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Sample records for oxygen isotope record

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

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

  2. High-Resolution Cellulose Oxygen Isotope Records From Indonesian Trees

    NASA Astrophysics Data System (ADS)

    Poussart, P. F.; Schrag, D. P.; Evans, M. N.; D'Arrigo, R. D.

    2002-12-01

    Tropical paleoclimate records such as those derived from ice cores, lake sediments, and corals have yielded valuable insights into the Holocene history of the major modes of climate variability, in particular the El Niño/Southern Oscillation. However, because tropical trees generally lack visible, annual growth rings, their potential as recorders of climate variability has not been fully explored. To circumvent this difficulty, we made high-resolution oxygen isotopic measurements on cellulose extracted from tree samples from Indonesia. First, we examined teak samples, which are one of the rare tropical trees that display well-defined annual growth rings. The samples cover the period from 1800 to the present and show annual to bi-annual cycles, coherent with the visible rings. We use these samples to explore intra-site and intra-tree variability. Second, we measured δ18O time series from three suar wood samples with no visible rings. The oxygen isotopic values are compared to radiocarbon-based age models and show a positive correlation between estimated growth rates and amplitude of the 18O seasonal cycle, suggesting a common environmental forcing. Although the isotopic seasonal cycles are not always regular enough for perfect chronological control, they provide encouraging support for the use of high-resolution isotope records from tropical trees as proxies for multi-century reconstructions of climate variability.

  3. 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

  4. Sea Surface Temperature and Seawater Oxygen Isotope Variability Recorded in a Madagascar Coral Record

    NASA Astrophysics Data System (ADS)

    Zinke, J.; Dullo, W. Chr; Eisenhauer, A.

    2003-04-01

    We analysed a 336 year coral oxygen isotope record off southwest Madagascar in the Mozambique Channel. Based on temporal variability of skeletal oxygen isotopes annual mean sea surface temperatures are reconstructed for the period from 1659 to 1995. Sr/Ca ratios were measured for selected windows with monthly resolution (1973 to 1995, 1863 to 1910, 1784 to 1809, 1688 to 1710) to validate the SST reconstructions derived from oxygen isotopes. The coral proxy data were validated against gridded SST data sets. The coral oxygen isotope record is coherent with Kaplan-SST and GISST2.3b on an interdecadal frequency of 17 years, which is the most prominent frequency band observed in this region. The Sr/Ca-SST agree well with SST observations in the validation period (1863 to 1910), whereas the d18O derived SST show largest discrepencies during this time interval. By taking into account the SST values derived from coral Sr/Ca, we were able to reconstruct d18O seawater variability. This indicates that d18O seawater variations contributed significantly to interannual and interdecadal variations in coral d18O. We propose that the local surface-ocean evaporation-precipitation balance and remote forcing by ENSO via South Equatorial Current and/or Indonesian throughflow variability may contribute to observed d18O variability. Our results indicate that coral d18O may be used to reconstruct temporal variations in the fresh water balance within the Indian Ocean on interannual to interdecadal time scales.

  5. 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

  6. 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.

  7. Influence of changing deep ocean circulation on the Phanerozoic oxygen isotopic record

    SciTech Connect

    Railsback, L.B. )

    1990-05-01

    Isotopic segregation in seawater caused by changing ocean circulation may in part explain the enigmatic oxygen isotopic record of Phanerozoic marine carbonates. Paleoceanographic evidence suggests that circulation of warm saline deep waters has occurred during at least two periods of warm global climate; those saline deep waters should have preferentially stored {sup 18}O in the deep oceans. Corresponding depletion of {sup 18}O in surface waters would have resulted in lower {delta}{sup 18}O of marine carbonates deposited on continental shelves. Modeling of paleoceanographic isotopic data suggests that this storage effect is similar in magnitude (but opposite in sign) to that of modern enrichment of {sup 18}O in the oceans by glacial storage. Modeling of carbonate compositions through time that takes into account such storage effects (as predicted by changing global climate) suggests that large changes in the mean oceanic isotopic composition, but neither extreme temperatures nor sudden changes in mean ocean compositions are needed to explain the isotopic record.

  8. Sea Surface Temperature and Seawater Oxygen Isotope Variability Recorded in a Madagascar Coral Record

    NASA Astrophysics Data System (ADS)

    Zinke, J.; Dullo, W.; Eisenhauer, A.

    2002-12-01

    Within KIHZ a coral from the lagoon of Ifaty off southwest Madagascar in the Mozambique Channel was examined. Based on temporal variability of skeletal oxygen isotopes annual mean sea surface temperatures are reconstructed for the period from 1658 to 1995. Sr/Ca ratios were measured for selected windows with monthly resolution (1973 to 1995, 1863 to 1910, 1784 to 1809, 1688 to 1710) to validate the SST reconstructions derived from oxygen isotopes. The coral proxy data were validated against gridded SST data sets. The Sr/Ca-SST agree well with SST observations in the validation period (1863 to 1910), whereas the d18O derived SST show largest discrepencies during this time interval. By taking into account the SST values derived from coral Sr/Ca, we were able to reconstruct d18O seawater variability. This indicates that d18O seawater variations contributed significantly to interannual and interdecadal variations in coral d18O. We propose that remote forcing by South Equatorial Current and/or Indonesian throughflow variability may contribute to observed d18O variability. The local surface-ocean evaporation-precipitation balance is also of importance. Our results indicate that coral d18O may be used to reconstruct temporal variations in the fresh water balance within the Indian Ocean on interannual to interdecadal time scales.

  9. Diagnose oscillation properties observed in an Antarctic ice core oxygen isotope record

    NASA Astrophysics Data System (ADS)

    Motizuki, Y.

    2013-12-01

    We investigate water isotope ratio profile obtained in a shallow ice core drilled at Dome Fuji, East Antarctica. Two sets of time series will be discussed; the first set was analyzed at NIPR (National Institute of Polar Research) with temporal resolution of about 5 years for the past 1900 years, and the second was obtained at RIKEN very recently with temporal resolution of less than a year for the past 400 years. Paying our attention on uncertainty in the depth-age relation, time series analyses to the measured oxygen isotope variations will be presented. A preliminary result for the former time series shows a ~200-year periodicity, which is by chance the same with one of solar activity cycles reported from tree ring studies. We note that snow and ice core samples obtained at Dome Fuji are known to contain much information on the stratosphere than those recovered from other sites in both the hemisphere. Considering this, we will further discuss possible mechanism to cause oscillation in oxygen isotope record in a Dome Fuji ice core.

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2005-06-01

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

  12. Survivor or opportunist? Oxygen isotope records from Stylaster miniata in the Florida Straits

    NASA Astrophysics Data System (ADS)

    Rosenheim, B. E.; Adamic, J. F.; Reed, J. K.; Rosenberg, A. D.; Grasmueck, M.; Swart, P. K.; Eberli, G. P.; Correa, T. S.

    2009-12-01

    Deep on the flanks of the Florida Straits, several reefs exist with numerous colonies of standing-dead coral interspersed with species of Stylasterid corals. The Stylasterids appear to either be survivors of widespread die-off or opportunistic species that are occupying a recently vacated niche. In the former scenario, the environmental records within their skeletons may be helpful in determining the cause of death of other species of corals. Timing and cause of death from surrounding corals can be approached by 1. dates from the standing dead corals and 2. environmental records and dates from the living Stylasterids. The latter has proven difficult due to the paucity of knowledge of growth habits and rates of the Stylasterids. Here we present stable oxygen isotope records from Stylaster miniata collected in 2007 from a depth of 156 m at the summit of a Stylasterid-dominated deep-water coral bioherm on Pourtales Terrace in the Florida Straits. Cyclical trends in δ18O of 1 ‰ VPDB are observed in the base of the coral skeleton and suggest a growth rate of approximately 18mm/y if they are assumed to be annual in nature. Extrapolated over the length of the entire coral, this growth rate suggests an age approximately 10 years, and suggests that Stylasterids only recently inhabited the reef. However, radiocarbon and U/Th dating of coral rubble suggests a sustained rate of death on adjacent reefs.

  13. Regime shift signatures from stable oxygen isotopic records of otoliths of Atlantic cod (Gadus morhua).

    PubMed

    Gao, Y W

    2002-12-01

    The sudden collapse of Atlantic cod (Gadus morhua) may relate to ocean climate, or regime shifts as demonstrated in production of Pacific salmon. This paper reports the results of stable oxygen isotope ratio analyses (18O/16O or delta18OA) from 91 otoliths of cod over a period of about 20 years. Seasonal delta18OA variations of individual otoliths started at an initial value of about -0.5 to 0 per thousand VPDB, and then reached a stable level in the range of +2.5 to +3.5 per thousand VPDB after 4-5 years. The initial low values correspond to the natal sources of mature cod, while the higher delta18OA values represent the water conditions before the cod was caught. This pattern of delta18OA variation was observed over the life history of all cod examined. Furthermore, the calculated isotopic temperatures agreed with those obtained from summer bottom trawl survey, indicating that delta18OA of otoliths could be used as a thermometer in determining the ambient seawater temperature where the cod lived. Comparison of long-term delta18OA records and biological and meteorological observations suggested that decadal-scale ecosystem changes did occur in the late 1970s and early 1990s in Atlantic Canada, comparable to regime shifts occurred in the North Pacific. PMID:12725428

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

    NASA Astrophysics Data System (ADS)

    Juillet-Leclerc, A.; Reynaud, S.

    2009-04-01

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

  15. Obliquity forcing of East Asian summer monsoon: oxygen isotopic records from Chinese loess

    NASA Astrophysics Data System (ADS)

    Li, Gaojun; Zhang, Zeke; An, Zhisheng; Li, Tao

    2016-04-01

    East Asian summer monsoon (EASM) is the largest monsoon system out of the tropics. The temporal changes of EASM on orbital time scale have been highly debated largely due to the lack of proxy purely recording monsoonal rainfall. Oxygen isotope of rain water is a widely used hydrological tracer and has been well documented in the cave deposits of South Asia. The speleothem δ18O, which is dominated by procession cycles of ~23 kyrs, is believed to be controlled by upstream depletion that reflects tropical convections modulated by solar insolation of low latitudes. A δ18O record of monsoonal rainfall in higher latitudes of East Asia therefore is desired to investigate the variation of EASM. Here we reconstruct δ18O of summer precipitation over the past 500 kyrs based on microcodium, an authigenic carbonate in the loess deposits. Two parallel sections on Chinese Loess Plateau show consistent fluctuations of δ18O featured by strong obliquity cycles of ~41 kyrs and weaker precession cycles of ~23 kyrs. The procession signal may inherit from tropics as seen in the speleothem. However, the presence ~41 cycles in microcodium δ18O record argues that obliquity may influence the intensity of EASM and thus the integrated amount of precipitation between the speleothem sites and Chinese Loess Plateau. The obliquity signal cannot be generated by the effects of ice-volume, temperature, or pCO2 on EASM because the predominant glacial cycles of ~100 kyrs in these variables have not been detected in the δ18O records. Summer insolation of mid-latitudes also cannot produce a higher obliquity signal compared to that of precession. We propose that the obliquity forcing of EASM may originate from the meridional gradient of summer insolation that modifies the thermal contrast between Asian inland at relatively higher latitudes and surrounding oceans at relatively lower latitudes.

  16. Changes in ENSO Frequency and Character as Recorded in NE Indian Speleothem Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Oster, J. L.; Myers, C. G.; Breitenbach, S. F. M.; Sharp, W. D.

    2014-12-01

    Oxygen isotopes (δ18O) from speleothems in monsoon regions such as NE India have provided important records of monsoon strength on decadal to multi-millennial timescales. However, recent precipitation and cave drip water studies suggest that regional rain and drip water δ18O variability may be driven by changes in moisture sources and transport pathways rather than mainly reflecting changes in rainfall amount. Hence, we compare a modern δ18O speleothem time-series with historical meteorological records and global climate indices to identify dominant influences on speleothem δ18O.We have constructed a high resolution (7-8 samples per year) δ18O time-series using a stalagmite (MAW 02-01) from Mawmluh Cave in NE India that grew during the ~50 years preceding collection in 2013. U-series dates (±1-2 years) provide an age model and confirm that visible stalagmite laminations are approximately annual. We compared the stalagmite time-series with local meteorologic records and indices of the El Niño/Southern Oscillation (Niño3, Niño4) and the Indian Ocean Dipole (IOD). Our record shows no significant correlation with rainfall amount and reveals the same seasonal signal observed in local rain and drip water δ18O. We observe significant positive correlations, with a 6 month lag, between our dataset and the Niño4 Sea Surface Temperature (SST) index (r = 0.49, p < 0.001) and the IOD (r = 0.41, p < 0.001). A cross-wavelet analysis between MAW 02-01 δ18O and Niño4 highlights a shared 4-6 year frequency throughout and a strong in-phase 8-12 year frequency beginning in 1990 and persisting for the duration of the record. The latter may reflect an increase in strength and frequency of central Pacific (CP) El Niño events since 1990. Such events, with stronger SST anomalies in the central Pacific, are more likely to restrict Indian Summer Monsoon (ISM) strength through enhanced westward migration of the descending arm of the Walker Cell. HYSPLIT back-trajectory analysis

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Huyghe, Damien; Mouthereau, Frédéric; Emmanuel, Laurent

    2012-09-01

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

  19. Controlling factors on a paleo-lake oxygen isotope record (Yammoûneh, Lebanon) since the Last Glacial Maximum

    NASA Astrophysics Data System (ADS)

    Develle, Anne-Lise; Herreros, Julien; Vidal, Laurence; Sursock, Alexandre; Gasse, Françoise

    2010-04-01

    Late Quaternary paleoclimatic changes in the Levant are difficult to extract from carbonate oxygen isotope records partly because the factors controlling the terrestrial δ 18O signals are not fully understood in this region characterized by sharp climatic gradients. Here, we address this purpose by presenting the first 14C-dated isotope record from the northern Levant. The record is based on oxygen isotopes from ostracod shells from lacustrine-palustrine deposits accumulated in a small karstic, hydrologically open basin (Yammoûneh), located on the eastern flank of Mount Lebanon. We have first constructed a composite isotopic record obtained from three different ostracod taxa. This yields an oxygen isotope record of ostracods (δ ost) related to the most widespread species ( Ilyocypris inermis), and converted to δ 18O values coeval with calcite precipitated in equilibrium (δ C) with the lake water (δ L). As with other records from the Mediterranean region, the Yammoûneh profile shows maximum and minimum δ C values during the LGM and the early Holocene, respectively, and a slight late Holocene increase. In order to discuss the potential causes of the observed δ 18O values fluctuations (e.g., changes in the isotopic composition of the moisture source, temperature, precipitation minus evaporation (P-E) balance, or atmospheric circulation), we tentatively reconstruct the lake water isotope composition by correcting the δ C values for lake water temperature using regional paleotemperature estimates. Inferred δ L values were then corrected for the isotopic composition of the Eastern Mediterranean sea surface water (the moisture source) derived from planktonic foraminifera δ 18O values corrected for alkenone-based sea surface temperature. Our study suggests that Holocene δ L fluctuations are primarily linked to changes in the sea surface water composition (source effect) amplified by enhanced inland rainfall during the early Holocene. During the LGM, low δ L

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  1. Oxygen 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

    Shu, Y.; Feng, X.

    2002-12-01

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

  7. 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.

  8. Calibration of sclerosponge oxygen isotope records to temperature using high-resolution δ 18O data

    NASA Astrophysics Data System (ADS)

    Rosenheim, Brad E.; Swart, Peter K.; Willenz, Philippe

    2009-09-01

    A revised calibration is presented relating the oxygen isotope composition of the aragonite-secreting sclerosponge Ceratoporella nicholsoni, oxygen isotope composition of seawater, and ambient water temperature. This new relationship has been obtained using high-resolution δ 18O data measured in sclerosponges from the Bahamas and Jamaica compared to ambient temperature measurements and δ 18O values of seawater from the two locations, both measured and published. New data improve an existing calibration which was determined using measurements of salinity rather than directly measured δ 18O values of the seawater and was composed of measurements from different species of sclerosponge and other aragonite-secreting organisms. The updated calibration ( n = 12, r2 = 0.95) is: T(°C)=16.1(±3.1)-[6.5(±1.1)](δ-δ), where T is temperature in degrees Celsius, δ arag is the δ 18O value of aragonite normalized to VPDB, and δ sw is the δ 18O value of water normalized to VSMOW. This calibration improves accuracy and precision of Caribbean sclerosponges for reconstructions of temperature as well as δ 18O values of seawater.

  9. 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.

  10. Stable carbon and oxygen isotope record of central Lake Erie sediments

    USGS Publications Warehouse

    Tevesz, M.J.S.; Spongberg, A.L.; Fuller, J.A.

    1998-01-01

    Stable carbon and oxygen isotope data from mollusc aragonite extracted from sediment cores provide new information on the origin and history of sedimentation in the southwestern area of the central basin of Lake Erie. Sediments infilling the Sandusky subbasin consist of three lithologic units overlying glacial deposits. The lowest of these is a soft gray mud overlain by a shell hash layer containing Sphaerium striatinum fragments. A fluid mud unit caps the shell hash layer and extends upwards to the sediment-water interface. New stable isotope data suggest that the soft gray mud unit is of postglacial, rather than proglacial, origin. These data also suggest that the shell hash layer was derived from erosional winnowing of the underlying soft gray mud layer. This winnowing event may have occurred as a result of the Nipissing flood. The Pelee-Lorain moraine, which forms the eastern boundary of the Sandusky subbasin, is an elevated area of till capped by a sand deposit that originated as a beach. The presence of both the shell hash layer and relict beach deposit strengthens the interpretation that the Nipissing flood was a critical event in the development of the southwestern area of the central basin of Lake Erie. This event, which returned drainage from the upper lakes to the Lake Erie basin, was a dominant influence on regional stratigraphy, bathymetry, and depositional setting.

  11. 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.

  12. Geomorphic Drainage Capture Recorded by Oxygen Isotopes of Green River Formation Lacustrine Mudstone, Eocene, Wyoming

    NASA Astrophysics Data System (ADS)

    Doebbert, A. C.; Booth, A. L.; Carroll, A.; Chamberlain, C.; Rhodes, M.

    2005-12-01

    The isotopic composition of cement and other meteoric precipitates are increasingly being used to interpret orogenic uplift histories, based on the relationship between altitude and rainwater δ18O. However, other variables such as changing regional drainage patterns may also affect the downstream composition of surface waters, especially when multiple drainages commingle in a lake. The Green River Formation contains some of the best documented lacustrine deposits in the world, making it ideal for examining such issues. Carbonate mudstone in balanced-fill facies of the lower LaClede Bed averages 3.41‰ (PDB), and records a deep, saline to brackish lake that fluctuated near its sill. In contrast, overfilled facies of the upper LaClede Bed record a freshwater lake, and δ18O reaches values as low as -9.72‰. This transition occurred shortly after deposition of the Analcite Tuff at 48.94 ± 0.12 Ma (Smith et al., 2003), and was geologically abrupt. Based on 40Ar/39Ar-calibrated sediment accumulation rates it required no more than 200-300 ky. An almost identical transition occurs in two cores separated by about 30 km, making local diagenesis an unlikely cause. The magnitude of δ18O change is similar to that in some uplift studies, but its rapidity virtually excludes uplift as a controlling mechanism. Instead, we propose that both the change in sedimentation and the sharp decrease in δ18O are the result of a drainage capture event. The addition of a new drainage to the basin may have adjusted isotopic values in two ways: by introducing runoff with relatively low δ18O, and by decreasing residence time (and therefore evaporation) of lake water. Decreasing 87Sr/86Sr across the same transition suggests that the newly added waters may have been sourced from rising volcanic topography to the north in the Absaroka province. Although this rising topography allows for the possibility of some uplift component, the rate of change in lacustrine δ18O is consistent with

  13. Comparison of planktic foraminiferal oxygen and carbon isotope records in two Southern California basins from LGM to present

    NASA Astrophysics Data System (ADS)

    Gill, D.; Quintana Krupinski, N. B.; Paytan, A.

    2012-12-01

    The Southern California Bight is known for its high-resolution sediment records which provide a growing body of evidence suggesting that this region has a strong atmospheric teleconnection to North Atlantic climate changes. However, some discussion exists over whether climatic changes observed from Santa Barbara Basin (SBB) sediment primarily reflect global climate events, or whether regional or local effects play a significant role in the climate signal observed in SBB. Santa Monica Basin (SMB), located adjacent to SBB, is well-located to help answer this question. We present a new SMB record of carbon and oxygen isotopes from G. bulloides and N. incompta to reconstruct a climatic record for the last 30,000 years. From this record we are able to see the transition from the last glacial maximum through the Holocene; furthermore, we are able to capture with decade-to-century-scale resolution the Younger Dryas and Bolling-Allerod. These results will be compared to records from SBB and other California Borderland Basins to investigate regional variability in their response to climate, circulation, and productivity over the past 30 ka.

  14. Oxygen isotope cosmothermometer.

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

    Variations in oxygen isotopic abundances of meteoritic minerals, chondrules, whole meteorites, and planets are discussed in terms of a model involving isotopic exchange between primordial dust and a cooling solar nebular gas. From the temperature-dependence of the isotopic fractionation factors, temperatures have been assigned to the processes of initial condensation, chondrule formation, and planetary accretion. Separated phases from carbonaceous chondrites fall into three isotopic groups representing widely differing conditions of formation: (1) low-iron olivine and pyroxene, and calcium-aluminum silicates condensed at temperatures above 1000 K; (2) high-iron olivine and pyroxene melted to form chondrules after prior cooling and exchange to temperatures of 530-620 K; and (3) hydrous silicates condensed at temperatures below 400 K.

  15. Characterizing seawater oxygen isotopic variability in a regional ocean modeling framework: Implications for coral proxy records

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    Reconstructions of the El Niño-Southern Oscillation (ENSO) are often created using the oxygen isotopic ratio in tropical coral skeletons (δ18O). However, coral δ18O can be difficult to interpret quantitatively, as it reflects changes in both temperature and the δ18O value of seawater. Small-scale (10-100 km) processes affecting local temperature and seawater δ18O are also poorly quantified and contribute an unknown amount to intercoral δ18O offsets. A new version of the Regional Ocean Modeling System capable of directly simulating seawater δ18O (isoROMS) is therefore presented to address these issues. The model is used to simulate δ18O variations over the 1979-2009 period throughout the Pacific at coarse (O(50 km)) resolution, in addition to 10 km downscaling experiments covering the central equatorial Pacific Line Islands, a preferred site for paleo-ENSO reconstruction from corals. A major impact of downscaling at the Line Islands is the ability to resolve fronts associated with tropical instability waves (TIWs), which generate large excursions in both temperature and seawater δ18O at Palmyra Atoll (5.9°N, 162.1°W). TIW-related sea surface temperature gradients are smaller at neighboring Christmas Island (1.9°N, 157.5°W), but the interaction of mesoscale features with the steep island topography nonetheless generates cross-island temperature differences of up to 1°C. These nonlinear processes alter the slope of the salinity:seawater δ18O relationship at Palmyra and Christmas, as well as affect the relation between coral δ18O and indices of ENSO variability. Consideration of the full physical oceanographic context of reef environments is therefore crucial for improving δ18O-based ENSO reconstructions.

  16. Oxygen Isotopes in Meteorites

    NASA Astrophysics Data System (ADS)

    Clayton, R. N.

