amplitude. They interpret benthic-planktonic covariance to reflect substantial ice volume increases near the bases of Zones Mi2 (circa 16.1 Ma), Mi3 (circa 13.6 Ma), and possibly Mi5 (circa 11.3 Ma). Possible glacioeustatic lowerings are associated with the {delta}{sup 18}O increases which culminated with the bases of Zone Mi4 (circa 12.6 Ma) and Mi6 (circa 9.6 Ma), although low-latitude planktonic {delta}{sup 18}O records are required to test this. These inferred glacioeustatic lowerings can be linked to seismic and rock disconformities.

  20. In Situ Oxygen Isotope Analysis of Conodonts by SIMS and Its Implication for Paleo-sea Surface Temperature

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Chen, J.; Chen, Z.; Chen, Y.; Wang, R.; Tang, G.; Li, X.; Lv, J.; Zhuang, X.

    2013-12-01

    Oxygen isotope composition of biogenic apatite is potentially useful in paleotemperature reconstruction of contemporaneous surface seawater temperature (SST). Combined with abundant researches on their biostratigraphy, the geochemical analysis of conodonts contains more significant signatures indicating paleoenvironmental changes. However, the small size is always a limited factor for the accurate analysis. In this work, we tested the oxygen isotope of conodont using Cameca IMS-1280 secondary ion mass spectrometry (SIMS) for the first time and acquired reliable records on contemporaneous SST. We found that SST raised rapidly following the Late Permian biocrisis, implying that the rapid increase in paleo-temperature may have been one of the crucial killers responsible for the Permian-Triassic mass extinction. Compared with the previous Ag3PO4 method, our analysis technique is faster with both high resolution and high spatial resolution, so we can avoid the position easily contaminated during the late diagensis and acquire the original oxygen isotopic compositions.

  1. 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.

  2. Turnover of oxygen and hydrogen isotopes in the body water, CO 2, hair, and enamel of a small mammal

    NASA Astrophysics Data System (ADS)

    Podlesak, David W.; Torregrossa, Ann-Marie; Ehleringer, James R.; Dearing, M. Denise; Passey, Benjamin H.; Cerling, Thure E.

    2008-01-01

    Oxygen and hydrogen isotope signatures of animal tissues are strongly correlated with the isotope signature of local precipitation and as a result, isotope signatures of tissues are commonly used to study resource utilization and migration in animals and to reconstruct climate. To better understand the mechanisms behind these correlations, we manipulated the isotope composition of the drinking water and food supplied to captive woodrats to quantify the relationships between drinking water ( δdw), body water ( δbw), and tissue ( δt). Woodrats were fed an isotopically constant food but were supplied with isotopically depleted or enriched water. Some animals were switched between these waters, allowing simultaneous determination of body water turnover, isotope change recorded in teeth and hair, and fractional contributions of atmospheric O 2, drinking water, and food to the oxygen and hydrogen budgets of the animals. The half-life of the body water turnover was 3-6 days. A mass balance model estimated that drinking water, atmospheric O 2, and food were responsible for 56%, 30%, and 15% of the oxygen in the body water, respectively. Drinking water and food were responsible for 71% and 29% of the hydrogen in the body water, respectively. Published generalized models for lab rats and humans accurately estimated δbw, as did an updated version of a specific model for woodrats. The change in drinking water was clearly recorded in hair and tooth enamel, and multiple-pool and tooth enamel forward models closely predicted these changes in hair and enamel, respectively. Oxygen and hydrogen atoms in the drinking water strongly influence the composition of the body water and tissues such as hair and tooth enamel; however, food and atmospheric O 2 also contribute oxygen and/or hydrogen atoms to tissue. Controlled experiments allow researchers to validate models that estimate δt based on δdw and so will increase the reliability of estimates of resource utilization and climate

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

    NASA Astrophysics Data System (ADS)

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

    1988-04-01

    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 ( Δ qz - mt=10.0‰) within 2 3 meters of the orthogneiss contact to 600° C ( Δ 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 δ 18Owr value of 8.0±0.6‰. The greater Δ 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 α-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 ( D 0), consistent with the experimentally determined values, that will result in reasonable cooling rates for the Wind River iron formation. The discrepancy between the

  4. 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

  5. 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.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

    The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (< 3 days) is characterized by subtle and multiple changes in oxygen source and contribution that is likely due to the adjustment of the microbial metabolism from S to Fe2+-oxidation. A more detailed understanding of the microbial mechanisms and behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of

  8. 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.

  9. 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.

  10. Fractionation of Nitrogen and Oxygen Isotopes During Microbial Nitrate Reduction

    NASA Astrophysics Data System (ADS)

    Lehmann, M. F.; Bernasconi, S. M.; Reichert, P.; Barbieri, A.; McKenzie, J. A.

    2001-12-01

    Lakes represent an important continental sink of fixed nitrogen. Besides the burial of particulate nitrogen, fixed nitrogen is eliminated from lakes by emission of N2 and N2O to the atmosphere during dissimilative nitrate reduction within suboxic and anoxic waters or sediments. The understanding and quantification of this efficient nitrogen removal process in eutrophic lakes is crucial for nitrogen budget modelling and the application and evaluation of lake restoration measures. In order to use natural abundance N and O isotope ratios as tracers for microbial nitrate reduction and to obtain quantitative estimates on its intensity, it is crucial to constrain the associated isotope fractionation. This is the first report of nitrogen and oxygen isotope effects associated with microbial nitrate reduction in lacustrine environments. Nitrate reduction in suboxic and anoxic waters of the southern basin of Lake Lugano (Switzerland) is demonstrated by a progressive nitrate depletion coupled to increasing δ 15N and δ 18O values for residual nitrate. 15N and 18O enrichment factors (ɛ ) were estimated using a closed-system (Rayleigh-distillation) model and a dynamic reaction-diffusion model. Calculated enrichment factors ɛ ranged between -11.2 and -22‰ for 15N and between -6.6 and -11.3‰ for 18O with both nitrogen and oxygen isotope fractionation being greatest during times with the highest nitrate reduction rates. The closed-system model neglects vertical diffusive mixing and does not distinguish between sedimentary and water-column nitrate reduction. Therefore, it tends to underestimate the intrinsic isotope effect of microbial nitrate reduction. Based upon results from earlier studies that indicate that nitrate reduction in sediments displays a highly reduced N-isotope effect (Brandes and Devol, 1997), model-derived enrichment factors could be used to discern the relative importance of nitrate reduction in the water column and in the sediment. Sedimentary nitrate

  11. 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

  12. The Oxygen Isotope Composition of Dark Inclusions in HEDs, Ordinary and Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Greenwood, R. C.; Zolensky, M. E.; Buchanan, P. C.; Franchi, I. A.

    2015-01-01

    Dark inclusions (DIs) are lithic fragments that form a volumetrically small, but important, component in carbonaceous chondrites. Carbonaceous clasts similar to DIs are also found in some ordinary chondrites and HEDs. DIs are of particular interest because they provide a record of nebular and planetary processes distinct from that of their host meteorite. DIs may be representative of the material that delivered water and other volatiles to early Earth as a late veneer. Here we focus on the oxygen isotopic composition of DIs in a variety of settings with the aim of understanding their formational history and relationship to the enclosing host meteorite.

  13. 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.

  14. Oxygen isotope fractionation between human phosphate and water revisited.

    PubMed

    Daux, Valérie; Lécuyer, Christophe; Héran, Marie-Anne; Amiot, Romain; Simon, Laurent; Fourel, François; Martineau, François; Lynnerup, Niels; Reychler, Hervé; Escarguel, Gilles

    2008-12-01

    The oxygen isotope composition of human phosphatic tissues (delta18OP) has great potential for reconstructing climate and population migration, but this technique has not been applied to early human evolution. To facilitate this application we analyzed delta18OP values of modern human teeth collected at 12 sites located at latitudes ranging from 4 degrees N to 70 degrees N together with the corresponding oxygen composition of tap waters (delta18OW) from these areas. In addition, the delta18O of some raw and boiled foods were determined and simple mass balance calculations were performed to investigate the impact of solid food consumption on the oxygen isotope composition of the total ingested water (drinking water+solid food water). The results, along with those from three, smaller published data sets, can be considered as random estimates of a unique delta18OW/delta18OP linear relationship: delta18OW=1.54(+/-0.09)xdelta18OP-33.72(+/-1.51)(R2=0.87: p [H0:R2=0]=2x10(-19)). The delta18O of cooked food is higher than that of the drinking water. As a consequence, in a modern diet the delta18O of ingested water is +1.05 to 1.2 per thousand higher than that of drinking water in the area. In meat-dominated and cereal-free diets, which may have been the diets of some of our early ancestors, the shift is a little higher and the application of the regression equation would slightly overestimate delta18OW in these cases.

  15. 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.

  16. Ocean redox structure across the Late Neoproterozoic Oxygenation Event: A nitrogen isotope perspective

    NASA Astrophysics Data System (ADS)

    Ader, Magali; Sansjofre, Pierre; Halverson, Galen P.; Busigny, Vincent; Trindade, Ricardo I. F.; Kunzmann, Marcus; Nogueira, Afonso C. R.

    2014-06-01

    The end of the Neoproterozoic Era (1000 to 541 Ma) is widely believed to have seen the transition from a dominantly anoxic to an oxygenated deep ocean. This purported redox transition appears to be closely linked temporally with metazoan radiation and extraordinary perturbations to the global carbon cycle. However, the geochemical record of this transition is not straightforward, and individual data sets have been variably interpreted to indicate full oxygenation by the early Ediacaran Period (635 to 541 Ma) and deep ocean anoxia persevering as late as the early Cambrian. Because any change in marine redox structure would have profoundly impacted nitrogen nutrient cycling in the global ocean, the N isotope signature of sedimentary rocks (δ15Nsed) should reflect the Neoproterozoic deep-ocean redox transition. We present new N isotope data from Amazonia, northwest Canada, northeast Svalbard, and South China that span the Cryogenian glaciations (˜750 to 580 Ma). These and previously published data reveal a N-isotope distribution that closely resembles modern marine sediments, with a mode in δ15N close to +4‰ and range from -4 to +11‰. No apparent change is seen between the Cryogenian and Ediacarian. Data from earlier Proterozoic samples show a similar distribution, but shifted slightly towards more negative δ15N values and with a wider range. The most parsimonious explanation for the similarity of these N-isotope distribution is that as in the modern ocean, nitrate (and hence O2) was stable in most of the middle-late Neoproterozoic ocean, and possibly much of Proterozoic Eon. However, nitrate would likely have been depleted in partially restricted basins and oxygen minimum zones (OMZs), which may have been more widespread than in the modern ocean.

  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

    2006-02-02

    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.

  18. 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

  19. Evidence for rapid climate change in North America during the latest Paleocene thermal maximum: oxygen isotope compositions of biogenic phosphate from the Bighorn Basin (Wyoming)

    NASA Astrophysics Data System (ADS)

    Fricke, Henry C.; Clyde, William C.; O'Neil, James R.; Gingerich, Philip D.

    1998-07-01

    Oxygen isotope records of Cenozoic sea water temperatures indicate that a rapid warming event known as the Latest Paleocene Thermal Maximum (LPTM) occurred during the otherwise gradual increase in world temperatures during the Late Paleocene and Early Eocene. Oxygen isotope analysis of the carbonate and phosphate components of hydroxyapatite found in mammalian tooth enamel and body scales of river-dwelling fish from the Bighorn Basin in Wyoming were made to investigate corresponding changes in the terrestrial climate. A comparison of carbonate and phosphate isotope data from modern and fossil material indicates that some diagenetic alteration of the fossil material has occurred, although systematically larger intra-tooth ranges in the oxygen isotope composition of carbonate indicate that it is more likely to have been affected than phosphate. Carbonate and phosphate from the ecologically diverse mammals and fishes both record a shift to higher oxygen isotope ratios at the same time and of the same duration as the LPTM. These shifts reflect a change in the isotopic composition of regional precipitation, which in turn provides the first evidence for continental climate change during the LPTM. Assuming the present-day relation between the oxygen isotope composition of precipitation and temperature applies to conditions in the past, and that animal physiology and behavior is relatively invariant over time, the isotopic shift is equivalent to an increase of surface temperature in western North America of several degrees. This result is consistent with the magnitude of high-latitude ocean warming, and provides a basis for relating marine and terrestrial oxygen isotope records to records of terrestrial biotic change.

  20. Late Eocene-Middle Miocene paleoclimates of the south-west Pacific: oxygen isotopic evidence

    SciTech Connect

    Kennett, J.P.; Murphy, M.G.

    1985-01-01

    High resolution oxygen isotopic stratigraphy is presented for Late Eocene-Middle Miocene sequences in a traverse of 6 DSDP sites from the southwest Pacific at water depths ranging from 1300 to 2000 m and from the warm subtropics to the cool temperature water masses. The data record the progressive increase of latitudinal temperature gradients from the late Eocene. A pattern of increasing isotopic offset between the latitudinally distributed sites is linked to the establishment and strengthening of the circum-Antarctic Current. The intensification of this current system progressively decoupled the warm subtropical gyres from cool polar circulation, in turn leading to Antarctic glaciation. Enriched oxygen isotopic values clustering in the middle Oligocene, are interpreted to represent accumulations of Antarctic ice, although this must have been temporary and of relatively low volume. This Antarctic ice must have disappeared by the Early Miocene when delta/sup 18/O values were relatively depleted, reaching minimum values during the late Early Miocene (19.5 to 16.5), the climax of Neogene warmth. This climatic optimum was immediately followed by a major enrichment in benthic delta/sup 18/O values between approx. 16.5 and 13.5 Ma, which is interpreted to represent major, permanent accumulation of the East Antarctic ice sheet and cooling of bottom waters.

  1. 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.

  2. Skeletal isotope records of growth perturbations in Porites corals during the 1997-1998 mass bleaching event

    NASA Astrophysics Data System (ADS)

    Suzuki, A.; Gagan, M.; Fabricius, K.; Isdale, P.; Yukino, I.; Kawahata, H.

    2003-04-01

    Severe coral bleaching occurred throughout the tropics in 1997/98. We report skeletal UV fluorescence, oxygen isotope, and carbon isotope evidence for perturbations in coral skeletal growth due to bleaching at Ishigaki Island, Japan, and Pandora Reef, Great Barrier Reef. Bleached corals showed abrupt reductions in skeletal extension rate immediately after summer temperature maxima, indicating that bleaching inhibits coral calcification. A colony growing at the low tide line in Ishigaki exhibited clear blue UV fluorescent bands associated with recurrent growth interruptions. Based on the length of time-gaps observed in the annual isotopic cycle, the typical time required for a coral to recover from bleaching is estimated to be about 5--6 months. The effect of bleaching on the oxygen isotope ratio -- temperature relationship was negligible. However, the Ishigaki corals showed lower carbon isotope ratios during bleaching indicating depressed coral metabolism associated with a reduction in calcification. In contrast, skeletal carbon isotope ratios in the Pandora Reef corals exhibited little change in response to bleaching. This is because the records for Pandora Reef were derived from the shaded sides of coral colonies, where algal photosynthesis was particularly slow prior to bleaching, thus subduing the carbon isotope response to bleaching. Taken together, the isotopic and UV fluorescence signals can be used to reconstruct past bleaching events.

  3. The temperature and carbonate ion influence on Pleistocene high latitude planktonic foraminiferal carbon isotopic records

    NASA Astrophysics Data System (ADS)

    Charles, C.; Foreman, A. D.; Munson, J.; Slowey, N. C.; Hodell, D. A.

    2014-12-01

    Establishing a credible record of the carbon isotopic composition of high latitude surface ocean DIC over ice ages has been an enormous challenge, because the possible archives of this important variable in deep sea sediments all incorporate complex effects of the biomineralization process. For example, culture experiments (by Spero and colleagues) demonstrate a strong temperature and carbonate ion effect on the carbon isotopic composition of G. bulloides--the taxon of planktonic foraminifera that is most abundant in the majority of subpolar sediment sequences. Here we capitalize on the fortuitous observation of exceptionally strong covariation between the oxygen and carbon isotopic composition of G. bulloides in multiple sediment sequences from the Benguela upwelling region. The covariation is most clear during Marine Isotopic Stage 3 (an interval when the isotopic composition of the seawater was least variable) and undoubtedly results from the precipitation of tests under variable conditions of temperature and carbonate ion. The unusually clear isotopic relationship in planktonic foraminifera observed off Namibia constitutes a field calibration of the biomineralization effects observed in culture, and we apply it to previously published high latitude carbon isotopic records throughout the Southern Ocean. We find that many of the excursions toward lower planktonic foraminiferal δ13C that have been interpreted previously as the upwelling of nutrient rich water during deglaciations are better explained as increases in upper ocean temperature and carbonate ion. Conversely, the excursions toward high δ13C during ice age intervals that have been interpreted previously as increased export production (purportedly stimulated by dust) are also better explained by temperature and carbonate ion variability. After removal of the inferred temperature and carbonate ion signal from the planktonic foraminiferal time series, the residual is essentially (but not exactly) the same

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

    PubMed

    Barrick, R E; Showers, W J

    1994-07-08

    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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Reconstructing seasonal climate from high-resolution carbon and oxygen isotope measurements across tree rings

    NASA Astrophysics Data System (ADS)

    Schubert, B.; Jahren, H.

    2014-12-01

    Intra-annual records of carbon (δ13C) and oxygen (δ18O) isotope measurements across tree rings reveal significant changes in δ13C and δ18O value across each growing season. We previously found that across a broad range of climate regimes, the seasonal change in δ13C measured within tree rings reflects changes in seasonal precipitation amount, and demonstrated its utility for quantifying seasonal paleo-precipitation from non-permineralized, fossil wood. Here we produce an equation relating intra-ring changes in δ18O to seasonal changes in temperature and precipitation amount, but the equation yields for unknowns (summer and winter precipitation amounts, and cold and warm month mean temperatures). By combining high-resolution δ13C and δ18O records with independent estimates of mean annual temperature and mean annual precipitation, we show how our general, global relationships could be used to quantify seasonal climate information from fossil sites. We validate our approach using high-resolution δ13C and δ18O data from trees growing at five modern sites (Hawaii, Alaska, Norway, Guyana, and Kenya). The reconstructed estimates of seasonal precipitation and temperature showed excellent agreement with the known climate data for each site (precipitation: R2 = 0.98; temperature: R2 = 0.91). These results confirm that across diverse sites and tree species, seasonal climate information can be accurately quantified using a combination of carbon and oxygen intra-ring isotope profiles.

  11. 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.

  12. 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

  13. What processes control the oxygen isotopes of soil bio-available phosphate?

    NASA Astrophysics Data System (ADS)

    Gross, Avner; Angert, Alon

    2015-06-01

    The biological availability of phosphorus (P) is considered to be the limiting factor for plant growth in many natural and agricultural soils. Recent studies demonstrated that valuable information on soil P dynamics can be gained from the stable oxygen isotopes of soil phosphate (δ18OP). However, to interpret this information correctly, our understanding of the processes that controls soil phosphate δ18OP values needs to be improved since most of the current data is based primarily on laboratory studies of pure microbial cultures and enzymatic assays and may not be relevant to soils. Here we designed a series of controlled soil incubation experiments to study the actual isotopic effects induced by abiotic reactions, biological uptake, microbial turnover and organic-P mineralization on soil phosphate δ18OP values. We used this data to estimate the role of these processes in mediating soil P availability. Our study was conducted on Mediterranean soils sampled from the same site during winter, spring and summer. The soils were incubated with various mineral and organic-P compounds and their bioavailable phosphate concentrations and δ18OP values were measured. We confirmed that the role of abiotic reactions on phosphate δ18OP values was negligible and that the δ18OP values of the added phosphate were rapidly driven towards isotopic equilibrium with soil water. We suggest this process was mediated by rapid microbial phosphate turnover. Yet, we did not detect the expected isotopic enrichment effect associated with phosphate biological uptake. In another set of incubation experiments we demonstrated that mineralization of phosphate from organic compounds, such as phospho-mono-ester (PME) and phosphor-di-ester (PDE), produced an offset from isotopic equilibrium, as a result of the strong isotopic fractionation associated with the mineralization process. However, the δ18OP values recorded by the mineralized phosphate were gradually driven back towards isotopic

  14. Anomalous Oxygen Isotopic Fractionation in Vacuum Ultraviolet Photodissociation of Carbon Monoxide and Test of Self-Shielding: Relevance for Meteorite Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Chakraborty, S.; Ahmed, M.; Jackson, T. L.; Thiemens, M. H.

    2008-12-01

    Oxygen is the predominant elemental constituent of rocky planets and asteroids. It is the third most abundant element in the solar system after hydrogen and helium. The isotopic compo-sition of oxygen in three-isotope space (δ18O vs. δ17O plot) exhibits large heterogeneity among different bodies formed from the same primordial gas and dust mixture, termed the solar nebula. It is not possible to fully understand the formation and evolution of our own planetary system, unless we resolve the source of the oxygen isotopes. At present, there are two models: self shielding photochemistry in the solar nebula, and symmetry driven gas-phase and/or surface chemistry in the solar nebula, which can also involve photochemistry, but isn't required. Photochemistry is a dominant process at the outer layers of the nebular disk and isotopically selective photodissociation (a process known as isotopic self-shielding) of carbon monoxide, the most abundant nebular oxygen bearing molecule, has been suggested as a source of isotopically anomalous oxygen in the solar reservoir [1-3]. However, these models have had no experimental verification of the relevant isotopic fractionation associated with VUV-CO photodissociation at the relevant wavelengths. Recently, we have performed a series of CO photodissociation experiment with a windowless flow chamber at the Advanced Light Source (LBNL) synchrotron at Berkeley. These experiments demonstrate an anomalously enriched atomic oxygen reservoir is generated through CO photo-dissociation, but, without requiring isotopic self shielding [4]. These results emphasize the importance of chemistry in the solar nebula as we have previously demonstrated through recent laboratory experiments [5]. It is clear that the mass- independent oxygen isotopic composition, as observed in some of the first condensed solids in the solar system (Calcium-Aluminum rich Inclusions- CAIs, Chondrules etc.), can be generated through symmetry driven gas-phase chemical

  15. Determination of triple oxygen isotopic compositions of nitrate by using continuous-flow isotope ratio MS.

    NASA Astrophysics Data System (ADS)

    Komatsu, D. D.; Ohkubo, S.; Ishimura, T.; Nakagawa, F.; Tsunogai, U.

    2006-12-01

    The triple oxygen isotopic compositions (18O/16O and 17O/16O) of nitrate in natural waters can be a useful tracer to clarify the sources. The triple oxygen isotopic compositions of nitrate have been usually determined by using conventional IRMS system using O2 molecule converted from nitrate through multiple reaction/purification steps. The traditional methods, however, required at least 1-100 μmol quantities of nitrate so that applications of the methods to various environmental nitrate samples were difficult. Thus, we developed a rapid and sensitive analytical system to determine the triple oxygen isotopic compositions of nitrate in nmol quantities using continuous-flow IRMS (CF-IRMS) without the cumbersome and time-consuming pretreatments. Our method is based on the isotopic analysis of N2O quantitatively converted from nitrate based on the simple reactions using spongy cadmium and sodium azide in an acetic acid buffer. However, we cannot determine 17O/16O ratio of N2O directly by measuring the masses 44, 45, and 46 of N2O introduced to IRMS, because the measured output of mass 45 from IRMS consists of 14N15N16O, 15N14N16O, and 14N14N17O. Thus, addition to the N2O isotopic analysis at the masses 44, 45, and 46, the 15N/14N ratio is determined separately for the same sample N2O. To attain this purpose, two instrumental approaches were done. In the first system, the N2+ fragment ion beams of N2O at masses 28 and 29 were used to determine the 15N/14N ratio of N2O. While the analytical precisions better than 0.5 ‰ for 20 nmol N2O injections and better than 1.0 ‰ for 7 nmol N2O injections were obtained for 15N/14N ratio, we found that the accuracy strongly depended on the quantities introduced. In the second system, the N2 molecules, converted from N2O using an on line Cu reduction furnace (720 degree) was used to determine the 15N/14N ratio of N2O. The analytical precisions better than 0.1 ‰ for 5 nmol N2O injections and better than 0.4 ‰ for 1 nmol N2O

  16. Determination and application of the equilibrium oxygen isotope effect between water and sulfite

    NASA Astrophysics Data System (ADS)

    Wankel, Scott D.; Bradley, Alexander S.; Eldridge, Daniel L.; Johnston, David T.

    2014-01-01

    The information encoded by the two stable isotope systems in sulfate (δ34SSO4 and δ18OSO4) has been widely applied to aid reconstructions of both modern and ancient environments. Interpretation of δ18OSO4 records has been complicated by rapid oxygen isotope equilibration between sulfoxyanions and water. Specifically, the apparent relationship that develops between δ18OSO4 and δ18Owater during microbial sulfate reduction is thought to result from rapid oxygen isotope equilibrium between intracellular water and aqueous sulfite - a reactive intermediate of the sulfate reduction network that can back-react to produce sulfate. Here, we describe the oxygen equilibrium isotope effect between water and sulfite (referring to all the sum of all S(IV)-oxyanions including sulfite and both isomers and the dimer of bisulfite). Based on experiments conducted over a range of pH (4.5-9.8) and temperature (2-95 °C), where ε = 1000 * (α - 1), we find εSO3-H2O=13.61-0.299∗pH-0.081∗T °C. Thus, at a pH (7.0) and temperature (25 °C) typifying commonly used experimental conditions for sulfate reducing bacterial cultures, sulfite is enriched in 18O by 9.5‰ (±0.8‰) relative to ambient water. We examine the implication of these results in a sulfate reduction network that has been revised to reflect our understanding of the reactions involving oxygen. By evaluating previously published data within this new architecture, our results are consistent with previous suggestions of high reversibility of the sulfate reduction biochemical network. We also demonstrate that intracellular exchange rates between SO32- and water must be on average 1-3 orders of magnitude more rapid than intracellular fluxes of sulfate reduction intermediates and that kinetic isotope effects upstream of SO32- are required to explain previous laboratory and environmental studies of δ18OSO4 resulting as a consequence of sulfate reduction.

  17. Isotopic record of Pleistocene glacial/interglacial cycles in pelagic carbonates: Revisiting historical data from the Caribbean Sea

    NASA Astrophysics Data System (ADS)

    Hermoso, Michaël

    2016-04-01

    The glacial/interglacial cycles of the Pleistocene were first recognised by variations in the oxygen isotopic composition of planktonic foraminifera from cores in the Caribbean Sea. Since this pioneering work by Emiliani, this proxy has been extensively applied to a variety of carbonate biominerals over the entirety of the Meso-Cenozoic. However, palaeoceanographic studies have overwhelmingly focused on foraminifera compared to other calcifying microorganism fossils, such as the coccoliths. In this study, I revisit coccolith stable isotopic data obtained from the classic P6304-4 core in light of recent developments in the biogeochemistry of coccolithophores. In particular, I show that the coccolith stable isotope record of the last 13 Marine Isotope Stages (∼480 kyrs) is significantly biased by large vital effects. The magnitude of coccolith carbon and oxygen isotope vital effects is not uniform, but shows remarkable co-variance with the Vostok CO2 ice record. During periods of relatively elevated CO2 (interstadials), the expression of the vital effect is relatively small, whereas it can as high as +3‰ for the oxygen isotopes during glacial stadials, which I argue is a result of enhanced CO2 limitation of coccolithophores. Using this paradigm, I propose that coccolithophore vital effects are not a complicating factor, but rather the signal of interest. As the magnitude of the coccolith vital effect is shown to scale with pCO2, coccolith carbon and oxygen isotopes may be used in conjunction with foraminifera data to reconstruct and refine aqueous CO2 concentrations in the past.

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  20. 500,000-year stable carbon isotopic record from Devils Hole, Nevada

    USGS Publications Warehouse

    Coplen, T.B.; Winograd, I.J.; Landwehr, J.M.; Riggs, A.C.

    1994-01-01

    The record of carbon-13 (??13C) variations in DH-11 vein calcite core from Devils Hole, Nevada, shows four prominent minima near glacial terminations (glacial-interglacial transitions) V to II. The ??13C time series is inversely correlated with the DH-11 oxygen isotope ratio time series and leads it by as much as 7000 years. The ??13C variations likely record fluctuations in the ??13C of dissolved inorganic carbon of water recharging the aquifer. How such variations are transported 80 kilometers to Devils Hole without obliteration by waterrock reaction remains an enigma. The record may reflect (i) global variations in the ??13C of atmospheric CO2 and, hence, the ??13C of continental biomass or (ii) variations in extent and density of vegetation in the southern Great Basin. In the latter case, ??13C minima at 414, 334, 246, and 133 thousand years ago mark times of maximum vegetation.

  1. Stable oxygen isotopes (delta18(O)) in Austrocedrus chilensis tree rings reflect climate variability in northwestern Patagonia, Argentina.

    PubMed

    Roig, F A; Siegwolf, R; Boninsegna, J A

    2006-11-01

    The stable oxygen isotope (delta (18)O) composition of Austrocedrus chilensis (D. Don) Endl. (Cupressaceae) tree rings potentially provide retrospective views of changes in environment and climate in the semi-arid lands of Patagonia. We report the development of the first annually resolved delta (18)O tree-ring chronology obtained from natural forests of the foothills of the northwestern Patagonian Andes. The isotope record spans between 1890 and 1994 AD. We explore the probable links between this record and the climate of the region. Air temperatures during summer conditions are significantly, but not strongly, inversely correlated with annual delta (18)O values from Austrocedrus tree rings. The strongest correlations are between the southern oscillation index (SOI) and the tree rings. The existence of millennial-age Austrocedrus trees in northern Patagonia provides interesting possibilities for examining these climate-related isotopic signals over most of the last 1,000 years.

  2. Independent support for leaf homeothermy during carbon uptake and the implications for the interpretation of tree-ring oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Helliker, B. R.; Baldocchi, D. D.; Desai, A. R.; Goulden, M. L.; Davis, K. J.; Wofsy, S. C.; Munger, J. W.

    2010-12-01

    Tree rings provide an annual record of plant responses to climatic variability and the oxygen isotope ratio of tree-ring cellulose is thought to provide a record of leaf-to-air vapor pressure deficit. We recently developed a method to resolve tree-canopy leaf temperature when most carbon uptake occurs by using the oxygen isotope ratio of tree-ring cellulose and ambient relative humidity. We found a remarkably constant leaf temperature of 21.4 ± 2.2 °C in 39 tree species across 50° of latitude. There are two general mechanisms for this perceived leaf temperature homeostasis: (i) leaf temperature equals ambient air temperature and most photosynthesis occurs when ambient temperatures are near 21 °C. (ii) When carbon assimilation is maximal, the physiological and morphological properties of tree leaves and branches serve to maintain canopy leaf temperatures near 21 °C. To address these questions we calculated a temperature-weighted value for daytime net ecosystem exchange during the growing season for several biomes from published eddy covariance data. The results support the observation of a photosynthesis-weighted temperature near 21 °C determined through our isotope analysis. The results suggest that the controlling mechanism is likely a combination of points (i) and (ii) above. Further, these characteristics of tree ecophysiology must be considered when interpreting evaporative signals contained in tree ring oxygen isotopes- particularly those at high latitudes/altitudes.

  3. What drives interannual variation in tree ring oxygen isotopes in the Amazon?

    NASA Astrophysics Data System (ADS)

    Baker, J. C. A.; Gloor, M.; Spracklen, D. V.; Arnold, S. R.; Tindall, J. C.; Clerici, S. J.; Leng, M. J.; Brienen, R. J. W.

    2016-11-01

    Oxygen isotope ratios in tree rings (δ18OTR) from northern Bolivia record local precipitation δ18O and correlate strongly with Amazon basin-wide rainfall. While this is encouraging evidence that δ18OTR can be used for paleoclimate reconstructions, it remains unclear whether variation in δ18OTR is truly driven by within-basin processes, thus recording Amazon climate directly, or if the isotope signal may already be imprinted on incoming vapor, perhaps reflecting a pan-tropical climate signal. We use atmospheric back trajectories combined with satellite observations of precipitation, together with water vapor transport analysis to show that δ18OTR in Bolivia are indeed controlled by basin-intrinsic processes, with rainout over the basin the most important factor. Furthermore, interannual variation in basin-wide precipitation and atmospheric circulation are both shown to affect δ18OTR. These findings suggest δ18OTR can be reliably used to reconstruct Amazon precipitation and have implications for the interpretation of other paleoproxy records from the Amazon basin.

  4. Oxygen isotopes in calcite grown under cave-analogue conditions

    NASA Astrophysics Data System (ADS)

    Day, C. C.; Henderson, G. M.

    2011-07-01

    Speleothem oxygen isotopes and growth rates are valuable proxies for reconstructing climate history. There is debate, however, about the conditions that allow speleothems to grow in oxygen isotope equilibrium, and about the correct equilibrium fractionation factors. We report results from a series of carbonate growth experiments in karst-analogue conditions in the laboratory. The setup closely mimics natural processes (e.g. precipitation driven by CO 2-degassing, low ionic strength solution, thin solution film) but with a tight control on growth conditions (temperature, pCO 2, drip rate, calcite saturation index and the composition of the initial solution). Calcite is dissolved in water in a 20,000 ppmV pCO 2 environment. This solution is dripped onto glass plates (coated with seed-carbonate) in a lower pCO 2 environment (<2500 ppmV), where degassing leads to calcite growth. Experiments were performed at 7, 15, 25 and 35 °C. At each temperature, calcite was grown at three drip rates (2, 6 and 10 drips per minute) on separate plates. The mass of calcite grown in these experiments varies with temperature ( T in K) and drip rate ( d_ r in drips min -1) according to the relationship daily growth mass = 1.254 + 1.478 ∗ 10 -9 ∗ e0.0679 T + ( e0.00248 T - 2) ∗ (-0.779 d_ r2 + 10.05 d_ r + 11.69). This relationship indicates a substantial increase of growth mass with temperature, a smaller influence of drip rate on growth mass at low temperature and a non-linear relationship between drip rate and growth mass at higher temperatures. Low temperature, fast dripping conditions are found to be the most favourable for reducing effects associated with evaporation and rapid depletion of the dissolved inorganic carbon reservoir (rapid DIC-depletion). The impact of evaporation can be large so caves with high relative humidity are also preferable for palaeoclimate reconstruction. Even allowing for the maximum offsets that may have been induced by evaporation and rapid DIC

  5. A Bat's-Eye View of Holocene Climate Change in the Southwest: Resolving Ambiguities in Cave Isotopic Records

    NASA Astrophysics Data System (ADS)

    Cole, J. E.; Truebe, S. A.; Harrington, M. D.; Woodhead, J. D.; Overpeck, J. T.; Hlohowskyj, S.; Henderson, G. M.

    2015-12-01

    In dry environments, speleothems provide an outstanding archive of information on past climate change, particularly since lakes are typically absent or intermittent. Speleothem stable isotopes are widely used for climate reconstruction, but the isotope-climate relationship is complex in arid-region precipitation, and within-cave processes further complicate climate interpretations. Our isotope results from 3 southeastern Arizona caves, spanning the past 3.5-12 kyr, collectively indicate a weakening monsoon from 7kyr to present. These records exhibit substantial multidecadal-multicentury variability that is sometimes shared, and sometimes independent among caves. Strategies to overcome ambiguities in isotope records include long-term monitoring of cave dripwaters, multi-site comparisons, and multiproxy measurements. Monthly dripwater measurements from two caves spanning several years highlight substantial seasonal biases that create distinct differences in the climate sensitivity of individual cave records. These biases can lead to lack of correlation between records, but also creates opportunities for seasonally specific moisture reconstructions. New preliminary analyses suggest that elemental data can help to unravel the multivariate signal contained in speleothem oxygen isotope records.

  6. 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

  7. 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.

  8. 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.

  9. Oxygen isotope equilibrium between eclogite minerals and its constraints on mineral Sm-Nd chronometer

    NASA Astrophysics Data System (ADS)

    Zheng, Yong-Fei; Wang, Zheng-Rong; Li, Shu-Guang; Zhao, Zi-Fu

    2002-02-01

    Sm-Nd and oxygen isotope analyses were carried out for mineral separates of ultrahigh pressure eclogites from the Sulu terrane in eastern China. The results show a direct correspondence in equilibrium or disequilibrium state between the oxygen and Sm-Nd isotope systems of eclogite minerals. The omphacite-garnet pairs of oxygen isotope equilibrium at eclogite-facies conditions yield meaningful Triassic Sm-Nd isochron ages, whereas those of oxygen isotope disequilibrium give non-Triassic ages of geological meaninglessness. This can be reasonably interpreted by the fact that the rates of oxygen diffusion in garnet and pyroxene are lower than, or close to, those of Nd diffusion, and thus attainment of isotopic equilibrium in the omphacite-garnet O system suggests achievement of Nd isotope equilibrium in the same mineral pairs. The presence or absence of fluid in the eclogite protoliths is a major rate-controlling factor for isotopic equilibration during high-grade metamorphism. It appears that the state of oxygen isotope equilibrium between cogenetic minerals can provide a critical test for the validity of the Sm-Nd mineral chronometer. In addition, the exact timing of the ultrahigh pressure metamorphism in the Dabie-Sulu terranes is constrained at Early Triassic rather than Late Triassic.

  10. 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.

  11. Oxygen isotope geochemistry of mafic magmas at Mt. Vesuvius

    NASA Astrophysics Data System (ADS)

    Dallai, Luigi; Raffaello, Cioni; Chiara, Boschi; Claudia, D'oriano

    2010-05-01

    above the range of typical mantle minerals. The δ18Oolivine and δ18Ocpxof the minerals from all the studied eruptions define variable degrees of carbonate interaction and magma crystallization for the different eruptions, and possibly within the same eruption, and show evidence of oxygen isotope equilibrium at high temperature. However, energy-constrained AFC model suggest that carbonate assimilation was limited. On the basis of our data, we suggest that interaction between magma and a fluxing, decarbonation-derived CO2 fluid may be partly accounted for the measured O-isotope compositions.

  12. Molybdenum isotope records as a potential new proxy for paleoceanography

    NASA Astrophysics Data System (ADS)

    Siebert, Christopher; Nägler, Thomas F.; von Blanckenburg, Friedhelm; Kramers, Jan D.

    2003-06-01

    New high-precision isotope ratios of dissolved Mo in seawater from different ocean basins and depths show a homogeneous isotope composition ('mean ocean water 98Mo/ 95Mo' (MOMO)), as expected from its long ocean residence time (800 kyr). This composition appears to have been constant for the past 60 Myr at a 1-3 Myr time resolution as indicated from thick sections of Fe-Mn crusts from the Atlantic and Pacific. These records yield a constant offset from MOMO (average of -3.1 and -2.9‰). They are similar to our new data on recent oxic Mo sinks: pelagic sediments and six Fe-Mn crust surface layers range from -2.7 to -2.9‰ and -2.7 to -3.1‰, respectively. Recent suboxic Mo sinks from open ocean basins display heavier and more variable isotope ratios (-0.7 to -1.6‰ relative to MOMO). Crustal Mo sources were characterized by measuring two granites (and a mild acid leach of one granite), seven volcanic rocks and two clastic sediments. All show a narrow range of compositions (-2.0 to -2.3‰). These data indicate that isotope fractionation by chemical weathering and magmatic processes is insignificant on a global scale. They therefore represent good estimates of the composition of dissolved Mo input to the oceans and that of the average continental crust. Thus, the Mo input into the oceans appears to be distributed into lighter oxic sinks and heavier reducing sinks. This is consistent with steady-state conditions in the modern ocean. The constant isotope offset between oxic sediments and seawater suggests that the relative amounts of oxic and reducing Mo removal fluxes have not varied by more than 10% over the last 60 Myr. An equilibrium fractionation process is proposed assuming that Mo isotope fractionation occurs between (dominant) MoO 42- and (minor) Mo(OH) 6 species in solution, of which the latter is preferentially scavenged.

  13. The value of oxygen-isotope data and multiple discharge records in calibrating a fully-distributed, physically-based rainfall-runoff model (CRUM3) to improve predictive capability

    NASA Astrophysics Data System (ADS)

    Neill, Aaron; Reaney, Sim

    2015-04-01

    Fully-distributed, physically-based rainfall-runoff models attempt to capture some of the complexity of the runoff processes that operate within a catchment, and have been used to address a variety of issues including water quality and the effect of climate change on flood frequency. Two key issues are prevalent, however, which call into question the predictive capability of such models. The first is the issue of parameter equifinality which can be responsible for large amounts of uncertainty. The second is whether such models make the right predictions for the right reasons - are the processes operating within a catchment correctly represented, or do the predictive abilities of these models result only from the calibration process? The use of additional data sources, such as environmental tracers, has been shown to help address both of these issues, by allowing for multi-criteria model calibration to be undertaken, and by permitting a greater understanding of the processes operating in a catchment and hence a more thorough evaluation of how well catchment processes are represented in a model. Using discharge and oxygen-18 data sets, the ability of the fully-distributed, physically-based CRUM3 model to represent the runoff processes in three sub-catchments in Cumbria, NW England has been evaluated. These catchments (Morland, Dacre and Pow) are part of the of the River Eden demonstration test catchment project. The oxygen-18 data set was firstly used to derive transit-time distributions and mean residence times of water for each of the catchments to gain an integrated overview of the types of processes that were operating. A generalised likelihood uncertainty estimation procedure was then used to calibrate the CRUM3 model for each catchment based on a single discharge data set from each catchment. Transit-time distributions and mean residence times of water obtained from the model using the top 100 behavioural parameter sets for each catchment were then compared to

  14. Short-term coral bleaching is not recorded by skeletal boron isotopes.

    PubMed

    Schoepf, Verena; McCulloch, Malcolm T; Warner, Mark E; Levas, Stephen J; Matsui, Yohei; Aschaffenburg, Matthew D; Grottoli, Andréa G

    2014-01-01

    Coral skeletal boron isotopes have been established as a proxy for seawater pH, yet it remains unclear if and how this proxy is affected by seawater temperature. Specifically, it has never been directly tested whether coral bleaching caused by high water temperatures influences coral boron isotopes. Here we report the results from a controlled bleaching experiment conducted on the Caribbean corals Porites divaricata, Porites astreoides, and Orbicella faveolata. Stable boron (δ11B), carbon (δ13C), oxygen (δ18O) isotopes, Sr/Ca, Mg/Ca, U/Ca, and Ba/Ca ratios, as well as chlorophyll a concentrations and calcification rates were measured on coral skeletal material corresponding to the period during and immediately after the elevated temperature treatment and again after 6 weeks of recovery on the reef. We show that under these conditions, coral bleaching did not affect the boron isotopic signature in any coral species tested, despite significant changes in coral physiology. This contradicts published findings from coral cores, where significant decreases in boron isotopes were interpreted as corresponding to times of known mass bleaching events. In contrast, δ13C and δ18O exhibited major enrichment corresponding to decreases in calcification rates associated with bleaching. Sr/Ca of bleached corals did not consistently record the 1.2°C difference in seawater temperature during the bleaching treatment, or alternatively show a consistent increase due to impaired photosynthesis and calcification. Mg/Ca, U/Ca, and Ba/Ca were affected by coral bleaching in some of the coral species, but the observed patterns could not be satisfactorily explained by temperature dependence or changes in coral physiology. This demonstrates that coral boron isotopes do not record short-term bleaching events, and therefore cannot be used as a proxy for past bleaching events. The robustness of coral boron isotopes to changes in coral physiology, however, suggests that reconstruction of

  15. Short-Term Coral Bleaching Is Not Recorded by Skeletal Boron Isotopes

    PubMed Central

    Schoepf, Verena; McCulloch, Malcolm T.; Warner, Mark E.; Levas, Stephen J.; Matsui, Yohei; Aschaffenburg, Matthew D.; Grottoli, Andréa G.