    2003-12-01

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

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    PubMed

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

    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

  20. 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

  1. Patterns of moisture source and climate variability in the southeastern United States: a four-century seasonally resolved tree-ring oxygen-isotope record

    NASA Astrophysics Data System (ADS)

    Labotka, D. M.; Grissino-Mayer, H. D.; Mora, C. I.; Johnson, E. J.

    2016-04-01

    This study presents a climate reconstruction utilizing a seasonally resolved 417-year oxygen-isotope record of tree rings from southern Georgia, United States (1580-1997 CE). Oxygen isotopes within the cellulose predominately reflect moisture source observed on a seasonal scale between earlywood and latewood growth. Signatures of large climate oscillations were captured in modern and subfossil wood. Spectral and wavelet transform analyses of seasonally resolved oxygen isotopes showed distinct periodicities coinciding with the Atlantic multidecadal oscillation and other major climate oscillation phenomena. Oxygen-isotope values in latewood growth revealed a significant correlation with North Atlantic sea surface temperature anomalies. This correlation suggests that the precipitation source was strongly influenced by fluctuations in the Atlantic multidecadal oscillation and teleconnections with other major climate phenomena such as the North Atlantic subtropical high-pressure system, El Niño Southern Oscillation, and Pacific Decadal Oscillation. These results emphasize the utility of oxygen isotopes in tree rings for revealing seasonal influences associated with major climate drivers over centuries and enhance our understanding of long-term climate behavior on a detailed scale.

  2. Oxygen isotope geochemistry of zircon

    NASA Astrophysics Data System (ADS)

    Valley, John W.; Chiarenzelli, Jeffrey R.; McLelland, James M.

    1994-09-01

    ranging from 39 to 75 wt% SiO2. Only olivine metagabbros have lower average values (6.4/mil), consistent with the hypothesis that they represent nearly pristine samples of the anorthosite's parent magma. Whole-rock values of delta (O-18) are also high in the AMCG suite and increase with SiO2 content, as predicted for a process of assimilation and fractional crystallization. Taken together, these data suggest that the elevated values of oxygen isotope ratios result from partial melting and contamination involving metasediments in the deep crust, before the crystallization of zircon. More normal values elsewhere in the Grenville Province record deep-seated, pre-1150 Ma regional differences.

  3. A High-Resolution Oxygen Isotope Record for the Cariaco Basin, Venezuela Over the Last 6000 Years

    NASA Astrophysics Data System (ADS)

    Tedesco, K.; Thunell, R.; Tappa, E.

    2001-12-01

    Oxygen isotope records of three species of planktonic foraminifera (Globigerinoides ruber (pink), Globigerina bulloides and Neogloboquadrina dutertrei) from the Cariaco Basin, Venezuela were used to construct a high-resolution climate record for the Caribbean region for the mid to late Holocene. Our results indicate decreases in sea surface temperatures and/or increases in salinity in the basin at least four times over the last 4000 years (at ~3800-3200, 2800-2500, 2200-2000, and after 650 cal. yrs. B.P.). These events are coincident with high stands of Lake Titicaca, Bolivia/Peru suggesting a similar forcing mechanism. Paleoclimate records from the circum-Caribbean indicate arid conditions commenced in this region between about 3600-3200 cal. yrs. B.P.. This corresponds to a decrease in the δ 18O of G. ruber (pink) and decreases in the δ 18O differences between G. bulloides - G. ruber (pink) and N. dutertrei - G. ruber (pink). In addition, the deep dwelling planktonic foraminifera species Globorotalia crassaformis migrates into Cariaco Basin at about 3500 cal. yrs. B.P.. Taken together these data indicate colder sea surface temperatures and a shallow thermocline, possibly due to increased upwelling. Increased evaporation at this site would also result in higher G. ruber (pink) δ 18O values. Dry conditions in the circum-Caribbean tropics and wetter conditions in the Altiplano of Bolivia and Peru and the Amazon basin during the mid to late Holocene are consistent with a southward displacement of the Inter-Tropical Convergence Zone (ITCZ) resulting in decreased precipitation and increased trade wind intensity in the Cariaco Basin.

  4. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    Ocean acidification (OA) in response to rising atmospheric pCO2 is generally expected to reduce rates of calcification by reef calcifying organisms, with potentially severe implications for coral reef ecosystems. Reef dwelling foraminifera is one of the most important primary and carbonate producers in coral reef environments. Their shells are composed of high-Mg calcite and they are host to algal endosymbionts. In our previous culture experiment with two algal reef dwelling foraminifers, Amphisorus kudakajimensis and Calcarina gaudichaudii in the seawater of five different pCO2 conditions, net calcification of A. kudakajimensis was reduced under higher pCO2, whereas net calcification of C. gaudichaudii showed continued increasing trend with pCO2. These contrasting responses between the two species are possibly due to differences in calcification mechanisms and to links between calcification by the foraminifers and photosynthesis by the algal endosymbionts. But the factors affecting these calcification mechanisms are poorly understood. In this study, to get a better understanding of the effect of OA on their calcification, we cultured three reef dwelling foraminifers: Amphisorus hemprichii, belong to imperforate species, Baculogypsina sphaerulata, and C. gaudichaudii belong to perforate species, in the seawater of five different pCO2 conditions and we address the response of carbon and oxygen isotopes of the carbonate shells of foraminifers. The oxygen isotope ratio of cultured foraminiferal tests under five varied pCO2 seawater indicated no significant correlation to pCO2 values. On the other hand, the carbon isotope ratio of foraminiferal tests indicated heavy trend with rising pCO2 in all species. Alteration of carbonate chemistry result from ocean acidification may be effect strongly on carbon isotope composition relate to metabolic system (i.e. photosynthesis and respiration). In perforate species, both of oxygen and carbon isotope ratio were lighter than that

  6. 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.

  7. 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

  8. Oxygen isotope geospeedometry by SIMS

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  9. 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

  10. Punctuated evolution of global climate cooling during the late middle to early late Miocene: High-resolution planktonic foraminiferal and oxygen isotope records from the Mediterranean

    NASA Astrophysics Data System (ADS)

    Turco, E.; Hilgen, F. J.; Lourens, L. J.; Shackleton, N. J.; Zachariasse, W. J.

    High-resolution planktonic foraminiferal and oxygen isotope records are presented from a Mediterranean deep marine succession, dated astronomically between 12.12 and 9.78 Ma. Planktonic and benthic oxygen isotope records are punctuated by two episodes of δ18O increase, which have astronomical ages of 11.4 and 10.4 Ma and correspond to the Mi5 and Mi6 events of Miller et al. [1991a]. These ice growth events coincide with low-amplitude variations in the 1.2 Myr obliquity cycle and are accompanied by significant faunal changes in the Mediterranean, such as the arrival of neogloboquadrinids, the increase in abundance of the G. apertura-G. obliquus group, and the areal differentiation between N. atlantica and N. acostaensis. Short-term variations in the planktonic foraminiferal and oxygen isotope records correspond to dominantly precession-controlled sedimentary cycles. Features of the sapropel/gray marl layers indicate that the short-term astronomically controlled circum-Mediterranean climate changes remained basically the same over the last 12 Myr.

  11. Oxygen isotope heterogeneities in the earliest protosolar gas recorded in a meteoritic calcium aluminum-rich inclusion

    NASA Astrophysics Data System (ADS)

    Aléon, Jérôme; El Goresy, Ahmed; Zinner, Ernst

    2007-11-01

    Combined petrologic, oxygen and magnesium isotopic and trace element analyses of a compound calcium-aluminum-rich inclusion (CAI) from the Efremovka reduced CV3 carbonaceous chondrite reveal that it consists of a Mg-rich, 16O-rich xenolithic CAI, previously altered in the nebula, that impacted an extensively molten, 16O-depleted, type A host CAI shortly before the end of the host's crystallization. Convoluted regions in the xenolith were probably formed by rapid crystallization of the partial melt produced during impact. Oxygen isotopic ratios in the host CAI are correlated both with melilite chemistry and location in the inclusion. The region immediately inside the Wark-Lovering rim of the CAI consists of 16O-rich gehlenite with Δ 17O ranging down to - 20‰ but melilite becomes progressively 16O-poor (Δ 17O ˜ 0‰) and Mg-rich towards the interior. In the absence of Mg isotopic fractionation, this variation is best attributed to O isotopic exchange between the nebular gas and the partially molten inclusion during its crystallization. This event lasted less than 200 h, which implies that the host CAI was transported between two nebular reservoirs with distinct O isotopic compositions during this time. Examination of possible transport mechanisms suggests that the transport occurred over a distance of less than 1 astronomical unit. The close-to-canonical 26Al/ 27Al ratio of 4.1 × 10 - 5 determined from both inclusions implies that at most 670,000 yr after the birth of the Solar System, the 16O-rich reservoir was spatially limited and an 16O-poor reservoir with typical planetary isotopic composition was available for planet formation.

  12. Variability of the Asian summer monsoon during the penultimate glacial/interglacial period inferred from stalagmite oxygen isotope records from Yangkou cave, Chongqing, Southwestern China

    NASA Astrophysics Data System (ADS)

    Li, T.-Y.; Shen, C.-C.; Huang, L.-J.; Jiang, X.-Y.; Yang, X.-L.; Mii, H.-S.; Lee, S.-Y.; Lo, L.

    2013-11-01

    The orbital-timescale dynamics of the Quaternary Asian summer monsoons (ASM) are frequently attributed to precession-dominated Northern Hemisphere summer insolation. However, this ASM variability is inferred primarily from oxygen isotope records of stalagmites, mainly from Sanbao cave in mainland China, and may not provide a comprehensive picture of ASM evolution. A new spliced stalagmite oxygen isotope record from Yangkou cave tracks summer monsoon precipitation variation from 124-206 thousand years ago in Chongqing, southwest China. When superimposed on the Sanbao record, the Yangkou-inferred precipitation time series is shown to support the strong ASM periods at marine isotope stages (MIS) 6.3, 6.5, and 7.1 and weak ASM intervals at MIS 6.2, 6.4, and 7.0. This consistency confirms that ASM events affected most of mainland China. We show that change in glacial/interglacial (G/IG) ASM intensity was also governed by the Walker Circulation by combining our results with published paleo-Pacific thermal and salinity records. One of the strongest ASM events over the past fiver G/IG cycles, at MIS 6.5, was enhanced by such zonal forcing associated with prevailing trade winds in the Pacific.

  13. 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

  14. Plant Carbonate Fossils from the Ephemeral Pond Domain in South Texas/NE Mexico Yield a Record of Tropical Cyclone Activity: Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Lawrence, J. R.; Maddocks, R.; Slowey, N. C.; Roark, E.

    2013-05-01

    Tropical cyclones produce rain with anomalously low oxygen isotope ratios. When dry ponds suddenly receive a large influx of this rainwater, algal plants known as "Charo" grow rapidly and produce desiccation resistant seeds covered by a carbonate coating. The oxygen isotopic composition of the carbonate reflects the presence of tropical cyclone water. A sediment core was taken in 2010 and pond waters were collected. Three tropical cyclones flooded the pond that year. The pond waters exhibited low isotope ratios that gradually rose as evaporation took place over the following days. Carbonate coated seeds "Charo" were separated from the top centimeter of the core. Two of the analyzed samples exhibited distinctly low isotope ratios indicating that the pond had been flooded with water from tropical cyclones at least twice. Additional isotopic analyses of carbonate coating from the seeds deeper in the core are in progress. The quantity of carbonate coating the seeds is more than adequate for obtaining lead 210 and carbon 14 dates. The main objective of our study is to produce a longterm record of tropical cyclone activity in the South Texas / Northeast Mexico region.

  15. Punctuated Evolution of Global Climate Cooling during the late Middle to early Late Miocene: High-Resolution Planktonic Foraminiferal and Oxygen Isotope Records from the Mediterranean

    NASA Astrophysics Data System (ADS)

    Turco, E.; Hilgen, F. J.; Lourens, L. J.; Shackleton, N. J.; Zachariasse, W. J.; Kruk, R. W.

    2001-05-01

    High-resolution planktonic foraminiferal and oxygen isotope records are presented from a deep marine succession of late Middle to early Late Miocene age in the Mediterranean, dated astronomically between 12.12 and 9.78 Ma. Long-term changes in the faunal composition reflect the overall late Neogene cooling trend. The planktonic and benthic oxygen isotope records are punctuated by two episodes of δ 18O increase, which have astronomical ages of 11.4 and 10.4 Ma and correspond to the Mi5 and Mi6 events of Miller et al. (1991a). The first-order comparison with the astronomical time series for the variations in the tilt of the Earth's axis revealed that these ice growth events coincide with low amplitude variations in the 1.2 myr obliquity cycle. This phase relation is different from that found during the last 5 myr, pointing to a fundamentally different response of the ice sheets to long-term obliquity induced variations in insolation. The inferred global cooling during Mi5 and Mi6 is accompanied by significant faunal changes in the Mediterranean, such as the arrival of neogloboquadrinids, the increase in abundance of the G. apertura-G. obliquus group, and the areal differentiation between N. atlantica and N. acostaensis. Other faunal events, such as the disappearance of P. mayeri and the coiling changes in neogloboquadrinids are not related to these glacial episodes, but may have been controlled by short-term climate fluctuations superimposed on long-term astronomically and/or tectonically induced climate changes. Short-term variations in the planktonic foraminiferal and oxygen isotope records correspond to dominantly precession-controlled sedimentary cycles. The micropaleontological and stable isotopic features of sapropel/grey marl layers are identical to those observed for Late Miocene to Pleistocene sapropels, indicating that the short-term astronomically controlled circum-Mediterranean climate changes remained basically the same over the last 12 myr.

  16. Stable carbon isotopes of C3 plant resins and ambers record changes in atmospheric oxygen since the Triassic

    NASA Astrophysics Data System (ADS)

    Tappert, Ralf; McKellar, Ryan C.; Wolfe, Alexander P.; Tappert, Michelle C.; Ortega-Blanco, Jaime; Muehlenbachs, Karlis

    2013-11-01

    Estimating the partial pressure of atmospheric oxygen (pO2) in the geological past has been challenging because of the lack of reliable proxies. Here we develop a technique to estimate paleo-pO2 using the stable carbon isotope composition (δ13C) of plant resins-including amber, copal, and resinite-from a wide range of localities and ages (Triassic to modern). Plant resins are particularly suitable as proxies because their highly cross-linked terpenoid structures allow the preservation of pristine δ13C signatures over geological timescales. The distribution of δ13C values of modern resins (n = 126) indicates that (a) resin-producing plant families generally have a similar fractionation behavior during resin biosynthesis, and (b) the fractionation observed in resins is similar to that of bulk plant matter. Resins exhibit a natural variability in δ13C of around 8‰ (δ13C range: -31‰ to -23‰, mean: -27‰), which is caused by local environmental and ecological factors (e.g., water availability, water composition, light exposure, temperature, nutrient availability). To minimize the effects of local conditions and to determine long-term changes in the δ13C of resins, we used mean δ13C values (δ13Cmeanresin) for each geological resin deposit. Fossil resins (n = 412) are generally enriched in 13C compared to their modern counterparts, with shifts in δ13Cmeanresin of up to 6‰. These isotopic shifts follow distinctive trends through time, which are unrelated to post-depositional processes including polymerization and diagenesis. The most enriched fossil resin samples, with a δ13Cmeanresin between -22‰ and -21‰, formed during the Triassic, the mid-Cretaceous, and the early Eocene. Experimental evidence and theoretical considerations suggest that neither change in pCO2 nor in the δ13C of atmospheric CO2 can account for the observed shifts in δ13Cmeanresin. The fractionation of 13C in resin-producing plants (Δ13C), instead, is primarily influenced by

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

    USGS Publications Warehouse

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

    1978-01-01

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

  18. Oxygen isotope records from semi-tropical trees as high-resolution indicators of recent climate change, from South Florida to Brazil

    NASA Astrophysics Data System (ADS)

    Anderson, W. T.; Evans, S. L.; Pinzon, M. C.; Grissino-Mayer, H. D.

    2002-12-01

    The development of new proxy climate records and approaches 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 ice cores and varved lake sequences. Here we present the results of several projects which focus on the oxygen isotopic analysis of tree rings from semi-tropical trees. Typically trees in tropical hardwood hammocks lack the rings necessary for proper dendrochronology. However, in semi-tropical ecosystems where strong seasonality between wet and dry seasons occur, certain species do form annual rings. The species we used are Pinus elliottii from the Florida Keys, and Araucaria angustifolia from southeastern Brazil. Each species has distinct rings, although the chronologies are complicated by the presence of false rings. The analyses completed on the chronologies presented indicate it is possible to reconstruct the oxygen isotopic composition of the precipitation these trees where using over the last century.

  19. 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

  20. 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.

  1. 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.

  2. Oxygen and silicon isotopes in ALHA 81005

    NASA Astrophysics Data System (ADS)

    Mayeda, T. K.; Clayton, R. N.; Molini-Velsko, C. A.

    1983-09-01

    The Antarctic meteorite ALHA81005 has oxygen and silicon isotopic compositions identical with lunar highland rocks. The oxygen is distinctly unlike that in calcium-rich achondrites. The isotopic data are entirely consistent with a lunar origin for the meteorite.

  3. Spatial Asian Monsoon variability at MIS 6.2 inferred from oxygen isotope records of stalagmites from Yangkou Cave, Chongqing, China

    NASA Astrophysics Data System (ADS)

    Huang, L.; Li, T.; Yang, X.; Shen, C.

    2011-12-01

    Using the oxygen isotope records of stalagmites collected from different caves in China, Asian Monsoon (AM) variation over past 380 ka has been reconstructed (e.g. Wang et al., 2001, Science, 294, 2345-2348; Yuan et al., 2004, Science, 304, 575-578; Wang et al., 2008, Nature, 451, 1090-1093; Cheng et al., 2009, Science, 326, 248-252; Zhao et al., 2010, EPSL, 298, 191-198). Chinese cave δ18O records show that summer AM intensity primarily follows Northern Hemisphere summer insolation on orbital timescales. However, an unusual stalagmite δ18O-inferred weakest summer AM at the marine isotope stage (MIS) 6.2 (129-136 ka) is recorded in Sanbao Cave (Hubei province; 31°40'N, 110°26'E) (Wang et al., 2008, Nature, 451, 1090-1093). To clarify that this weakest summer AM during the penultimate deglaciation in Hubei province is site-specific or dominant in the entire mainland, we have collected stalagmite samples with deposition time intervals of interest from Yangkou Cave (Chongqing city; 29°2'N, 107°11'E) located about 400 km southwest to Sanbao Cave. Using MC-ICP-MS techniques on these stalagmites with high uranium levels of 1-20 ppm, we can refine the durations and intensities of the summer AM events during the entire MIS 6 and also further understand the spatial variability and possible mechanism for the weakest summer AM at the MIS 6.2.

  4. Oxygen isotope studies of ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Clayton, Robert N.; Mayeda, Toshiko K.; Olsen, Edward J.; Goswami, J. N.

    1991-01-01

    Several stages in the evolution of ordinary chondritic meteorites are recorded in the oxygen isotopic composition of the meteorites and their separable components (chondrules, fragments, clasts, and matrix). The whole-rock isotopic compositions reflect the iron-group of the meteorite (H, L, or LL). Isotopic uniformity of H3 to H6 and L3 to L6 are consistent with closed-system metamorphism within each parent body. LL3 chondrites differ slightly from LL4 to LL6, implying a small degree of open-system aqueous alteration and carbon reduction. On the scale of individual chondrules, the meteorites are isotopically heterogeneous, allowing recognition of the solar-nebular processes of chondrule formation. Chondrules for all classes of ordinary chondrites are derived from a common population, which was separate from the population of chondrules in carbonaceous or enstatite chondrites. Chondrules define an isotopic mixing line dominated by exchange between (O - 16)-rich and (O - 16)-poor reservoirs. The oxygen isotopic compositions of chondrites serve as 'fingerprints' for identification of genetic association with other meteorite types (achondrites and iron) and for recognition of source materials in meteoritic breccias.

  5. An oxygen isotope record of prograde and retrograde subduction fluids preserved in garnets from eclogite and related rocks from California and Greece

    NASA Astrophysics Data System (ADS)

    Page, F.; Strickland, A.; Essene, E. J.; Valley, J. W.

    2012-12-01

    In situ analysis of oxygen isotopes in garnet formed during subduction metamorphism offers a powerful new tool to unravel fluid histories of eclogite and related rocks. Slow intracrystalline diffusion rates in garnet allow it to preserve primary oxygen isotope ratios, and its utility in thermobarometry and geochronology allows oxygen isotope ratios to be tied to a P-T-t-fluids path. These paths can be used to identify when, in the history of a rock, fluid infiltration took place. Application of this method to orogenic eclogites has demonstrated external fluid interaction during prograde metamorphism (Russell et al., 2012 CMP in press). Analyses of garnets from metamafic and metasedimentary blocks in mélange-type subduction environments reveal a greater diversity in the timing of fluid infiltration events than those found in continental collision zones. Garnets from two glaucophane eclogites from Syros, Greece were found to be homogeneous within analytical uncertainty (δ18O=3.6±0.5‰ 2SD; 4.6±0.4‰). This result is consistant with existing studies in the region demonstrating limited fluid flow in eclogite blocks during metamorphism. Cation and oxygen isotope zoning in garnet from tectonic blocks of eclogite and garnet hornblendite from the Franciscan Formation reveals separate prograde and retrograde fluid histories. Garnet cores preserve a homogeneous prograde δ18O history with both high (11‰) and low (4‰) values in different samples. Multiple episodes of garnet resorption and regrowth record a dramatically changing bulk oxygen composition resulting in 6-7‰ neoformed garnet rims in both samples. Thermobarometry of inclusions (grt+cpx+phg) in eclogite garnet rims yields lower pressure blueschist-facies PT, requiring that low-δ18O fluid infiltration and garnet rim growth post-dates substantial exhumation. Tectonic blocks of metamafic and metasedimentary rocks are found in mélange on Santa Catalina Island. Samples of garnet hornblendite and garnet

  6. Model evaluation of the coherence of a common source water oxygen isotopic signal recorded by tree-ring cellulose and speleothem calcite

    NASA Astrophysics Data System (ADS)

    Managave, S. R.

    2014-04-01

    isotopic compositions (δ18O) of tree rings and speleothems inherit δ18O of precipitation (δ18Oppt) and are used to reconstruct past variations in the amount of precipitation or temperature. Integration of δ18O records of both the proxies for a multiproxy climate reconstruction necessitates understanding of the extent to which the initial δ18Oppt is modified in both the proxies before getting preserved in them. A forward modeling approach, assuming both the proxies have access to a common source water δ18O signal, is employed to assess the expected maximum correlation between the δ18O records of the two proxies on interannual time scale and the factors influencing the correlation. Variations in the leaf temperature, relative humidity, δ18O of atmospheric water vapor introduce variations in δ18O of tree-ring cellulose, while the variations in the cave temperature and oxygen isotopic equilibrium/disequilibrium conditions between calcite and drip water influence δ18O of speleothem calcite. Variation introduced by these factors in δ18O of individual proxies as compared to the variation in δ18Oppt is crucial in deciding the correlation between δ18O records of the two proxies. When the former is higher than or comparable with the latter, finding one to one correspondence between the δ18O records of the two proxies could be challenging. Modeling exercise revealed a favorable climatic condition at Jagdalpur (19.08°N, 82.03°E), a potential tropical location for tree ring and speleothem-based climate reconstruction, for inheriting a common source water δ18O signal in both the proxies. δ18O records of tree ring and annually resolved speleothem from Jagdalpur could be integrated for the multiproxy climate reconstruction.

  7. 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.

  8. 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

  9. A Plio-Pleistocene Synthesis of Tropical Planktonic Oxygen Isotope Records: Early Closure of the Isthmus of Panama and Late Development of the Walker Circulation

    NASA Astrophysics Data System (ADS)

    Wara, M. W.; Ravelo, A. C.; Ziegler, C. L.; Schilla, A. S.

    2001-12-01

    We present records from Ocean Drilling Program (ODP) Site 847 in the Eastern Equatorial Pacific (EEP) Ocean of oxygen (δ 18O) and carbon isotope measurements on the mixed layer dwelling planktonic foraminifera, Globogerinoides sacculifer (w/o sacc-like final chamber) and in the deep dwelling planktonic foraminifera Globoritalia tumida from 5 Ma to present. ODP Site 847 (0° N, 95° W, 3346 m water depth) is ideally located to record EEP conditions over this time interval because it is in the core of South Equatorial Current. A comparison of the ODP Site 847 G. sacculifer (w/o sacc) record with previously published planktonic foraminiferal δ 18O records from the western tropical Pacific (ODP Site 806), the eastern Indian Ocean (ODP Site 758) and the Caribbean Sea (ODP Site 999) indicates several major changes in tropical ocean circulation over the past 5 Ma. At 4.2 Ma significant changes in the δ 18O difference between the EEP (ODP Site 847) and the Caribbean (ODP Site 999) indicate that surface water exchange between the Atlantic and Pacific became restricted, or that there was a tropical climate reorganization that influenced surface salinity/temperature fields of both basins. Between 5 and 2 Ma, there is no gradient in δ 18O in the western (ODP Site 806) and eastern (ODP Site 847) tropical Pacific, indicative of a reduced or absent Walker circulation. After 2 Ma, the δ 18O gradient developed and then remained relatively constant during the past 1 Ma. At the same time as the gradient in the tropical Pacific developed, the difference between conditions in the eastern Indian Ocean (ODP site 758) and western tropical Pacific (ODP Site 806) was reduced. After 1 Ma, foraminifera at the two sites (806 and 758) had nearly identical δ 18O compositions. In sum, as the gradient between the eastern and western tropcial Pacific was established, the difference between the Indian and Pacific oceans was reduced. Thus, hydrographic gradients indicative of a modern vigorous

  10. Measuring Oxygen Isotopes with COSIMA

    NASA Astrophysics Data System (ADS)

    Paquette, J. A.; Engrand, C.; Stenzel, O.; Hilchenbach, M.

    2014-12-01

    Oxygen isotopes in a variety of solar system solids show non-mass-dependent fractionation, i.e. are fractionated along a slope = 1 line in a three isotope plot, rather than the equilibrium fractionation line whose slope is close to 0.5 (Clayton, 1973). Many models have been put forward to explain this observation, such as galactic chemical evolution (Clayton, 1988), photochemical self-shielding (Thiemens and Jackson, 1987; Clayton, 2002; Yurimoto and Kuramoto, 2004; Lyons and Young, 2005), quantum chemical explanations (Hathorn and Marcus, 1999, 2000; Gao and Marcus, 2002; Marcus, 2004), the processing of solids via nebular lightning (Nuth et al, 2011), and others. Some of the models were invalidated when the Genesis results showed that the oxygen isotopic fractionation of solar wind (and hence of the Sun) was relatively much richer in 16O than such bodies as the Earth or the Moon. Whatever the process that produced non-mass-dependent fractionation in some chondrules and calcium aluminum inclusions, its signature may also be detectable in other solar system solids. If at least some cometary dust was produced in the inner nebula and only later transported outward to be incorporated into comets, then such dust may also show some degree of non-mass-dependent fractionation. The COSIMA instrument on the Rosetta spacecraft (Kissel et al 2009) is a secondary ion mass spectrometer designed to measure the composition of cometary dust. Using calibration data from the COSIMA reference model and flight data if possible, measurement all three isotopes of oxygen will be attempted, and the results compared to other solar system bodies.

  11. 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

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

    SciTech Connect

    Grootes, P.M.; Stuiver, M.

    1986-01-01

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

  13. Major, trace element and oxygen isotope study of glass cosmic spherules of chondritic composition: The record of their source material and atmospheric entry heating

    NASA Astrophysics Data System (ADS)

    Cordier, Carole; Folco, Luigi; Suavet, Clément; Sonzogni, Corinne; Rochette, Pierre

    2011-09-01

    New geochemical data on cosmic spherules (187 major element, 76 trace element, and 10 oxygen isotope compositions) and 273 analyses from the literature were used to assess the chemical diversity observed among glass cosmic spherules with chondritic composition. Three chemical groups of glass spherules are identified: normal chondritic spherules, CAT-like spherules (where CAT refers to Ca-Al-Ti-rich spherules), and high Ca-Al spherules. The transition from normal to high Ca-Al spherules occurs through a progressive enrichment in refractory major elements (on average from 2.3 wt.% to 7.0 wt.% for CaO, 2.8 wt.% to 7.2 wt.% for Al 2O 3, and 0.14 wt.% to 0.31 wt.% for TiO 2) and refractory trace elements (from 6.2 μg/g to 19.3 μg/g for Zr and 1.6CI-4.3CI for Rare Earth Elements-REEs) relative to moderately refractory elements (Mg, Si) and volatile elements (Rb, Na, Zn, Pb). Based on a comparison with experimental works from the literature, these chemical groups are thought to record progressive heating and evaporation during atmospheric entry. The evaporative mass losses evaluated for the high Ca-Al group (80-90%) supersede those of the CAT spherules which up to now have been considered as the most heated class of stony cosmic spherules. However, glass cosmic spherules still retain isotopic and elemental evidence of their source and precursor mineralogy. Four out of the 10 normal and high Ca-Al spherules analysed for oxygen isotopes are related to ordinary chondrites ( δ18O = 13.2-17.3‰ and δ17O = 7.6-9.2‰). They are systematically enriched in Ni and Co (Ni = 24-500 μg/g) with respect to spherules related to carbonaceous chondrites (Ni < 1.2 μg/g, δ18O = 13.1-28.0‰ and δ17O = 5.1-14.0‰). REE abundances in cosmic spherules, which are not fractionated according to parent body or atmospheric entry heating, can then be used to unravel the precursor mineralogy. Spherules with flat REE pattern close to unity when normalized to CI are the most abundant in our

  14. 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

  15. 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.

  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. 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

  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 Isotope Biomarkers in the Search for Extraterrestrial Life

    NASA Astrophysics Data System (ADS)

    Blake, R. E.

    2002-12-01

    Of the five key light stable isotope biomarkers, C, H, O, N and S, oxygen has received relatively limited application to the search for life and previous oxygen isotope studies of extraterrestrial materials have often focused on oxygen in carbonates and silicates. This is due, in part, to the limited study and development of other oxygen isotope ratio systems relevant to biological activity (e.g., phosphate, sulfate, nitrate) specifically for application to the search for extraterrestrial life. An overview of oxygen isotope biomarker systematics will be presented with emphasis on development of O isotope ratios of phosphate as a new biomarker in the search for life on Mars and Europa. Phosphate is central to life on Earth and has been widely recognized and applied as a biomarker molecule in the form of phosphate minerals, in studies of ancient life on Earth. The lack of multiple stable isotopes of P precludes direct stable isotope ratio studies of P, however, it­A~\\x9Ds occurrence as predominantly orthophosphate, PO4, permits the use of oxygen isotope ratios of PO4 to trace enzymatic reactions and biological cycling of P in natural environments. The unique chemical properties of PO4 also make δ18O values of inorganic environmental PO4 (e.g., PO4 in soils, rocks; dissolved PO4) an ideal signature of the presence of both extant and extinct biological (enzymatic) activity as well as hydrothermal activity. Fundamental processes underlying the recording of biological signals in oxygen isotope ratios of environmental phosphate and development and application of δ18OP as a biomarker for Mars will be discussed, including characterization of δ18OP signatures of key Martian PO4 source reservoirs by analysis of Martian meteorites, and consideration of the co-evolution of δ18OP signatures with life on Mars and in terrestrial analogue systems.

  2. Oxygen isotopes implanted in the LDEF spacecraft

    NASA Technical Reports Server (NTRS)

    Saxton, J. M.; Lyon, I. C.; Chatzitheodoridis, E.; Vanlierde, P.; Gilmour, J. D.; Turner, G.

    1993-01-01

    Secondary ion mass spectrometry was used to study oxygen implanted in the surface of copper from the Long Duration Exposure Facility (LDEF). Oxidation that occurred in orbit shows a characteristic oxygen isotope composition, depleted in O-18. The measured depletion is comparable to the predicted depletion (45 percent) based on a model of the gravitational separation of the oxygen isotopes. The anomalous oxygen was contained within 10nm of the surface. Tray E10 was calculated to have received 5.14 x 10(exp 21) atoms of oxygen cm(sup -2) during the LDEF mission and so there is sufficient anomalous implanted oxygen present in the surface to obtain a reliable isotopic profile.

  3. Interdecadal-decadal climate variability from multicoral oxygen isotope records in the South Pacific Convergence Zone region since 1650 A.D.

    NASA Astrophysics Data System (ADS)

    Linsley, Braddock K.; Zhang, Peipei; Kaplan, Alexey; Howe, Stephen S.; Wellington, Gerard M.

    2008-06-01

    In the South Pacific, interdecadal-decadal oceanic and atmospheric variability, referred to as the Interdecadal Pacific Oscillation (IPO), is most pronounced in the South Pacific Convergence Zone (SPCZ) salinity front region. Here we have used annual average oxygen isotope (δ18O) time series from five coral cores collected from Fiji and Tonga in this region to construct a Fiji-Tonga Interdecadal-Decadal Pacific Oscillation (F-T IDPO) index of low-frequency (>9 and <55 years) climate variability back to 1650 A.D. We first demonstrate the consistency between this F-T IDPO index and a mean sea level (MSL) pressure-based SPCZ position index (SPI) (1891-2000), thus verifying the ability of coral δ18O to record past interdecadal-decadal climatic variations in this region back to 1891. The F-T IDPO index is then shown to be synchronous with the IPO index (1856-2000), suggesting that this coral-based index effectively represents the interdecadal-decadal scale climate variance back to 1650. The regularity of the F-T IDPO index indicates that interdecadal-decadal variability in the SPCZ region has been relatively constant over the past 350 years with a mean frequency of ˜20 years (variance peaks near 11 and 35 years). There is a consistent antiphase correlation of the F-T IDPO index and the interdecadal-decadal components in equatorial Pacific coral δ18O series from Maiana and Palmyra. This observation indicates that the eastward expansion (westward contraction) of the eastern salinity front of the Western Pacific Warm Pool (WPWP) occurs simultaneously (±<1 year) with the westward (eastward) shift of the SPCZ salinity front during positive IPO (negative IPO) phases. This is the same relationship observed during the phases of the El Niño Southern Oscillation.

  4. 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.

  5. Oxygen isotope relationships in iron meteorites

    NASA Technical Reports Server (NTRS)

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

    1983-01-01

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

  6. 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

  7. 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

  8. Normalization of oxygen and hydrogen isotope data

    USGS Publications Warehouse

    Coplen, T.B.

    1988-01-01

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

  9. Age and origin of post collision Baltoro granites, south Karakoram, North Pakistan: Insights from in-situ U-Pb, Hf and oxygen isotopic record of zircons

    NASA Astrophysics Data System (ADS)

    Mahar, Munazzam Ali; Mahéo, Gweltaz; Goodell, Philip C.; Pavlis, Terry L.

    2014-09-01

    Origin of post collision plutonism is critical to understand the tectonothermal evolution of the over thickened continental crust in collision zones. This has proven difficult to reconcile with the conventional whole rock geochemical and field based studies alone. We report in-situ study of zircon U-Pb, Hf and O isotopes from five samples of the Baltoro Plutonic Unit (BPU) in south Karakoram. The plutonic unit is the western part of the southern Asian margin of the India-Asia convergent zone. Baltoro granites and a biotite-rich enclave yielded similar and overlapping U-Pb ages ranging from 26 to 15 Ma. Hafnium isotopic composition (εHf (0)) is very heterogeneous ranging from - 17.1 to + 4.4 while the oxygen isotopic composition of the granites is homogeneous with mean δ18O ranging from 7.2 to 9.4‰. Based on U-Pb geochronology and Hf-O isotopic composition, the involvement of two main sources is suggested (1) Cretaceous calc-alkaline Karakoram crust and (2) Karakoram gneisses. Moreover, possible involvement of metasomatized Asian lithospheric mantle is supported by elevated oxygen composition of granites and identical Hf composition of biotite-rich enclave to the mantle derived Baltoro lamprophyre. However, direct contribution from juvenile pristine mantle is unlikely as no juvenile mantle type Hf and oxygen values were obtained. This also precludes the involvement of southward juvenile arc related component of Kohistan-Ladakh batholith. Our new U-Pb and Hf data are comparable to the Mesozoic Karakoram batholith, Miocene two-mica leucogranites in the Pangong Range and magmatism from the Lhasa terrane in south Tibet, suggesting a genetic link between the Karakoram and the rocks to the east. This magmatic event is best explained by lower crust partial melting promoted by both thermal equilibration following crustal thickening and heat advection by ultrapotassic magmas associated with the breakoff of the Indian continental margin.

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

  11. 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

  12. Formation temperatures of clays from the volcaniclastic series of Site 841 ODP: an oxygen isotopic record of a paleothermal flux into the Tonga forearc

    NASA Astrophysics Data System (ADS)

    Vitali, Frédéric; Blanc, Gérard; Gauthier-Lafaye, François; France-Lanord, Christian

    Oxygen isotopic compositions of clay minerals were determined on representative samples of the volcano-sedimentary series from Site 841 ODP (Tonga forearc). This isotopic study has demonstrated an abnormally high crystallisation temperature of the clay minerals with respect to temperature expected in burial diagenesis. Formation temperatures obtained using 18O reach up to 200°C in a Fe-chlorite-corrensite paragenesis found in the vicinity of basaltic andesite sills intruded into the Miocene tuffs. The paleothermal flux resulting from the cooling of the sills has produced very low grade contact metamorphism in the Miocene Tonga forearc deposits. The consequence of this was the formation of a large amount of hydrous silicates characterised near the sills by a Fe-clays-analcime mineralogical association.

  13. Oxygen isotopes in deep sea spherules

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

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

  14. 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.

  15. Oxygen isotope record of oceanic and high-pressure metasomatism: a P-T-time-fluid path for the Monviso eclogites (Italy)

    NASA Astrophysics Data System (ADS)

    Rubatto, Daniela; Angiboust, Samuel

    2015-12-01

    Fluids are considered a fundamental agent for chemical exchanges between different rock types in the subduction system. Constraints on the sources and pathways of subduction fluids thus provide crucial information to reconstruct subduction processes. The Monviso ophiolitic sequence is composed of mafic, ultramafic and minor sediments that have been subducted to ~80 km depth. In this sequence, both localized fluid flow and channelized fluids along major shear zones have been documented. We investigate the timing and source of the fluids that affected the dominant mafic rocks using microscale U-Pb dating of zircon and oxygen isotope analysis of mineral zones (garnet, zircon and antigorite) in high-pressure rocks with variable degree of metasomatic modification. In mafic eclogites, Jurassic zircon cores are the only mineralogical relicts of the protolith gabbros and retain δ18O values of 4.5-6 ‰, typical of mantle melts. Garnet and metamorphic zircon that grew during prograde to peak metamorphism display low δ18O values between 0.2 and 3.8 ‰, which are likely inherited from high-temperature alteration of the protolith on the sea floor. This is corroborated by δ18O values of 3.0 and 3.6 ‰ in antigorite from surrounding serpentinites. In metasomatized eclogites within the lower shear zone, garnet rim formed at the metamorphic peak shows a shift to higher δ18O up to 6 ‰. The age of zircons in high-pressure veins and metasomatized eclogites constrains the timing of fluid flow at high pressure at around 45-46 Ma. Although the oxygen data do not contradict previous reports of interaction with serpentinite-derived fluids, the shift to isotopically heavier oxygen compositions requires contribution from sediment-derived fluids. The scarcity of metasediments in the Monviso sequence suggests that such fluids were concentrated and fluxed along the lower shear zone in a sufficient amount to modify the oxygen composition of the eclogitic minerals.

  16. 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.

  17. Carbon and oxygen isotopic records from Lake Tuosu over the last 120 years in the Qaidam Basin, Northwestern China: The implications for paleoenvironmental reconstruction

    NASA Astrophysics Data System (ADS)

    Li, Xiangzhong; Zhou, Xin; Liu, Weiguo; Wang, Zheng; He, Yuxin; Xu, Liming

    2016-06-01

    Isotopic compositions of total organic carbon (TOC) and authigenic carbonate in lakes have been widely used to reconstruct paleoclimatic changes and the depositional environments of lake sediments. However, since these proxies are often controlled by multiple environmental factors, detailed examinations of modern environmental processes is necessary before further applying them into paleoclimatic studies, especially in arid/semi-arid northwestern China. Here we generate High-resolution multi-proxy sedimentary records from Lake Tuosu, a hydrologically closed, saline and alkaline lake located at the north margin of the Qaidam Basin, through analysis of carbon isotope of TOC, and δ18O and δ13C values of ostracods over the last 120 years. Together with the meteorological data (precipitation and temperature), lake area record, and other tree-ring evidence, we examine how these sedimentary indices respond to changes in hydrologic balance and climate at interannual to decadal timescales. We found that sedimentary δ13Corg values resemble the variation of lake areas of Lake Tuosu over the last 40 years, suggesting that δ13Corg values would be an ideal indicator of lake area/level fluctuations and thus effective moisture variations (precipitation vs. evaporation). However, ostracod δ18O, which was previously used as proxies of effective precipitation, is not well correlated with δ13Corg values in Lake Tuosu. Therefore, the changes of ostracod δ18O values cannot be straightforwardly explained as the effective precipitation. Instead, the isotopic composition of carbonate would be additionally controlled by other factors including isotopic compositions of input water and drainage pattern.

  18. Oxygen isotope ratios in eclogites from kimberlites.

    PubMed

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

    1971-06-01

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

  19. Oxygen Isotopes in the Terrestrial Planets

    NASA Astrophysics Data System (ADS)

    Clayton, R. N.

    2004-12-01

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

  20. 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. PMID:25393769

  1. 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.

  2. 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.

  3. 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.

  4. Oxygen isotope fractionation in synthetic magnesian calcite

    NASA Astrophysics Data System (ADS)

    Jiménez-López, Concepción; Romanek, Christopher S.; Huertas, F. Javier; Ohmoto, Hiroshi; Caballero, Emilia

    2004-08-01

    Mg-bearing calcite was precipitated at 25°C in closed system free-drift experiments from solutions containing NaHCO 3, CaCl 2 and MgCl 2. The chemical and isotope composition of the solution and precipitate were investigated during time course experiments of 24-h duration. Monohydrocalcite and calcite precipitated early in the experiments (<8 h), while Mg-calcite was the predominant precipitate (>95%) thereafter. Solid collected at the end of the experiments displayed compositional zoning from pure calcite in crystal cores to up to 23 mol% MgCO 3 in the rims. Smaller excursions in Mg were superimposed on this chemical record, which is characteristic of oscillatory zoning observed in synthetic and natural solid-solution carbonates of differing solubility. Magnesium also altered the predominant morphology of crystals over time from the {104} to {100} and {110} growth forms. The oxygen isotope fractionation factor for the magnesian-calcite-water system (as 10 3lnα Mg-cl-H 2O ) displayed a strong dependence on the mol% MgCO 3 in the solid phase, but quantification of the relationship was difficult due to the heterogeneous nature of the precipitate. Considering only the Mg-content and δ 18O values for the bulk solid, 10 3lnα Mg-cl-H 2O increased at a rate of 0.17 ± 0.02 per mol% MgCO 3; this value is a factor of three higher than the single previous estimate (Tarutani T., Clayton R.N., and Mayeda T. K. (1969) The effect of polymorphims and magnesium substitution on oxygen isotope fractionation between calcium carbonate and water. Geochim. Cosmochim. Acta 33, 987-996). Nevertheless, extrapolation of our relationship to the pure calcite end member yielded a value of 27.9 ± 0.02, which is similar in magnitude to published values for the calcite-water system. Although no kinetic effect was observed on 10 3lnα Mg-cl-H 2O for precipitation rates that ranged from 10 3.21 to 10 4.60 μmol · m -2 · h -1, it was impossible to disentangle the potential effect(s) of

  5. Triple Oxygen Isotopes: Fundamental Relationships and Applications

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  6. 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.

  7. 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

  8. Oxygen Isotope Trajectories of Crystallizing Arc Magmas

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  9. 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.

  10. 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

  11. Crystallization kinetics of rhyolitic melts using oxygen isotope ratios

    NASA Astrophysics Data System (ADS)

    Befus, Kenneth S.

    2016-01-01

    Crystals provide the means to understand igneous systems, but natural constraints on crystallization kinetics are rare because thermal conditions and crystallization timescales are typically unknown. Oxygen isotope ratios in quartz and alkali feldspar crystals in spherulites provide a natural record of the temperature interval of crystallization and crystal growth rates in rhyolitic melts. Oxygen isotope compositions in both phases change progressively with position from the spherulite core to rim. Quartz δ18O increases from 5.0 ± 0.3‰ in the core to 5.6 ± 0.3‰ at the rims, whereas alkali feldspar decreases from 3.7 ± 0.4‰ in the core to 2.7 ± 0.9‰ at the rims. Fractionation therefore increases from 1.3 ± 0.7‰ in the cores to 2.9 ± 1.1‰ at the rims. Oxygen isotope thermometry tracks crystallization temperature with position. Spherulites nucleate at 578 ± 160°C and continue to grow until 301 ± 88°C. The in situ analyses demonstrate that spherulites self-contain a record of their thermal history and that of the host lava.

  12. 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.

  13. Oxygen isotope record of fluid-rock-SiO 2 interaction during Variscan progressive deformation and quartz veining in the meta-volcanosediments of Belle-Ile (Southern Brittany)

    NASA Astrophysics Data System (ADS)

    Schulz, Bernhard; Audren, Claude; Triboulet, Claude

    2002-08-01

    Belle-Ile in the South Armorican Domain is composed of Palaeozoic volcano-detrital sequences with sericite phyllites and porphyroids. Fine-banded and folded meta-tuffites, microquartzites and graphitic quartzites occur in the basal part at Plage de Bordardoué. Phengite compositions constrain that Variscan metamorphism did not exceed 430 °C/4.5 kbar. Four generations (1-4) of centimeter-thick quartz veins were precipitated during Variscan progressive deformation and recorded changing fluid compositions. Values of 26‰ δ18O SMOW in vein 1 quartz exceed high δ18O SMOW in the host rocks. Decrease of quartz δ18O SMOW from margins to centers can be observed from the syntaxial veins. Younger veins 4 have lower δ18O. Their inclusions indicate lower salinities and traces of CH 4 in the fluid when compared with veins 1. Veins 1 were overprinted by shearing and fissuring. Subgrain rotation recrystallization occurred along briquette structures and subgrain boundaries. The initial isotope values have been preserved. Larger domains with small-grained quartz can be identified by lower values of δ18O. Homogeneous isotopic compositions are found in hinges of folded veins 2 with grain boundary migration recrystallization. The small-scale oxygen isotope variations and the changing fluid compositions point to a locally hosted fluid system with a limited contribution of meteoric water during multiphase deformation and vein formation.

  14. 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.