    2014-01-01

    Coral skeletal boron isotopes have been established as a proxy for seawater pH, yet it remains unclear if and how this proxy is affected by seawater temperature. Specifically, it has never been directly tested whether coral bleaching caused by high water temperatures influences coral boron isotopes. Here we report the results from a controlled bleaching experiment conducted on the Caribbean corals Porites divaricata, Porites astreoides, and Orbicella faveolata. Stable boron (δ11B), carbon (δ13C), oxygen (δ18O) isotopes, Sr/Ca, Mg/Ca, U/Ca, and Ba/Ca ratios, as well as chlorophyll a concentrations and calcification rates were measured on coral skeletal material corresponding to the period during and immediately after the elevated temperature treatment and again after 6 weeks of recovery on the reef. We show that under these conditions, coral bleaching did not affect the boron isotopic signature in any coral species tested, despite significant changes in coral physiology. This contradicts published findings from coral cores, where significant decreases in boron isotopes were interpreted as corresponding to times of known mass bleaching events. In contrast, δ13C and δ18O exhibited major enrichment corresponding to decreases in calcification rates associated with bleaching. Sr/Ca of bleached corals did not consistently record the 1.2°C difference in seawater temperature during the bleaching treatment, or alternatively show a consistent increase due to impaired photosynthesis and calcification. Mg/Ca, U/Ca, and Ba/Ca were affected by coral bleaching in some of the coral species, but the observed patterns could not be satisfactorily explained by temperature dependence or changes in coral physiology. This demonstrates that coral boron isotopes do not record short-term bleaching events, and therefore cannot be used as a proxy for past bleaching events. The robustness of coral boron isotopes to changes in coral physiology, however, suggests that reconstruction of

  16. Drought and flood signals in subtropical estuaries recorded by stable isotope ratios in bivalve shells

    NASA Astrophysics Data System (ADS)

    Walther, B. D.; Rowley, J. L.

    2013-11-01

    Isotope ratios of carbon and oxygen recorded in biogenic carbonates can be effective proxies for ambient conditions in estuaries including salinity and temperature. Together, they have the potential to allow periods of drought and flooding to be identified in subtropical estuaries that receive stochastic and aperiodic delivery of freshwater inflow. We investigated the ability of δ13C and δ18O values in shell increments from the eastern oyster Crassostrea virginica sampled from subtropical estuaries in the western Gulf of Mexico to indicate differences in temperature and salinity dynamics at fine spatial scales. Oyster shells at locations that experienced both hypersalinity during droughts and dramatic decreases in salinity during floods showed distinct variations in shell δ13C and δ18O values that reflected local salinity conditions. In contrast, oysters at sites where no major salinity fluctuation occurred showed only seasonal fluctuations in isotopes reflecting temperature and possibly feeding patterns. Further, similar isotopic patterns were observed across multiple individuals from each site. Our results show that δ13C and δ18O values in shells measured together provide a powerful method to identify droughts and floods in subtropical estuaries and therefore extend records of dynamic inflow to these stressed ecosystems.

  17. 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.

  18. Bioapatite Recrystallization During Burning and its Effects on Phosphate Stable Oxygen Isotope Composition

    NASA Astrophysics Data System (ADS)

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

    2003-04-01

    Stable oxygen isotopic compositions of phosphate from mammal bones are commonly used in palaeoenvironmental reconstructions. However, preservation of the primary bone oxygen isotopic composition is of concern during post-mortem alteration. Particularly in studies of archaeological interest, bone samples are often obtained from contexts where they have been heated, either in middens, or near hearths. Hence, in addition to alteration resulting from natural diagenetic processes, burning may also have contributed to modification of the primary oxygen isotopic signal. Various techniques can be employed to evaluate the degree of preservation of bone during burning. Anthropologists commonly use colour comparisons (Munsell Colour Chart) to assess the temperature of burning. Recrystallization of the carbonated hydroxyapatite, i.e., bioapatite, in bone is more rigorously assessed using X-ray diffraction and infra-red spectroscopy. In this study, 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, incrementally burned, colour-typed, ground to a standardized grain-size (45<63mm), and analysed using differential thermal analysis (DTA), thermogravimetric analysis (TGA), rotating anode X-ray diffraction (XRD), and Fourier transform infra-red spectroscopy (FTIR). Heating temperatures ranged from 25 to 900^oC, increasing in intervals of 25^oC. Two major stages of weight loss were recorded in the DTA/TGA data, 25-260^oC representing dehydration, and 270-600^oC reflecting incineration of organic matter. The end-product (900^oC) resembled pure hydroxyapatite. XRD patterns of the bioapatite remained virtually unchanged from 25-250^oC, after which peak intensity, sharpness and the XRD crystallinity index (XRD CI) increased from 0.80 at 250^oC to 1.26 at 900^oC. FTIR patterns showed analogous behaviour, demonstrating minimal fluctuations in the FTIR crystallinity

  19. Seasonally Resolved Oxygen Isotope Paleoclimate Proxy in Tree-Ring Cellulose from the Southeastern U.S.

    NASA Astrophysics Data System (ADS)

    Miller, D. L.; Mora, C. I.; Grissino-Mayer, H. D.; Mock, C. J.

    2004-12-01

    Stable isotopes in precipitation reflect changes in climate, moisture source, and extreme events such as tropical cyclones, and an oxygen isotope proxy record of these changes through time and space is preserved in tree-ring cellulose. Extreme climate events such as droughts and hurricanes are formidable natural disasters in the southeastern United States, and considerable efforts have been made to understand factors controlling their frequency, whether natural or anthropogenic. Tree rings offer an unusually well-resolved, dateable record of climate events extending beyond modern or historical (documentary) records. Oxygen isotopes in alpha-cellulose of shallowly-rooted conifers predominately reflect the composition of precipitation. Tropical storm convection results in marked 18O depletion in storm precipitation, to -15‰ relative to source seawater (~0‰ ). The depletion increases towards the eyewall of the cyclone, however, isotopically depleted precipitation may extend outward many 100's of km. Storm water 18O depletion translates to soil water 18O depletion that may persist for many weeks until ameliorated by soil water evaporation. Tree growth during that time will take up the anomalous isotopic compositions. Distinctive earlywood (EW ~March-June) versus latewood (LW ~July-October) growth allows the rings to be resolved at an intra-annual (seasonal) scale. By comparison to average soil water, droughts result in 18O-enriched soil water compositions. Seasonal drought or years of continued drought will be similarly captured in the isotope compositions of tree-ring cellulose. A 227-year (1770-1997) seasonally-resolved record of tropical cyclone and drought activity was obtained from cross-sections of felled slash pines (Pinus elliottii Engelm.) and remnant longleaf pines (Pinus palustris Mill.) from southern Georgia. Interpretations of drought or hurricane events were tested by comparison with recent, detailed meteorological records. The 227-year record reveals

  20. Tropical Cyclone Activity and Climate Fluctuations Captured by Oxygen Isotopes in Tree-Ring Cellulose From the Southeastern US

    NASA Astrophysics Data System (ADS)

    Miller, D. L.; Mora, C. I.; Grissino-Mayer, H. D.; Mock, C. J.; Uhle, M. E.

    2003-12-01

    Tropical cyclone activity in the Atlantic Ocean and Gulf of Mexico fluctuates on seasonal to century scales. Large climate oscillations, such as the El Nino Southern Oscillation, Atlantic Multidecadal Oscillation, and the Pacific Decadal Oscillation may affect this tropical cyclone activity. To better discern and understand factors influencing long-term trends in hurricane occurrence, proxies are needed that extend the record beyond historical documents. Tree rings preserve excellent records of climate that can be tracked on an intra-annual scale. Two trees in southern Georgia, slash and longleaf pine, were collected and dated using dendrochronological techniques and a 156- year record (1840-1997) was examined. The tree rings were processed to alpha cellulose, with intra-annual resolution, for examination of oxygen isotopes from both earlywood (EW) and latewood (LW) growing seasons. In the southeastern U.S., temperature variation across the growing season for slash and longleaf pines is modest (27-33° C) and oxygen isotope compositions largely reflect the composition of precipitation. Tropical cyclones produce precipitation that is significantly depleted in 18O compared to average seasonal rainfall and generally occur during the LW growing season. The relatively depleted oxygen isotope ratios are incorporated into LW cellulose and thus the annual ring set is marked by a large difference between EW and LW δ 18O values. For years without a significant event, EW-LW differences are expected to be nominal. The 156-year long tree-ring oxygen isotope record of major hurricane occurrence corresponds well with known tropical cyclone occurrence in the study area. The record also captures evidence of EW drought. The tropical cyclone record appears to be overprinted upon a much larger climate oscillation that is characterized by periods of relative separation (i.e., apart from the larger differences due to hurricanes) vs. coincidence of the EW/LW oxygen isotope compositions

  1. 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.

  2. Oxygen isotopes in refractory stratospheric dust particles - Proof of extraterrestial origin

    NASA Technical Reports Server (NTRS)

    Mckeegan, Kevin D.

    1987-01-01

    The oxygen and magnesium isotopic compositions of five individual particles that were collected from the stratosphere and that bear refractory minerals were measured by secondary ion mass spectrometry. Four of the particles exhibit excesses of oxygen-16 similar to those observed in anhydrous mineral phases of carbonaceous chondrites and thus are extraterrestrial. The oxygen and magnesium isotopic abundances of one corundum-rich particle are consistent with a terrestial origin. Magnesium in the four extraterrestrial particles is isotopically normal. It is unlikely that these particles are derived from carbonaceous chondrites and thus such particles probably represent a new type of collected extraterrestrial material.

  3. 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.

  4. Multiple oxygen and sulfur isotopic analyses on water-soluble sulfate in bulk atmospheric deposition from the southwestern United States

    USGS Publications Warehouse

    Bao, H.; Reheis, M.C.

    2003-01-01

    Sulfate is a major component of bulk atmospheric deposition (including dust, aerosol, fog, and rain). We analyzed sulfur and oxygen isotopic compositions of water-soluble sulfate from 40 sites where year-round dust traps collect bulk atmospheric deposition in the southwestern United States. Average sulfur and oxygen isotopic compositions (??34S and ??18O) are 5.8 ?? 1.4 (CDT) and 11.2 ?? 1.9 (SMOW) (n = 47), respectively. Samples have an oxygen 17 anomaly (?? 17O), with an average value of 1.0 ?? 0.6???. Except for a weak positive correlation between ??18O and ??17O values (r2 ??? 0.4), no correlation exists for ??18O versus ??34S, ?? 17O versus ??34S, or any of the three isotopic compositions versus elevation of the sample site. Exceptional positive ?? 17O values (up to 4.23???) are found in samples from sites in the vicinity of large cities or major highways, and near-zero ?? 17O values are found in samples close to dry lakes. Comparison of isotopic values of dust trap sulfate and desert varnish sulfate from the region reveals that varnish sulfate has average isotopic values that are ???4.8??? lower for ??18O, ???2.1??? higher for ??34S , and ???0.3??? lower for ?? 17O than those of the present-day bulk deposition sulfate. Although other factors could cause the disparity, this observation suggests a possibility that varnish sulfate may have recorded a long-term atmospheric sulfate deposition during the Holocene or Pleistocene, as well as the differences between sulfur and oxygen isotopic compositions of the preindustrial bulk deposition sulfate and those of the industrial era.

  5. 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.

  6. 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.

  7. 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.

  8. Uranium Isotope Evidence for Temporary Ocean Oxygenation Following the Sturtian Glaciation

    NASA Astrophysics Data System (ADS)

    Lau, K. V.; Maher, K.; Macdonald, F. A.; Payne, J.

    2015-12-01

    The link between widespread ocean oxygenation in the Neoproterozoic and the rise of animals has long been debated, largely because the timing and nature of oxygenation of the oceans remain poorly constrained. Strata deposited during the Cryogenian non-glacial interlude (660 to 635 Ma), between the Sturtian and Marinoan Snowball Earth glaciations, contain the earliest fossil evidence of animals. To quantitatively estimate patterns of seafloor oxygenation during this critical interval, we present uranium isotope (δ238U) data from limestone of the Taishir Formation (Fm) in Mongolia in two stratigraphic sections that are separated by ~75 km across the basin. The Taishir Fm hosts two large δ13C excursions that co-vary in total organic and inorganic (carbonate) carbon: a basal carbonate δ13C excursion to -4‰ in the Sturtian cap carbonate, followed by a rise to enriched values of +8‰, a second negative δ13C excursion to -7‰ referred to as the Taishir excursion, followed by a second rise to +10‰. Above the Sturtian glacial deposits, in the stratigraphic interval below the Taishir excursion, δ238U compositions have a mean value that is similar to that of modern seawater. After the Taishir excursion, the δ238U record exhibits a step decrease of ~0.3‰, and δ238U remains approximately constant until the erosional unconformity at the base of the Marinoan glacial deposits. We use a box model to constrain the uranium cycle behavior that best explains our observations. In the model, the best explanation for the less negative post-Sturtian values of δ238U is extensive oxygenation of the seafloor. Moreover, the model demonstrates that the higher δ238U values of the post-Sturtian limestones are inconsistent with an increased flux of uranium to the oceans due to post-Snowball weathering as the primary driver of the excursion. Thus, we favor a scenario in which there was a rise in oxygen levels following the Sturtian glaciation followed by a decrease in seafloor

  9. 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

  10. 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

  11. From snowball earth to the cambrian explosion: the interpretative potential of the isotope record

    NASA Astrophysics Data System (ADS)

    Shields, G.

    2003-04-01

    The interval in Earth history between 750 Ma and 530 Ma represents the erratic transition between the distinctly different "Earth systems" of the Proterozoic and the Phanerozoic. Geologists have developed several indirect methods to study this key interval but perhaps none with as much wanton enthusiasm as isotope geochemistry. Here I attempt a review of the isotope record across this key transition period, with special emphasis on the interpretative role that isotopes can play in understanding events such as the "Snowball Earth" glaciations and the "Cambrian Explosion". The marine isotope record reveals the Proterozoic-Phanerozoic transition to have been a unique period in Earth history with first-order features in all three of the major isotope proxies: 87Sr/86Sr, 34S/32S and 13C/12C ratios. Seawater 87Sr/86Sr, increased sharply between about 900 Ma and 500 Ma from 0.704 to 0.709, the largest rise ever. Although attributed to increasing rates of continental erosion, this remains only the most plausible explanation because few aspects of the rise have been satisfactorily linked to particular tectonic events. Much of the uncertainty surrounding the Proterozoic 87Sr/86Sr record is due to poor age dating and discrepancies in stratigraphic correlation schemes, which together with diagenetic alteration have led to the current inability to realise the potential of the 87Sr/86Sr record for global stratigraphic correlation. Carbon isotopes have played a key role in recent palaeoenvironmental interpretations of the Proterozoic-Phanerozoic transition, most of which have already been discarded or merely forgotten. Nevertheless, it is clear that the extraordinary δ13C values of the later Neoproterozoic (and the earliest Cambrian) demand extraordinary explanations, for which there is still much scope for future invention. Carbon isotopes may also play an important supporting role in correlation, however, the role that δ13C may play in global stratigraphic correlation has

  12. 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.

    PubMed

    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(18)O cellulose = 0.48 delta(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 (18)O in the form of O(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(2) of normal (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.

  13. 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 1

    PubMed Central

    Cooper, Lee W.; DeNiro, Michael J.

    1989-01-01

    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, δ18O cellulose = 0.48 δ18O water + 24.1%‰. 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 18O in the form of O2 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 O2 of normal 18O 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. PMID:16667066

  14. 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.

  15. A refined method for calculating paleotemperatures from linear correlations in bamboo coral carbon and oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Saenger, Casey; Watkins, James M.

    2016-06-01

    Bamboo corals represent an emerging paleoclimate archive with the potential to record variability at intermediate depths throughout much of the global ocean. Realizing this potential has been complicated by biologically mediated vital effects, which are evident in linear correlations of skeletal carbon (δ13C) and oxygen (δ18O) isotope composition. Previous efforts to develop a bamboo coral δ18O paleothermometer by accounting for such vital effects have not been completely successful as they still rely on empirical calibrations that are offset from the temperature dependence of abiogenic experiments. Here we describe an approach that better corrects for bamboo coral vital effects and allows paleotemperatures to be calculated directly from the abiogenic temperature dependence. The success of the method lies in calculating apparent equilibrium carbon and oxygen isotope fractionation at the temperature, pH, and growth rate of each coral, as well as in the use of model II regressions. Rigorous propagation of uncertainty suggests typical errors of ±2-3°C, but in select cases errors as low as ±0.65°C can be achieved for densely sampled and strongly correlated data sets. This lower limit approaches the value attributed to uncertainty in pH and growth rate estimates alone, as predicted by a series of pseudoproxy experiments. The incorporation of isotopically light metabolic CO2 appears to be negligible in most Pacific corals, but may be significant in Atlantic specimens, potentially requiring an additional correction. The success of the method therefore hinges on how well complex environmental systems and biomineralization strategies are constrained, with the most reliable temperatures occurring when calcifying fluid pH, growth rate, and incorporation of metabolic carbon into skeletal calcite are constrained using multiple geochemical proxies.

  16. Modern and Cenozoic records of seawater magnesium from foraminiferal Mg isotopes

    NASA Astrophysics Data System (ADS)

    Pogge von Strandmann, P. A. E.; Forshaw, J.; Schmidt, D. N.

    2014-09-01

    Magnesium is an element critically involved in the carbon cycle, because weathering of Ca-Mg silicates removes atmospheric CO2 into rivers, and formation of Ca-Mg carbonates in the oceans removes carbon from the ocean-atmosphere system. Hence the Mg cycle holds the potential to provide valuable insights into Cenozoic climate-system history, and the shift during this time from a greenhouse to icehouse state. We present Mg isotope ratios for the past 40 Myr using planktic foraminifers as an archive. Modern foraminifera, which discriminate against elemental and isotopically heavy Mg during calcification, show no correlation between the Mg isotope composition (δ26Mg, relative to DSM-3) and temperature, Mg / Ca or other parameters such as carbonate saturation (ΔCO3). However, inter-species isotopic differences imply that only well-calibrated single species should be used for reconstruction of past seawater. Seawater δ26Mg inferred from the foraminiferal record decreased from ~0‰ at 15 Ma, to -0.83‰ at the present day, which coincides with increases in seawater lithium and oxygen isotope ratios. It strongly suggests that neither Mg concentrations nor isotope ratios are at steady state in modern oceans, given its ~10 Myr residence time. From these data, we have developed a dynamic box model to understand and constrain changes in Mg sources to the oceans (rivers) and Mg sinks (dolomitisation and hydrothermal alteration). Our estimates of seawater Mg concentrations through time are similar to those independently determined by pore waters and fluid inclusions. Modelling suggests that dolomite formation and the riverine Mg flux are the primary controls on the δ26Mg of seawater, while hydrothermal Mg removal and the δ26Mg of rivers are more minor controls. Using Mg riverine flux and isotope ratios inferred from the 87Sr / 86Sr record, the modelled Mg removal by dolomite formation shows minima in the Oligocene and at the present day (with decreasing trends from 15 Ma

  17. Miocene to Pleistocene osmium isotopic records of the Mediterranean sediments

    NASA Astrophysics Data System (ADS)

    Kuroda, Junichiro; Jiménez-Espejo, Francisco J.; Nozaki, Tatsuo; Gennari, Rocco; Lugli, Stefano; Manzi, Vinicio; Roveri, Marco; Flecker, Rachel; Sierro, Francisco J.; Yoshimura, Toshihiro; Suzuki, Katsuhiko; Ohkouchi, Naohiko

    2016-01-01

    In the late Miocene the Mediterranean Sea experienced a salinity crisis and thick sequences of evaporites precipitated across the deep and marginal basins. In this study we report Os isotopic records from Deep Sea Drilling Project and Ocean Drilling Project cores in the Mediterranean: the Balearic Sea (Site 372), the Tyrrhenian Sea (Site 654), the Ionian Basin (Site 374), and the Florence Rise (Sites 375-376), as well as Integrated Ocean Drilling Project Site U1387 in Gulf of Cadiz, North Atlantic. Pliocene-Pleistocene sediments at all sites show 187Os/188Os values close to that of the coeval ocean water, indicating that the Mediterranean was connected to the North Atlantic. Evaporitic sediments deposited during the latest Miocene, however, have 187Os/188Os values significantly lower than coeval ocean water values. The offset of the Mediterranean evaporite 187Os/188Os is attributed to limited exchange with the North Atlantic during the Messinian salinity crisis. The source of unradiogenic Os is likely to be weathering of ultramafic rocks (ophiolites) cropping out in the Mediterranean's drainage basins. Based on a box model we estimated the amount of unradiogenic Os and the Atlantic-Mediterranean exchange rate to explain this offset. Os isotopic ratios of the pre-evaporite sediments in the western Mediterranean are almost identical to that of the coeval ocean water. In contrast, equivalent sediments from the Florence Rise have significantly lower 187Os/188Os values. The offset in the Os isotopic ratio on the Florence Rise is attributed either to limited water exchange between eastern and western Mediterranean or to local effects associated with exhumation of the Troodos ophiolites (Cyprus).