  15. Oxygen isotopes implanted in the LDEF spacecraft

    NASA Technical Reports Server (NTRS)

    Saxton, J. M.; Lyon, I. C.; Chatzitheodoredis, E.; Gilmour, J. D.; Turner, G.

    1992-01-01

    Depth profiles of O-16 and O-18/O-16 were measured on stainless steel nuts and copper sheet (from a grounding strap) recovered from the leading edge of LDEF (Tray E10). The measurements were obtained by dynamic SIMS (secondary ion mass spectrometry) using a VG Isolab 54 ion microprobe. Plots of O-18/O-16 against time, show large depletions of up to a factor of 2 compared to the O-18/O-16 value at sea level. The O-16 current decreases by 2 orders of magnitude in the interior of the metal, and the corresponding profile of anomalous O-16 is strongly peaked in the outer few tens of nanometers of the surface. This depth scale is a tentative one based on estimated sputtering rates. Plots of O-18/O-16 against 1/O-16 should be linear if two isotopically distinct components, one of variable concentration (orbital component) and one of fixed concentration (normal oxygen), are mixed. Data to be presented at the meeting show departures from linearity which result from variability in the concentration of normal oxygen, but may also arise from the implantation of oxygen with a range of fractionation due to the decaying orbit of the LDEF, sputtering of the surface by atomic oxygen, and the different momenta of the two isotopes due to their equal velocities. The potential for using this method as a means of identifying exposure to low-Earth orbit, de-convoluting the effects of space exposure from terrestrial contamination, and using the implanted anomolous oxygen as a means of studying the atomic oxygen density and upper atmosphere temperature height profile will be discussed at the meeting.

  16. Oxygen isotope composition of trinitite postdetonation materials.

    PubMed

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

    2013-12-17

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

  17. 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.

  18. Stable isotopes of oxygen and carbon compositions in the Neoproterozoic of South Gabon (Schisto-Calcaire Subgroup, Nyanga Basin): Are cap carbonates and lithoherms recording a particular destabilization event after the Marinoan glaciation?

    NASA Astrophysics Data System (ADS)

    Préat, Alain; Prian, Jean-Pierre; Thiéblemont, Denis; Obame, Rolf Mabicka; Delpomdor, Franck

    2011-06-01

    Geologic evidence of tropical sea level glaciation in the Neoproterozoic remains a matter of debate in the Snowball Earth hypothesis. The Niari Tillite Formation and the cap carbonates record the late Neoproterozoic Marinoan glaciation in South Gabon. These cap carbonates are located at the base of the Schisto-Calcaire Subgroup a predominantly carbonate succession that rests with sharp contact on top of the Niari Tillite. Integrating sedimentological and stable isotope data, a consistent sequence of precipitation events is proposed, with strongly negative δ 13C values pointing to a particular event in the cap carbonates (average δ 13C value = -3.2‰ V-PDB) and in a further newly defined lithohermal unit (average δ 13C value = -4.6‰ V-PDB). Subsequent shallow evaporitive platform carbonates display carbon and oxygen isotopic compositions indicative of relatively unaltered seawater values. Strongly negative δ 18O values in the lithoherms and replacement of aragonite fans by equigranular calcite suggest flushing of meteoric water derived from glacial meltwater.

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

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

  20. Carbon and oxygen isotope microanalysis of carbonate.

    PubMed

    Velivetskaya, Tatiana A; Ignatiev, Alexander V; Gorbarenko, Sergey A

    2009-08-30

    Technical modification of the conventional method for the delta(13)C and delta(18)O analysis of 10-30 microg carbonate samples is described. The CO(2) extraction is carried out in vacuum using 105% phosphoric acid at 95 degrees C, and the isotopic composition of CO(2) is measured in a helium flow by gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The feed-motion of samples to the reaction vessel provides sequential dropping of only the samples (without the sample holder) into the acid, preventing the contamination of acid and allowing us to use the same acid to carry out very large numbers of analyses. The high accuracy and high reproducibility of the delta(13)C and delta(18)O analyses were demonstrated by measurements of international standards and comparison of results obtained by our method and by the conventional method. Our method allows us to analyze 10 microg of the carbonate with a standard deviation of +/-0.05 per thousand for delta(13)C and delta(18)O. The method has been used successfully for the analyses of the oxygen and carbon isotopic composition of the planktonic and benthic foraminifera in detailed palaeotemperature reconstructions of the Okhotsk Sea. PMID:19603476

  1. Himalayan inverted metamorphism constrained by oxygen isotope thermometry

    NASA Astrophysics Data System (ADS)

    Vannay, Jean-Claude; Sharp, Zachary D.; Grasemann, Bernhard

    Inverted metamorphic field gradients are preserved in two amphibolite facies metapelitic sequences forming the crystalline core zone of the Himalayan orogen in the Sutlej valley (NW India). In the High Himalayan Crystalline Sequence (HHCS), metamorphic conditions increase upwards from the staurolite zone at the base, through the kyanite-in and sillimanite-in isograds, finally to reach partial melting conditions at the top. The structurally lower Lesser Himalayan Crystalline Sequence (LHCS) shows a gradual superposition of garnet-in, staurolite-in and kyanite+sillimanite-in isograds. Although phase equilibria constraints imply inverted temperature field gradients in both units, garnet-biotite (GARB) rim thermometry indicates final equilibration at a nearly uniform temperature around T 600°C across these sequences. The P-T path and garnet zoning data show that this apparent lack of thermal field gradient is mainly the consequence of a resetting of the GARB equilibria during cooling. In order to constrain peak temperature conditions, 20 samples along the studied section have been analysed for oxygen isotope thermometry. The isotopic fractionations recorded by quartz-garnet and quartz-aluminosilicate mineral pairs indicate temperatures consistent with phase equilibria and P-T path constraints for metamorphic peak conditions. Together with barometry results, based on net transfer continuous reactions, the oxygen isotope thermometry indicates peak conditions characterized by: (1) a temperature increase from T 570 to 750°C at a nearly constant pressure around P 800MPa, from the base to the top of the HHCS unit; (2) a temperature increase from T 610 to 700°C and a pressure decrease from P 900 to 700MPa, from the base to the top of the LHCS metapelites. Oxygen isotope thermometry thus provides the first quantitative data demonstrating that the Himalayan inverted metamorphism can be associated with a complete inversion of the thermal field gradient across the crystalline

  2. 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

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

    NASA Astrophysics Data System (ADS)

    Müller, I. A.; Brunner, B.

    2012-12-01

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

  4. Temperature measurements from oxygen isotope ratios of fish otoliths.

    PubMed

    Devereux, I

    1967-03-31

    Measurements have shown that the temperature of a fish's habitat can be deduced from the Oxygen isotope ratio of its otoliths (ear bones). Isotope ratios Obtained from fossil otoliths indicate a water temperature which agrees wiht that found by isotope measurements on associated benthonic foraminifera. PMID:6020293

  5. 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.

  6. 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.

  7. 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.

  8. Oxygen isotope correlation of cetacean bone phosphate with environmental water

    NASA Astrophysics Data System (ADS)

    Yoshida, Naohiro; Miyazaki, Nobuyuki

    1991-01-01

    The variation with time in the oxygen isotope ratio of the oceans is of prime interest in a variety of research fields. An excellent correlation between oxygen isotope ratios of cetacean (whales, dolphins, and porpoises) bone phosphate and their environmental water is found in this study. Bone phosphate samples of dolphins living in fresh waters are more depleted in oxygen 18 than those of cetaceans living in the oceans, reflecting the clear difference in the isotope composition of water. Cetaceans distributed in the higher latitudes in the oceans are more depleted in oxygen 18 than those distributed in the lower latitudes where seawater is slightly enriched in oxygen 18 relative to that in the higher latitudes. The present results provide a promising tool for estimating the oxygen isotope ratio of the oceanic water of the past without assuming water temperature.

  9. Late Holocene expansion of Siberian dwarf pine (Pinus pumila) in Kamchatka in response to increased snow cover as inferred from lacustrine oxygen-isotope records

    NASA Astrophysics Data System (ADS)

    Hammarlund, Dan; Klimaschewski, Andrea; St. Amour, Natalie A.; Andrén, Elinor; Self, Angela E.; Solovieva, Nadia; Andreev, Andrei A.; Barnekow, Lena; Edwards, Thomas W. D.

    2015-11-01

    Holocene records of cellulose-inferred lake-water δ18O were produced from two lake-sediment sequences obtained in central and northern Kamchatka, Russian Far East. The sediment records share similar fluctuations in δ18O during the interval of ca. 5000-800 cal yr BP that correspond (inversely) with changes in K+ content of the GISP2 ice-core record from Greenland, a proxy for the relative strength of the Siberian High, suggesting control by climate-related variability in δ18O of regional precipitation. The dramatic expansion of Siberian dwarf pine (Pinus pumila) in northern and central Kamchatka between ca. 5000 and 4000 cal yr BP, as inferred from pollen records from the same and neighbouring sites, appears to have occurred at a time of progressively declining δ18O of precipitation. This development is interpreted as reflecting a regional cooling trend accompanied by increasing winter snowfall related to gradual intensification of the Siberian High from ca. 5000 to ca. 3000 cal yr BP. A thicker and more long-lasting snow cover can be assumed to have favoured P. pumila by providing a competitive advantage over other boreal and subalpine tree and shrub species in the region during the later part of the Holocene. These results, which are the first of their kind from Kamchatka, provide novel insight into the Holocene vegetational and climatic development in easternmost Asia, as well as long-term atmospheric circulation dynamics in Beringia.

  10. 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.

  11. Using Oxygen Isotopes in Fish Scale Apatite to Reconstruct Past Temperatures and Water Isotope Ratios

    NASA Astrophysics Data System (ADS)

    Lambert, T. D.; Paytan, A.

    2009-12-01

    Oxygen isotope ratios (δ18O) of apatite phosphate in fish bones and teeth vary according to the temperature and δ18O of water during formation. Since isotope ratios in apatite are often well preserved over geologic timescales, fish bones and teeth have been used to determine past environmental conditions. Fish scales offer several advantages over bones and teeth: they are relatively common in certain sedimentary basins, and they are more easily identified to species level. Analysis of paired bone and scale samples will be presented. The data indicate that fish scale apatite similarly records environmental conditions during growth. Thus δ18O of apatite phosphate in fish scales may provide useful paleoecological information and also indicate past environmental conditions.

  12. Oxygen isotopic composition of hydrous and anhydrous mantle peridotites

    NASA Astrophysics Data System (ADS)

    Chazot, Gilles; Lowry, David; Menzies, Martin; Mattey, David

    1997-01-01

    Oxygen isotope ratios, determined using the laser fluorination technique, are reported for minerals from anhydrous and hydrous (i.e., amphibole-bearing) spinel lherzolites from Yemen, as well as from hydrous spinel lherzolites and amphibole megacrysts from Nunivak Island, Alaska. Oxygen isotopic compositions of olivine vary from 5.1-5.4%c and of pyroxene from 5.5-6.0%c and no systematic difference exists between minerals in hydrous and anhydrous lherzolites. The oxygen isotopic composition of the amphibole in the peridotites and of the amphibole megacrysts is also very homogeneous and varies from δ 18O = 5.3-5.6%o. These results indicate that the metasomatic minerals in the lherzolites are in oxygen isotopic equilibrium with the peridotitic minerals. The only isotopic disequilibria are observed in minerals which have grown in melt-pockets formed by partial melting of amphibole. The homogeneity of the oxygen isotopic ratios of mantle minerals in this study indicate that the fluids circulating in the mantle and precipitating amphibole or mica had the same oxygen isotopic compositions as the mantle protolith or that the fluids had been buffered by the isotopic composition of the olivine, the most abundant mineral, during percolation through the peridotites.

  13. 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

  14. 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

  15. 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

  16. Oxygen Isotope Variability within Nautilus Shell Growth Bands.

    PubMed

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

    2016-01-01

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

  17. 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

  18. 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.

  19. Multiple Oxygen Isotope Photochemistry of Nitrate in Ice

    NASA Astrophysics Data System (ADS)

    McCabe, J. R.; Boxe, C. S.; Colussi, A.; Hoffman, M. R.; Thiemens, M. H.

    2004-12-01

    Nitrate (NO3 -) is a major anion in polar ice [de Angelis and Legrand, 1995;Dibb et al., 1998;Silvente and Legrand, 1995]. As the primary sink for atmospheric NOx, nitrate's chemical history is a link to understanding the nitrogen budget and oxidation capacity of the polar atmosphere over time. Our understanding of variations in ice core nitrate concentrations has been limited by depositional and post-depositional loss processes, associated with temperature, accumulation rate, diffusion, photochemistry and volatilization [Wolff, 1995]. The first report of multiple oxygen isotope composition of nitrate in ice cores (Alexander et al., 2004) demonstrates the ability to observe changes in the oxidation capacity of past atmospheres. To accurately interpret this and future isotopic data, we need to ascertain the oxygen isotope fractionation (δ 17O, δ ^{18}O) associated with the photolysis of nitrate in ice. Post-depositional processes, such as nitrate photolysis and volatilization may alter the initial isotopic signal of nitrate in the snowpack. A series of nitrate photolysis experiments were conducted on 10 mM solutions of Fisher KNO_{3} and USGS-35 NaNO_{3} at 313 ± 20 nm over 12 to 48 hours and between -30 and 25 ° C. With initial mass-dependent nitrate, a strict mass-dependent fractionation was observed in the residual irradiated nitrate. However, after 12 and 24 hours of irradiation, mass-independent USGS-35 NaNO3 (Δ 17O = 21.0 \\pm 0.4 ‰ ) displayed a decrease of 1.6 ± 0.4 and 2.0 \\pm 0.4 % at 25 \\degC, 1.2 ± 0.4 and 1.3 \\pm 0.4 ‰ at -5\\degC, 0.2 ± 0.4 \\permil and 1.1 \\pm 0.4 ‰ at -30\\degC, respectively. The greater isotope effect at higher temperatures may be due to a thicker quasi-liquid layer (QLL) allowing faster rates for secondary nitrate producing reactions between H_{2}O and photoproducts NO, NO_{2}, NO_{2}$-. In the aqueous phase this effect is even greater. Hence, we infer that the production of nitrate via these 'secondary processes

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  1. 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.

  2. 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

  3. Oxygen isotope fractionation in stratospheric CO2

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

  4. 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

  5. Comparison of the Climate during Marine Isotope Stage 9 and 11 Inferred from a Speleothem Isotope Record from Northern Norway

    NASA Astrophysics Data System (ADS)

    Berstad, Ida M.; Lundberg, Joyce; Lauritzen, Stein-Erik; Linge, Henriette C.

    2002-11-01

    A stalagmite from northern Norway is dated with 12 thermal ionization mass spectrometry U-Th dates, and at least four separate growth periods are identified that correspond with marine isotope stages 9, 11, 13, and probably 15. The calcite is tested for isotopic equilibrium with the Hendy test. Oxygen isotope measurements on 231 subsamples on a vertical transect are used as a paleotemperature proxy. The detailed isotopic record from MIS 9 show apparent similarities to a Holocene record from the same cave, both in the climatic evolution and the overall temperatures: both show temperature oscillations changing from high-frequency, low-amplitude cycles in the beginning of the interglacial period to lower frequency, higher amplitude cycles in the later part of the interglacial period. The isotope record from MIS 11 shows a distinct isotopic event toward heavier values. The isotopic record together with the porous, humus-rich calcite are interpreted as indicating a warmer than present interglacial period with several episodes of heavy rainfall.

  6. Hydrogen burning of the rare oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Buckner, Matthew Quinn

    2014-10-01

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

  7. 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

  8. 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.

  9. Carbon and oxygen isotope fractionation in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Langer, W. D.; Graedel, T. E.; Frerking, M. A.; Armentrout, P. B.

    1984-01-01

    It is pointed out that isotope fractionation as a result of chemical reactions is due to the small zero-point energy differences between reactants and products of isotopically distinct species. Only at temperatures near absolute zero does this energy difference become significant. Favorable conditions for isotope fractionation on the considered basis exist in space within dense interstellar clouds. Temperatures of approximately 10 K may occur in these clouds. Under such conditions, ion-molecule reactions have the potential to distribute isotopes of hydrogen, carbon, oxygen unequally among the interstellar molecules. The present investigation makes use of a detailed model of the time-dependent chemistry of dense interstellar clouds to study cosmological isotope fractionation. Attention is given to fractionation chemistry and the calculation of rate parameters, the isotope fractionation results, and a comparison of theoretical results with observational data.

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

    NASA Technical Reports Server (NTRS)

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

    2004-01-01

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

  11. Regional Atmospheric Circulation Change in the North Pacific During the Holocene Inferred from Lacustrine Carbonate Oxygen Isotopes, Yukon Territory, Canada

    NASA Astrophysics Data System (ADS)

    Anderson, L.; Abbott, M. B.; Finney, B. P.; Burns, S. J.

    2004-12-01

    Analyses of sediment cores from Jellybean Lake, a small, hydrologically-open groundwater-fed lake, provide a record of changes in North Pacific atmospheric circulation for the last 7500 years at twenty to thirty-year resolution. A regional isotope hydrology study in the southern Yukon indicates that the oxygen isotope composition of water from Jellybean Lake reflects the oxygen isotope composition of mean annual precipitation. Thus, the oxygen isotope history of Jellybean Lake inferred from sedimentary carbonate oxygen isotope ratios suggests multi-decadal shifts in the oxygen isotope composition of mean annual precipitation superimposed on century and millennial trends. Recent fluctuations of Jellybean oxygen isotopes correlate well with changes in the North Pacific Index, a measure of the intensity and position of the Aleutian Low. We propose that oxygen isotope variability of precipitation in the interior of the Yukon is related to the degree of fractionation during moisture transport from the Gulf of Alaska across the St Elias Mountains that is ultimately controlled by the position and strength of the Aleutian Low. Following this model, Aleutian Low intensity during the early to middle Holocene was relatively reduced and increasing intensity coincided with the initial onset of Neoglacial advances. Rapid shifts during the last two millennia corresponds with glacial activity, changes in North Pacific salmon abundance, and shifts in atmospheric circulation over the Beaufort Sea.

  12. 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.

  13. Oxygen isotope variability within Nautilus shell growth bands

    DOE PAGESBeta

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

    2016-04-21

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

  14. 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

  15. Antiphase hydrogen and oxygen isotope periodicity in chert nodules

    NASA Astrophysics Data System (ADS)

    Sharp, Zachary D.; Durakiewicz, Tomasz; Migaszewski, Zdzislaw M.; Atudorei, Viorel N.

    2002-09-01

    Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial "sigmoidal" periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ 18O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ˜10°C. Data for a second chert fall on a subparallel δD-δ 18O line with δD values that are almost 50‰ lower. The δD-δ 18O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.

  16. Atmospheric methane isotope records during MIS 4

    NASA Astrophysics Data System (ADS)

    Sowers, Todd; Bock, Michael; Mitchell, Hailey

    2014-05-01

    The long-term δ13CH4record has led to a new paradigm in our thinking of the biogeochemistry of atmospheric CH4 (Möller et al. 2013). Throughout the last glacial period, abrupt D/O CH4changes appear to be decoupled from δ13CH4, while for δDCH4 we are still missing the big picture. The lack of a clear long-term relationship between loading changes and the isotopic composition of atmospheric CH4suggests multiple sources/sinks were responsible for the observed changes and/or that the characteristic isotope value for some of these sources may have changed over time. During the early part of MIS 4, we observed a ~4o increase in δ13CH4during a period when CH4changes were less than 50 ppb. We measured 12 ice core samples from the NEEM core for δDCH4 covering DO 8 and the MIS 5-4 transition. These new δDCH4 data compliment previously published δDCH4 data from EDML covering the same period (Möller et al. 2013). Replicate analyses of NEEM ice from DO 8 agreed with previously measured samples from NGRIP (Bock et al., 2010). External precision of the analyses based on replicate air standards run throughout each analytical day were ±1.8‰These data were overlain on previously measured δ13CH4data from the Vostok and EDML ice cores from the same periods. The δ13CH4data for the MIS4 start at ~ -48o around 75ka and increase to -44o at 65ka and then decrease to -46o by 59ka. In contrast, NEEM δDCH4 values start at -90o at 70ka and decrease to -97o at 64ka before increasing to -92o by 59ka. These two records appear to be roughly in phase with one another but opposite in the sign of their changes. Comparison between NEEM and EDML δDCH4 data for MIS4 suggest the interpolar δDCH4 difference increases somewhat during the δ13CH4transition. We plan to discuss these records in terms of constraints on the biogeochemistry of atmospheric methane during MIS 4. Bock, M., J. Schmitt, L. Möller, R. Spahni, T. Blunier and H. Fischer (2010). "Hydrogen Isotopes Preclude Marine

  17. 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

  18. 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.

  19. Oxygen isotope exchange and isotopic fractionation during N2O production by denitrification

    NASA Astrophysics Data System (ADS)

    Lewicka-Szczebak, Dominika; Well, Reinhard; Kaiser, Jan

    2014-05-01

    Stable isotopic analyses of N2O may help in quantification of soil denitrification processes. N2O reduction to N2 during denitrification is associated with significant isotopic fractionation. Theoretically, this would allow the product ratio (N2O/(N2+N2O)) to be calculated based on the isotopic signature of the remaining N2O if the isotopic signature of the produced N2O were precisely predictable. Oxygen isotopes are especially useful, in particular the 17O excess, Δ(17O), to quantify any oxygen isotope exchange between soil water and intermediate products (NO2-, NO). This significantly influences the δ(18O) values of the N2O produced. Previous studies showed this exchange to be nearly complete, up to 90% 1,2. However, there are very few studies on the associated oxygen isotopic fractionation and its potential coupling to the magnitude of oxygen isotope exchange with soil water 2,3. We hypothesize that for high oxygen exchange, the oxygen isotopic fractionation will show little variability. In previous experiments, an 18O-enriched tracer was applied to quantify the magnitude of oxygen exchange 1,2. Such an approach does not permit determining any oxygen isotope fractionation. Here, we applied two novel experimental approaches: (1) waters of two different δ(18O) values within the natural range (-1.5 and -14.8 o relative to VSMOW) were used for rewetting the incubated soils and the oxygen exchange was calculated from comparing the relative isotope ratio difference between N2O and H2O for these two water treatments; (2) soils were amended with Chile Saltpeter characterized by a high 17O excess (20.2 o ) and the 17O excess of the N2O product was measured. Both approaches were applied simultaneously on the same soil samples, which allowed quantifying the oxygen isotope exchange with two independent methods at the same time. The N2O reduction was inhibited with acetylene method and δ(18O) values of the N2O produced were measured to determine the oxygen fractionation

  20. 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.

  1. 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.

  2. Triple-Oxygen Isotope Analyses of Sulfate Occluded in Caliches

    NASA Astrophysics Data System (ADS)

    Howell, K. J.; Bao, H.