  18. 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

  19. 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

  20. Oxygen isotope composition as a tracer for the origins of rubies and sapphires

    NASA Astrophysics Data System (ADS)

    Giuliani, Gaston; Fallick, Anthony E.; Garnier, Virginie; France-Lanord, Christian; Ohnenstetter, Daniel; Schwarz, Dietmar

    2005-04-01

    Oxygen isotopic compositions of rubies and sapphires from 106 deposits worldwide, as well as heated natural corundum, have been measured in this study. Artificially heated corundums have the same oxygen isotopic composition as unheated material. The 18O/16O ratio of natural corundum is a good indicator of its geological environment of formation. The consistently restricted δ18O range found for each type of deposit is explained by host-rock buffering during fluid-rock interaction. The δ18O constrains the geological source of the major type of gem-quality rubies sold on the market and brings new insight to gems found in placers. High-quality blue sapphires from Kashmir, Andranondambo, and Sri Lanka have specific oxygen isotopic ranges, but they overlap those of Mogok in Myanmar. Combined with traditional gemology techniques, oxygen isotope analysis will contribute toward defining the origin of some commercial high-value blue sapphires, especially from Kashmir.

  1. Oxygen Isotope Analysis of a Genesis Solar Wind Concentrator Sample With MegaSIMS

    NASA Astrophysics Data System (ADS)

    Kallio, A. P.; McKeegan, K. D.; Mao, P. H.; Jarzebinski, G.; Coath, C. D.; Kunihiro, T.; Wiens, R. C.; Allton, J.; Callaway, M.; Rodriguez, M.; Burnett, D.

    2008-05-01

    The determination of the oxygen isotopic composition of the sun is the highest priority science objective of the GENESIS mission. We have performed the first oxygen isotopic analyses of the GENESIS solar wind concentrator sample #60001 using the UCLA MegaSIMS instrument. The MegaSIMS is a hybrid secondary ionisation and accelerator multicollector mass spectrometer. The problems of instrumental background, sample surface contamination (both adsorbed and particulate) and detector cross-talk can now be dealt with and we can measure consistently solar wind oxygen depth profiles. Our preliminary oxygen isotope data indicate that the solar wind sample is 16O enriched compared to terrestrial but the details of isotopic fractionation in the concentrator and in the solar wind itself have to be worked out before a value for the sun can be calculated.

  2. New Oxygen Isotope Measurements of Four Stardust Impact Crater Residues Show IDP-Like Compositions

    NASA Astrophysics Data System (ADS)

    Snead, C. J.; McKeegan, K. D.

    2015-07-01

    We have measured the oxygen isotope compositions of four Stardust impact crater residues. These analyses reveal compositions that are similar to those found in interplanetary dust particles, antarctic micrometeorites and CI chondrite components.

  3. Multidecadal climate variability in Brazil's Nordeste during the last 3000 years based on speleothem isotope records

    NASA Astrophysics Data System (ADS)

    Novello, Valdir F.; Cruz, Francisco W.; Karmann, Ivo; Burns, Stephen J.; Stríkis, Nicolás M.; Vuille, Mathias; Cheng, Hai; Lawrence Edwards, R.; Santos, Roberto V.; Frigo, Everton; Barreto, Eline A. S.

    2012-12-01

    We present the first high resolution, approximately ∼4 years sample spacing, precipitation record from northeastern Brazil (hereafter referred to as ‘Nordeste’) covering the last ∼3000 yrs from 230Th-dated stalagmites oxygen isotope records. Our record shows abrupt fluctuations in rainfall tied to variations in the intensity of the South American summer monsoon (SASM), including the periods corresponding to the Little Ice Age (LIA), the Medieval Climate Anomaly (MCA) and an event around 2800 yr B.P. Unlike other monsoon records in southern tropical South America, dry conditions prevailed during the LIA in the Nordeste. Our record suggests that the region is currently undergoing drought conditions that are unprecedented over the past 3 millennia, rivaled only by the LIA period. Using spectral, wavelet and cross-wavelet analyses we show that changes in SASM activity in the region are mainly associated with variations of the Atlantic Multidecadal Oscillation (AMO) and to a lesser degree caused by fluctuations in tropical Pacific SST. Our record also shows a distinct periodicity around 210 years, which has been linked to solar variability.

  4. Palaeoclimatology: the record for marine isotopic stage 11.

    PubMed

    Raynaud, Dominique; Barnola, Jean-Marc; Souchez, Roland; Lorrain, Reginald; Petit, Jean-Robert; Duval, Paul; Lipenkov, Vladimir Y

    2005-07-07

    The marine isotopic stage 11 (MIS 11) is an extraordinarily long interglacial period in the Earth's history that occurred some 400,000 years ago and lasted for about 30,000 years. During this period there were weak, astronomically induced changes in the distribution of solar energy reaching the Earth. The conditions of this orbital climate forcing are similar to those of today's interglacial period, and they rendered the climate susceptible to other forcing--for example, to changes in the level of atmospheric carbon dioxide. Here we use ice-core data from the Antarctic Vostok core to reconstruct a complete atmospheric carbon dioxide record for MIS 11. The record indicates that values for carbon dioxide throughout the interglacial period were close to the Earth's pre-industrial levels and that both solar energy and carbon dioxide may have helped to make MIS 11 exceptionally long. Anomalies in the oceanic carbonate system recorded in marine sediments at the time, for example while coral reefs were forming, apparently left no signature on atmospheric carbon dioxide concentrations.

  5. 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.

  6. Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria

    NASA Astrophysics Data System (ADS)

    Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.

    2012-04-01

    Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7

  7. Fifteen Years of Stable Oxygen, Hydrogen, and Carbon Isotopic Data from the Surface Waters in South Florida

    NASA Astrophysics Data System (ADS)

    Swart, P. K.; Price, R. M.

    2008-05-01

    The flow of water into the coastal zone of South Florida has been subject to significant anthropogenic modification over the past 100 years. Information on pre-anthropogenic conditions has been usually obtained from proxy indicators such as the oxygen isotope ratios contained in sedimentological archives such as corals and sediment cores. The current effort to restore water flows to historic conditions combined with a 10 year record of stable oxygen and hydrogen isotopic measurements from > 100 locations in the Everglades, Biscayne Bay, and the west coast and a > 15 year record from Florida Bay offers a unique opportunity to study the influence of changes in water management upon this proxy. Such information is important in assessing the veracity of previous oxygen isotopic interpretations as well as the influence of the restoration effort to influence water flows. Two of the significant findings are; 1) There has been a continual decline in the δ18O of the freshwater end-member reaching the western portion of Florida Bay suggesting a reduction a change in the hydrological status of this portion of Florida Bay; 2) there has been a decline in the δ13C of the dissolved inorganic carbon in all the coastal environments, which is ten times the rate of decline in the δ13C of the atmosphere originated from the burning of fossil fuel. These two examples suggest multiple influences upon the coastal ecosystem relating to anthropogenic activity.

  8. 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.

  9. 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...

  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. Predictions of oxygen isotope ratios in stars and of oxygen-rich interstellar grains in meteorites

    NASA Astrophysics Data System (ADS)

    Boothroyd, Arnold I.; Sackmann, I.-Juliana; Wasserburg, G. J.

    1994-07-01

    We carried out detailed, self-consistent calculations for stars from 1 to 9 solar mass over a wide range of metallicities, following the evolution and nucleosynthesis from the pre-main sequence to the asymptotic giant branch (AGB), in order to provide a self-consistent grid for evaluating stellar oxygen isotopic variations. These were calculated for first and second dredge-up, and for some masses also for third dredge-up and 'hot bottom' convective envelope burning on the AGB. We demonstrate that 0-16/0-17 in red giant envelopes is primarily a function of the star's mass, while 0-16/0-18 is primarily a function of the initial composition. Uncertainties in the 0-17-destruction rate have no effect on the 0-16/0-17 ratio for stars from 1 to 2.5 solar mass, but do affect the ratios for higher masses: the stellar 0-16/0-17 observations are consistent with the Landre et al. (1990) rates using f = 0.2 for 0-17(p,gamma) F-18 and -17(p. alpha) N-14, and with the Caughlan & Fowler (1988) rates using f approximately equals 1. The stellar 0-16/0-18 observations require f approximately equals 0 in the Caughlan & Fowler 0-18(p, alpha) N-15 rate. First dredge-up has the largest effect on the oxygen isotope ratios, decreasing 0-16/0-17 significantly from the initial value and increasing 0-16/0-18 slightly. Second and third dredge-up have only minor effects for solar metallicity stars. The absence of very low observed 0-16/0-18 ratios is consistent with a major increase in the 0-18(alpha, gamma) Ne-22 rate over the Caughlan & Fowler (1988) value. Hot bottom burning in stars above about 5 solar mass can cause a huge increase in 0-16/0-18 to approximately greater than 106, and possibly a significant decrease in 0-16/0-17; these are accompanied by a huge increase in Li-7 and a value of C-12/C-13 approximately = 3. The oxygen isotope ratios in the Al203 grains (Orgueil grain B, the Murchison 83-5 grain, and the new Bishunpur B39 grain) can be accounted for if they originated in stars

  13. Oxygen Isotope Mass-Balance Constraints on Pliocene Sea Level and East Antarctic Ice Sheet Stability

    NASA Astrophysics Data System (ADS)

    Winnick, M. J.; Caves, J. K.

    2015-12-01

    The mid-Pliocene Warm Period (MPWP, 3.3-2.9 Ma), with reconstructed atmospheric pCO2 of 350-450 ppm, represents a potential analogue for climate change in the near future. Current highly cited estimates place MPWP maximum global mean sea level (GMSL) at 21 ± 10 m above modern, requiring total loss of the Greenland (GIS) and marine West Antarctic Ice Sheets (WAIS) and a substantial loss of the East Antarctic Ice Sheet (EAIS), with only a concurrent 2-3 ºC rise in global temperature. Many estimates of Pliocene GMSL are based on the partitioning of oxygen isotope records from benthic foraminifera (δ18Ob) into changes in deep-sea temperatures and terrestrial ice sheets. These isotopic budgets are underpinned by the assumption that the δ18O of Antarctic ice (δ18Oi) was the same in the Pliocene as it is today, and while the sensitivity of δ18Ob to changing meltwater δ18O has been previously considered, these analyses neglect conservation of 18O/16O in the ocean-ice system. Using well-calibrated δ18O-temperature relationships for Antarctic precipitation along with estimates of Pliocene Antarctic surface temperatures, we argue that the δ18Oi of the Pliocene Antarctic ice sheet was at minimum 1‰-4‰ higher than present. Assuming conservation of 18O/16O in the ocean-ice system, this requires lower Pliocene seawater δ18O (δ18Osw) without a corresponding change in ice sheet mass. This effect alone accounts for 5%-20% of the δ18Ob difference between the MPWP interglacials and the modern. With this amended isotope budget, we suggest that Pliocene GMSL was likely 9-13.5 m and very likely 5-17 m above modern, which suggests the EAIS is less sensitive to radiative forcing than previously inferred from the geologic record.

  14. 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.

  15. Stable carbon and oxygen isotopes reveal Sahel drought events and ground water fluctuations in sub-Saharan Africa

    NASA Astrophysics Data System (ADS)

    Gebrekirstos, Aster

    2014-05-01

    Tree rings are important proxies for paleoclimate studies because they contain continuous historical records of inter-annual and intra-annual time resolutions, which range over hundreds of years. This study uses stable carbon and oxygen isotopes in tree rings to understand the drivers and impacts of climate change in sub-Saharan Africa and their ability to reconstruct past regional climate variability and climatic trends. Our approach considers large scale climate gradients and different temporal scales (inter-annual and intra-annual variations) and combines multi- parameter measurements (carbon and oxygen isotopes, whole wood and cellulose measurements). The study species are Faidherbia albida and Sclerocarya birrea from south and West Africa, respectively. Both are very important deciduous trees, and widely distributed in sub-Saharan Africa. Particularly, F. albida has a distinctive phenology; it bears leaves and flowers during the dry season and sheds its leaves during the rainy season. Stable carbon (δ13C) and oxygen (δ18O) mean values showed similar inter annual patterns. In general, both δ13C and δ18O show negative correlations with rainfall, humidity and PDSI. On the contrary, they are positively correlated with sunshine hours, maximum temperature and evaporation. The reverse phenology of Faidherbia and intra seasonal resolution measurements reveals seasonal ground water fluctuations. Both carbon and oxygen stable isotopes showed strong climatic signals including the long Sahel drought events and climatic recovery phases.

  16. Influence of diagenesis on the stable isotopic composition of biogenic carbonates from the Gulf of Tehuantepec oxygen minimum zone

    NASA Astrophysics Data System (ADS)

    Blanchet, C. L.; Kasten, S.; Vidal, L.; Poulton, S. W.; Ganeshram, R.; Thouveny, N.

    2012-04-01

    In order to evaluate the influence of diagenetic and post-sampling processes on the stable oxygen and carbon isotope compositions of biogenic carbonates, we conducted a multiproxy study of organic-rich sediments from the eastern Pacific oxygen minimum zone. Core MD02-2520, which was retrieved from the Gulf of Tehuantepec (Mexico), has seasonal laminations and covers the last 40 kyr. Together with the presence of gypsum crystals and inorganic calcite aggregates, the occurrence of large excursions in the stable oxygen and carbon isotope records of both planktonic and benthic foraminifera (as large as +3‰ in δ18O and -5‰ in δ13C) point to significant secondary transformations. Storage-related gypsum precipitation was ruled out since it implies sulfide reoxidation by oxygen that triggers biogenic calcite dissolution, which proved to be of minor importance here. Instead, precipitation of authigenic calcite during early diagenesis appears to be the most likely process responsible for the observed isotopic excursions. The δ13C composition for inorganic calcite aggregates (-5 to -7‰) suggests a major contribution from anaerobic oxidation of organic matter. The δ34S composition for gypsum crystals (-10 to +15‰) suggests a major contribution from anaerobic reoxidation of authigenic sulfides, potentially involving reactions with metal oxides and sulfur disproportionation. A minor part of the gypsum might possibly have formed as a result of local pore water salinity increases induced by gas hydrate formation.

  17. Baboons, water, and the ecology of oxygen stable isotopes in an arid hybrid zone.

    PubMed

    Moritz, Gillian L; Fourie, Nicolaas; Yeakel, Justin D; Phillips-Conroy, Jane E; Jolly, Clifford J; Koch, Paul L; Dominy, Nathaniel J

    2012-01-01

    Baboons regularly drink surface waters derived from atmospheric precipitation, or meteoric water. As a result, the oxygen isotope (δ(18)O) composition of their tissues is expected to reflect that of local meteoric waters. Animal proxies of the oxygen isotope composition of meteoric water have practical applications as paleoenvironmental recorders because they can be used to infer aridity and temperature in historic and fossil systems. To explore this premise, we measured the δ(18)O values of hair from two baboon species, Papio anubis and Papio hamadryas, inhabiting Awash National Park, Ethiopia. The hybridizing taxa differ in their ranging behavior and physiological response to heat. Papio hamadryas ranges more widely in the arid thornbush and is inferred to ingest a greater proportion of leaf water that is enriched in (18)O as a result of evaporative fractionation. It is also better able to conserve body water, which reduces its dependence on meteoric waters depleted in (18)O. Taken together, these factors would predict relatively higher δ(18)O values in the hair (δ(18)O(hair)) of P. hamadryas. We found that the δ(18)O(hair) values of P. hamadryas were higher than those of P. anubis, yet the magnitude of the difference was marginal. We attribute this result to a common source of drinking water, the Awash River, and the longer drinking bouts of P. hamadryas. Our findings suggest that differences in δ(18)O values among populations of Papio (modern or ancient) reflect different sources of drinking water (which might have ecological significance) and, further, that Papio has practical value as a paleoenvironmental recorder.

  18. Variations in triple isotope composition of dissolved oxygen and primary production in a subtropical reservoir

    NASA Astrophysics Data System (ADS)

    Jurikova, Hana; Guha, Tania; Abe, Osamu; Shiah, Fuh-Kwo; Wang, Chung-Ho; Liang, Mao-Chang

    2016-12-01

    Lakes and reservoirs play an important role in the carbon cycle, and therefore monitoring their metabolic rates is essential. The triple oxygen-isotope anomaly of dissolved O2 [17Δ = ln(1+δ17O) - 0.518 × ln(1 + δ18O)] offers a new, in situ, perspective on primary production, yet little is known about 17Δ from freshwater systems. We investigated the 17Δ together with the oxygen : argon ratio [Δ(O2 / Ar)] in the subtropical Feitsui Reservoir in Taiwan from June 2014 to July 2015. Here, we present the seasonal variations in 17Δ, GP (gross production), NP (net production) and the NP / GP (net to gross ratio) in association with environmental parameters. The 17Δ varied with depth and season, with values ranging between 26 and 205 per meg. The GP rates were observed to be higher (702 ± 107 mg C m-2 d-1) in winter than those (303 ± 66 mg C m-2 d-1) recorded during the summer. The overall averaged GP was 220 g C m-2 yr-1 and NP was -3 g C m-2 yr-1, implying the reservoir was net heterotrophic on an annual basis. This is due to negative NP rates from October to February (-198 ± 78 mg C m-2 d-1). Comparisons between GP rates obtained from the isotope mass balance approach and 14C bottle incubation method (14C-GP) showed consistent values on the same order of magnitude with a GP / 14C-GP ratio of 1.2 ± 1.1. Finally we noted that, although typhoon occurrences were scarce, higher than average 17Δ values and GP rates were recorded after typhoon events.

  19. Biochemical effects of salinity on oxygen isotope fractionation during cellulose synthesis.

    PubMed

    Ellsworth, Patricia V; Sternberg, Leonel S L

    2014-05-01

    The current isotope tree ring model assumes that 42% of the sucrose oxygen exchanges with stem water during cellulose synthesis and that the oxygen isotope biochemical fractionation is c. 27‰. However, previous studies have indicated that this model can overestimate the cellulose oxygen isotope ratio of plants under salinity or water stress. Saline stress increases soluble carbohydrates and osmolytes, which can alter exchange and biochemical fractionation during cellulose synthesis. To test the effect of salinity as well as the synthesis of osmolytes on exchange and biochemical fractionation, we grew wild-type and a transgenic mannitol synthesizer Arabidopsis thaliana hydroponically with fresh and saline water. We then measured the oxygen isotope ratios of leaf water, stem water and stem cellulose to determine the effects on exchange and biochemical fractionation. Biochemical fractionation did not change, but oxygen isotope exchange was twice as high for plants grown in saline water relative to freshwater-treated plants (0.64 and 0.3, respectively). Mannitol (osmolyte) synthesis did not affect exchange or biochemical fractionation regardless of salinity. Increases in salinity increased oxygen isotope exchange during cellulose synthesis, which may explain the overestimation of cellulose δ(18) O values under saline conditions.

  20. 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.

  1. 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

  2. Hydrogen Isotope Ratios of Leaf Waxes in C3 and C4 Grasses Record Meteoric Water and Aridity Signatures

    NASA Astrophysics Data System (ADS)

    Smith, F. A.; Freeman, K. H.; Ehleringer, J. R.; Helliker, B.

    2004-12-01

    Hydrogen isotope ratios of sedimentary n-alkanes (C27-C33) from vascular plants potentially provide a valuable record of past hydrologic conditions. To explore this, we analyzed grasses grown in a greenhouse and calculated fractionation factors (epsilon) between source water and n-alkane for each sample. An average difference of 21 permil is observed between C3 and C4 grasses, which is comparable to that determined for grasses collected from the Great Plains. The more positive isotope values in C4 grasses likely reflects smaller interveinal distance compared to C3 grass leaves, allowing greater back-diffusion of transpirationally enriched water from stomata, as documented with the oxygen isotope ratios of grass leaf water and cellulose by Helliker and Ehleringer (2000). The oxygen isotope difference is magnified at low relative humidity, when transpiration rates are higher. A similar effect is expected in hydrogen isotope ratios of leaf water and plant compounds. However, preliminary results from grasses grown hydroponically at different relative humidities suggest that there may be a decoupling of the hydrogen isotope ratio of leaf-wax n-alkanes and the oxygen isotope ratio of leaf water and cellulose. To examine the effects of source water delta D and climate on n-alkane delta D values, we analyzed grasses collected from the Great Plains. We use river water delta D values as a proxy for source water and the epsilon values determined in the greenhouse experiments, to predict expected values for C3 and C4 grass lipids. Measured values compare well to predicted values, with the exception of two semi-arid sites where evapotranspiration may have led to leaf-waters that are enriched in deuterium. Residual delta D values (measured-expected) correspond strongly with measures of aridity, such as annual precipitation and recipitation/evaporation ratios.

  3. Biosynthesis of gallic acid in Rhus typhina: discrimination between alternative pathways from natural oxygen isotope abundance.

    PubMed

    Werner, Roland A; Rossmann, Andreas; Schwarz, Christine; Bacher, Adelbert; Schmidt, Hanns-Ludwig; Eisenreich, Wolfgang

    2004-10-01

    The biosynthetic pathway of gallic acid in leaves of Rhus typhina is studied by oxygen isotope ratio mass spectrometry at natural oxygen isotope abundance. The observed delta18O-values of gallic acid indicate an 18O-enrichment of the phenolic oxygen atoms of more than 30 per thousand above that of the leaf water. This enrichment implies biogenetical equivalence with oxygen atoms of carbohydrates but not with oxygen atoms introduced by monooxygenase activation of molecular oxygen. It can be concluded that all phenolic oxygen atoms of gallic acid are retained from the carbohydrate-derived precursor 5-dehydroshikimate. This supports that gallic acid is synthesized entirely or predominantly by dehydrogenation of 5-dehydroshikimate.