    2005-12-01

    Sulfate is the ultimate sink of atmospheric sulfur compounds and can provide important information about atmospheric compositions and processes. For example, ozone signatures are readily recorded in sulfate of atmospheric origin; however, atmospheric sulfate is rarely preserved in geologic records because it is extremely soluble and easily carried away by surface water. The only known cases of preserved atmospheric sulfate are in old, hyperarid desert surfaces like the Atacama Desert and the Antarctic Dry Valleys. Caliches, pedogenically formed calcite-rich layers or nodules in semi-arid to arid environments, could be potential reservoirs for preserving atmospheric sulfate because of the relatively dry climate in the regions where caliche forms. Here, two types of caliche are examined: modern caliche formed on limestones, basalts, and rhyolites in western Texas and New Mexico and fossil caliche formed on late-Cenozoic volcaniclastic deposits in western Nebraska. Analysis of the modern samples shows generally high caliche-associated sulfate (CAS) concentrations ranging from ~100 to 2000 ppm, with caliche developed on limestone having some of the highest concentrations and those formed on basalts and rhyolites having some of the lowest. Triple-oxygen stable isotope measurements show that the CAS has Δ 17O values (i.e., 17O-anomaly) ranging from -0.1 to 0.7 ‰ with higher 17O anomalies associated with igneous parent materials. Analysis of the fossil caliches from western Nebraska reveals CAS concentrations ranging from ~10 to 300 ppm and Δ 17O values ranging from 0.5 to 2.3 ‰. These data suggest atmospheric sulfate has survived the soil processes unaltered before being incorporated into solid caliche formation. Further confirmation of atmospheric sulfate records in much older caliches may lead to a new proxy for probing ancient atmospheric compositions and chemical processes.

  3. Oxygen Isotope Ratios in Protoplanetary Disks

    NASA Astrophysics Data System (ADS)

    Brittain, Sean; Najita, Joan; Carr, John; Doppmann, Greg

    2009-08-01

    Meteorites provide important clues about the environment from which our solar system formed. Their mineralogical and isotopic composition provides important insight into the thermal, chemical and dynamical history of the protoplanetary disk. One of the most intriguing discoveries to come from the study of meteorites is the depletion of the ^18O/^16O and ^17O/^16O ratios in the oldest components of meteorites relative to Earth. These measurements suggest that the gas from which the sun condensed was more ^16O-rich than the material from which planets formed. The leading explanation for this isotopic anomaly is the selective dissociation of CO in the outer protoplanetary disk or envelope. The basic premise is that the freed ^17,18O atoms in the outer disk formed water that then enriched the ^17,18O abundance in rocky material. Thus, bodies that formed later (such as planets) were increasingly enriched in ^17,18O. To test this scenario, we will probe the efficiency of selective dissociation of CO in nearby protoplanetary disk systems. We will measure the isotopic ratio of C^17O/C^18O/C^16O by acquiring high-resolution absorption spectra of ro-vibrational CO lines from edge-on disks and envelopes.

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. Exploring Neutron-Rich Oxygen Isotopes with MoNA

    SciTech Connect

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

    2007-11-30

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

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

    PubMed

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

    2003-05-01

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

  10. 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...

  11. 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

  12. 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

  13. 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.

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

    PubMed

    Casciotti, Karen L

    2016-01-01

    The marine nitrogen cycle is a complex web of microbially mediated reactions that control the inventory, distribution, and speciation of nitrogen in the marine environment. Because nitrogen is a major nutrient that is required by all life, its availability can control biological productivity and ecosystem structure in both surface and deep-ocean communities. Stable isotopes of nitrogen and oxygen in nitrate and nitrite have provided new insights into the rates and distributions of marine nitrogen cycle processes, especially when analyzed in combination with numerical simulations of ocean circulation and biogeochemistry. This review highlights the insights gained from dual-isotope studies applied at regional to global scales and their incorporation into oceanic biogeochemical models. These studies represent significant new advances in the use of isotopic measurements to understand the modern nitrogen cycle, with implications for the study of past ocean productivity, oxygenation, and nutrient status. PMID:26747521

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

    PubMed

    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

  16. 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

  17. 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

  18. 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.

  19. Box-modeling of bone and tooth phosphate oxygen isotope compositions as a function of environmental and physiological parameters.

    PubMed

    Langlois, C; Simon, L; Lécuyer, Ch

    2003-12-01

    A time-dependent box model is developed to calculate oxygen isotope compositions of bone phosphate as a function of environmental and physiological parameters. Input and output oxygen fluxes related to body water and bone reservoirs are scaled to the body mass. The oxygen fluxes are evaluated by stoichiometric scaling to the calcium accretion and resorption rates, assuming a pure hydroxylapatite composition for the bone and tooth mineral. The model shows how the diet composition, body mass, ambient relative humidity and temperature may control the oxygen isotope composition of bone phosphate. The model also computes how bones and teeth record short-term variations in relative humidity, air temperature and delta18O of drinking water, depending on body mass. The documented diversity of oxygen isotope fractionation equations for vertebrates is accounted for by our model when for each specimen the physiological and diet parameters are adjusted in the living range of environmental conditions. PMID:14711171

  20. 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. PMID:25587823

  1. 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.

  2. 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

  3. Oxygen isotopic signature of CO2 from combustion processes

    NASA Astrophysics Data System (ADS)

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

    2008-11-01

    For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires), and human induced (fossil fuel combustion, biomass burning) in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects in the order of about 26‰ became obvious, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature), sample geometries (e.g. texture and surface-volume ratios) and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive) transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original 18O signature of the material appeared to have little or no influence.

  4. Oxygen isotopic signature of CO2 from combustion processes

    NASA Astrophysics Data System (ADS)

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

    2011-02-01

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

  5. 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.

  6. Evaluation of Oxygen, Carbon, and Nitrogen Isotopic Paleoenvironmental Proxies in Lake Erie Sediments

    NASA Astrophysics Data System (ADS)

    Meyers, P. A.; Knowlton, C.; Eadie, B. J.; Robbins, J. A.; Lansing, M.

    2004-05-01

    The oxygen isotopic composition of calcium carbonate that precipitates in hardwater lakes is affected by meteorologic factors whereas the inorganic and organic carbon and nitrogen isotopic compositions of lake sediments are influenced by biological productivity within the lake. All of these isotopic proxies are potentially subject to post-depositional diagenesis. We have measured the isotopic compositions at 1-cm intervals in four sediment cores that were collected in 1988, 1991, and 2003 from eastern Lake Erie to evaluate the effects of diagenesis on records of paleoenvironmental change. We have compared the isotopic contents and the mass accumulation rates of the aquatic productivity proxies organic carbon and calcium carbonate of the different cores to each other and to meteorological records beginning in 1895. Eutrophication accelerated calcite dissolution, but isotopic proxies are preserved. Calcite del 18O values that become smaller from 1980 to 1998 in the absence of evidence of a summer temperature change suggest a change in air mass trajectories. In contrast, a shift to larger del 18O values from 1905 to 1910 that is accompanied by diminished calcite precipitation and higher lake levels suggests a period of cooler summer temperatures. Increases in inorganic and organic del 13C values, del 15N values, and organic carbon accumulation starting in 1960 reflect the heightened productivity caused by anthropogenic nutrient increases to Lake Erie.

  7. 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.

  8. 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.

  9. Oxygen isotope stratigraphy in the Gulf of Alaska (IODP Exp. 341)

    NASA Astrophysics Data System (ADS)

    Asahi, H.; Mix, A. C.; Suto, I.; Belanger, C. L.; Fukumura, A.; Gupta, S.; Konno, S.; Matsuzaki, K. M.; Romero, O. E.; Gulick, S. P. S.; Jaeger, J. M.; Schneider, L. J.

    2014-12-01

    Age constrains provided by oxygen isotope stratigraphy, biostratigraphy and paleomagnetics can provide fundamental insights for interpreting other paleoceanographic reconstructions at orbital scale. In the case of the high latitude in the North Pacific, most paleoceanographic studies investigating the evolution of the North Pacific climate since the intensification of Northern Hemisphere Glaciation (iNHG) face difficulties in establishing orbital-scale age models due to the low preservation of foraminifer fossils. Most North Pacific studies targeting the Pleistocene heavily rely on alternative approaches with higher preservation potential (e.g. MS: Magnetic Susceptibility) for orbital-scale age models, and assume such data are mainly reflecting the Glacial-Interglacial (G-IG) cycle. A continuous oxygen iope record from the subarctic North Pacific is long anticipated data set to test such assumptions. Two sites (Sites U1417 and U1418) in the Gulf of Alaska (GoA) drilled during IODP Exp. 341 are expected to provide continuous sediment records back to the middle Pleistocene (U1418) and Miocene (U1417), respectively. Here we present age models at Sites U1417 and U1418 derived from refined biostratigraphy and planktic foraminiferal (PF) oxygen isotope (Neogloboquadrina pachyderma sinistral, 150-250 μm fraction) stratigraphy (~1.2Ma at Site U1418 and ~3.0Ma at U1417, respectively). General agreement between oxygen isotope stratigraphy and other age constraints (biostratigraphy and paleomagnetism) at Site U1418 confirms the reliability of those age models. Furthermore, general trends seen in PF oxygen isotope time series roughly matches MS, suggesting that MS can be used for further age model tuning or as an alternative solution for the orbital scale age constrains in the GoA.

  10. Phosphate oxygen isotope analysis on microsamples of bioapatite: removal of organic contamination and minimization of sample size.

    PubMed

    Wiedemann-Bidlack, Felicitas B; Colman, Albert S; Fogel, Marilyn L

    2008-06-01

    Modern and fossil teeth record seasonal information on climate, diet, and migration through stable isotope compositions in enamel and dentine. Climatic signals such as seasonal variation in meteoric water isotopic composition can be recovered through a microscale histology-based sampling and isotopic analysis of enamel phosphate oxygen. The phosphate moiety in bioapatite is particularly resistant to post mortem diagenesis. In order to determine the phosphate oxygen isotope composition of enamel, phosphate must be chemically purified from other oxygen sources in the enamel lattice and matrix, mainly hydroxyl and carbonate ions, and trace quantities of organics. We present a wet chemical technique for purifying phosphate from microsampled enamel and dentine. This technique uses a sodium hypochlorite oxidation step to remove interferences from residual organic constituents of the enamel and/or dentine scaffold, isolates phosphate as relatively large and easily manipulated Ag(3)PO(4) crystals by using a strongly buffered, moderate-temperature microprecipitation, and preserves the oxygen isotope composition of the initial tooth phosphate. The reproducibility of phosphate oxygen isotope compositions thus determined (measured as delta(18)O, V-SMOW scale) is typically 0.2-0.3 per thousand (1 s.d.) on samples as small as 300 microg of enamel or dentine, a considerable improvement over available techniques for analyses of bioapatite phosphate oxygen. PMID:18470876

  11. 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

  12. Sulfur and oxygen isotope studies of sulfate reduction

    NASA Astrophysics Data System (ADS)

    Farquhar, J.; Canfield, D. E.; Bao, H.; Masterson, A.; Johnston, D. T.; Wing, B. A.

    2007-12-01

    I will discuss insights into sulfur and oxygen isotope fractionations of dissimilatory sulfate reduction and specifically insight provided by experiments with natural populations of sulfate-reducing bacteria from Faellestrand, Denmark. The experiments yielded relatively large magnitude sulfur isotope fractionations for dissimilatory sulfate reduction (up to approximately 45 ‰ for 34S/32S), with higher δ18O accompanying higher δ34S, similar to that observed in previous studies. The seawater used in the experiments was spiked by addition of 17O-labelled water and the 17O content of residual sulfate was found to depend on the fraction of sulfate reduced in the experiments. The 17O data provides evidence for recycling of sulfur from metabolic intermediates and for an 18O/16O fractionation of ~25-30 ‰ for dissimilatory sulfate reduction, a magnitude that is consistent with isotopic exchange between a sulfite species and cell water. The molar ratio of oxygen exchange to sulfate reduction was found to be about 2.5. Using recent models of sulfur isotope fractionations we find that our combined sulfur and oxygen isotopic data places constraints on the proportion of sulfate recycled to the medium (78-96 %), the proportion of sulfur intermediate sulfite that was recycled by way of APS to sulfate and released back to the external sulfate pool (~70%) and also that a fraction of the sulfur intermediates between sulfite and sulfide were recycled to sulfate. These parameters can be constrained because of the independent information provided by δ18O, δ34S, 17O labels, and Δ33S.

  13. Nucleosynthesis in AGB Stars Traced by Oxygen Isotopic Ratios

    NASA Astrophysics Data System (ADS)

    De Nutte, R.; Decin, L.; Olofsson, H.; de Koter, A.; Lombaert, R.; Milam, S.; Ramstedt, S.

    2015-08-01

    Isotopic ratios are by far the best diagnostic tracers of the stellar origin of elements, as they are very sensitive to the precise conditions in the nuclear burning regions. They allow us to give direct constraints on stellar evolution models and on the progenitor mass. However, up to now different isotopic ratios have been well constrained for only a handful of Asymptotic Giant Branch (AGB) stars. We present new data on isotopologue lines of a well-selected sample of AGB stars, covering the three spectral classes of C-, S- and M-type stars. We report on the first efforts made in determining accurate isotopologue fractions, focusing on oxygen isotopes which are a crucial tracer of the poorly constrained extra mixing processes in stellar atmospheres.

  14. Lake isotope records of the 8200-year cooling event in western Ireland: Comparison with model simulations

    NASA Astrophysics Data System (ADS)

    Holmes, Jonathan A.; Tindall, Julia; Roberts, Neil; Marshall, William; Marshall, Jim D.; Bingham, Ann; Feeser, Ingo; O'Connell, Michael; Atkinson, Tim; Jourdan, Anne-Lise; March, Anna; Fisher, Elizabeth H.

    2016-01-01

    The early Holocene cooling, which occurred around 8200 calendar years before present, was a prominent abrupt event around the north Atlantic region. Here, we investigate the timing, duration, magnitude and regional coherence of the event as expressed in carbonate oxygen-isotope records from three lakes on northwest Europe's Atlantic margin in western Ireland, namely Loch Avolla, Loch Gealáin and Lough Corrib. An abrupt negative oxygen-isotope excursion lasted about 200 years. Comparison of records from three sites suggests that the excursion was primarily the result of a reduction of the oxygen-isotope values of precipitation, which was likely caused by lowered air temperatures, possibly coupled with a change in atmospheric circulation. Comparison of records from two of the lakes (Loch Avolla and Loch Gealáin), which have differing bathymetries, further suggests a reduction in evaporative loss of lake water during the cooling episode. Comparison of climate model experiments with lake-sediment isotope data indicates that effective moisture may have increased along this part of the northeast Atlantic seaboard during the 8200-year climatic event, as lower evaporation compensated for reduced precipitation.

  15. 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.

  16. Leaf water oxygen isotope measurement by direct equilibration.

    PubMed

    Song, Xin; Barbour, Margaret M

    2016-08-01

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

  17. 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

  18. Stable isotope record of Holocene climate and ecological change from brine shrimp cyst chitin for the Great Salt Lake, UT

    NASA Astrophysics Data System (ADS)

    Nielson, K. E.; Bowen, G. J.

    2009-12-01

    We present a record of oxygen and hydrogen isotopes in brine shrimp cysts from the Great Salt Lake, a terminal lake in the Great Basin, US. Water balance for the region is influenced by strength of the El Niño in Pacific and by the strength of the summer monsoon. Brine shrimp cysts are a novel proxy for isotope reconstruction, and allow reconstruction of water isotopes (oxygen, hydrogen) and ecology (hydrogen). Oxygen isotopes in chitin respond to water, while both diet and growth water contribute to hydrogen isotopes, allowing reconstruction of both environmental and ecological information from a single molecule. Values of δ18O decrease from about +15‰ to about +11‰ over course of the 8000 year record. This may suggest the importance of snow melt increased over the Holocene, or it may suggest lake is larger today than it was in mid-Holocene. Hydrogen isotopes are relatively stable for most of record, fluctuating around -140‰. Modeled hydrogen isotopes in food, also stable in the beginning of the record at about -150‰, become much heavier, shifting toward about -75‰ starting about 5000 ybp. This may suggest a shift from a primarily aquatic diet in the Mid-Holocene to a diet with a greater contribution of terrestrial material later in the Holocene. These observations agree broadly with previous inferences of a warm Mid-Holocene and associated low terrestrial productivity, followed by a more moist, and consequently more productive Late Holocene.

  19. 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

  20. 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

  1. Online Method for Oxygen Triple Isotope Analyses of Nitrate

    NASA Astrophysics Data System (ADS)

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

    2004-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-05-01

    Nitrate contamination of shallow aquifers and surface waters associated with agricultural activities has become a major concern in river basins, like the Neuse, where significant agricultural land use is coupled with growing numbers of intensive animal operations (ILO's). The development of effective management practices to preserve water quality, or remediation strategies for basins already polluted requires source identification. The stable isotopes of nitrogen and oxygen in nitrate has been used as tracers to evaluate nitrogen sources on small scales, such as agricultural fields, or small watersheds with one dominate land use. This discrimination is possible because of the large fractionation associated with the volatilization of ammonia from animal wastes. Using stable isotopes on larger scales to evaluate nutrient sources is complicated by multiple sources, overlapping point and non-point sources, and co-existing biogeochemical processes that alter nitrate concentrations. To evaluate the potential of stable isotopes to determine the character of nutrient fluxes on larger scales, the isotopic/discharge relationship was examined for a watershed with little agricultural activity, an urban watershed, a watershed with mixed urban and agricultural land use, a watershed dominated by swine ILO's, and a watershed dominated by poultry ILO's. The watershed with little agricultural activity and the poultry watershed have similar isotope/discharge relationships with isotopic values at natural background levels and no change in concentration or isotopic composition in different discharge states. The urban watershed is dominated by point source isotopic values at all flow levels, the mixed urban and agricultural watershed is dominated by point source values during low flow conditions, and fertilizer non-point source values during high flow conditions. In this watershed nutrient concentrations also increase during low flow conditions. The swine watershed is dominated by

  3. 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.

  4. Unraveling P-T-Time-Fluids Paths: in-situ Geochronology Combined with Oxygen Isotopes in Metamorphic Rocks

    NASA Astrophysics Data System (ADS)

    Rubatto, D.; Angiboust, S.

    2014-12-01

    Geochronology of metamorphic rocks aims to determine pressure-temperature-time paths. The development of in-situ oxygen isotope analysis by ion microprobe permits to add fluid evolution to metamorphic histories. Accurate oxygen isotope analysis requires matrix-matched standards and, for chemically complex minerals, also appropriate matrix corrections. We will report on recent progresses on the analysis of oxygen isotopes in monazite, allanite and garnet using the SHRIMP ion microprobe. Zircon is a prime candidate for retrieving the oxygen composition of the pre-metamorphic protolith, as inherited zircons are preserved in many high-grade rocks. Metamorphic zircon rims that differ from the cores in δ18O offer insight into the origin of the fluid and the timing as well as degree of fluid-rock interaction. Garnet is another exceptional recorder of multiple metamorphic stages. Highly zoned garnets are found in a variety of eclogite-facies rocks and they can preserve dramatic oxygen isotopic variations (differences of a few to 10 δ18O ‰ within single crystal). Garnet and zircons from eclogite-facies metamorphic veins and shear zones within the metamorphosed Lago Superiore Unit from the Monviso ophiolite (W. Alps) have distinct growth zones with different oxygen isotopes composition. The shift in oxygen isotopes between the magmatic zircon core and the metamorphic zircon rim testifies to metasomatism by fluids equilibrated with serpentinites. The oxygen isotopes zoning in garnet confirms large scale fluid metasomatism concentrated in shear zones. It also indicates that some major shear zones from the Monviso ophiolitic sequence possibly underwent two stages of metasomatism, an event before or during early subduction and a later stage at around 550°C/2.5 GPa at peak pressure metamorphism.

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

    similar oxygen isotope compositions to the brachinites. It remains unclear whether the brachinites and related olivine-rich achondrites are from a single or multiple parent bodies. The primitive achondrites and related samples represent material from at most only 18 parent bodies, compared to an estimated 65 for the iron meteorites. This suggests that asteroidal mantle material is underrepresented in the meteorite record. Early fragmentation of differentiated asteroids, followed by preferential destruction of their silicate-rich mantles, offers a possible explanation for this discrepancy. On an oxygen three-isotope diagram, primitive chondrule-bearing winonaites (Dho 1222, NWA 725, NWA 1052, NWA 1463, Mt. Morris (Wisconsin)) plot close to the Young & Russell (Y&R) slope 1 line, with more evolved samples extending away from it towards the CCAM line. A similar relationship is shown by the CR chondrites. The acapulcoite-lodranite clan plots between the slope 1 and CCAM lines. However, the precursor material to the clan may have had a composition close to the slope 1 line prior to parent body processing. These relationships support the view that primordial oxygen isotope variation in the early solar system is best represented by the slope 1 (Y&R) line.

  6. 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. PMID:18497821

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  9. Oxygen isotopic identity of the Delaware Coastal Current

    NASA Astrophysics Data System (ADS)

    Khim, Boo-Keun; Krantz, David E.

    1996-07-01

    Results are presented and discussed from a preliminary study on the oxygen isotopic composition of coastal and inner shelf waters from the Middle Atlantic Bight between the mouths of Delaware Bay and Chesapeake Bay. The water samples were collected during the spring, April/May 1993, in conjunction with a detailed hydrographic survey of the Delaware Coastal Current. The relationship between salinity and δ18O, both of which are generally accepted conservative properties of seawater, allows identification of the fresh and saline mixing end-members for the Delaware Coastal Current. The main source of freshwater to the Delaware Coastal Current is a mixture of runoff into Delaware Bay with an estimated δ18OS = 0 composition of -7.08‰. The freshwater input is dominated by Delaware River discharge with a mean δ18O of -8.0‰ based on previous studies; there appears to be a secondary contribution of freshwater that is isotopically heavier from coastal-plain drainage. The extrapolated δ18OS = 32.35 value (-0.93‰) of the saline component implies exchange with Middle Atlantic Bight Shelf Water through along-shelf and across-shelf mixing processes. Limited data suggest that the oxygen isotopic composition of low-salinity water exiting the Chesapeake Bay mouth is discernible compared with that of the Delaware Coastal Current.

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

    SciTech Connect

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

    2012-01-01

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

  11. Ostracod-based isotope record from Lake Ohrid (Balkan Peninsula) over the last 140 ka

    NASA Astrophysics Data System (ADS)

    Belmecheri, Soumaya; von Grafenstein, Ulrich; Andersen, Nils; Eymard-Bordon, Amandine; Régnier, Damien; Grenier, Christophe; Lézine, Anne-Marie

    2010-12-01

    The stable isotope composition of benthic ostracods from a deep-lake sediment core (JO2004-1) recovered from Lake Ohrid (Albania-Macedonia) was studied to investigate regional responses to climate change at the interface between the north-central European and Mediterranean climate systems. Ostracod valves are present only during interglacial intervals, during the Marine Isotope Stage (MIS) 5 and 1. The ostracod oxygen isotope values (δ 18O) quantitatively reflect changes in the oxygen isotope signal of the lake water (δ 18O L). The interpretation of this record however, is far from straight forward. δ 18O L variations throughout MIS 5/6 transition (TII), MIS 5 and MIS 1 appear to be controlled by site specific hydrological processes as shown by modern isotope hydrology. The δ 18O L trends at TII, MIS 5 and MIS 1 match the timing and the main structural feature of the major regional climate records (Corchia cave δ 18O, Iberian margin Sea Surface Temperature) suggesting that the Ohrid δ 18O L responded to global-scale climate changes, although it seems certain that the lake experienced a significant degree of evaporation and varying moisture availability. The carbon isotope signal (δ 13C) seems to respond more accurately to climate changes in agreement with other JO2004-1 proxies. δ 13C of the ostracod calcite is directly linked to the δ 13C of the dissolved inorganic carbon (DIC) in the lake, which in this case is controlled by the isotopic composition of the DIC in the incoming water and by the internal processes of the lake. High δ 13C during cold periods and low values during warm periods reflect changing vegetation cover and soil activity. These results suggest that Lake Ohrid has the potential to capture a long record of regional environment related-temperature trends during interglacial periods, particularly given the exceptional thickness of the lake sediment covering probably the entire Quaternary.