  4. The geochemical record of the ancient nitrogen cycle, nitrogen isotopes, and metal cofactors.

    PubMed

    Godfrey, Linda V; Glass, Jennifer B

    2011-01-01

    The nitrogen (N) cycle is the only global biogeochemical cycle that is driven by biological functions involving the interaction of many microorganisms. The N cycle has evolved over geological time and its interaction with the oxygen cycle has had profound effects on the evolution and timing of Earth's atmosphere oxygenation (Falkowski and Godfrey, 2008). Almost every enzyme that microorganisms use to manipulate N contains redox-sensitive metals. Bioavailability of these metals has changed through time as a function of varying redox conditions, and likely influenced the biological underpinnings of the N cycle. It is possible to construct a record through geological time using N isotopes and metal concentrations in sediments to determine when the different stages of the N cycle evolved and the role metal availability played in the development of key enzymes. The same techniques are applicable to understanding the operation and changes in the N cycle through geological time. However, N and many of the redox-sensitive metals in some of their oxidation states are mobile and the isotopic composition or distribution can be altered by subsequent processes leading to erroneous conclusions. This chapter reviews the enzymology and metal cofactors of the N cycle and describes proper utilization of methods used to reconstruct evolution of the N cycle through time.

  5. 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.

  6. 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.

  7. 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.

  8. Stable oxygen and carbon isotope characteristics in speleothems from Southern Africa - how good are they?

    NASA Astrophysics Data System (ADS)

    Holmgren, K.

    2009-04-01

    Much remains to be understood about the interaction between the African climate system, its surrounding ocean-atmosphere climate variability and the global climate system. A better understanding of the regional climate evolution is crucial for understanding global climate dynamics and issues surrounding environmental change throughout Africa and a prerequisite for increasing climate forecasting capabilities for the region. As part of developing this understanding, a longer term perspective that reaches beyond the information available from instrumental records is required. Speleothems are frequently abundant in southern Africa. Quite a few records are now available, reporting significant changes in climate and environmental conditions over longer and shorter time scales. Conclusions are mainly based on the stable isotopic composition of the speleothems. The interpretation of the stable isotope data is, however, not always straight-forward, since many processes contribute to the observed signal in the speleothem and these processes may influence the signal differently at different spatial and temporal scales. For example was the Makapansgat speleothem oxygen isotope record, originally interpreted as being generally determined by shifts in atmospheric circulation pattern (Lee-Thorp et al. 2001, Holmgren et al. 2003), recently challenged and re-interpreted by Partin et al. (2008) to reflect annual rainfall amounts. Historically, less attention has been paid to the stable carbon isotope composition in speleothems. Today, an increasing number of studies demonstrate the potential of stable carbon variations as providing additional information on climate and environment. Measured variations can be a function of the amount of C3 versus C4 vegetation, vegetation cover and soil biological activity, bedrock proportion, rainfall amount and the drip rate. Clearly the multitudes of plausible processes behind the isotopic composition of speleothems in southern Africa (as well as

  9. 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

  10. 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

  11. Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method

    USGS Publications Warehouse

    Casciotti, K.L.; Sigman, D.M.; Hastings, M. Galanter; Böhlke, J.K.; Hilkert, A.

    2002-01-01

    We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate.1Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO3-), lack of interference by other solutes, and ease of sample preparation.

  12. Determining the nitrogen and oxygen isotope effects of microbial denitrification

    NASA Astrophysics Data System (ADS)

    Philp, C.; Martin, T. S.; Casciotti, K. L.

    2013-12-01

    The nitrogen cycle describes how nitrogen, a critical nutrient for life, moves throughout the ground, oceans, and atmosphere. An essential component of the nitrogen cycle is denitrification, in which bioavailable nitrogen is transformed into nitrous oxide and nitrogen gas and can no longer be harnessed by most organisms. We can further understand the importance of this nitrogen cycle process by examining the N and O isotope effects of microbial denitrification. We have cultured four denitrifying bacteria: P. stutzeri, P. putida, P. aureofaciens, and P. aeruginosa. After providing them with an initial amount of nitrite we tracked the rate at which each type of bacteria consumed the nitrite through a time series experiment. We then measured the N and O isotope ratios of the nitrite at each time point using a gas-source isotope ratio mass spectrometer. The subsequent isotope effects calculated using the Rayleigh equation provide an important tool for modeling denitrification in the environment.

  13. Carbon isotopic record of terrestrial ecosystems spanning the Late Miocene extinction of Oreopithecus bambolii, Baccinello Basin (Tuscany, Italy).

    PubMed

    Matson, Samuel D; Rook, Lorenzo; Oms, Oriol; Fox, David L

    2012-07-01

    Oreopithecus bambolii is a Late Miocene hominoid with an extensive fossil record in the Baccinello Basin (Tuscany, Italy), and was the only western European hominoid to survive a major extinction event ca. 9.6 Ma (millions of years ago). Oreopithecus lived in the insular Tusco-Sardinian paleobioprovince, where it evolved many unique anatomical specializations that make it important for understanding the mechanisms and history of Late Miocene hominoid evolution. The eventual extinction of Oreopithecus and its associated fauna ca. 6.5 Ma has generally been attributed to interaction with species that arrived from continental Europe following tectonic collision of the Tusco-Sardinian province with mainland Italy, but palynological, paleontological, and sedimentological records indicate an environmental shift toward more variable climate across the extinction event. To explore the possibility of environmental change as a contributing factor in the extinction of Oreopithecus, we developed a stable carbon and oxygen isotope record from organic matter in paleosols from the Baccinello Basin. These data show very low temporal and spatial variability (indicating plant ecosystem stability through time and space) and provide no evidence for ecologically significant changes in floral composition spanning the extinction event, suggesting that environmental change was not an underlying cause for the extinction of Oreopithecus and its associated fauna. The carbon isotope values fall entirely within the range of isotopic variability for modern plants following the C(3) photosynthetic pathway (trees, shrubs, cool-season grasses), indicating that C(4) vegetation (warm-season grasses) was not an important component of biomass. When corrected for temporal variation in the carbon isotopic composition of atmospheric carbon dioxide, the paleosol carbon isotope values are consistent with predicted values based on modern plants and the Baccinello palynoflora, supporting the reliability of

  14. 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.

  15. Mollusk-isotope records of Plio-Pleistocene marine paleoclimate, U. S. Middle Atlantic Coastal Plain

    SciTech Connect

    Krantz, D.E. )

    1990-08-01

    Stable oxygen and carbon isotope profiles from fossil scallop shells provide detailed paleoenvironmental information for the Pliocene and early Pleistocene of the Middle Atlantic Coastal Plain. Scallop specimens were collected from strata which represent at least five major marine transgressions. Minimum and maximum paleotemperatures were calculated from the {delta}{sup 18}O ranges recorded in each shell profile, after adjusting for changes in seawater {delta}{sup 18}O related to changes in global ice volume. Paleotemperature ranges from each stratigraphic unit were compared with modern conditions on the shelves of the Middle and South Atlantic Bight, and with paleotemperatures estimated by Hazel (1971b, 1988) from the ostracode faunas. The mollusk-isotope records indicate that the marine climate of the Atlantic Shelf was mild temperate during the deposition of the Sunken Meadow Member of the Yorktown Formation in the early Pliocene. The climate became warm temperate during the middle and late Pliocene transgressions which deposited the Rushmere, Morgarts Beach and Moore House Members of the Yorktown Formation and the Chowan River Formation. During the deposition of the James City Formation in the early Pleistocene, temperatures returned to a mild temperate climate similar to that of the modern Virginia Bight shelf. The character of the isotope profiles indicates that hydrographic conditions were generally stable and similar to those of the modern Middle Atlantic Bight. The {delta}{sup 13}C profiles of most of the shells show trends suggestive of spring phytoplankton blooms and summer water-column stratification. Anomalies in several profiles are interpreted as reduced salinity events, probably related to river discharge, which most commonly occur in the spring. There is no convincing evidence in the shell profiles for upwelling.

  16. Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record

    PubMed Central

    Leavitt, William D.; Halevy, Itay; Bradley, Alexander S.; Johnston, David T.

    2013-01-01

    Phanerozoic levels of atmospheric oxygen relate to the burial histories of organic carbon and pyrite sulfur. The sulfur cycle remains poorly constrained, however, leading to concomitant uncertainties in O2 budgets. Here we present experiments linking the magnitude of fractionations of the multiple sulfur isotopes to the rate of microbial sulfate reduction. The data demonstrate that such fractionations are controlled by the availability of electron donor (organic matter), rather than by the concentration of electron acceptor (sulfate), an environmental constraint that varies among sedimentary burial environments. By coupling these results with a sediment biogeochemical model of pyrite burial, we find a strong relationship between observed sulfur isotope fractionations over the last 200 Ma and the areal extent of shallow seafloor environments. We interpret this as a global dependency of the rate of microbial sulfate reduction on the availability of organic-rich sea-floor settings. However, fractionation during the early/mid-Paleozoic fails to correlate with shelf area. We suggest that this decoupling reflects a shallower paleoredox boundary, primarily confined to the water column in the early Phanerozoic. The transition between these two states begins during the Carboniferous and concludes approximately around the Triassic–Jurassic boundary, indicating a prolonged response to a Carboniferous rise in O2. Together, these results lay the foundation for decoupling changes in sulfate reduction rates from the global average record of pyrite burial, highlighting how the local nature of sedimentary processes affects global records. This distinction greatly refines our understanding of the S cycle and its relationship to the history of atmospheric oxygen. PMID:23733944

  17. Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record.

    PubMed

    Leavitt, William D; Halevy, Itay; Bradley, Alexander S; Johnston, David T

    2013-07-09

    Phanerozoic levels of atmospheric oxygen relate to the burial histories of organic carbon and pyrite sulfur. The sulfur cycle remains poorly constrained, however, leading to concomitant uncertainties in O2 budgets. Here we present experiments linking the magnitude of fractionations of the multiple sulfur isotopes to the rate of microbial sulfate reduction. The data demonstrate that such fractionations are controlled by the availability of electron donor (organic matter), rather than by the concentration of electron acceptor (sulfate), an environmental constraint that varies among sedimentary burial environments. By coupling these results with a sediment biogeochemical model of pyrite burial, we find a strong relationship between observed sulfur isotope fractionations over the last 200 Ma and the areal extent of shallow seafloor environments. We interpret this as a global dependency of the rate of microbial sulfate reduction on the availability of organic-rich sea-floor settings. However, fractionation during the early/mid-Paleozoic fails to correlate with shelf area. We suggest that this decoupling reflects a shallower paleoredox boundary, primarily confined to the water column in the early Phanerozoic. The transition between these two states begins during the Carboniferous and concludes approximately around the Triassic-Jurassic boundary, indicating a prolonged response to a Carboniferous rise in O2. Together, these results lay the foundation for decoupling changes in sulfate reduction rates from the global average record of pyrite burial, highlighting how the local nature of sedimentary processes affects global records. This distinction greatly refines our understanding of the S cycle and its relationship to the history of atmospheric oxygen.

  18. 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.

  19. 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.

  20. 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.

  1. A molecular organic carbon isotope record of miocene climate changes

    SciTech Connect

    Schoell, M. ); Schouten, S.; Sinninghe Damste', J.S.; Leeuw, J.W. de ); Summons, R.E. )

    1994-02-25

    The difference in carbon-13 ([sup 13]C) contents of hopane and sterane biomarkers in the Monterey formation (Naples Beach, California) parallels the Miocene inorganic record of the change in [sup 18]O ([delta][sup 18]O), reflecting the Miocene evolution from a well-mixed to a highly stratified photic zone (upper 100 meters) in the Pacific. Steranes ([delta][sup 13]C = 25.4 [+-] 0.7 per mil versus the Pee Dee belemnite standard) from shallow photic-zone organisms do not change isotopically throughout the Miocene. In contrast, sulfur-bound C[sub 35] hopanes (likely derived from bacterial plankton living at the base of the photic zone) have systematically decreasing [sup 13]C concentrations in Middle and Late Miocene samples ([delta][sup 13]C = 29.5 to [minus]31.5 per mil), consistent with the Middle Miocene formation of a carbon dioxide-rich cold water mass at the base of the photic zone.

  2. Drought signals in tree-ring stable oxygen isotope series of Qilian juniper from the arid northeastern Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Qin, Chun; Yang, Bao; Bräuning, Achim; Grießinger, Jussi; Wernicke, Jakob

    2015-02-01

    For the mechanistic understanding of hydroclimate variability, stable oxygen isotopic ratios (δ18O) of tree-ring α-cellulose can play a key role in paleoclimatic research. On the north-east Tibetan Plateau (TP), a region particularly sensitive to climate change, there exists a distinct lack of δ18O research in tree-ring archives. The few currently existing tree-ring δ18O chronologies were obtained by pooling the wood material from the same year from different trees prior to preparation and analysis. Although this method is time and cost efficient, it might impede the analysis of changes within the internal variability of oxygen isotope signals and a deeper understanding of the resulting climate reconstruction. We selected five Qilian juniper (Sabina przewalskii Kom.) trees covering the period 1951-2011 on the north-east TP to investigate the climate signals contained in stable oxygen isotopic composition records obtained using single tree analysis. Although the inter-series correlation between the five individual δ18O series indicates a highly significant relationship (mean r = 0.59, n = 59, p = 0.01), the five individual δ18O series show significantly differently mean values. We found significant negative correlations between drought/hydroclimatically triggered climate parameters (PDSI, precipitation) and each of the individual δ18O series. Spatial correlation maps indicate negative correlation of tree-ring δ18O and Indian Ocean sea surface temperatures, and inverse correlation patters of moisture conditions on the northern and southern TP. Our results provide a reference for future research on stable oxygen isotope/climate signals in the species S. przewalskii Kom..

  3. 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.

  4. Positive precipitation-evaporation budget from AD 460 to 1090 in the Saloum Delta (Senegal) indicated by mollusk oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Azzoug, Moufok; Carré, Matthieu; Chase, Brian M.; Deme, Abdoulaye; Lazar, Alban; Lazareth, Claire E.; Schauer, Andrew J.; Mandeng-Yogo, Magloire; Simier, Monique; Thierno-Gaye, Amadou; de Morais, Luis Tito

    2012-12-01

    There is a critical need to document the long-term variability of the West African Monsoon (WAM) in the Sahel region. We present here a multidecadal proxy record of the past hydrology from AD 460 to 1090 in the Saloum Delta, Senegal. The Saloum Delta is a hypersaline estuary where the salinity and the water isotopic composition are highly sensitive to rainfall variations. The past hydrology was studied using the oxygen isotopic ratio of Anadara senilis fossil shells, since mollusk shell isotopic composition (δ18O) in this environment is primarily determined by the precipitation-evaporation budget. Successive samples of shells were taken along the stratigraphy of the massive Dioron Boumak fossil shell middens for new insights into the past WAM multi-decadal to centennial variability. The averaged δ18O value of fossil shells was more negative by 1.4‰ compared to modern shells' isotopic signature. This result indicates substantially fresher mean conditions in the Saloum Delta, that was likely not hypersaline as it is today. The precipitation-evaporation budget was thus more positive in response to a more intense and/or longer monsoon season during the studied period. Our record suggests that strong multidecadal droughts as observed in the Sahel in the late 20th century did likely not occur in Senegal during this ~ 600-yr time period.

  5. 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

  6. Oxygen and Chlorine Isotopic Fractionation During Microbial Reduction of Perchlorate

    NASA Astrophysics Data System (ADS)

    Beloso, A. D.; Sturchio, N. C.; Böhlke, J. K.; Streger, S. H.; Heraty, L. J.; Hatzinger, P. B.

    2006-12-01

    Perchlorate is a widespread environmental contaminant that has both anthropogenic and natural sources. Stable isotope ratios of O and Cl in perchlorate have been used recently to distinguish perchlorate of different origins. Isotopic ratios may also be useful for identifying the occurrence and extent of biodegradation of perchlorate in natural environments, information that is critical for assessing natural attenuation of this contaminant. For this approach to be useful, however, the extent of isotopic fractionation of both Cl and O by bacteria must be determined, and the influence of environmental variables on this process must be defined. During this laboratory study, the O and Cl isotope ratios of perchlorate were monitored as a function of degradation by two separate bacterial species (Azospira suillum JPLRND and Dechlorospirillum sp. FBR2) at both 10 °C and 22 °C with acetate as the electron donor. Perchlorate was completely degraded by both strains within 280 hr at 22 °C and 615 hr at 10 °C. Measured values of isotopic fractionation factors were ɛ18O = -36.6 to -29.0 ‰ and ɛ37Cl = -14.5 to - 11.5 ‰, and these showed no apparent systematic variation with either temperature or bacterial strain. One experiment using 18O-enriched water (δ18O = 200‰) gave results indistinguishable from those observed in isotopically normal water, indicating little or no isotopic exchange between perchlorate and water during biodegradation. The fractionation factor ratio ɛ18O/ɛ37Cl was nearly invariant in all experiments at 2.50 ± 0.04. These data indicate that isotopic analysis will be useful for documenting perchlorate biodegradation in soils and groundwater. The establishment of a microbial fractionation factor ratio (ɛ18O/ɛ37Cl) also has significance for forensic studies, as these data indicate that fractionation via biodegradation will not cause the reported mass-dependent Cl and O isotopic signatures of synthetic and natural perchlorate to overlap.

  7. Validation of Chlorine and Oxygen Isotope Ratio Analysis to Differentiate Perchlorate Sources and to Document Perchlorate Biodegradation

    DTIC Science & Technology

    2011-12-01

    Guidance Document Validation of Chlorine and Oxygen Isotope Ratio Analysis To Differentiate Perchlorate Sources and to Document Perchlorate...Manual for Forensic Analysis of Perchlorate in Grotmdwater using W912-HQ-0 5-C-0022 Chlorine and Oxygen Isotopic Analyses 5b. GRANT NUMBER NA 5c...natural. Chlorine and oxygen isotopic analyses of perchlorate provide the primaty direct approach whereby different sources of perchlorate can be

  8. 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

  9. Latitudinal variations of nitrogen and triple oxygen isotopic composition of nitrate in the marine boundary layer over the Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Morin, S.; Frey, M. M.; Grudzieu, A.; Martins, J.; Savarino, J.

    2007-12-01

    The analysis of the isotopic composition of nitrate (NO3-) in various environments is a fast-growing field of investigation. Atmospheric nitrate oxygen isotopes feature the appealing potential to record a footprint of the cycling between ozone (O3) and nitrogen oxides (NOx), through the transmission of an isotope anomaly (Δ17O=δ17O - 0.52 ×~δ18O) borne by the ozone molecule. This discovery has lead to the idea that the isotopic composition of nitrate preserved in firn and ice of the polar ice caps could be used as a proxy of past ozone chemistry and thus provide the long-awaited link between the climate record from ice cores and the oxidative capacity of ancient atmospheres. To better constrain the relationships between nitrate oxygen isotopes and the oxidative state of the atmosphere, we have carried out a series of ship-borne measurements in the marine boundary layer (MBL) between Cape Town, Rep. South Africa (30°S) and Bremerhaven, Germany (50°N) covering a wide range of meteorological and atmospheric chemistry conditions. Onboard the R/V Polarstern, we measured surface ozone and collected size-segregated aerosols with a latitudinal resolution of 4°. Besides major ions concentrations, nitrate contained in these samples was analyzed for all stable isotopes of its constituents (namely δ15N, δ17O and δ18O), using the denitrifier technique (based on Kaiser et al., Anal. Chem., 2007), thus providing an unprecedented latitudinal profile of nitrate isotopes in the MBL. Variations of nitrate isotopic compositions are studied as a function of particle size and changing MBL background chemistry, ranging from the remote and unpolluted Southern Atlantic Ocean (O3 20 nmol~mol-1) to the polluted English Channel area (O3 45 nmol~mol-1), through air masses influenced by North-African desert dust in the subtropical North Atlantic. Known main chemical mechanisms responsible for the formation of atmospheric nitrate are used to test our understanding of the causes for the

  10. 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.

  11. 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

  12. Determination of fractionation of oxygen isotopes between rice grain and environmental water

    NASA Astrophysics Data System (ADS)

    Kaushal, R.; Ghosh, P.

    2013-12-01

    Oxygen isotopic composition (δ18O) of plant organic matter (POM) serves as a valuable proxy for paleoclimatic studies [1].The δ18O of POM emulates the isotopic composition of the source water [2]. Rice crop cultivation goes back to 12,000 years, when rice was first domesticated in China and the earliest cultivation of rice observed in India was during 3000- 2500 BC. Presently rice is cultivated in many countries around the world including India where the prerequisite of saturated soil water condition for optimum growth of rice crop is provided by the South west monsoons. Earlier studies on δ18O of rice have been limited to its geographic characterization [3]. However, detailed investigations to determine fractionation of oxygen isotopes in water, in different parts of a rice plant, with rice seed organic matter is the primary objective of this work. This is important for understanding the mechanism responsible for the transfer of source water signature to the seed organics and can facilitate understanding of past monsoonal regime using well preserved rice grain remains from archaeological sites. Water from the leaves and culms was extracted by means of heating and cryogenic distillation in a vacuum extraction system [4]. The source water and the water extracted from plant parts were analysed by CO2 equilibration method using Gas Bench peripheral. Rice seed powder, after removal of husk, is composed primarily of starch and were analysed using High Temperature Conversion-Elemental Analyser. Both these peripherals were coupled to an Isotope Ratio Mass spectrometer- MAT253 (Thermo Finnigan). Experimental results discussed here were based on greenhouse and field based studies of water and seed organic composition. The water fed to the plant in the green house showed an average δ18O value of -0.50‰ whereas the field water from irrigation covering the time of grain filling ranges between -1.03‰ and -3.08‰. Figure 1 displays the extent of enrichment recorded in

  13. 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.