  12. 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.

  13. Oxygen isotopic constraints on the composition of the moon

    NASA Technical Reports Server (NTRS)

    Grossman, L.; Clayton, R. N.; Mayeda, T. K.

    1974-01-01

    The mean oxygen isotopic composition of 5 Apollo 17 soils, one Apollo 17 breccia and one Apollo 12 soil is delta O-18 = 5.63 + or - .05 and delta O-17 = 3.8 + or - .2%. These values are within several tenths of a part permil of the composition of a large fraction of the lunar interior. High-temperature condensate aggregates from Allende and other C2 and C3 chondrites are vastly enriched in O-16 compared to this composition. The moon cannot be a mixture of ordinary chondrites and Allende inclusions, nor can it be derived from such a mixture by chemical fractionation processes. The moon's isotopic composition is consistent with a mixture of high- and low-temperature condensates but the refractory fraction would have to be free of the O-16-rich component so prevalent in the meteoritic aggregates, a fact which makes such models less attractive than they once seemed.

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

    USGS Publications Warehouse

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

    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.

  15. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2004-12-01

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

  17. 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

  18. 400-year May-August precipitation reconstruction for Southern England using oxygen isotopes in tree rings

    NASA Astrophysics Data System (ADS)

    Rinne, K. T.; Loader, N. J.; Switsur, V. R.; Waterhouse, J. S.

    2013-01-01

    Few long and well-dated summer precipitation reconstructions that extend beyond the longest records of instrumental measurements exist in Europe. Further understanding of the past trends in summer precipitation and the mechanisms driving that variability are necessary to improve the predictions of climate models. Tree rings are unique in their ability to provide high-resolution, absolutely dated climate signals for the study of palaeoclimatology. The physiological processes controlling oxygen isotope composition (δ18O) in wood are reasonably well understood highlighting its potential as a climate proxy in a variety of environments. Significant correlation between wood δ18O and precipitation has been demonstrated worldwide reflecting both direct rainout processes and indirectly evaporative enrichment. We present an annually resolved reconstruction of precipitation based upon oxygen isotope variations in tree ring cellulose covering the most recent ˜400 years for England. The May-August precipitation series, which was formed by combining reconstructed values based on oxygen isotope composition (δ18O) in tree ring cellulose of pedunculate oak (Quercus robur) (1613-1893) and instrumental data (1894-2003), indicates significant decadal and centennial precipitation variability culminating in dry conditions in the early-middle 17th century and the late 20th century. The analysis demonstrated statistically robust May-August precipitation signal in the δ18O values of oak cellulose back to 1697, the first year of the oldest instrumental precipitation series in England.

  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. Unlocking the Ice House: Oligocene-Miocene oxygen isotopes, eustasy, and margin erosion

    NASA Astrophysics Data System (ADS)

    Miller, Kenneth G.; Wright, James D.; Fairbanks, Richard G.

    1991-04-01

    Oxygen isotope records and glaciomarine sediments indicate at least an intermittent presence of large continental ice sheets on Antarctica since the earliest Oligocene (circa 35 Ma). The growth and decay of ice sheets during the Oligocene to modern "ice house world" caused glacioeustatic sea level changes. The early Eocene was an ice-free "greenhouse world," but it is not clear if ice sheets existed during the middle to late Eocene "doubt house world." Benthic foraminiferal δ18O 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 δ18O 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 δ18O record because of the lack of adequate data and problems in stratigraphic correlations that obscure isotope events. We improved Oligocene to Miocene correlations of δ18O records and erected eight oxygen isotope zones (Oi1-Oi2, Mi1-Mi6). Benthic foraminiferal δ18O increases which are associated with the bases of Zones Oil (circa 35.8 Ma), Oi2 (circa 32.5 Ma), and Mil (circa 23.5 Ma) can be linked with δ18O increases in subtropical planktonic foraminifera and with intervals of glacial sedimentation on or near Antarctica. Our new correlations of middle Miocene benthic and western equatorial planktonic δ18O records show remarkable agreement in timing and amplitude. We 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 δ18O increases which culminated with the bases of Zone Mi4 (circa 12.6 Ma) and Mi6 (circa 9

  1. Oxygen Isotope Variations in Lunar Mare Basalts through Fractional Crystallization

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Spicuzza, M.; Day, J. M.; Valley, J. W.; Taylor, L. A.

    2009-12-01

    Mare basalts, derived from partial melts from the lunar mantle, provide information on the early differentiation and evolution of the Moon. Highly precise and accurate oxygen isotope ratios were obtained on mg-size samples of low-Ti and high-Ti mare basalts from the Apollo 11, 12, 15 and 17 missions. Low-Ti basalts studied include Apollo 12 pigeonite and ilmenite basalts, Apollo 15 olivine- and quartz-norm basalts. High-Ti mare basalts studied include seven chemical groups (Apollo 11 Types A, B1, B3, and Apollo 17 Types A, B1, B2 and C) largely defined on the basis of trace elements, indicative of different mantle sources. High-Ti basalts display significant variation in δ18O, correlating with major elements. Values of δ18O in these high-Ti basalts increase by ~0.3‰ from Mg# = 53 to Mg# = 34, suggesting a fractional crystallization control. The variation within a given chemical group can be successfully modeled by mass-balance involving ~32% fractionation of olivine+ armalcolite + pyroxene + ilmenite+ plagioclase. This model demonstrates that high-Ti basalts with >12 wt% TiO2 and high Mg# are more primitive than those with 7-12 wt% TiO2. A weaker correlation of oxygen isotopes with major elements in low-Ti basalts is also observed. From Mg# of 48 to 38, values of δ18O increase by up to 0.1‰, consistent with removal of a minor quantity of olivine. Low-Ti mare basalts with the highest Mg# (55) have slightly lower 18O values than those with Mg# of 48, consistent with possible olivine accumulation. More primitive samples in low-Ti and high-Ti groups still display distinct δ18O values.18O versus major-element plots. This implies that low- and high-Ti basalts are derived from separate sources, each with homogeneous oxygen isotopic compositions. The hypothesis that high-Ti basalts were generated from the assimilation of ilmenite-bearing rocks by low-Ti basalts is not supported by oxygen isotope compositions. The major-element and δ18O variations of low- and high

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

    SciTech Connect

    Epstein, S.; Zeiri, L. )

    1988-03-01

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

  3. Carbonate Ion Effects on Coccolith Carbon and Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

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

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

    PubMed

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

    2016-07-01

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

  5. Authigenic Molybdenum Isotopes Record Lake Baikal in the Past

    NASA Astrophysics Data System (ADS)

    Yu, E.; Liu, H.; Lee, D.

    2013-12-01

    Authigenic molybdenum isotope signatures in marine sediments reflect the mechanisms of deposits under both oxic and reducing conditions. The studies are mainly focusing on marine environment, and the application on lake record is rare. A three-meters long gravity core (GC-99; 52°05'23'N, 105°50'24'E; water depth 201m) from Lake Baikal is studied for Mo isotopes and concentration. The result is using to examine the sources of material or/and the changes in conditions of Lake Baikal with climate changes. To approach on extracting Mo isotope signal directly related to lake water, a sequential leaching technique to extract the Mo isotopes coating on the Fe-Mn oxides and a robust chromatography technique to purify molybdenum isotopes is modified and used for all lake sediment samples. Then, Mo isotope composition is measured by applying double spike method with Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). According to the Mo concentration and its isotope composition δ98/95Mo relative to NIST-SRM-3134, the results imply Lake Baikal stayed oxic condition over the last 24 ka. Moreover, the sediment core GC-99 from Lake Baikal imply two stages fluctuations of the lake environment separated at core depth of 100cm (around 12ka); and the shifting of δ98/95Mo isotope composition shows that the lake during interglacial period was more oxic than the last glacial period due to absence of ice cover.

  6. 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.

  7. Oxygen isotope geochemistry of the amphiboles: Isotope effects of cation substitutions in minerals

    SciTech Connect

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

    1998-06-01

    The occurrence of coexisting amphiboles in rocks and the likelihood of concurrent isotope closure allows equilibrium oxygen isotope fractionations among the amphiboles to be recovered from natural samples. Oxygen isotope analyses of mineral separates using laser fluorination show that coexisting amphiboles increasingly partition {sup 18}O in the order: hornblende {much_lt} gedrite < cummingtonite {le} anthophyllite. The observed fractionations at {approximately}575 C are: {Delta}(Ged-Hbl) = 0.8%, {Delta}(Cum-Hbl) = 0.9, {Delta}(Cum-Ged) = 0.2, {Delta}(Ath-Ged) = 0.3, and {Delta}(Ath-Hbl) > 0.9. Previously published data for hornblende, actinolite, glaucophane, and garnet show that {Delta}(Act-Hbl) {approximately} 0.2, {Delta}(Gin-Grt) {much_gt} 1, and {Delta}(Hbl-Grt) {approximately} 0. Thus, glaucophane strongly partitions {sup 18}O relative to the calcic amphiboles. The fractionation between two amphiboles of arbitrary composition can be predicted from the known fractionations for mica endmembers, pyroxene endmembers, and exchange components. Applications of the exchange component method reproduce measured amphibole fractionations to within {+-}0.1 to {+-}0.2%, whereas other predictive methods cause misfit for typical metamorphic hornblende of {ge}0.5% at 575 C. Although the isotope effects of cation exchanges may be small at high-T, they magnify dramatically for minerals formed in surficial, diagenetic, and low-T metamorphic environments. Different composition clays are predicted to have equilibrium {delta}{sup 18}O differences of 2--9%. If the isotope fractionation can be determined for one mineral endmember, then calibrated exchanges allow accurate prediction of the isotope fractionations for intermediate compositions of most ortho-, ring-, chain-, and sheet-silicates.

  8. Oxygen Isotope of Phytoliths in Modern Wetland Plants and the Application to Paleoclimate Reconstruction

    NASA Astrophysics Data System (ADS)

    Huang, Z.; Webb, E. A.; Longstaffe, F. J.

    2009-05-01

    Because the oxygen-isotope composition of phytoliths in modern plants is controlled primarily by the oxygen- isotope composition of source water, temperature and relative humidity, isotope analyses of ancient phytoliths extracted from soils have the potential to reveal paleoclimate information. A controlled-temperature, growth- chamber experiment was conducted to determine the relationships among temperature, relative humidity, soil water evaporation, plant-water isotope composition and oxygen-isotope composition of phytoliths in cattails and horsetails. Typha, a cattail species that grows in wetland conditions, and Equisetum, a horsetail species that prefers dry soils, were each grown in four separate chambers at 15, 20, 25 and 30 degrees Celsius. The oxygen- and hydrogen-isotope compositions of watering water, soil water, vapour in the growth chambers and plant water from the leaves and stems were analyzed throughout the eight-month long artificial growing season. The oxygen-isotope compositions of phytoliths extracted from the transpiring tissues of the plants at the end of the growing season were also analyzed.The results show that the oxygen-isotope composition of phytoliths is strongly correlated with oxygen isotope composition of average plant water from late growing season, rather than plant water extracted earlier in the season or from the stem, leaf-base or leaf- apex alone. As the temperature increases, the oxygen-isotope fractionation between phytoliths and plant water decreases. This trend is comparable to the oxygen-isotope thermometer equation developed by Shahack- Gross et al. (1996: Geochim. Cosmochim. Acta 60, 3949-3953), but the separation in oxygen-isotope values between silica and water at a given temperature is about 4 ‰ lower. This discrepancy is likely from uncertainties in the oxygen-isotope value of leaf water at the site of phytolith precipitation, which varied over the growing season as a result of fluctuations in relative humidity and

  9. 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

  10. 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.

    2012-12-01

    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 archaeological shell 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 Mytilus 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 archaeological shell middens from prehistoric settlements in Greenland.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

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

  13. 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.

  14. 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

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

    NASA Technical Reports Server (NTRS)

    Vidor, S. B.

    1975-01-01

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

  16. 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

  17. 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.

  18. 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

  19. Oxygen isotope geochemistry of back-arc lavas

    NASA Astrophysics Data System (ADS)

    Bonifacie, M.; Eiler, J. M.; Stolper, E. M.; Langmuir, C. H.

    2007-12-01

    Oxygen isotope ratios of arc-related magmas can constrain the amount and nature of slab-derived components contributing to their mantle sources because: (i) most geological solids and fluids contain similar concentration of oxygen; and (ii) possible slab components (fluids, melts or rocks from sedimentary, mafic or ultramafic parts of the lithosphere) differ from one another in δ18O values and these distinctive oxygen-isotope compositions can be preserved in deeply subducted materials. Previous laser fluorination oxygen isotope data on back-arc basin basalts (BABB) show slightly but consistently elevated δ18O values (from 5.5 to 6.1 ‰ [1-3]) with respect to mid-ocean ridge basalts or MORB (δ18O = 5.5 ± 0.2 ‰ [4]). The subtle elevations in δ18O characteristic of BABB are generally associated with 'enriched' radiogenic isotope compositions (e.g., high 87Sr/86Sr) and high apparent degrees of melting of their peridotitic sources that may reflect fluxed melting of the mantle by fluids and/or hydrous melts released from subducted oceanic lithosphere [1-3]. These trends could be used to precisely define the sources and amounts of slab- derived components delivered to the back arc mantle. However, two issues demand that this problem be better constrained through further studies. First, the subtle difference in δ18O between MORB and BABB involves comparison of data generated in different laboratories that may not share common standardization; this difference must be demonstrated within a single laboratory using a common set of standards. Second, the trends of δ18O vs. other geochemical indices observed in BABB lavas are based on samples from several relatively small and unrelated suites of lavas. These trends must be documented through study of one or more relatively large and diverse suites of closely related lavas. We are performing new laser-fluorination oxygen isotope measurements of a comprehensive suite of fresh back-arc glasses collected along the Eastern

  20. 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.

  1. 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.

  2. Oxygen isotope constraints on the origin of island arc granitoids

    NASA Astrophysics Data System (ADS)

    Perez, R. J.; Cavosie, A. J.; Valley, J. W.

    2007-12-01

    Granitic intrusions in island arcs constitute additions of juvenile crust from oceanic environs that ultimately get accreted to continents. The genesis of island arc granitoids is thus important to studies of the growth of oceanic and continental crust. Puerto Rico (USA) is a composite island arc terrane that preserves a record of plutonism from 85 Ma to 38 Ma (Cavosie et al., 2007 AGU). Mid-crustal granitoid plutons are exposed (~1 to 500 km2), but their origins are unknown, as no suspected parental magmas associated with the plutons (e.g., gabbro) are exposed. This study uses petrography, WR major elements, and oxygen isotopes of WR and zircon from granitoids and xenoliths to place better constraints on the origin of granitoid in the Greater Antilles island arc. WR δ18O analyses were made with laser fluorination by IRMS at the Univ. of Wisconsin (uncertainties = 0.10 to 0.20‰, 2sd). The main plutons (Caguas, Rio Blanco, San Lorenzo, Utuado, Vieques) yield primitive δ18O(WR) values, ranging from 6.24 to 7.72‰ over a range of wt.% SiO2= 58.03 to 66.54. Smaller stocks (<20 km2) yield higher δ18O(WR) values, ranging from 7.47 to 10.27‰. Qualitative petrographic analysis reveals that granitoids with δ18O(WR) >~7.5‰ are partially to pervasively altered. Zircon preserves magmatic δ18O and is used here to quantitatively evaluate the measured δ18O(WR) values. If δ18O(Zrc) and wt.% SiO2 are known, a comparison of measured vs. predicted δ18O(WR) can be made (Valley et al., 2005, CMP). The measured δ18O(WR) values record variable amounts of alteration, ranging from virtually undetectable, to WR δ18O elevations of ~4‰, indicative of low-T subsolidus alteration. The Δ18O (WR-Zrc) values using calculated δ18O(WR) yield the following fractionations: -1.57 to 1.00‰ for granodiorites (wt.% SiO2=66 to 57); -0.85‰ for diorite (wt.% SiO2=55); and -0.56‰ for the only gabbro analyzed (wt.% SiO2=50). Mafic xenoliths (53-57 wt.% SiO2) from 4 granitoids yield

  3. 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

  4. Miocene benthic foraminiferal isotope records: A synthesis

    USGS Publications Warehouse

    Savin, S.M.; Douglas, R.G.; Keller, G.; Killingley, J.S.; Shaughnessy, L.; Sommer, M.A.; Vincent, E.; Woodruff, F.

    1981-01-01

    18O 16O and 13C 12C ratios of Miocene benthic foraminifera from a number of Atlantic, Pacific and Indian Ocean DSDP sites (71, 77B, 206, 208, 238, 279, 289, 296, 329, 357 and 366A) have been compiled. These provide a rather detailed history of Miocene deep water especially in the Pacific Ocean. Bottom-water temperatures rose during the early Miocene and then declined rapidly during the middle Miocene. This decline was accompanied by an increase in Antarctic glaciation. Late Miocene bottom temperatures and Antarctic ice volumes are inferred to be similar to today's, but exhibited some fluctuation. The early Miocene ocean was less thermally stratified at intermediate and abyssal depths while the late Miocene deep ocean had a thermal structure generally similar to the modern ocean. Foraminiferal carbon isotope ratios at most of the sites varied quasi-sympathetically throughout the Miocene. These variations must reflect comparable variations in the mean 13C 12C of marine HCO3-. However, the causes of such variations are not yet clear. ?? 1981.

  5. 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.

  6. Oxygen and Nitrogen Isotopes in the Sun and Solar Nebula

    NASA Astrophysics Data System (ADS)

    Lyons, J. R.

    2014-12-01

    The record of light stable isotope signatures in early solar system materials provides key constraints on the formation environment, mixing processes, and loss processes that influenced the solar nebula. Considering first the Sun, the NASA Genesis mission showed that the solar wind has a 17O depletion that is slightly more negative than the isotopically lightest CAIs (McKeegan et al. 2011), but still only yields an inferred photospheric (and bulk) solar O isotope composition. Recent reanalysis of astronomical measurement of O isotopes from infrared CO lines (Ayres et al. 2013) argues for a similarity in d18O for the directly observed photosphere and the inferred photosphere from Genesis, in contrast to the wildly divergent astronomical values previously reported. The accuracy of the Ayres et al. results are limited by the accuracy of the IR oscillator strength models; I will report on the impact of new oscillator strength models for CO. Turning to the CAIs, the Genesis O isotope results are consistent with CO self-shielding as the mechanism for producing the CAI mixing line from a mixture of photo-produced H2O (17O-enriched) and solar-like initial material (Clayton 2002; Lyons and Young 2005). Two other mechanisms have been proposed: 17O enrichment from 1) high temperature SiO reactions with OH (Chakraborty et al. 2013), and 2) transfer from low temperature O3 formation on dust. I will critique both of these suggested mechanisms. Finally, N isotope ratios, which span a range in d15N values from ~-400 permil for the Sun (Marty et al. 2011) and solar nebula, to +1000s permil for hotspots in CB chondrites, are influenced by low temperature ion-molecule reactions, and potentially by photoprocesses. Heays et al. (2014) have shown that N2 photolysis can produce very large 15N enrichments in product HCN in a static protoplanetary disk. I will present similar calculations for a turbulently mixed disk. Implications for cometary isotopic composition will be presented.

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

    NASA Astrophysics Data System (ADS)

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

    1993-07-01

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

  8. Biogeochemical Processes in Late Archean Marine Biosphere Revealed by Isotopic and Molecular Records

    NASA Astrophysics Data System (ADS)

    Eigenbrode, J. L.; Freeman, K. H.; Summons, R. E.

    2004-12-01

    The presence of shallow-marine oxygen oases and associated aerobic ecosystems in an otherwise anoxic and anaerobic world has been proposed by researchers to explain the anomalous 40 permil spread in organic-carbon isotope values during the late Archean. To test this hypothesis, we studied isotopic, molecular, and lithologic records of 2.7-2.5 Ga rocks of different depositional facies from the Hamersley Province, Western Australia. Kerogen carbon-isotopic compositions indicate that extreme 13C-depletion (more than -45 permil) was associated with shallow-marine-carbonate environments at 2.72 Ga and with deepwater environments thereafter. Moreover, kerogen-carbon-isotope values associated with carbonate environments became enriched by more than 10 permil over 100-150 Ma. These observations suggest that microbial processes responsible for extreme 13C-depletion became less significant in shallow carbonate environments, but remained important in deeper settings. Molecular biomarker ratios determined for associated bitumens: 1) strongly correlate to kerogen carbon-isotope values and other biomarker ratios, and, 2) show relationships with depositional facies and dolomite abundance giving credence to a syngenetic relationship with host rocks. The biomarker data confirm aerobic methanotrophs in the Late Archean biosphere, but not in strong association with extreme 13C-depletion. Biomarker patterns reflect a greater association of aerobic respiration and oxygenic photosynthesis in shallow carbonate environments compared to deeper settings. Collectively, the data record dramatic changes in carbon cycling associated with environmental partitioning of microbial processes and ecosystems over 100-150 Ma. Most likely, this represents increased bioavailability of strong electron acceptors with the expansion of oxidant-rich oases prior to rise in atmospheric oxygen.

  9. An oxygen isotope study of illite and calcite in three Appalachian Paleozoic vertic paleosols

    SciTech Connect

    Mora, C.I.; Sheldon, B.T.; Driese, S.G.; Elliott, W.C.

    1998-05-01

    The oxygen isotope compositions of pedogenic calcite and illite in three Paleozoic vertic red bed paleosols record a complex history of pedogenic and diagenetic processes. The paleosols are preserved in the upper Mississippian (Chesterian) Mauch Chunk (Pennsylvania), Hinton (West Virginia), and Pennington (Tennessee) Formations in the Appalachian Basin and were buried to 7--8 km (230--260 C), 3--4 km (100--145 C), and 1.5--3 km (70--100 C), respectively. The submicron-size clay fractions of the paleosols are presently composed of R3-ordered illite/smectite (I/S), inferred from K-Ar dates and soil morphology to have been authigenically produced by the reaction of smectite to illite. Oxygen isotope fractionations, calculated pore-fluid compositions, and K-Ar dates were used to constrain the conditions and timing of I/S and pedogenic calcite (re)crystallization in each of the paleosols. The data were interpreted in light of three possible end-member environments for formation and recrystallization: (1) the pedogenic environment; (2) the burial diagenetic environment; and (3) a burial environment dominated by hot, tectonically driven fluid. The {delta}{sup 18}O values of pedogenic calcite and authigenic I/S in vertic red bed paleosols generally reflect recrystallization and exchange during burial diagenesis and are thus not suitable for interpretation of paleoenvironment or paleoclimate. The involvement of orogenic fluids during burial cannot be ruled out, but it is not required by any of the paleosols. In the coastal-margin Pennington Formation paleosol, I/S formation may have been initiated in the pedogenic environment in response to cyclical wetting and drying of the soil clay matrix. Continued smectite transformation and coarsening and ordering of I/S during a long period of shallow burial led to its isotopic reequilibration with pore fluids at slightly elevated temperature, but oxygen isotope compositions of pedogenic calcite in the paleosol are preserved.

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

    PubMed

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

    2006-02-01

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

  11. The Oxygen Isotopic Signature of Nitrous Oxide is Determined by Oxygen Exchange

    NASA Astrophysics Data System (ADS)

    Kool, D. M.; Wrage, N.; Oenema, O.; Harris, D.; van Groenigen, J.