  14. Oxygen and strontium isotope tracing of human migration at the Bell Beaker site Le Tumulus des Sables, France.

    NASA Astrophysics Data System (ADS)

    Willmes, Malte; James, Hannah; Boel, Ceridwen; Courtaud, Patrice; Chancerel, Antoine; McMorrow, Linda; Armstrong, Richard; Kinsley, Les; Aubert, Maxime; Eggins, Stephen; Moffat, Ian; Grün, Rainer

    2014-05-01

    Oxygen (δ18O) and strontium (87Sr/86Sr) isotopes were used as tools to investigate human migration at the early Bell Beaker site (2500-2000 BC) Le Tumulus des Sables, Saint-Laurent-Médoc, south-west France. The O and Sr isotope ratios measured in tooth enamel record the average dietary isotope signature ingested by that individual during their childhood. When this data is compared to the isotope signature of the burial site it can be used to indicate if the individual migrated into this area during their lifetime. The O isotopic composition of meteoric water changes depending on climate, temperature and quantity of precipitation. O isotope ratios in skeletal and dental remains are related to body water, which in turn is influenced by diet, physiology and climate. Most of the water consumed by large mammals comes from drinking water, typically sourced locally. Sr isotope ratios on the other hand vary between different geologic regions, depending on their age and composition. Sr is released through weathering and transported into the soil, ground and surface water, where it becomes available for uptake by plants, enters the food cycle and eventually ends up in skeletal and dental tissue where it substitutes for calcium. We analysed the teeth of 18 adult and 8 juvenile disarticulated skeletons from Le Tumulus des Sables. O isotopes were analysed in-situ by Sensitive High Resolution Ion Micro Probe (SHRIMP).The Sr isotope analysis involved drilling a 0.2-0.5 mg sample of enamel from the tooth. The Sr was then chemically separated and analysed by Thermal Ionization Mass Spectrometry (TIMS). These results were then compared to the O isoscape of Europe and bioavailable Sr isotope data (fauna, plants, soils) from the IRHUM database. We found that most of the individuals at Le Tumulus des Sables show O and Sr isotope ratios corresponding to the local environmental signal and we interpret these as part of the local population. 3 adults however show slightly higher 87Sr/86

  15. Atmospheric record in the Hadean Eon from multiple sulfur isotope measurements in Nuvvuagittuq Greenstone Belt (Nunavik, Quebec)

    PubMed Central

    Thomassot, Emilie; O’Neil, Jonathan; Francis, Don; Cartigny, Pierre; Wing, Boswell A.

    2015-01-01

    Mass-independent fractionation of sulfur isotopes (S-MIF) results from photochemical reactions involving short-wavelength UV light. The presence of these anomalies in Archean sediments [(4–2.5 billion years ago, (Ga)] implies that the early atmosphere was free of the appropriate UV absorbers, of which ozone is the most important in the modern atmosphere. Consequently, S-MIF is considered some of the strongest evidence for the lack of free atmospheric oxygen before 2.4 Ga. Although temporal variations in the S-MIF record are thought to depend on changes in the abundances of gas and aerosol species, our limited understanding of photochemical mechanisms complicates interpretation of the S-MIF record in terms of atmospheric composition. Multiple sulfur isotope compositions (δ33S, δ34S, and δ36S) of the >3.8 billion-year-old Nuvvuagittuq Greenstone Belt (Ungava peninsula) have been investigated to track the early origins of S-MIF. Anomalous S-isotope compositions (Δ33S up to +2.2‰) confirm a sedimentary origin of sulfide-bearing banded iron and silica-rich formations. Sharp isotopic transitions across sedimentary/igneous lithological boundaries indicate that primary surficial S-isotope compositions have been preserved despite a complicated metamorphic history. Furthermore, Nuvvuagittuq metasediments recorded coupled variations in 33S/32S, 34S/32S, and 36S/32S that are statistically indistinguishable from those identified several times later in the Archean. The recurrence of the same S-isotope pattern at both ends of the Archean Eon is unexpected, given the complex atmospheric, geological, and biological pathways involved in producing and preserving this fractionation. It implies that, within 0.8 billion years of Earth’s formation, a common mechanism for S-MIF production was established in the atmosphere. PMID:25561552

  16. Atmospheric record in the Hadean Eon from multiple sulfur isotope measurements in Nuvvuagittuq Greenstone Belt (Nunavik, Quebec).

    PubMed

    Thomassot, Emilie; O'Neil, Jonathan; Francis, Don; Cartigny, Pierre; Wing, Boswell A

    2015-01-20

    Mass-independent fractionation of sulfur isotopes (S-MIF) results from photochemical reactions involving short-wavelength UV light. The presence of these anomalies in Archean sediments [(4-2.5 billion years ago, (Ga)] implies that the early atmosphere was free of the appropriate UV absorbers, of which ozone is the most important in the modern atmosphere. Consequently, S-MIF is considered some of the strongest evidence for the lack of free atmospheric oxygen before 2.4 Ga. Although temporal variations in the S-MIF record are thought to depend on changes in the abundances of gas and aerosol species, our limited understanding of photochemical mechanisms complicates interpretation of the S-MIF record in terms of atmospheric composition. Multiple sulfur isotope compositions (δ(33)S, δ(34)S, and δ(36)S) of the >3.8 billion-year-old Nuvvuagittuq Greenstone Belt (Ungava peninsula) have been investigated to track the early origins of S-MIF. Anomalous S-isotope compositions (Δ(33)S up to +2.2‰) confirm a sedimentary origin of sulfide-bearing banded iron and silica-rich formations. Sharp isotopic transitions across sedimentary/igneous lithological boundaries indicate that primary surficial S-isotope compositions have been preserved despite a complicated metamorphic history. Furthermore, Nuvvuagittuq metasediments recorded coupled variations in (33)S/(32)S, (34)S/(32)S, and (36)S/(32)S that are statistically indistinguishable from those identified several times later in the Archean. The recurrence of the same S-isotope pattern at both ends of the Archean Eon is unexpected, given the complex atmospheric, geological, and biological pathways involved in producing and preserving this fractionation. It implies that, within 0.8 billion years of Earth's formation, a common mechanism for S-MIF production was established in the atmosphere.

  17. 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

  18. Biomarker and molecular isotope approaches to deconvolve the terrestrial carbon isotope record: modern and Eocene calibrations

    NASA Astrophysics Data System (ADS)

    Diefendorf, A. F.; Freeman, K. H.; Wing, S.; Currano, E. D.

    2010-12-01

    Climate, biome, and plant community are important predictors of carbon isotope patterns recorded in leaves and leaf waxes. However, signatures recorded by terrestrial organic carbon and lipids that have mixed floral sources (e.g., n-alkanes) potentially reflect both plant community changes and climate. More taxonomically specific proxies for plants (i.e., di- and tri-terpenoids for conifers and angiosperms, respectively), can help to resolve the relative influences of changing community and climate, provided differences in biomarker production and lipid biosynthetic fractionation among plants can be better constrained. We present biomarker abundance and carbon isotope values for lipids from leaves, branches and bark of 44 tree species, representing 21 families including deciduous and evergreen conifers and angiosperms. n-alkane production differs greatly between conifer and angiosperm leaves. Both deciduous and evergreen angiosperms make significantly more n-alkanes than conifers, with n-alkanes not detected in over half of the conifers in our study. Terpenoid abundances scale strongly with leaf habit: evergreen species have significantly higher abundances. We combine these relative differences in lipid production with published estimates of fluxes for leaf litter from conifer and angiosperm trees to develop a new proxy approach for estimating paleo plant community inputs to ancient soils and sediments. To test our modern calibration results, we have evaluated n-alkanes and terpenoids from laterally extensive (~18 km) carbonaceous shales and mudstones in Eocene sediments (52.6 Ma) at Fifteenmile Creek in the Bighorn Basin (WY, USA). Our terpenoid-based proxy predicts on average a 40% conifer community, which is remarkably close in agreement with a fossil-based estimate of 36%. n-alkane carbon isotope fractionation (leaf-lipid) differs among plant types, with conifer n-alkanes about 2-3‰ 13C enriched relative to those in angiosperms. Since conifer leaves are

  19. Astronomical calibration and global correlation of the Santonian (Cretaceous) based on the marine carbon isotope record

    NASA Astrophysics Data System (ADS)

    Thibault, N.; Jarvis, I.; Voigt, S.; Gale, A. S.; Attree, K.; Jenkyns, H. C.

    2016-06-01

    High-resolution records of bulk carbonate carbon isotopes have been generated for the Upper Coniacian to Lower Campanian interval of the sections at Seaford Head (southern England) and Bottaccione (central Italy). An unambiguous stratigraphic correlation is presented for the base and top of the Santonian between the Boreal and Tethyan realms. Orbital forcing of carbon and oxygen isotopes at Seaford Head points to the Boreal Santonian spanning five 405 kyr cycles (Sa1 to Sa5). Correlation of the Seaford Head time scale to that of the Niobrara Formation (Western Interior Basin) permits anchoring these records to the La2011 astronomical solution at the Santonian-Campanian (Sa/Ca) boundary, which has been recently dated to 84.19 ± 0.38 Ma. Among the five tuning options examined, option 2 places the Sa/Ca at the 84.2 Ma 405 kyr insolation minimum and appears as the most likely. This solution indicates that minima of the 405 kyr filtered output of the resistivity in the Niobrara Formation correlate to 405 kyr insolation minima in the astronomical solution and to maxima in the filtered δ13C of Seaford Head. We suggest that variance in δ13C is driven by climate forcing of the proportions of CaCO3 versus organic carbon burial on land and in oceanic basins. The astronomical calibration generates a 200 kyr mismatch of the Coniacian-Santonian boundary age between the Boreal Realm in Europe and the Western Interior, due either to diachronism of the lowest occurrence of the inoceramid Cladoceramus undulatoplicatus between the two regions or to remaining uncertainties of radiometric dating and cyclostratigraphic records.

  20. 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. "

  1. 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.

  2. Oxygen isotope variability within Nautilus shell growth bands

    SciTech Connect

    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 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. 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

  3. 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.

  4. 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.

  5. 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.

  6. Carbon and oxygen isotopes of Maastrichtian Danian shallow marine carbonates: Yacoraite Formation, northwestern Argentina

    NASA Astrophysics Data System (ADS)

    Marquillas, Rosa; Sabino, Ignacio; Nobrega Sial, Alcides; Papa, Cecilia del; Ferreira, Valderez; Matthews, Stephen

    2007-04-01

    The Maastrichtian-Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ 13C, +2‰ δ 18O). The top of the member reveals an isotopic shift of δ 13C (-5‰) and δ 18O (-10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (-2‰ δ 13C, -1‰ δ 18O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si-Mn-Fe-Na, low Ca-Mg-Sr). These isotopic and lithological changes relate to the Cretaceous-Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.

  7. 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

  8. 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.

  9. The influence of climate on the oxygen isotopes in tree rings.

    PubMed

    Saurer, M

    2003-06-01

    Natural variations in the oxygen isotope ratio 18O/16O are occurring in the hydrological cycle as a result of isotope fractionations during evaporation and condensation. These processes imprint a valuable climatic signal in the precipitation, which is stored in ice caps as well as in the cellulose of trees. Recent developments in the continuous-flow analysis of 18O/16O of organic matter now enable a systematic application of this method in tree rings. It becomes possible to build maps of the past oxygen isotope distribution in continental areas, yielding important information on regional climate changes. In this paper, the factors influencing the isotope composition of tree rings are discussed with an example from trees in northern Eurasia. Oxygen isotope values of Larix, Picea and Pinus trees were measured over a large climatic gradient extending from Norway to Siberia. The spatial isotope variations were highly correlated to the annual mean temperature (r2 = 0.84), whereby the slope of the corresponding regression line was 0.35%/degrees C. When considering the changes in 18O/16O during the 20th century, not only the temperature, but also changes in the precipitation patterns have to be considered, in particular the observed increase in the amount of winter precipitation.

  10. 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.

  11. 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).

  12. 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.

  13. 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

  14. Astronomical calibration of the Boreal Santonian (Cretaceous) based on the marine carbon isotope record and correlation to the tropical realm

    NASA Astrophysics Data System (ADS)

    Thibault, Nicolas; Jarvis, Ian; Voigt, Silke; Gale, Andy; Attree, Kevin; Jenkyns, Hugh

    2016-04-01

    New high-resolution records of bulk carbonate carbon isotopes have been generated for the Upper Coniacian to Lower Campanian interval of the reference sections at Seaford Head (southern England) and Bottaccione (Gubbio, central Italy). These records allow for a new and unambiguous stratigraphic correlation of the base and top of the Santonian between the Boreal and Tethyan realms. Orbital forcing of stable carbon and oxygen isotopes can be highlighted in the Seaford Head dataset, and a floating astronomical time scale is presented for the Santonian of the section, which spans five 405 kyr cycles (Sa1 to Sa5). Macro-, micro- and nannofossil biostratigraphy of the Seaford section is integrated along with magnetostratigraphy, carbon-isotope chemostratigraphy and cyclostratigraphy. Correlation of the Seaford Head astronomical time scale to that of the Niobrara Formation (U.S. Western Interior Basin) allows for anchoring these records to the La2011 astronomical solution at the Santonian-Campanian (Sa/Ca) boundary, which has been recently dated to 84.19±0.38 Ma. Five different astronomical tuning options are examined. The astronomical calibration generates a c. 200 kyr mismatch of the Coniacian-Santonian boundary age between the Boreal Realm in Europe and the Western Interior, likely due either to slight diachronism of the first occurrence of the inoceramid Cladoceramus undulatoplicatus between the two regions, or to remaining uncertainties of radiometric dating and the cyclostratigraphic records.

  15. Influences on the stable oxygen and carbon isotopes in gerbillid rodent teeth in semi-arid and arid environments: Implications for past climate and environmental reconstruction

    NASA Astrophysics Data System (ADS)

    Jeffrey, Amy; Denys, Christiane; Stoetzel, Emmanuelle; Lee-Thorp, Julia A.

    2015-10-01

    The stable isotope composition of small mammal tissues has the potential to provide detailed information about terrestrial palaeoclimate and environments, because their remains are abundant in palaeontological and archaeological sites, and they have restricted home ranges. Applications to the Quaternary record, however, have been sparse and limited by an acute lack of understanding of small mammal isotope ecology, particularly in arid and semi-arid environments. Here we document the oxygen and carbon isotope composition of Gerbillinae (gerbil) tooth apatite across a rainfall gradient in northwestern Africa, in order to test the relative influences of the 18O/16O in precipitation or moisture availability on gerbil teeth values, the sensitivity of tooth apatite 13C/12C to plant responses to moisture availability, and the influence of developmental period on the isotopic composition of gerbil molars and incisors. The results show that the isotopic composition of molars and incisors from the same individuals differs consistent with the different temporal periods reflected by the teeth; molar teeth are permanently rooted and form around the time of birth, whereas incisors grow continuously. The results indicate that tooth choice is an important consideration for applications as proxy Quaternary records, but also highlights a new potential means to distinguish seasonal contexts. The oxygen isotope composition of gerbil tooth apatite is strongly correlated with mean annual precipitation (MAP) below 600 mm, but above 600 mm the teeth reflect the oxygen isotope composition of local meteoric water instead. Predictably, the carbon isotope composition of the gerbil teeth reflected C3 and C4 dietary inputs, however arid and mesic sites could not be distinguished because of the high variability displayed in the carbon isotope composition of the teeth due to the microhabitat and short temporal period reflected by the gerbil. We show that the oxygen isotope composition of small

  16. Steady-State Oxygen Isotope Effects of N2O Production in Paracoccus denitrificans.

    PubMed

    Barford, Carol; Montoya, Joseph; Altabet, Mark; Mitchell, Ralph

    2017-03-21

    Knowledge of isotopic discrimination, or fractionation, by denitrifying bacteria can benefit agricultural fertilizer management, wastewater treatment, and other applications. However, the complexity of N transformation pathways in the environment and the sensitivity of denitrification to environmental conditions warrant better isotopic distinction between denitrification and other processes, especially for oxygen isotopes. Here, we present a dataset of δ(18)O measurements in continuous culture of Paracoccus denitrificans. The authors hope that it will be useful in further studies of N2O in the environment.

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

    USGS Publications Warehouse

    Shackleton, N.J.; Backman, J.; Zimmerman, H.; Kent, D.V.; Hall, M.A.; Roberts, David G.; Schnitker, D.; Baldauf, J.G.; Desprairies, A.; Homrighausen, R.; Huddlestun, P.; Keene, J.B.; Kaltenback, A.J.; Krumsiek, K.A.O.; Morton, A.C.; Murray, J.W.; Westberg-Smith, J.

    1984-01-01

    We report here that DSDP Site 552A, cored with the hydraulic piston corer on the west flank of Rockall Bank, recovered an undisturbed sequence of alternating white deep-sea carbonate oozes and dark-coloured layers that are rich in glacial debris. Oxygen isotope analysis of the sequence together with detailed nannofossil and palaeomagnetic stratigraphy shows that the first major horizon of ice-rafting occurred at about 2.4 Myr, and was preceded by a minor pulse of ice-rafting at about 2.5 Myr. The carbon isotope record shows that the site has been bathed by a water mass of similar characteristics to present-day North Atlantic deep water at least since 3.5 Myr. ?? 1984 Nature Publishing Group.

  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. 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.

  20. 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.

  1. 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.

  2. Boron, Thorium and Oxygen Isotopes in Icelandic Tephra

    NASA Astrophysics Data System (ADS)

    Rose-Koga, E. F.; Sigmarsson, O.

    2006-12-01

    Important Th-isotope variations in silicic rocks from Iceland have been interpreted in terms of partial melting of a metabasic crust. This hypothesis was tested by boron systematics, since both the B-isotope ratios and their concentration are significantly different in the altered oceanic crust and the underlying mantle. Here we present new boron isotope compositions and concentrations measured by ion microprobe (3f, Nancy, France) on Holocene tephra samples from 6 Icelandic volcanoes. The B concentrations vary by more than a factor 20, from 1.48±0.03 to 36.38±4.46 ppm in basaltic tholeiite and trachytes, respectively. A large range is also observed for B isotope compositions, between - 9.8±2.0 in a trachyte to +7.6±2.6‰ in a subalkaline rhyolite from Askja volcano. Furthermore, the δ^{11}B correlates positively with Th/B (0.26 < Th/B < 2.90) and negatively with 230Th/232Th (0.940 < (230Th/232Th) < 1.067) and with δ18O (-0.2 to +5.3‰). The variations of B isotope compositions in the Icelandic tephra and the correlations with both δ18O and (230Th/232Th) strongly support the crustal melting model for most Icelandic rhyolites. In fact, the co-variation is interpreted as a mixing between mantle derived basalts and crustal melts derived from the anatexis of hydrothermally altered basaltic crust. The highest δ^{11}B (+7.6±2.6 and +7.1±2.1‰) measured in rhyolites from the rift-related Askja and Krafla volcanoes represent the B-isotope composition for the altered Icelandic crust. These values are indeed well within the range of values proposed for altered oceanic crust (between +0.1 and +9.2‰, Spivack and Edmond, 1987 ; +3.4±1.1‰, Smith et al., 1995). In contrast, the lowest δ^{11}B values (-9.8 to -5.7‰) are observed in samples with the highest δ18O (+4.95 to +5.30‰) and (230Th/232Th; 0.990 to 1.067) corresponding to a "normal-mantle" signature (δ^{11}B =- 9.9±1.3‰; Chaussidon and Marty, 1995).

  3. Climate forcings of changes in paleoprecipitation patterns in Brazil from oxygen isotope ratios on speleothems

    NASA Astrophysics Data System (ADS)

    da Cruz, F.; Cheng, H.; Barreto, E. S.; Wang, X.; Vuille, M.; Edwards, R.; Karmann, I.; Burns, S. J.; Auler, A.

    2009-12-01

    Stable oxygen isotope records in speleothems have provided new insights into changes in the tropical precipitation patterns over South America during Holocene. This is evident in the antiphasing observed between rainfall in northeastern Brazil and in areas affected by the South American Summer Monsoon (SASM), such as southern Brazil, the Amazon and the tropical Andes on orbital time-scales (Cruz et al., 2009). This pattern is attributed to changes in the strength of both Hadley and Walker-cells due to the influence of insolation on the global summer monsoons. A higher incoming austral summer insolation can intensify the SASM by favoring moisture convergence in the Amazon Basin and promote a substantial increase in monsoon precipitation in southern Brazil. Simultaneously, northeastern Brazil experiences arid conditions because of increased west-east upper-level subsidence induced by the convection in the monsoon core. A new speleothem record from Bahia State in NE Brazil confirms this antiphasing pattern of long-term precipitation for last 90 ky B.P. in Brazil, but in contrast with what is seen in southern Brazil, the records from the NE part of the country are mostly in phase with the Chinese speleothem records. Besides, it also shows that insolation exerts a strong forcing during MIS 5c to 5a, which is not as apparent during the MIS 4, 3 and 2. We suggest that the glacial boundary conditions play an important role in the SASM intensification between 60 and 20 ky during the latter marine isotope stages triggering wetter and drier conditions in southern and northeastern Brazil, respectively. On the other hand, the abrupt increases in precipitation during Heinrich events indicate a similar rainfall pattern everywhere in Brazil and suggest a more direct response from changes in oceanic conditions on millennial time-scales, which is relatively independent of monsoon activity in South America. References Cruz, F.W; Vuille, M.; Burns, S.J.; Wang, X.; Cheng H; Werner M

  4. The oxygen isotope composition of nitrate generated by nitrification in acid forest floors

    NASA Astrophysics Data System (ADS)

    Mayer, Bernhard; Bollwerk, Sandra M.; Mansfeldt, Tim; Hütter, Birgit; Veizer, Jan

    2001-09-01

    The oxygen isotope composition of nitrate is used increasingly for identifying the origin of nitrate in terrestrial and aquatic ecosystems. This novel isotope tracer technique is based on the fact that nitrate in atmospheric deposition, in fertilizers, and nitrate generated by nitrification in soils appear to have distinct oxygen isotope ratios. While the typical ranges of δ 18O values of nitrate in atmospheric deposition and fertilizers are comparatively well known, few experimental data exist for the oxygen isotope composition of nitrate generated by nitrification in soils. The objective of this study was to determine δ 18O values of nitrate formed by microbial nitrification in acid forest floors. Evidence from laboratory incubation experiments and field studies suggests that during microbial nitrification in acid forest floor horizons, up to two of the three oxygen atoms in newly formed nitrate are derived from water, particularly if ammonium is abundant and nitrification rates are high. It was, however, also observed that in ammonium-limited systems with low nitrification rates, significantly less than two thirds of the oxygen in newly formed nitrate can be derived from water oxygen, presumably as a result of heterotrophic nitrification. It can be concluded from the presented data that the δ 18O values of nitrate formed by microbial nitrification in acid forest floors typically range between +2 and +14‰, assuming that soil water δ 18O values vary between -15 and -5‰. Hence, oxygen isotope ratios of nitrate formed by nitrification in forest floors are usually distinct from those of other nitrate sources such as atmospheric deposition and synthetic fertilizers and, therefore, constitute a valuable qualitative tracer for distinguishing among these sources of nitrate. A quantitative source apportionment appears, however, difficult because of the wide range of δ 18O values, particularly for atmospheric nitrate deposition and for nitrate from microbial

  5. 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.