    2008-12-01

    In order to derive accurate budget estimations and effective mitigation strategies for the greenhouse gas nitrous oxide (N2O), it is essential to identify the processes involved in its production. Analyses of the isotopic composition of N2O are increasingly used to characterize the importance of these processes. However, we argue that the reliability of results based on oxygen (O) isotopic analysis of N2O may be questioned due to insufficient consideration of O exchange between H2O and nitrogen oxides. We studied the process of O exchange in 12 widely varying soils using a novel combination of 18O and 15N tracing experiments. Incorporation of O from 18O-enriched H2O into N2O exceeded theoretical maxima based on reaction stoichiometry, revealing the presence of O exchange. Novel methodology based on the retention of the 18O:15N-enrichment ratio of NO3- in N2O allowed to quantify O exchange during denitrification: up to 97% of N2O-O originated from H2O instead of NO3-. Our results show that in soil, the main source of N2O, the conventional assumption that the O isotopic composition of N2O is determined by reaction stoichiometry and isotopic fractionation during its production does not hold. In all cases, the O isotopic signature of N2O was found to be dominated by the effect of O exchange between nitrogen oxides and water. We speculate that the implications of O exchange will extend across terrestrial and aquatic ecosystems, and possibly to other nitrogen oxides as well. Especially, a potential effect of O exchange on the O isotopic signature of NO3- needs to be studied, as this is routinely used for NO3- source determination. Our results may facilitate the development of improved methodology to study and understand the global N cycle.

  12. 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.

  13. 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

  14. Oxygen isotopes and emerald trade routes since antiquity

    PubMed

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

    2000-01-28

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

  15. 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.

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

    PubMed

    Barrick, R E; Showers, W J

    1994-07-01

    The oxygen isotopic composition of vertebrate bone phosphate (delta(p)) is related to ingested water and to the body temperature at which the bone forms. The delta(p) is in equilibrium with the individual's body water, which is at a physiological steady state throughout the body. Therefore, intrabone temperature variation and the mean interbone temperature differences of well-preserved fossil vertebrates can be determined from the deltap variation. Values of delta(p) from a well-preserved Tyrannosaurus rex suggest that this species maintained homeothermy with less than 4 degrees C of variability in body temperature. Maintenance of homeothermy implies a relatively high metabolic rate that is similar to that of endotherms. PMID:17750663

  17. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

  19. Constraints on Phanerozoic paleotemperature and seawater oxygen isotope evolution from the carbonate clumped isotope compositions of Late Paleozoic marine fossils (Invited)

    NASA Astrophysics Data System (ADS)

    Henkes, G. A.; Passey, B. H.; Grossman, E. L.; Pérez-Huerta, A.; Shenton, B.; Yancey, T. E.

    2013-12-01

    of burial. Consideration of the thermal history of samples is essential for identifying the possibility of clumped isotope alteration via C-O bond reordering. Our experimental results further suggest that even nascent reordering (<5-10%) is enough to measurably bias reconstructed paleotemperatures (and calculated seawater oxygen isotope compositions) to higher values. We also investigate the use of electron backscatter diffraction (EBSD), which resolves crystallographic orientation at high spatial resolution, as an alternative method for identifying sub-microstructural diagenesis in calcite. Preliminary results of EBSD on the experimental and natural Paleozoic brachiopod shells will be presented and discussed with respect to their clumped isotope compositions and the Phanerozoic record.

  20. 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.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

  3. 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.

  4. Oxygen isotope systematics in magmatic and subsolidus epidote

    NASA Astrophysics Data System (ADS)

    Morrison, J.; Anderson, J. L.

    2003-04-01

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

  5. 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

  6. 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

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  9. The influence of kinetics on the oxygen isotope composition of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Watkins, James M.; Nielsen, Laura C.; Ryerson, Frederick J.; DePaolo, Donald J.

    2013-08-01

    Paleotemperature reconstructions rely on knowledge of the equilibrium separation of oxygen isotopes between aqueous solution and calcium carbonate. Although oxygen isotope separation is expected on theoretical grounds, the temperature-dependence remains uncertain because other factors, such as slow exchange of isotopes between dissolved CO2-species and water, can obscure the temperature signal. This is problematic for crystal growth experiments on laboratory timescales and for interpreting the oxygen isotope composition of crystals formed in natural settings. We present results from experiments in which inorganic calcite is precipitated in the presence of 0.25 μM dissolved bovine carbonic anhydrase (CA). The presence of dissolved CA accelerates oxygen isotope equilibration between the dissolved carbon species CO2, H2CO3, HCO3-, CO32- and water, thereby eliminating this source of isotopic disequilibrium during calcite growth. The experimental results allow us to isolate, for the first time, kinetic oxygen isotope effects occurring at the calcite-water interface. We present a framework of ion-by-ion growth of calcite that reconciles our new measurements with measurements of natural cave calcites that are the best candidate for having precipitated under near-equilibrium conditions. Our findings suggest that isotopic equilibrium between calcite and water is unlikely to have been established in laboratory experiments or in many natural settings. The use of CA in carbonate precipitation experiments offers new opportunities to refine oxygen isotope-based geothermometers and to interrogate environmental variables other than temperature that influence calcite growth rates.

  10. Developing stable isotopic records from organic material preserved in speleothems

    NASA Astrophysics Data System (ADS)

    Blyth, A.; Baker, A.

    2011-12-01

    Speleothems form excellent archives of environmental change as they are easy to date and preserve multiple environmental records. However, although the stable isotopic composition of speleothem calcite is well characterised, the isotopic composition of organic matter in speleothems has not been investigated in-depth. The approach has considerable potential value in providing isotopic records directly linked to the overlying ecosystem. For stable carbon isotopes, this will provide records independent of the calcite signal, and enable identification of the local primary controls (vegetation type, climate, soil conditions). However, the detailed measurement of isotopic records in speleothem organic matter is hindered by methodological constraints, including extraction of sufficient material, and recovery without adding carbon contamination. Here we present results from a number of methodological techniques and discuss which show most potential for future palaeoenvironmental work. Isotopic records in organic matter can be divided into two main types - analyses of the bulk organic fraction, and compound-specific analyses of molecules of interest (e.g. plant waxes, bacterial lipids etc.). From the point of view of sample size, bulk analysis is the most amenable. Our work shows that TOC in stalagmites can be as low as <0.1 mg/g calcite. However, this is still sufficient to produce bulk organic signals at a sample size of between 100 and 500 mg of calcite powder, which provides a workable temporal resolution at a decadal-centennial scale on many samples. The main obstacle is the recovery of bulk organics without carbon contamination, but whilst avoiding excess acid salts which might damage the instrumentation. One method we propose is the use of an iTOC-CDRS analyser, which measures total organic carbon, and also 12C and 13C isotopes. The approach has the advantage of requiring minimal sample preparation, with drilled powders simply being dissolved in acid. The major

  11. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  13. 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

  14. 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

  15. 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.

  16. Preliminary evaluation of oxygen isotopic exchange between chlorite and water

    SciTech Connect

    Cole, D.R.

    1985-01-01

    Variations in the oxygen isotopic composition of biotites altering to chlorite have been monitored as a function of time from 16 hydrothermal granite-water experiments conducted at the following conditions: T = 170/sup 0/ - 300/sup 0/C; P = 100-300 bars; mNaCl = 0.1-1.0; water/biotite mass ratio = 1-60 for periods up to 900 hours. The magnitude of delta/sup 18/O depletion in biotite increased with increasing temperature and time. Detailed thin section, x-ray and SEM studies demonstrated that biotite is altered exclusively to chlorite in 11 of the 16 experiments. The amounts of chlorite formed in these experiments increased with increasing temperature as well as time. The isotopic compositions of chlorite were calculated from mass balance, and compared with the final measured delta/sup 18/O of the fluids. These fractionations (..delta..Ch1-w) average 0.26, 0.77, and 3.74 per thousand for T = 300/sup 0/, 250/sup 0/, and 200/sup 0/C, respectively. Several lines of evidence will be discussed that suggest these data may represent equilibrium values. A least-squares regression of the data yields the following preliminary equation: 1000 ln ..cap alpha../sub/ Chl-W/ = 08.38 (10/sup 3//T) + 4.81 (10/sup 6//T/sup 2/). The error about this curve is at least +/-0.5 per thousand at 250/sup 0/ and 300/sup 0/C, and +/- 1 per thousand at 200/sup 0/C. There is excellent agreement between this curve and the curve given by Wenner and Taylor (1971) for the temperature range of 250/sup 0/ to 300/sup 0/C. However, below 250/sup 0/C, the new chloride-water results predict consistently higher temperatures compared to previous estimates.

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

    PubMed

    Mandernack; Bazylinski; Shanks; Bullen

    1999-09-17

    A series of carefully controlled laboratory studies was carried out to investigate oxygen and iron isotope fractionation during the intracellular production of magnetite (Fe(3)O(4)) by two different species of magnetotactic bacteria at temperatures between 4 degrees and 35 degrees 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 Fe(3)O(4) and water that is consistent with that observed for Fe(3)O(4) produced extracellularly by thermophilic Fe(3+)-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 Fe(3)O(4) may be useful in paleoenvironmental studies for determining the oxygen-18 isotope values of formation waters and for inferring paleotemperatures. PMID:10489363

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

    USGS Publications Warehouse

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

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  1. 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.

  2. 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

  3. Precision performance of a Cavity Ring-down isotope spectrometer for carbon and oxygen isotopes of carbonate materials

    NASA Astrophysics Data System (ADS)

    Cunningham, K. L.; Hoffnagle, J.; He, Y.; Fleck, D.; Saad, N.; Dennis, K.

    2013-12-01

    We have developed a novel laser spectrometer intended specifically for the measurement of δ18O and δ13C in solid carbonate material. Carbonate carbon and oxygen isotopes provide key contributions into our understanding of climate, biogeochemical processes and the carbon cycle. For this reason, the isotopic measurements of carbonates are one of the most abundant measures made by Earth scientists today. Conventional measurement techniques using isotope ratio mass spectrometry (IRMS), although optimized and prevalent, require dedicated personnel and can be expensive to operate. Here we present a new laser-based technique that will simplify measurements of δ18Ocarb and δ13Ccarb without compromising precision. To date, there have been no laser-based instruments with a demonstrated ability to meet the requirements of the carbonates community -- typically better than 0.1 ‰ for δ13C and δ18O for CO2 evolved from 1 mg of pure CaCO3. We will present data showing that the new Picarro G2171-i spectrometer meets these requirements. The spectrometer uses the laser-based spectroscopy technique of Cavity Ring-Down Spectroscopy (CRDS), a technology that has been successfully applied to many other isotopic ratio measurements including δ13C of CO2, δ13C of CH4, and δ18O and δD of H2O. The spectrometer has been optimized to analyze the absorption spectra of concentrated CO2, specifically the isotopologues 12C16O16O, 13C16O16O, 12C16O18O, and 12C18O16O. We employ a new sample delivery technique that enables a longer integration time period, and hence more precise data. Long-term results for a run of 540 pulses of tank CO2 (90 hours) records a 1σ standard deviation precision for δ18O and δ13C of < 0.08 ‰ and < 0.055 ‰, respectively. We coupled the CRDS spectrometer to an optimized sample acidification system and analyzed standards to assess the accuracy of the CRDS. We will present an inter-comparison between CRDS and IRMS for carbonates using standards commonly used

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  5. 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.

  6. High-resolution Oxygen Isotope Profiles in Tree-rings and How to Interpret Them

    NASA Astrophysics Data System (ADS)

    Schubert, B.; Jahren, H.

    2013-12-01

    Workers have long sought to gain environmental information from oxygen isotope measurements in both modern and ancient wood cellulose (δ18Ocellulose). A quantitative mechanistic relationship for interpreting seasonal changes has proven difficult because multiple environmental parameters, such as temperature and precipitation, affect the δ18O value of meteoric water (δ18OMW), which forms the primary source of oxygen for plant tissue construction. Here we present new high-resolution δ18Ocellulose profiles across tree rings from five widely distributed sites, and combine these new data with 26 other similar records from the literature to form a global dataset of intra-annual changes in δ18Ocellulose from 781 tree rings measured at 31 sites. Using the International Atomic Energy Agency Global Network of Isotopes in Precipitation month-by-month database we first develop relationships between the seasonal changes in temperature and precipitation amount to seasonal changes in δ18OMW. We then use these relationships based on modern precipitation to relate the seasonal change in δ18Ocellulose measured across tree rings to these seasonal climate parameters. Our analysis results in a unifying relationship explaining the intra-annual δ18Ocellulose patterns observed in tree rings worldwide that can be used to reconstruct seasonal temperature and precipitation amount from modern and fossil wood.

  7. 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.

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

    PubMed

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

    2006-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-11-01

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

  10. 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

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

    NASA Astrophysics Data System (ADS)

    Barbour, M. M.

    2007-12-01

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

  12. 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.

  13. Areal Distribution of the Oxygen-Isotope Ratio in Greenland

    NASA Technical Reports Server (NTRS)

    Zwally, H. Jay; Giovinetto, Mario B.

    1997-01-01

    Mean values of the oxygen-isotope ratio relative to standard mean ocean water reported for 46 sites on the Greenland ice sheet are compiled together with data on mean annual surface temperature, latitude, 6180 elevation, and mean annual shortest distance to the open ocean denoted by the 10% sea-ice concentration boundary. Stepwise regression analyses, with 6180 as the dependent variable, define two robust models. In the forward mode at the 99.9% confidence level, only temperature enters the model. In the backward mode at the 95% confidence level, only temperature, latitude, and distance to the open ocean remain in the model. Inversions of the models on the basis of 160 gridpoint locations 100 km apart in the area delimited by the surface equilibrium line produce four contoured distributions of 6"0. Two distributions are based on the bivariate model and two on the multivariate model. The second distribution for each model is obtained substituting mean annual surface-temperature values obtained from the Nimbus-7 Temperature Humidity Infrared Radiometer (THIR) database. All four distributions are considered valid, and differences between them are evaluated using contoured anomaly maps. It is suggested that the inversion of the multivariate model using THIR data provides the more reliable pattern for studies of atmospheric advection or for the derivation of ice-flow adjustments for 6180 series obtained from deep-core or ablation-zone sites.

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

    USGS Publications Warehouse

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

    2005-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Bao, Huiming; Reheis, Marith C.

    2003-07-01

    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 (δ34S and δ18O) are 5.8 ± 1.4 (CDT) and 11.2 ± 1.9 (SMOW) (n = 47), respectively. Samples have an oxygen 17 anomaly (Δ17O), with an average value of 1.0 ± 0.6‰. Except for a weak positive correlation between δ18O and Δ17O values (r2 ≈ 0.4), no correlation exists for δ18O versus δ34S, Δ17O versus δ34S, or any of the three isotopic compositions versus elevation of the sample site. Exceptional positive Δ17O values (up to 4.23‰) are found in samples from sites in the vicinity of large cities or major highways, and near-zero Δ17O 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 δ18O, ˜2.1‰ higher for δ34S, and ˜0.3‰ lower for Δ17O 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.

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. Phosphorus Speciation and Phosphate Oxygen Isotope Systematics of Type Euxinic Marine Deposits from Middle Devonian North America

    NASA Astrophysics Data System (ADS)

    Carney, C. P.; Arthur, M. A.

    2010-12-01

    Perturbation to the P cycle is thought to be an important forcing in episodes of ocean oxygen depletion and enhanced organic C burial, but this relationship remains underconstrained by geochemical data. This geochemical study applies sequential P extraction and subsequent phase-specific PO4-oxygen isotope analyses to the Marcellus Shale Formation - a type euxinic marine unit. Analysis of sedimentary P is assimilated with bulk geochemical data and detailed lithostratigraphy to capture the relationship of P-cycling with evolving sediment inputs, sea level, water column redox conditions, and water column stratification. It is also possible to study the effects of variable thermal history on lithified sediments, as the thermal history of the Marcellus Shale Formation is known throughout the basin. Thermal maturity is compared to variability in P-speciation and PO4-oxygen isotopic composition to control for the effects of secondary diagenesis. A high-resolution oxygen isotope-derived temperature record is important in paleoceanographic reconstruction. In the Middle Devonian, and the Paleozoic in general, diagenetically-robust PO4-oxygen has begun to supplant the CO3-oxygen isotope system in paleothermometry applications due to near pervasive signal overprinting. Conodont elements are the typical source of PO4 for these analyses, but the spatio-temporal distribution of these fossils is limited, and collection from non-carbonate facies is prohibitively labor-intensive. Oxygen isotope analyses of specific fractions of bulk sedimentary phosphate provide a feasible, but relatively unproven alternative. Two recent studies have demonstrated that a large fraction of authigenic P is precipitated in isotopic equilibrium with seawater and that phase partitioning of P can be preserved on hundred-Myr timescales. These results suggest that a PO4 isotope paleoproxy is viable. This study expands the scope of application to paleosediments with high-resolution data and complimentary

  1. Oxygen and hydrogen isotope measurements of water from fluid inclusions in stalagmites using cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Uemura, R.; Nakamoto, M.; Gibo, M.; Asami, R.

    2012-12-01

    The oxygen isotope composition of stalagmite calcite is useful to reconstruct past climate change. However, the interpretation of the isotope record is not straightforward because it is controlled by both precipitation amount and temperature. If the isotope composition of the parent dripwaters could be measured, differences between inclusion and calcite isotope composition will give temperature changes where stalagmite formed. Several methods for extracting and measuring the isotope composition of fluid inclusion of stalagmites have been proposed. A traditional isotope ratio mass spectrometer requires pre-treatment processes (e.g., high-temperature furnace or equilibration device) because H2O has to be converted to other measurable gases (H2, CO, or CO2). To simplify such processes, we have developed a method to measure isotope ratios of water from fluid inclusions using cavity ring-down spectroscopy (Picarro L-2120i WS-CRDS), which can measure H2O molecules directly. The water from stalagmite sample was extracted by heating (up to 500 degC). The extracted water was purified, and then sent to the WS-CRDS with dry N2 gas. Stalagmites samples, which appear to be still growing, were collected in a cave (Gyokusendo, Okinawa, Japan). The isotope composition of water from inclusion are δ18O = -6.0 ± 0.4 permil, and δ2H = -34.8 ± 3.9 permil (n=4). The values are close to modern isotope compositions of precipitation in Okinawa (precipitation-amount weighted values (2008 to 2011); δ18O = -5.7 permil and δ2H = -32.3 permil) and modern cave dripwaters in the cave (average δ18O = -5.6 permil, and average δ2H = -32.2 permil, in 2010). The results suggest that isotope compositions of the past dripwaters can be recovered.

  2. Preservation of premetamorphic oxygen isotope ratios in granitic orthogneiss from the adirondack mountains, New York, USA

    NASA Astrophysics Data System (ADS)

    Eiler, John M.; Valley, John W.

    1994-12-01

    The Adirondack Mountains, New York, expose a diverse group of Proterozoic igneous rocks that were metamorphosed to granulite facies conditions during the Ottawan phase of the Grenville orogeny. Oxygen isotope data for seventy whole rock samples of gabbroic to granitic meta-igneous rocks, primarily from the charnockite suites from the Tupper and Saranac sheets in the central Adirondacks, demonstrate a correlation between δ18Owr and major element composition within continuous, mappable, meta-plutonic units. No such relationship is seen among nonconsanguineous granitoids. Variations in mineral δ18O values and large differences in δ18O between rocks with nonconsanguineous protoliths but similar bulk composition demonstrate that these rocks were not infiltrated by, or isotopically equilibrated through, a pervasive metamorphic fluid. Values of δ18O for mineral separates preserve generally high temperature fractionations indicative of dominantly closed-system retrograde exchange. Values of δ18Owr in Adirondack orthogneisses were not significantly shifted during granulite facies metamorphism and were dominantly controlled by processes active during premetamorphic magmatism. Values of δ18Owr may thus serve as a petrogenetic indicator, allow discrimination of rock units, and serve as a source constraint for meta-igneous rocks. Fayalite meta-granites with low δ18Owr values can be discriminated from surrounding granitoids having high δ18Owr values. A record of assimilation in the evolution of differentiated granitic units is preserved. The preservation of primary igneous δ18Owr values in granulite facies orthogneiss imposes constraints on the synmetamorphic and postmetamorphic fluid history of the Adirondack Highlands. Oxygen isotopic compositions at the hand-sample scale have been preserved through granulite-facies metamorphism. Fluid absence or low fluid/rock ratios on a regional scale are indicated.

  3. 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.

  4. Carbon and Oxygen Isotopic Ratios for Nearby Miras

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  5. 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.

  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. 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

  8. 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

  9. 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.

  10. Coupled Oxygen and Hydrogen Isotope Analysis of Water Along the Soil-Plant- Atmosphere Continuum

    NASA Astrophysics Data System (ADS)

    Huang, Z.; Webb, E. A.; Longstaffe, F. J.

    2008-12-01

    The oxygen and hydrogen isotope compositions of water within a plant vary with transpiration rates and the isotopic composition of soil water. Both of these parameters are affected by temperature and relative humidity. A controlled-temperature, growth-chamber experiment was conducted to determine the relationships among temperature, relative humidity, soil water evaporation and plant-water isotope composition in cattails and horsetails. Typha, a cattail species that grows in wetland conditions, and Equisetum, a horsetail species that prefers dry soils, were each grown in four chambers at 15, 20, 25 and 30 degrees Celsius. The oxygen and hydrogen isotope compositions of watering water, soil water, vapour in the growth chambers and plant water from the leaves and stems were analyzed throughout the eight-month long artificial growing season. Although the oxygen isotope composition of the watering water remained constant, the soil water, atmospheric vapour and plant water were progressively enriched in oxygen-18 and deuterium in each of the four chambers from low to high temperatures as a result of increasing evaporation. The oxygen isotope composition of plant water along the length of a single stem or leaf was increasingly enriched in the heavier isotopes towards the apex. There was no significant difference in the magnitude of this trend between species. These results indicate that the isotopic composition of plant water is primarily controlled by environmental conditions. The oxygen isotope composition of the water vapour in the growing chamber increased with temperature, consistent with equilibration between the vapour and the oxygen-18 enriched soil and plant water reservoirs. The magnitude and interaction of these variables, as measured for these modern samples of cattails and horsetails, should be useful in calibrating paleoclimate proxies based on fossilized plant materials (e.g., cellulose, phytoliths).

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

    PubMed

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

    2009-06-01

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

  12. 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. PMID:22902370

  13. Stable Carbon Isotope Record in a Palau Sclerosponge

    NASA Astrophysics Data System (ADS)

    Grottoli, A. G.

    2002-12-01

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

  14. 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.

  15. 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.

  16. 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. PMID:22243529

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

    PubMed

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

    2012-10-16

    We present a unique proxy for the reconstruction of variation in precipitation over the Amazon: oxygen isotope ratios in annual rings in tropical cedar (Cedrela odorata). A century-long record from northern Bolivia shows that tree rings preserve the signal of oxygen isotopes in precipitation during the wet season, with weaker influences of temperature and vapor pressure. Tree ring δ(18)O correlates strongly with δ(18)O in precipitation from distant stations in the center and west of the basin, and with Andean ice core δ(18)O showing that the signal is coherent over large areas. The signal correlates most strongly with basin-wide precipitation and Amazon river discharge. We attribute the strength of this (negative) correlation mainly to the cumulative rainout processes of oxygen isotopes (Rayleigh distillation) in air parcels during westward transport across the basin. We further find a clear signature of the El Niño-Southern Oscillation (ENSO) in the record, with strong ENSO influences over recent decades, but weaker influence from 1925 to 1975 indicating decadal scale variation in the controls on the hydrological cycle. The record exhibits a significant increase in δ(18)O over the 20th century consistent with increases in Andean δ(18)O ice core and lake records, which we tentatively attribute to increased water vapor transport into the basin. Taking these data together, our record reveals a fresh path to diagnose and improve our understanding of variation and trends of the hydrological cycle of the world's largest river catchment. PMID:23027960

  18. 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

  19. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  1. 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.