  6. Water isotopes in the snows of Denali record much more than canonical isotope-meteorology transform functions

    NASA Astrophysics Data System (ADS)

    vachon, R. W.; White, J. W.

    2011-12-01

    In 2000 fresh snow and annual pits were sampled from 7,000 to 20,000 feet on Mount McKinley (Denali). Water isotope analysis reveals complex meteorology producing fascinatingly multifarious relationships between elevation and isotopic concentration. Previous studies have show that isotopic trends in cold regions correlate powerfully with temperatures, however this is not universally apparent on the slopes of Denali. It is believed that low elevation precipitation is largely sourced from the Gulf of Alaska, mid elevations represent a turbulent mixing zone and higher reaches receive moisture from a comparatively cold water body, such as the Bering Sea or even the Arctic Ocean. The differential sourcing of moisture suggests that temporal trends in isotopes, at different elevations, not only record local temperatures but contributions from regionally distinct decadal oscillations such as ENSO, the Pacific Decadal Oscillation or the Arctic Oscillation. Understand these inputs will facilitate the untangling of causes for Alaska's extensive contemporary climate changes. This study highlights the need for robust, modern calibrations of isotope-meteorology relationships before long-term isotope records, such as ice cores, can be leveraged as "Rosetta Stones" for past climate changes.

  7. Detailed record of the Neogene Sr isotopic evolution of seawater from DSDP Site 590B. [Deep Sea Drilling Project

    SciTech Connect

    DePaolo, D.J.

    1986-02-01

    A detailed study of strontium isotope variations in Neogene marine carbonate sediments from Deep Sea Drilling Project Site 590B, using techniques that allow the /sup 87/Sr//sup 86/Sr ratio to be determined to better than +/- 0.000 01, gives a high-resolution record of the Sr isotopic evolution of seawater. The data show that the rate of change of the marine /sup 87/Sr//sup 86/Sr ratio has varied significantly even on time scales as short as 1 m.y. Periods of particularly rapid growth appear to follow major marine regressions and probably reflect an increase in the delivery of radiogenic Sr from the continents coupled with a decreased submarine carbonate dissolution rate (greater carbonate compensation depth). Periods of relatively slowly changing /sup 97/Sr//sup 86/Sr follow major marine transgressions. On the basis of correlations with the marine oxygen isotope record and the times of major continental glacier growth, it is inferred that the effects of sea-level variations are modified by climatic factors that affect the intensity of continental weathering and runoff. The effects of sea-floor generation rate variations are not discernible for the Neogene. The maximum attainable stratigraphic resolution using Sr isotopes is between 0.1 and 2 m.y. for this time period. 24 references.

  8. 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.

  9. Oxygen and carbon stable isotopes of modern land snail shells as environmental indicators from a low-latitude oceanic island

    NASA Astrophysics Data System (ADS)

    Yanes, Yurena; Romanek, Christopher S.; Delgado, Antonio; Brant, Heather A.; Noakes, John E.; Alonso, María R.; Ibáñez, Miguel

    2009-07-01

    Land snails provide a unique opportunity to study terrestrial paleoenvironments because their shells, which are generally highly abundant and well-preserved in the fossil record, contain a temporal record of environmental change in the form of isotope codes. To evaluate the utility of this approach for a low-latitude oceanic setting, 207 modern shells of 18 species of land snail were analyzed for their oxygen and carbon isotope composition along a north and south facing altitudinal gradient (10-2160 m a.s.l.) in Tenerife Island (˜28°N) of the Canary Archipelago. Shells collected at each locality showed a relatively large range in isotope composition which was greater along the south facing transect (drier and hotter), suggesting that the variance in shell isotope values may be related to water-stress. Although pooled isotope values did not generally show strong relationships with environmental variables (i.e., altitude, temperature and precipitation), mean isotope values were strongly associated with some climatic factors when grouped by site. The mean δ 18O value of the shell (δ 18O shell) by site displayed a negative correlation with elevation, which is consistent with the positive relationship observed between temperature and the δ 18O value of rain (δ 18O rain). Calculated δ 18O values of the snail body water (δ 18O body) derived from observed temperatures and δ 18O shell values (using the equation of Grossman and Ku [Grossman E. L. and Ku T. L. (1986) Oxygen and carbon isotope fractionation in biogenic aragonite. Chem. Geol. (Isotope Geosci. Sec.)59, 59-74]) displayed a trend with respect to altitude that was similar to measured and hypothetical δ 18O values for local rain water. The calculated δ 18O body values from the shell declined 0.17‰ (VSMOW) per 100 m, which is consistent with the "altitude effect" observed for tropical rains in Western Africa, and it correlated negatively with rainfall amount. Accordingly, lower δ 18O shell values

  10. Understanding continental-scale variation in plant hydrogen and oxygen isotope ratios - Pseudotsuga menziesii across a 1500 km transect

    NASA Astrophysics Data System (ADS)

    West, J. B.; Wilson, E.; Hyodo, A.

    2013-12-01

    The isotopic composition of plant tissues provides an important recorder of vegetation response to climate. Hydrogen and oxygen isotope ratios have been used to infer precipitation isotope ratios and therefore variability in temperature. While this is the case, important questions remain about the primary drivers of plant tissue hydrogen and oxygen isotope ratio variation, including fundamental questions about the role of plant physiology. Relatively recent work suggests, in some species, an important role of physiology in organic matter d2H, in particular stomatal conductance, while other work suggests a distinct lack of influence of physiology. It is critical that mechanistic models of plant tissue variation in δ2H and δ18O can encompass landscape and larger-scale variability in plant isotope ratios. In particular existing models need to be compared to large-scale observations in order to assess their ability to describe variation in climate and plant physiology driven by such geographic variables as continentality and elevation. We report on ongoing work to better understand the role of climate and other drivers in plant tissue isotopic composition across relatively large spatial scales. An approximately 1500 km-long transect was established from the Continental Divide in North America (at approximately 39° N latitude) to the Coast Range. Leaf, branch, and tree core samples of Pseudotsuga menziesii were collected, along with surface waters. At each location, samples were collected from at least three elevations and on the western and eastern slopes of the target mountain range. Xylem water broadly reflected local precipitation as inferred from a global precipitation isoscape model and local surface water measurements. There was also a clear difference across the transect in apparent access to surface water, with the drier interior showing greater source water evaporative enrichment. In addition, the relationships between leaf water and stem water changed

  11. 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].

  12. 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

  13. A Two-year Record of Daily Rainfall Isotopes from Fiji: Implications for Reconstructing Precipitation from Speleothem δ18O

    NASA Astrophysics Data System (ADS)

    Brett, M.; Mattey, D.; Stephens, M.

    2015-12-01

    Oxygen isotopes in speleothem provide opportunities to construct precisely dated records of palaeoclimate variability, underpinned by an understanding of both the regional climate and local controls on isotopes in rainfall and groundwater. For tropical islands, a potential means to reconstruct past rainfall variability is to exploit the generally high correlation between rainfall amount and δ18O: the 'amount effect'. The GNIP program provides δ18O data at monthly resolution for several tropical Pacific islands but there are few data for precipitation isotopes at daily resolution, for investigating the amount effect over different timescales in a tropical maritime setting. Timescales are important since meteoric water feeding a speleothem has undergone storage and mixing in the aquifer system and understanding how the isotope amount effect is preserved in aquifer recharge has fundamental implications on the interpretation of speleothem δ18O in terms of palaeo-precipitation. The islands of Fiji host speleothem caves. Seasonal precipitation is related to the movement of the South Pacific Convergence Zone, and interannual variations in rainfall are coupled to ENSO behaviour. Individual rainfall events are stratiform or convective, with proximal moisture sources. We have daily resolution isotope data for rainfall collected at the University of the South Pacific in Suva, covering every rain event in 2012 and 2013. δ18O varies between -18‰ and +3‰ with the annual weighted averages at -7.6‰ and -6.8‰ respectively, while total recorded rainfall amount is similar in both years. We shall present analysis of our data compared with GNIP, meteorological data and back trajectory analyses to demonstrate the nature of the relationship between rainfall amount and isotopic signatures over this short timescale. Comparison with GNIP data for 2012-13 will shed light on the origin of the amount effect at monthly and seasonal timescales in convective, maritime, tropical

  14. What climate information is recorded in stable isotope ratios of wood lignin methoxyl groups?

    NASA Astrophysics Data System (ADS)

    Greule, Markus; Keppler, Frank

    2010-05-01

    The stable isotope composition of the bioelements C, O, H and N in plant organic matter is known to be a very powerful for various environmental impacts. Particularly tree rings are suitable for this analysis because they exhibit a "climate archive" with a yearly or even biannual resolution. One of the most determined wood compounds is cellulose which amongst others is used to reconstruct the temperature due to measurement of stable hydrogen and oxygen isotopes. Therefore cellulose is converted into cellulose nitrate to eliminate the exchangeable hydroxyl hydrogen or equilibration methods are used. However, a general problem associated with the determination of the stable hydrogen values of marker compounds for the study of climate and environmental conditions is the isolation of the pure compound for analysis by isotope ratio mass spectrometry. Exploitation of components of wood as markers, in particular, has been restricted by the very labour intensive and time consuming preparation of samples (e.g. cellulose nitrate). An alternative way to record climate information from tree rings was recently proposed by Keppler et al. (2007) who measured the stable hydrogen values of methoxyl groups in wood. Lignin methoxyl groups are considered to be stable, i.e. the hydrogen atoms of the methoxyl moiety do not exchange with those of plant water during ongoing metabolic reactions in the plant. Thus the initial deuterium content of the methoxyl groups of lignin in woody tissue at formation is retained throughout the lifetime of the tree and in preserved tissue. The methoxyl content of lignin in wood is usually determined by the Zeisel method (Zeisel, 1885) - the reaction between methyl ethers and hydroiodic acid to form methyl iodide. Exploiting this reaction for the measurement of stable hydrogen values of lignin methoxyl groups ensures that during the entire analytical procedure the isotope signal is preserved since no isotopic exchange occurs between the methyl groups and

  15. Preservation of REE and Fe isotopes in altered stromatolites and the paleo-environmental record

    NASA Astrophysics Data System (ADS)

    Nies, S. M.; Shapiro, R. S.; Lalonde, S.

    2015-12-01

    Geochemical proxies are increasingly being used to unravel ancient ecosystems and environmental perturbations back to the earliest rock record on Earth. Along with more traditional fossils (stromatolites) and other biosignatures (e.g., lipids), the geochemical record is used specifically to evaluate biogenecity and to understand oxygenation of the atmosphere and ocean in the Archean and Paleoproterozoic. However, the effects of diagenesis, metamorphism, and other modes of secondary alteration are still poorly constrained, particularly as technological advances allow us to expand farther across the periodic table. Our study focused on the robustness and preservation of rare earth element (REE) and Fe isotope compositions of two stromatolitic units that have undergone contact and regional metamorphism. 18 samples were collected from cores, open pit mines, and field locations in Minnesota and Ontario from silicified iron formation (Biwabik-Gunflint formations). The samples were carefully constrained to one of two meter-scale stromatolitic units. Metamorphic grade ranged from essentially unmetamorphosed through prehnite-pumpellyite up to amphibolite (fayalite+hypersthene). Samples were also collected that represented deep secondary weathering, likely related to Cretaceous climatic extremes. Polished samples were first analyzed by electron microprobe and selected samples were further analyzed via laser ablation HR-ICP-MS to constrain trace element (n=13) and Fe isotopic variations (n=8). Preliminary results indicate that transition metal concentrations are surprisingly resilient to high-temperature metamorphic recrystallization. REE concentrations were analyzed in individual iron oxide grains, with full resolution (La to Lu) achieved for some samples and partial resolution (La to Nd) achieved for all samples. Core samples exhibited a relatively stable positive Ce anomaly occurring from low to extremely high alteration. Outcrop and mine samples indicate a shift from a

  16. Compound-specific nitrogen isotopes of equatorial Pacific sedimentary record

    NASA Astrophysics Data System (ADS)

    Sauthoff, W.; Ravelo, A. C.; Mccarthy, M. D.

    2014-12-01

    Compound specific nitrogen isotopic analysis of amino acids (δ15N-AA) is a technique that is widely used in regional ecology and food web studies, with newly expanding applications in organic geochemistry. However, its applicability to marine sediment has been minimally examined. This study is one of the first δ15N-AA applications into the paleorecord of marine sediment. We explore how δ15N-AA measurements provide insights into past changes in water column N cycling and N utilization, and into post-depositional processes that impact sedimentary N. This is possible because δ15N-AA investigates the molecular-level basis of the bulk sedimentary δ15N signal, revealing possible diagenetic alteration of sedimentary organic matter. Our goal was is to investigate the extent of alteration (vs. preservation) of individual sedimentary amino acid δ15N values from surface nitrate δ15N across a wide range of depositional environments. The δ15N of bulk sediment differs from that of the surface nitrate δ15N signal because of water column processes or more often because of alteration of the signal during initial sedimentation. To investigate this alteration we compare δ15N-AA to bulk δ15N measurements in a suite of equatorial Pacific core tops (378-4360 m below sea level) across contrasting oceanographic and sedimentary depositional conditions (e.g. high vs. low productivity, hypoxic vs. oxic bottom waters). To examine down core diagenetic alteration of the sediment record, we present δ15N-AA and bulk δ15N of selected deeper depths to observe 1) if diagenetic shift is coherently resolved by both types of measurements and 2) if select individual δ15N-AA values remain representative of the surface organic δ15N signal. We hypothesize that compound specific analysis (δ15N-AA) will provide a molecular level assessment of mechanism for diagenetic changes in bulk organic δ15N values while also preserving detailed information about planktonic ecosystem structure.

  17. The Early Cretaceous Sulfur Isotope Record: New Data, Revised Ages, and Updated Modeling

    NASA Astrophysics Data System (ADS)

    Kristall, B.; Hurtgen, M.; Sageman, B. B.; Jacobson, A. D.

    2015-12-01

    The Early Cretaceous is a time of significant transformation with the continued break-up of Pangea, the emplacement of several LIPs, and a climatic shift from a cool greenhouse to a warm greenhouse. The timing of these major events and their relationship to seawater geochemistry (as recorded in isotope records) is critical for understanding changes in global biogeochemical cycles during this time. Within this context, recent revisions to the Cretaceous portion of the geologic timescale necessitate a reevaluation of the Cretaceous S isotope record as recorded in marine barite (Paytan et al., 2004). We present a revised Early Cretaceous S isotope record and present new δ34Sbarite data that extend the record further back in time and provide more detail during two major S isotope shifts of the Early Cretaceous. The new data maintain the major ~5‰ negative shift but raise questions on the timing and structure of this perturbation. Furthermore, recently updated estimates for global rates of marine microbial sulfate reduction (MSR) (Bowles et al., 2014) and sulfate burial during the Phanerozoic (Halevy et al., 2012) require notable revisions in the fluxes and isotopic values used to model the global S cycle. We present a revised global S cycle box model and reconstruct the evolution of the Early Cretaceous S isotope record primarily through perturbations in volcanic and hydrothermal fluxes (e.g., submarine LIPs). Changes to the weathering and pyrite burial fluxes and the global integrated fractionation factor for MSR are also used to modulate, balance, and smooth the LIP-driven perturbation. The massive evaporite burial during the Late Aptian post dates the major -5‰ shift and has little affect on the modeled S isotope composition of seawater sulfate, despite causing a major drop in sulfate concentration. The S cycle box model is coupled to a Sr cycle box model to provide additional constraints on the magnitude and timing of perturbations within the S isotope record.

  18. 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.

  19. Theoretical analysis of isotope effects on ozone formation in oxygen photochemistry

    NASA Technical Reports Server (NTRS)

    Kaye, J. A.

    1986-01-01

    In situ measurements of stratospheric ozone and laboratory studies of ozone production in electric discharge through oxygen have shown previously that ozone containing heavy isotopes of oxygen (O-17, O-18) may be formed preferentially. In order to assess the relevance of thee latter experiment to the stratospheric measurements, detailed understanding of the effect of isotopic substitution on the O3 formation reaction O + O2 + M yields O3 + M and on the O atom exchange reaction O + O2 + O yields O2 + O is necessary. In this work, an estimate of the effect of isotopic substitution on the recombination rate is made by us of approximate dynamical theories and statistical mechanics. The results indicate the possibility of isotope effects on the O + O2 recombination rate of the order of several percent at stratospheric temperatures. In general, recombination reactions involving heavy (mass 49, 50) O3 formation are found to be slower than the reaction leading to normal (mass 48) O3 formation. The calculated isotope effects are sufficiently small that the uncertainties in the model input and the approximations in the dynamical theories will probably make the quantitative nature of these results subject to considerable uncertainty. This isotope effect should not be observable in the atmosphere given the precision of the current measurements but may be crucial in the understanding of the laboratory experiments, where observed enhancements are only of the order of several percent. Possible reasons for this discrepancy between the observed enhancement and predicted depletion are presented.

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

    PubMed Central

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

    2016-01-01

    ABSTRACT Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ15NNO2− and δ18ONO2−, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of “Candidatus Nitrosocaldus.” The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ18O value of nitrite produced from ammonia oxidation varied with the δ18O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ18ONO2− in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. IMPORTANCE Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying

  1. Determining the Impactor of the Ordovician Lockne Crater: Oxygen Isotopes in Chromite Versus Sedimentary PGE Signatures

    NASA Astrophysics Data System (ADS)

    Schmitz, B.; Heck, P. R.; Alwmark, C.; Kita, N. T.; Peucker-Ehrenbrink, B.; Ushikubo, T.; Valley, J. W.

    2009-03-01

    Oxygen isotopic results for chromite from the Lockne cCater and new PGE results show that the claims by Tagle and Schmitt (2008, LPSC abstr. #1418) that the Lockne Crater was caused by a nonmagmatic iron meteorite lacks substance entirely.

  2. 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 ...

  3. 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...

  4. Bulk Oxygen-Isotope Compositions of Different Lithologies in Sutter's Mill

    NASA Astrophysics Data System (ADS)

    Ziegler, K.; Garvie, L. A. J.

    2013-09-01

    We correlate mineralogy data with bulk oxygen-isotope data of the clay-rich and the ol-rich lithologies in order to assess the possibility of more than one parent material, and the possibility of different alteration environments on the parent body.

  5. 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,

  6. The oxygen isotopic composition of the Sun inferred from captured solar wind.

    PubMed

    McKeegan, K D; Kallio, A P A; Heber, V S; Jarzebinski, G; Mao, P H; Coath, C D; Kunihiro, T; Wiens, R C; Nordholt, J E; Moses, R W; Reisenfeld, D B; Jurewicz, A J G; Burnett, D S

    2011-06-24

    All planetary materials sampled thus far vary in their relative abundance of the major isotope of oxygen, (16)O, such that it has not been possible to define a primordial solar system composition. We measured the oxygen isotopic composition of solar wind captured and returned to Earth by NASA's Genesis mission. Our results demonstrate that the Sun is highly enriched in (16)O relative to the Earth, Moon, Mars, and bulk meteorites. Because the solar photosphere preserves the average isotopic composition of the solar system for elements heavier than lithium, we conclude that essentially all rocky materials in the inner solar system were enriched in (17)O and (18)O, relative to (16)O, by ~7%, probably via non-mass-dependent chemistry before accretion of the first planetesimals.

  7. Magmatic differentiation processes at Merapi Volcano: inclusion petrology and oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Troll, Valentin R.; Deegan, Frances M.; Jolis, Ester M.; Harris, Chris; Chadwick, Jane P.; Gertisser, Ralf; Schwarzkopf, Lothar M.; Borisova, Anastassia Y.; Bindeman, Ilya N.; Sumarti, Sri; Preece, Katie

    2013-07-01

    Indonesian volcano Merapi is one of the most hazardous volcanoes on the planet and is characterised by periods of active dome growth and intermittent explosive events. Merapi currently degasses continuously through high temperature fumaroles and erupts basaltic-andesite dome lavas and associated block-and-ash-flows that carry a large range of magmatic, coarsely crystalline plutonic, and meta-sedimentary inclusions. These inclusions are useful in order to evaluate magmatic processes that act within Merapi's plumbing system, and to help an assessment of which phenomena could trigger explosive eruptions. With the aid of petrological, textural, and oxygen isotope analysis we record a range of processes during crustal magma storage and transport, including mafic recharge, magma mixing, crystal fractionation, and country rock assimilation. Notably, abundant calc-silicate inclusions (true xenoliths) and elevated δ18O values in feldspar phenocrysts from 1994, 1998, 2006, and 2010 Merapi lavas suggest addition of limestone and calc-silicate materials to the Merapi magmas. Together with high δ13C values in fumarole gas, crustal additions to mantle and slab-derived magma and volatile sources are likely a steady state process at Merapi. This late crustal input could well represent an eruption trigger due to sudden over-pressurisation of the shallowest parts of the magma storage system independently of magmatic recharge and crystal fractionation. Limited seismic precursors may be associated with this type of eruption trigger, offering a potential explanation for the sometimes erratic behaviour of Merapi during volcanic crises.

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

    specific humidity, below which air flask samples can be trusted. This approach may allow segregation of suspect and trusted data, and thus provide an improved record of oxygen isotopic ratios of carbon dioxide over the past two decades.

  9. 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

  10. Moisture sources of precipitation over Postojna (Slovenia) and implication of its oxygen isotope composition

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    The source of moisture is an important part of the hydrological cycle that affects climate system. Potentially, moisture sources are important controls of the isotope composition of precipitation, but their studies in the continental mid- and low-latitudes are still scarce due to the complexity of general circulation models with integrated isotope modules. We identify moisture uptake locations of precipitation over Postojna (Slovenia) for period from 2009 to 2013. By using HYSPLIT trajectory model of NOAA we did 5-day reconstruction of air mass history for the days with precipitation and determination of moisture uptake locations along back trajectories. Moisture uptake locations were identified along each trajectory using HYSPLIT output data and standard equations for saturation humidity mixing ratio, saturation vapour pressure and specific humidity. Although NNE winds were prevailing during the period 2001-2014, our analysis showed that during this period around 45% of the precipitation over Postojna originated from Mediterranean and south Atlantic area, with majority of locations originated in the Adriatic Sea. On the other hand, 41% of precipitation originated from moisture recycled over continents, predominantly from Pannonian basin. The comparison of monthly oxygen isotope composition of precipitation with the percentage of precipitation originated in different source regions shows a significant correlation only for the north Atlantic region. However, less than 7% of the variability of oxygen isotope composition of precipitation is associated with this moisture source. Multivariable analyses of source regions do not explain any additional variability of the oxygen isotope composition of precipitation over Postojna. This research shows that at this location, although significant, moisture sources are not important controls of the oxygen isotope composition of precipitation.

  11. Seawater osmium isotope evidence for a middle Miocene flood basalt event in ferromanganese crust records

    USGS Publications Warehouse

    Klemm, V.; Frank, M.; Levasseur, S.; Halliday, A.N.; Hein, J.R.

    2008-01-01

    Three ferromanganese crusts from the northeast, northwest and central Atlantic were re-dated using osmium (Os) isotope stratigraphy and yield ages from middle Miocene to the present. The three Os isotope records do not show evidence for growth hiatuses. The reconstructed Os isotope-based growth rates for the sections older than 10??Ma are higher than those determined previously by the combined beryllium isotope (10Be/9Be) and cobalt (Co) constant-flux methods, which results in a decrease in the maximum age of each crust. This re-dating does not lead to significant changes to the interpretation of previously determined radiogenic isotope neodymium, lead (Nd, Pb) time series because the variability of these isotopes was very small in the records of the three crusts prior to 10??Ma. The Os isotope record of the central Atlantic crust shows a pronounced minimum during the middle Miocene between 15 and 12??Ma, similar to a minimum previously observed in two ferromanganese crusts from the central Pacific. For the other two Atlantic crusts, the Os isotope records and their calibration to the global seawater curve for the middle Miocene are either more uncertain or too short and thus do not allow for a reliable identification of an isotopic minimum. Similar to pronounced minima reported previously for the Cretaceous/Tertiary and Eocene/Oligocene boundaries, possible interpretations for the newly identified middle Miocene Os isotope minimum include changes in weathering intensity and/or a meteorite impact coinciding with the formation of the No??rdlinger Ries Crater. It is suggested that the eruption and weathering of the Columbia River flood basalts provided a significant amount of the unradiogenic Os required to produce the middle Miocene minimum. ?? 2008 Elsevier B.V.

  12. 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.

  13. A mid-european decadal isotope-climate record from 15,500 to 5000 years B.P

    PubMed

    von Grafenstein U; Erlenkeuser; Brauer; Jouzel; Johnsen

    1999-06-04

    Oxygen-isotope ratios of precipitation (delta18OP) inferred from deep-lake ostracods from the Ammersee (southern Germany) provide a climate record with decadal resolution. The record in detail shows many of the rapid climate shifts seen in central Greenland ice cores between 15,000 and 5000 years before the present (B.P.). Negative excursions in the estimated delta18OP from both of these records likely reflect short weakenings of the thermohaline circulation caused by episodic discharges of continental freshwater into the North Atlantic. Deviating millennial-scale trends, however, indicate that climate gradients between Europe and Greenland changed systematically, reflecting a gradual rearrangement of North Atlantic circulation during deglaciation.

  14. 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

  15. Oxygen isotope anomaly observed in water vapor from Alert, Canada and the implication for the stratosphere.

    PubMed

    Lin, Ying; Clayton, Robert N; Huang, Lin; Nakamura, Noboru; Lyons, James R

    2013-09-24

    To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003-2005 at Alert station, Canada (82°30'N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ(17)O and δ(18)O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λMDF(H2O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003-2005. An oxygen isotopic anomaly of Δ(17)O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ(17)O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930-1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ(17)O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l'Environnement, Gif sur Yvette, France, had (17)Oexcess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water.

  16. Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils.

    PubMed

    Tian, Liyan; Guo, Qingjun; Zhu, Yongguan; He, Huijun; Lang, Yunchao; Hu, Jian; Zhang, Han; Wei, Rongfei; Han, Xiaokun; Peters, Marc; Yang, Junxing

    2016-12-01

    Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ(18)OP) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L(-1) NaHCO3 (pH = 8.5), 0.1 mol L(-1) NaOH and 1 mol L(-1) HCl) of agricultural soils from the Beijing area. The δ(18)OP results of the water extracts and NaHCO3 extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ(18)OP value of the water extracts and NaHCO3 extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ(18)OP values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ(18)OP values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ(18)Op values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.

  17. Last Glacial Maximum and deglacial abyssal seawater oxygen isotopic ratios

    NASA Astrophysics Data System (ADS)

    Wunsch, Carl

    2016-06-01

    An earlier analysis of pore-water salinity (chlorinity) in two deep-sea cores, using terminal constraint methods of control theory, concluded that although a salinity amplification in the abyss was possible during the LGM, it was not required by the data. Here the same methodology is applied to δ18Ow in the upper 100 m of four deep-sea cores. An ice volume amplification to the isotopic ratio is, again, consistent with the data but not required by it. In particular, results are very sensitive, with conventional diffusion values, to the assumed initial conditions at -100 ky and a long list of noise (uncertainty) assumptions. If the calcite values of δ18O are fully reliable, then published enriched values of the ratio in seawater are necessary to preclude sub-freezing temperatures, but the seawater δ18O in pore fluids does not independently require the conclusion.

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

    PubMed Central

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

    2008-01-01

    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 δ2H and δ18O 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

  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.

  20. Relative humidity across the Paleocene-Eocene Thermal Maximum via combined hydrogen-oxygen isotope paleohygrometry (Invited)

    NASA Astrophysics Data System (ADS)

    McInerney, F. A.; Bloch, J. I.; Secord, R.; Wing, S. L.; Kraus, M. J.; Boyer, D. M.

    2009-12-01

    The Paleocene-Eocene Thermal Maximum (PETM) presents an opportunity to characterize continental hydrologic changes during rapid and extreme global warming. The Bighorn Basin, Wyoming, USA, has long been recognized for the PETM sequences preserved there and sits in an ideal location for recording hydrologic changes in the interior of North America. The southeast Bighorn Basin is of particular interest because it contains not only alluvial paleosols and vertebrate fossils, but also macrofloral remains from the PETM. The carbon isotope excursion associated with this event is preserved in this part of the Basin in leaf wax lipids, tooth enamel, and bulk organic matter. To characterize the hydrologic changes that occurred during the PETM we are applying a suite of isotopic, paleobotanical and paleopedological approaches to sections in the southeast Bighorn Basin. Reported here are results from the combined hydrogen and oxygen isotope analysis aimed at reconstructing relative humidity. Oxygen isotope ratios (δ18O) of biogenic apatite from mammalian tooth enamel and fish scales vary with environment, physiology and diet. Because mammals are homeothermic, they primarily track surface water values with predictable physiological offsets. Hydrogen isotope ratios (δD) of leaf-wax lipids (long-chain n-alkanes) reflect both meteoric water δD values and additional D-enrichment caused by evapotranspiration. The enrichment factor between water δD and n-alkane δD can therefore be used as a proxy for relative humidity (RH). In this study, δ18O of surface water is estimated using the δ18O of Coryphodon tooth enamel. We use these δ18O values to estimate surface water δD values using the Global Meteoric Water Line (δD = 8δ18O + 10). We then calculate relative humidity from n-alkane δD values using a Craig-Gordon type isotopic model for D-enrichment caused by transpiration from leaves. Results of the combined hydrogen-oxygen isotope paleohygrometer indicate a general rise in

  1. Coral isotopic records during the medieval period from Ishigaki Island, northwestern Pacific

    NASA Astrophysics Data System (ADS)

    Morimoto, Maki; Abe, Osamu

    2013-04-01

    Proxy-based paleoclimate reconstructions in high time-resolution and modeling studies have been greatly advanced in recent years to understand global temperature history over the past 1000 years. However, most proxy data for these reconstructions are from terrestrial sources such as tree-rings, speleothems, etc., and very few marine records in annual resolution have been obtained over 500 years. This is considered to be one of reasons for large uncertainties of global scale climatic reconstructions. Marine sediments can provide long consecutive records from several thousands of years to several million years. However, their time-resolutions of several tens to several thousands of years are insufficient for reconstructing decadal to centennial climate variabilities. Coral skeletal proxies, such as oxygen isotope ratios (δ18O) and Sr/Ca, have been used to reconstruct tropical and subtropical sea surface paleoenvironment in much higher time-resolution of weeks to months, which could provide comparable results with tree-ring records. The Northwestern Pacific is one of regions with sparse long paleoclimate records in high time-resolution for the last 1000 years. We collected a medieval fossil coral (Porites sp.) with a height of more than 5 m from a fringing reef of the southern coast of the Ishigaki Island, southern Japan, where the East Asian monsoon is predominant. Using combined annual age determination by annual band analysis and high resolution isotope measurements, yearly δ18O was obtained spanning 300 years of about 1000 years ago (1535+-35 ~ 1260+-80 14C age (ca. cal AD 850 ~ 1150)). This period corresponds to the beginning of the Medieval Warm Period, recently more commonly referred to as the Medieval Climate Anomaly (Stine, 1994), and it also is marked by a tendency for La Niña-like conditions in the tropical Pacific (Mann et al., 2009). Here we discuss about the transition to the warm period of the northwestern Pacific and its degree by comparing with

  2. Oxygen isotopes in western Australian coral reveal Pinatubo aerosol-induced cooling in the Western Pacific Warm Pool

    SciTech Connect

    Gagan, M.K.; Chivas, A.R.

    1995-05-01

    The authors report a 12 year record study of oxygen 18 isotope signals in a coral (Ningaloo Reef), which is situated so as to give an ideal measure of the sea-surface temperature variation of the local Leeuwin Current. This record consists of nearly weekly readings from 1981 to 1993, and brackets the period following the June 1991 eruption of Mt. Pinatubo. Extended study shows a strong correlation of sea-surface temperature on this coral with changes in the Western Pacific Warm Pool (WPWP), with a lag of 2.5 years. A distinct cooling signal was seen in the inferred sea-surface temperatures from coral measurements, in 1992 and 1993, which suggests the WPWP was cooled roughly 0.5{degrees}C by aerosol induced effects.

  3. The silicon isotope record of early silica diagenesis

    NASA Astrophysics Data System (ADS)

    Tatzel, Michael; von Blanckenburg, Friedhelm; Oelze, Marcus; Schuessler, Jan A.; Bohrmann, Gerhard

    2015-10-01

    The heavy isotopes of silicon are strongly enriched in some of the youngest, early diagenetically formed porcellanite layers from the Southwest Indian Ridge (Pleistocene) and the Maud Rise (Pliocene). These porcellanite layers are composed of opal-CT and were formed by the conversion of amorphous silica (opal-A) from siliceous sediment via dissolution-reprecipitation. Their bulk δ30Si values range between 1.7 and 2.3‰. Detritus-poor siliceous sediment surrounding these layers is significantly lower at -0.3 to 1.5‰. Sequential chemical extractions of bulk siliceous sediment show (i) preferential dissolution of diatoms featuring higher δ30Si than radiolaria and Al-Si components. The detailed investigation of porcellanite layers by micro-scale Si isotope and Al/Si analyses using UV femtosecond laser ablation ICP mass spectrometry show that (ii) precipitation of authigenic aluminum silicates enriched in light Si isotopes drives pore waters to even higher δ30Si. We suggest that the same processes redistributed stable silicon isotopes in precursor siliceous sediments of ancient chert. We infer that past environmental conditions can be reconstructed with high fidelity from the stable Si isotope composition of chert when initial seawater Si concentrations were high (such as in the Precambrian). Exchange of Si between layers during phase transformation (from opal-A to opal-CT and from opal-CT to quartz) is impeded when variable amounts of detrital minerals are present, because they control rates of silica phase transformation and hence the timing of dissolution-reprecipitation during burial.

  4. The Precambrian Biogeochemical Carbon Isotopic Record: Contributions of Thermal Versus Biological Processes

    NASA Technical Reports Server (NTRS)

    DesMarais, David J.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Superplumes offer a new approach for understanding global C cycles. Isotopes help to discern the impacts of geological, environmental and biological processes ujpun the evolution of these cycles. For example, C-13/C-12 values of coeval sedimentary organics and carbonates give global estimates of the fraction of C buried as organics (Forg), which today lies near 0.2. Before Oxygenic photosynthesis arose, our biosphere obtained reducing power for biosynthesis solely from thermal volatiles and rock alteration. Thus Forg was dominated by the mantle redox state, which has remained remarkably constant for greater than Gy. Recent data confirm that the long-term change in Forg had been small, indicating that the mantle redox buffer remains important even today. Oxygenic photosynthesis enabled life to obtain additional reducing power by splitting the water molecule. Accordingly, biological organic production rose above the level constrained by the mantle-derived flux of reduced species. For example, today, chemoautotrophs harvesting energy from hydrothermal emanations can synthesize at most between 0.2 x 10(exp 12) and 2x 10(exp 12) mol C yr-1 of organic C globally. In contrast, global photosynthetic productivity is estimated at 9000 x 10(exp 12) mol C yr-1. Occasionally photosynthetic productivity did contribute to dramatically -elevated Forg values (to 0.4 or more) as evidenced by very high carbonate C-13/C-12. The interplay between biological, tectonic and other environmental factors is illustrated by the mid-Archean to mid-Proterozoic isotopic record. The relatively constant C-13/C-12 values of Archean carbonates support the view that photosynthetically-driven Forg increases were not yet possible. In contrast, major excursions in C-13/C-12, and thus also in Forg, during the early Proterozoic confirmed the global importance of oxygenic photosynthesis by that time. Remarkably, the superplume event at 1.9 Ga did not trigger another major Forg increase, despite the

  5. Photoneutron cross sections for unstable neutron-rich oxygen isotopes.

    PubMed

    Leistenschneider, A; Aumann, T; Boretzky, K; Cortina, D; Cub, J; Datta Pramanik, U; Dostal, W; Elze, T W; Emling, H; Geissel, H; Grünschloss, A; Hellstr, M; Holzmann, R; Ilievski, S; Iwasa, N; Kaspar, M; Kleinböhl, A; Kratz, J V; Kulessa, R; Leifels, Y; Lubkiewicz, E; Münzenberg, G; Reiter, P; Rejmund, M; Scheidenberger, C; Schlegel, C; Simon, H; Stroth, J; Sümmerer, K; Wajda, E; Walús, W; Wan, S

    2001-06-11

    The dipole response of stable and unstable neutron-rich oxygen nuclei of masses A = 17 to A = 22 has been investigated experimentally utilizing electromagnetic excitation in heavy-ion collisions at beam energies about 600 MeV/nucleon. A kinematically complete measurement of the neutron decay channel in inelastic scattering of the secondary beam projectiles from a Pb target was performed. Differential electromagnetic excitation cross sections d sigma/dE were derived up to 30 MeV excitation energy. In contrast to stable nuclei, the deduced dipole strength distribution appears to be strongly fragmented and systematically exhibits a considerable fraction of low-lying strength.

  6. Oxygen Isotopes in Fresh Water Biogenic Opal: Northeastern US Alleroed-Younger Dryas Temperature Shift

    NASA Technical Reports Server (NTRS)

    Shemesh, Aldo; Peteet, Dorothy

    1997-01-01

    The first oxygen isotope analysis of biogenic opal from lake sediments, from the Allerod/Younger Dryas transition in a core from Linsley Pond, Connecticut, gives an average estimate of a 6 C drop in temperature during the Younger Dryas. This shift represents temperatures during the bloom season, and may be less than the winter temperature drop. The sharp transition itself, with a duration of about 200 years, suggests that the temperature decrease may have been as large as 12 C. Previous estimates of the Allerod/Younger Dryas temperature shifts are controversial, and range from 3-20 C, suggesting that further interdisciplinary research on the same samples is warranted. One way that global climate change manifests itself is by redistributing energy throughout the globe. The Northern Hemisphere latitudinal temperature gradient during the late-glacial is at present a controversial topic. The magnitude of air temperature shifts during the Allerod/Younger Dryas (YD) oscillation are estimated from mid-latitude pollen records surrounding the North Atlantic to be 3-5 C in Europe [Lowe et al., 19941 and 3-4 C in the eastern US [Peteet et al., 1993]. In contrast, lake temperatures estimates derived from aquatic midge larvae in the Canadian eastern maritimes and Maine range from 6-20 C, with larger shifts at more southern sites [Levesque et al., 1997]. The magnitude of YD cooling in Greenland ice cores ranges from at least 7 C from the Bolling warming [Dansgaard et al., 1989] to 15 C - a more recent estimate from borehole temperatures [Cuffey et al., 1995]. The ice core geochemical records reveal that massive frequent and short-term (decadal or less) changes in atmospheric composition occurred throughout this event, suggesting a very dynamic circulation [Mayewski et al., 1993).

  7. Oxygen Isotope Perspectives on Magma Sources and Pluton Assembly in Convergent Margin Batholiths

    NASA Astrophysics Data System (ADS)

    Lackey, J.

    2008-12-01

    Oxygen isotope (δ18O) analysis of zircon in the Sierra Nevada batholith (SNB) yields fresh insight on the origin of this and other convergent margin batholiths. Zircon precisely and accurately maps (δ18O) variation by circumventing the effects of differentiation and sub-solidus alteration[1]. New temporal and spatial δ18O patterns are recognized, and the findings have bearing in current debates on the tempo and mode of pluton and intrusive suite assembly [2-4]. At large scales, regional belts of high and low δ18O reveal markedly contrasting budgets of crust and mantle in magma sources at different points during formation of the batholith. Contrary to original thinking, recycling of supracrustal rocks is greater in the western than eastern SNB. Gradients of δ18O show variable input of crust and mantle within these regional belts; however, sharp shifts in δ18O between some belts suggest pre-batholith lithospheric breaks. Generally, δ18O breaks do not coincide with the 0.706 Sri line suggesting isotopic decoupling, either in sources or during crustal contamination. Where present, crustal contamination is limited to veneers on plutons, and is largely restricted to the western SNB. Careful investigation of individual intrusive suites, reveals details of source longevity. In the Tuolumne suite, limited variability of δ18O suggests remarkably source homogeneity despite evidence for protracted emplacement[2,4]. In contrast, the John Muir suite shows distinct trends in its older and younger plutons, with a δ18O transition recorded in the Lake Edison granodiorite. Thus, some suites may draw from stable sources over several million years, with differentiation in the upper crust creating zoning and textural diversity; others record source switching or depletion of sources. Over time, shifts in δ18O in the SNB are punctuated by major pulses of magmatism suggesting reorganization of sources, likely in response to intra-arc deformation[5]. Overall, results show that a

  8. Non-mass-dependent oxygen isotope effect observed in water vapor from Alert, Canada

    NASA Astrophysics Data System (ADS)

    Lin, Ying

    Twenty-seven precipitation samples from Chicago, IL and northwest part of Indiana were collected from 2003 to 2005. Twenty-five water vapor samples were collected at Alert, Canada (82° 30'N, 62° 19'W) from 2002 to 2005 by Lin Huang and her co-workers. Seven ice core samples from Dasuopu glacier, Chinese Himalayas (28° 23' N, 85° 43'W) were drilled by Lonnie G. Thompson and prepared by Mary E. Davis. Sample of Standard Light Antarctic Precipitation (SLAP) is available in the laboratory. Water samples were reacted with bromine pentafluoride to produce oxygen, which were then purified through molecular sieve and measured by Delta E gas source mass spectrometer. A lambda(MDF) = 0.529 +/- 0.003 (2sigma) for water is determined from measurement of local precipitation samples. No significant oxygen isotopic anomaly is found in SLAP and in ice core samples from Dasuopu glacier, Chin