  2. 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...

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

    NASA Technical Reports Server (NTRS)

    Schmidt, Gavin A.

    1999-01-01

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

  4. Oxygen isotopes in tree rings show good coherence between species and sites in Bolivia

    NASA Astrophysics Data System (ADS)

    Baker, Jessica C. A.; Hunt, Sarah F. P.; Clerici, Santiago J.; Newton, Robert J.; Bottrell, Simon H.; Leng, Melanie J.; Heaton, Timothy H. E.; Helle, Gerhard; Argollo, Jaime; Gloor, Manuel; Brienen, Roel J. W.

    2015-10-01

    A tree ring oxygen isotope (δ18OTR) chronology developed from one species (Cedrela odorata) growing in a single site has been shown to be a sensitive proxy for rainfall over the Amazon Basin, thus allowing reconstructions of precipitation in a region where meteorological records are short and scarce. Although these results suggest that there should be large-scale (> 100 km) spatial coherence of δ18OTR records in the Amazon, this has not been tested. Furthermore, it is of interest to investigate whether other, possibly longer-lived, species similarly record interannual variation of Amazon precipitation, and can be used to develop climate sensitive isotope chronologies. In this study, we measured δ18O in tree rings from seven lowland and one highland tree species from Bolivia. We found that cross-dating with δ18OTR gave more accurate tree ring dates than using ring width. Our "isotope cross-dating approach" is confirmed with radiocarbon "bomb-peak" dates, and has the potential to greatly facilitate development of δ18OTR records in the tropics, identify dating errors, and check annual ring formation in tropical trees. Six of the seven lowland species correlated significantly with C. odorata, showing that variation in δ18OTR has a coherent imprint across very different species, most likely arising from a dominant influence of source water δ18O on δ18OTR. In addition we show that δ18OTR series cohere over large distances, within and between species. Comparison of two C. odorata δ18OTR chronologies from sites several hundreds of kilometres apart showed a very strong correlation (r = 0.80, p < 0.001, 1901-2001), and a significant (but weaker) relationship was found between lowland C. odorata trees and a Polylepis tarapacana tree growing in the distant Altiplano (r = 0.39, p < 0.01, 1931-2001). This large-scale coherence of δ18OTR records is probably triggered by a strong spatial coherence in precipitation δ18O due to large-scale controls. These results

  5. 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

  6. The mechanism of oxygen isotope fractionation during N2O production by denitrification

    NASA Astrophysics Data System (ADS)

    Lewicka-Szczebak, D.; Dyckmans, J.; Kaiser, J.; Marca, A.; Augustin, J.; Well, R.

    2015-10-01

    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 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. We performed several soil incubation experiments. For the first time, Δ17O isotope tracing was applied to simultaneously determine the extent of oxygen isotope exchange and any associated oxygen isotope effect. We found bacterial denitrification to be typically associated with almost complete oxygen isotope exchange and a stable difference in δ18O between soil water and the produced N2O of δ18O(N2O / H2O) = (17.5 ± 1.2) ‰. However, some experimental setups yielded oxygen isotope exchange as low as 56 % and a higher δ18O(N2O / H2O) of up to 37 ‰. The extent of isotope exchange and δ18O(N2O / H2O) showed a very significant correlation (R2 = 0.70, p < 0.00001). We hypothesise 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 different magnitudes of

  7. Understanding Intrabasinal Organic Carbon Records: A New Carbon Isotope Record for the Early Cretaceous Abu Dhabi, UAE

    NASA Astrophysics Data System (ADS)

    Al-Suwaidi, A. H.

    2014-12-01

    The Aptian-Albian (~125-100 Ma, Early Cretaceous) is considered to be an interval of elevated greenhouse gases, intensified hydrologic cycle, limited polar ice, and elevated high latitude temperatures, with evidence for Oceanic Anoxic Events (OAE) as recorded by organic matter and carbonate δ13C perturbations in both the marine and continental realm (Jenkyns et al., 2004; Poulsen, 2004; Robinson & Hesselbo, 2004 and Ufnar et al., 2004). In this study four cores from Aptian­-Albian marine sediments from a single offshore basin in Abu Dhabi, UAE were examined petrographically and samples were collected to generate a high resolution organic carbon δ13C chemostratigraphic profile. The cores represent sediments from the Early Cretaceous upper most Thamama and lowermost Wasia Group and represent interbedded shale and limestone units from the Arabian Shelf. Three of the cores, cores A­-C, show a 3‰ negative excursion in δ13Corg with values of -28‰ occurring with a concurrent increase in organic carbon, likely indicative of Aptian OAE 1a. These cores also show a transition from more oxic to euxinic waters as recorded in the pyrite framboid mean diameter. The remaining core, D, shows relatively isotopically light average δ13Corg values of -26‰, with an intervening positive isotope excursion and values of -23‰, and may represent a different event either earlier or later in the sequence, but due to limited biostratigraphic data could not easily be correlated using C-Isotopes alone with the other three cores. The four cores come from different localities within a single basin and highlight issues pertaining to correlating cores across a single basin for the same time interval, as well as variability in organic matter burial and oxygenation within a single basin, and may provide a useful case study specifically related to separating regional signals from global carbon isotope signals for the Aptian-Albian, and understanding how ancient Mesozoic basins are affected

  8. Can stable isotopes ride out the storms? The role of convection for water isotopes in models, records, and paleoaltimetry studies in the central Andes

    NASA Astrophysics Data System (ADS)

    Rohrmann, Alexander; Strecker, Manfred R.; Bookhagen, Bodo; Mulch, Andreas; Sachse, Dirk; Pingel, Heiko; Alonso, Ricardo N.; Schilgen, Taylor F.; Montero, Carolina

    2015-04-01

    Globally, changes in stable isotope ratios of oxygen and hydrogen (δ18O and δD) in the meteoric water cycle result from distillation and evaporation processes. Isotope fractionation occurs when air masses rise in elevation, cool, and reduce their water-vapor holding capacity with decreasing temperature. As such, d18O and dD values from a variety of sedimentary archives are often used to reconstruct changes in continental paleohydrology as well as paleoaltimetry of mountain ranges. Based on 234 stream-water samples, we demonstrate that areas experiencing deep convective storms in the eastern south-central Andes (22 - 28° S) do not show the commonly observed relationship between δ18O and δD with elevation. These convective storms arise from intermontane basins, where diurnal heating forces warm air masses upward, resulting in cloudbursts and raindrop evaporation. Especially at the boundary between the tropical and extra-tropical atmospheric circulation regimes where deep-convective storms are very common (~ 26° to 32° N and S), the impact of such storms may yield non-systematic stable isotope-elevation relationships as convection dominates over adiabatic lifting of air masses. Because convective storms can reduce or mask the depletion of heavy isotopes in precipitation as a function of elevation, linking modern or past topography to patterns of stable isotope proxy records can be compromised in mountainous regions, and atmospheric circulation models attempting to predict stable isotope patterns must have sufficiently high spatial resolution to capture the fractionation dynamics of convective cells. Rohrmann, A. et al. Can stable isotopes ride out the storms? The role of convection for water isotopes in models, records, and paleoaltimetry studies in the central Andes. Earth Planet. Sci. Lett. 407, 187-195 (2014).

  9. 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.

  10. Oxygen Fugacity Recorded by Xenoliths from Pacific Oceanic Islands

    NASA Astrophysics Data System (ADS)

    Wall, K.; Davis, F. A.; Cottrell, E.

    2014-12-01

    Oxygen fugacity (fO2) plays a vital role in determining mineral stability and depth of melting in the mantle. Several studies have used the spinel peridotite oxybarometer to estimate fO2; yet few data exist from ocean islands, despite the importance of fO2 to understanding ocean island basalt petrogenesis (Herzberg and Asimow, 2008). We report fO2 recorded by peridotite xenoliths from three ocean islands: Savai'i (average fO2 = QFM -1.4 to +0.9), Tahiti (QFM +0.6 to +0.7) and Tubuai (QFM -1.1 to +0.2). We calculate fO2 using methods and standards from Wood and Virgo (1989) and Wood (RiMG, 1990). Oxygen fugacities span a similar range to those reported for El Hierro, Oahu, and Tahiti by Ballhaus (1993): more reduced than arc peridotites, but more oxidized than abyssal peridotites. Spinels in several of the xenoliths are heterogeneous and record a range of apparent fO2 at the mm scale. We propose two distinct mechanisms for introducing fO2 heterogeneity: melt refertilization (Tubuai) and diffusive reequilibration (Savai'i and Tubuai). Spinels in one Tubuai sample record increasing fO2 from QFM-0.6 in the xenolith interior to +1.1 at the basalt interface. Apparent fO2 recorded by these spinels correlate with TiO2, an indicator of melt refertilization (Pearce et al., 2000). We suggest that spinels from the xenolith interior record the relatively low fO2 conditions of the lithospheric mantle, while host basalt has oxidized near-interface spinels. Uniformly high TiO2, fO2, and low olivine Mg# in Tahitian xenoliths from this study may indicate that refertilization has reset the fO2 recorded by these rocks. Closed-system diffusive reequilibration, caused by changes in temperature, can also change the fO2 recorded by a peridotite. In samples from Savai'i and Tubuai with multiple spinel habits, fine intergrowth spinels and the rims of large, equant spinels record higher apparent fO2 and lower Al2O3 than cores of large grains. Canil and O'Neill (1996) suggest that the MgAl2O4

  11. A High-Resolution Stalagmite Record of East-Central North America Hydroclimates during Marine Isotope Stages 3-5

    NASA Astrophysics Data System (ADS)

    Springer, G. S.; Rowe, H. D.; Hardt, B. F.; Cheng, H.; Edwards, R. L.

    2014-12-01

    Long-term, high-resolution stalagmite carbon and oxygen isotope records from eastern North America (ENA) provides a mid-latitude history of relative changes in moisture availability and climate states during the last interglacial and glacial inception (127.7 to 41.6 ka before present). The West Virginia carbon record (δ13C) shows low-amplitude variability at orbital time scales, superimposed on a long-term asymmetric pattern similar to global sea level changes. Relative moisture availability peaked at ~114ka and following a brief dry interval at ~96ka, moisture availability gradually decreased. The gradual changes in moisture availability over ENA may reflect similarly gradual changes in mid-latitude zonal circulation as the polar cell and Laurentide Ice Sheet expanded or decreased. However, high frequency isotopic fluctuations are present and correlative with climatic phenomena recorded in Greenland. In contrast to the gradual changes in carbon isotopes, our oxygen record (δ18O) is precession-modulated and in phase with spring insolation, perhaps due to changes in precipitation seasonality. Altered precipitation seasonality or seasonal moisture availabilities would, as a result of annual variability in meteoric δ18O, have caused a weighting effect in stalagmitic calcite precipitation. However, this explanation for changes in δ18O does not explain why the two isotopic records of eccentricity (carbon) and precession (oxygen) are paced differently because moisture availability might resonably be expected to covary with precipitation seasonality. The same pattern is observed in a stalagmite from the previous interglacial-glacial cycle, so it is a persistent feature in our study area. We will present possible explanations.

  12. 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

  13. Rare sulfur and triple oxygen isotope geochemistry of volcanogenic sulfate aerosols

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

    We present analyses of stable isotopic ratios 17O/ 16O, 18O/ 16O, 34S/ 32S, and 33S/ 32S, 36S/ 32S in sulfate leached from volcanic ash of a series of well known, large and small volcanic eruptions. We consider eruptions of Mt. St. Helens (Washington, 1980, ˜1 km 3), Mt. Spurr (Alaska, 1953, <1 km 3), Gjalp (Iceland, 1996, 1998, <1 km 3), Pinatubo (Phillipines, 1991, 10 km 3), Bishop tuff (Long Valley, California, 0.76 Ma, 750 km 3), Lower Bandelier tuff (Toledo Caldera, New Mexico, 1.61 Ma, 600 km 3), and Lava Creek and Huckleberry Ridge tuffs (Yellowstone, Wyoming, 0.64 Ma, 1000 km 3 and 2.04 Ma 2500 km 3, respectively). This list covers much of the diversity of sizes and the character of silicic volcanic eruptions. Particular emphasis is paid to the Lava Creek tuff for which we present wide geographic sample coverage. This global dataset spans a significant range in δ34S, δ18O, and Δ17O of sulfate (29‰, 30‰, and 3.3‰, respectively) with oxygen isotopes recording mass-independent ( Δ17O > 0.2‰) and sulfur isotopes exhibiting mass-dependent behavior. Products of large eruptions account for most of' these isotopic ranges. Sulfate with Δ17O > 0.2‰ is present as 1-10 μm gypsum crystals on distal ash particles and records the isotopic signature of stratospheric photochemical reactions. Sediments that embed ash layers do not contain sulfate or contain little sulfate with Δ17O near 0‰, suggesting that the observed sulfate in ash is of volcanic origin. Mass-dependent fractionation of sulfur isotopic ratios suggests that sulfate-forming reactions did not involve photolysis of SO 2, like that inferred for pre-2.3 Ga sulfates from Archean sediments or Antarctic ice-core sulfate associated with few dated eruptions. Even though the sulfate sulfur isotopic compositions reflect mass-dependent processes, the products of caldera-forming eruptions display a large δ34S range and exhibit fractionation relationships that do not follow the expected equilibrium

  14. Isotopic effect at oxygen diffusion in imperfect crystals of cerium oxide

    NASA Astrophysics Data System (ADS)

    Kovalenko, M. A.; Kupryazhkin, A. Ya.

    2015-02-01

    The surface and volume diffusion of oxygen isotopes in different phase states of Ce1 - x Gd x O2 - x/2 crystals are studied with the high-speed molecular dynamics method (using graphics processors). It is shown that the ratio between the oxygen isotope diffusion coefficients (the so-called isotopic effect) in the volume of simulated crystals, D(O16)/ D(O18) ≈ 1.05, agrees well with the well-known ratio and does not depend on the temperature, phase state, and particle-particle interaction potential. On the surface of nanocrystals, the isotopic effect is a linear function of temperature. The ratio between diffusion coefficients of light and heavy isotopes grows with decreasing temperature and equals D(O16)/ D(O18) ≈ 1.12 at T = 1000 K.

  15. Making an honest measurement scale out of the oxygen isotope delta-values.

    PubMed

    Gat, Joel R; DeBievre, Paul

    2002-01-01

    The differential measurement of the abundance of oxygen isotopes based on reference materials, such as VSMOW for the case of water, was used because the precision of the absolute mass-spectrometric determination of the abundance fell short of the differences to be measured. Since then these measurements have been much improved, so that a calibration scheme of the oxygen isotope abundance in water, carbonates, silica, phosphates, sulfates, nitrates and organic materials is suggested, based on an accredited primary standard of oxygen in air and using standard fluorination and O(2) to CO(2) conversion techniques. PMID:12442297

  16. Climate of Late Glacial and Early Holocene in Southern Slovakia reconstructed on the basis of high resolution stable isotope record from cave speleothem

    NASA Astrophysics Data System (ADS)

    Gąsiorowski, Michał; Hercman, Helena; Pawlak, Jacek; Gradziński, Michał; Bella, Pavel

    2015-04-01

    The Central Europe is a key region to understand climate variability (temperature, precipitation, air circulation, NAO index etc.) in Europe during post-LGM period. We studied stable isotopic record from 826 mm long stalagmite collected in the Jaskyňa na Kečovských Lúkach cave located in the Slovakian Karst. The record was precisely dated with 230Th/U dating method using mass spectrometry. Age-depth model was calculated using MOD-AGE software. Stable isotope record cover time from the termination of LGM (~21 kry) until the Holocene climate optimum (~7 kyr). Changes of 18O concentration indicated rapid warming around 20.5 kyr. After that, oxygen isotopes oscillated with millennial mode similar to Bond events. The specific peak of lighter and heavier oxygen isotope composition correlated with cold and warm period of the Late Glacial, i.e. the Older and the Younger Dryas, the Bølling and the Allerød oscillations, respectively. Much stronger excursion to the heavier values of delta 18O indicates beginning of the Holocene. The Bond events can be also identified during the Holocene and next rapid change to the lighter oxygen isotopic composition point to the 8.2 kyr cold event. The carbon isotope composition correlates negatively with oxygen isotope record, with much heavier carbon during LGM and lighter carbon signal ~17 kyr and on the beginning of the Holocene. The correlation between speleothem record and Greenland ice core records suggests that climate of Southern Sloviaka after the LGM was formed mainly by Atlantic air circulation with significant Mediterranean influences during Late Glacial.

  17. 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

  18. 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

  19. Oxygen isotope studies of ivory coast tektites and impactite glass from the bosumtwi crater, ghana.

    PubMed

    Taylor, H P; Epstein, S

    1966-07-01

    Oxygen isotope analyses were obtained for six Ivory Coast tektites, two samples of Bosumtwi Crater glass, and two new moldavites. The Ivory Coast tektites are 2 to 5 per mil richer in oxygen-18 than other known tektites, and they are similar in oxygen-18 content to the impactite glass from the nearby Bosumtwi Crater. These data are compatible with a terrestrial origin for the Ivory Coast tektites. PMID:17831505

  20. Oxygen isotopic transport and exchange during fluid flow: One-dimensional models and applications

    SciTech Connect

    Bowman, J.R. ); Willett, S.D. ); Cook, S.J. Environ Corp., Houston, TX )

    1994-01-01

    In this work the authors investigate the consequences of fluid flow and fluid-rock interaction to the isotopic evolution of fluids and rock with one-dimensional transport models of fluid flow and oxygen isotope exchange. Transport models dealing with stable isotopes are well established in recent geochemical literature. The authors extend previous treatments by presenting the derivation of both analytical and numerical solutions to the transport equations incorporating simultaneously advection, diffusion and hydrodynamic dispersion, and kinetics of isotopic exchange. The increased generality of numerical solutions allows the incorporation of other effects which control the spatial patterns of [delta][sup 18]O values developed in rocks and fluids including multiple reactive species and temperature gradients. The authors discuss the effects of flow parameters, conditions of isotopic exchange, and temperature gradients on the spatial patterns of isotopic shifts produced in rock sequences subjected to fluid flow, and on conventionally calculated W/R ratios for these rock sequences. Finally, the authors examine the implications of oxygen isotope transport for two natural systems where isotopic shifts or gradients could be interpreted in terms of unidirectional fluid infiltration. Solutions of one-dimensional transport equations including the mechanisms of advection, diffusion, hydrodynamic dispersion, and non-equilibrium exchange between water and rock indicate that the time-space evolution of oxygen isotopic compositions of rock and infiltrating fluid is dependent on (1) the rate of fluid infiltration, (2) the diffusive and dispersive properties of the rock matrix, (3) the rate of isotopic exchange, and (4) the rock-water mass oxygen ratio in a unit volume of water-saturated, porous rock. 56 refs., 18 figs., 2 tabs.

  1. Micron Scale Oxygen Isotope Heterogeneity in Anorthite of A Forsterite-bearing Type B CAI E60 from Efremovka

    NASA Astrophysics Data System (ADS)

    Nagashima, K.; Krot, A. N.; Huss, G. R.; Yurimoto, H.

    2010-03-01

    Oxygen isotope imaging with UH Cameca ims 1280+SCAPS isotope microscope of a Fo-B CAI E60 from Efremovka revealed complex distributions of O-isotopes in anorthite supporting isotopic exchange with 16O-poor gas during remelting and recrystallization.

  2. 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).

  3. Are Colorado Plateau Eclogite Xenoliths Franciscan?: Oxygen Isotope Evidence From Zoned Garnet

    NASA Astrophysics Data System (ADS)

    Hoover, W. F.; Page, F. Z.; Schulze, D. J.; Kitajima, K.; Valley, J. W.

    2014-12-01

    Eclogite xenoliths from the Moses Rock diatreme, UT, USA are of controversial (Proterozoic or Phanerozoic) age. In this study, seven garnets from four Moses Rock eclogite xenoliths were analyzed for δ18O by ion microprobe. Garnet core δ18O values are 7.8-10.3‰ VSMOW. All samples have a sharp change between cores and rim values of 5.8-6.9‰. These garnets have the first reported oxygen isotope zoning from mantle xenoliths. The core values are well outside the range of garnets equilibrated with the mantle, suggesting that they began growth during subduction from an altered oceanic crustal protolith. Most rim values reach the mantle range. This decrease in δ18O from core to rim is consistent with continued subduction of the eclogites into the mantle. The failure of some garnet rims to reach mantle δ18O values may indicate that they did not equilibrate fully with the mantle, or were exposed to a mixed mantle-slab fluid. Zoning in the samples from this study record a stepped shift from an altered upper oceanic crust protolith, to a mantle-influenced environment. The preservation of zoning in some of the samples from this study suggests that these eclogites were protected within the cool subducting slab and experienced a short mantle residence time. The preservation of cation and oxygen isotope zoning is more consistent with an origin during Franciscan subduction than Proterozoic subduction, unless the zoning is a late feature that formed just prior to volcanic emplacement. This is further supported by the similar patterns of increased pyrope content and decreasing δ18O found in some Franciscan eclogite garnets (e.g., Errico et al., 2013, CMP).

  4. Miocene to Pliocene osmium isotopic records of 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; Suzuki, Katsuhiko; Yoshimura, Toshihiro; Sierro, Francisco; Ohkouchi, Naohiko

    2015-04-01

    In the late Miocene the Mediterranean Sea experienced a salinity crisis and thick sequences of evaporites precipitated across the basin. In this study we report Os isotopic records from drilled cores in the Mediterranean; the Balearic Sea, the Tyrrhenian Sea, the Ionian Basin and the Florence Rise. Pliocene 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 late Miocene however, have 187Os/188Os values lower than coeval ocean water values and samples from the eastern Mediterranean and Ionian basins are particularly low. 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 of Mediterranean evaporite 187Os/188Os is attributed to limited exchange with the North Atlantic during the Messinian Salinity Crisis (MSC). The source of unradiogenic Os is likely to be weathering of ultramafic rocks (ophiolites) cropping out in the Mediterranean's drainage basins. The offset in the Os 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 ophiolites around the eastern Mediterranean Sea.

  5. 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.

  6. Oxygen Isotopic Analyses of Water Extracted from the Martian Meteorite NWA 7034

    NASA Astrophysics Data System (ADS)

    Nunn, M.; Agee, C. B.; Thiemens, M. H.

    2012-12-01

    Introduction: The NWA 7034 meteorite has been identified as Martian, but it is distinct from the Shergottite-Nakhlite-Chassignite (SNC) grouping of meteorites in its petrology (it is the only known Martian basaltic breccia) and bulk silicate oxygen isotopic composition (Δ17O = 0.56 ± 0.06 ‰, where Δ17O = δ17O - 0.528 x δ18O, compared to the average SNC Δ17O ≈ 0.3 ‰) [e.g., 1-2]. We report here measurements of the oxygen isotopic composition of water extracted from NWA 7034 by stepwise heating. Methods: A piece (~1.2g) of NWA 7034 was pumped to vacuum until outgassing had stopped before heating to 50, 150, 320, 500, and 1000°C. The sample was maintained at each temperature step for at least one hour while collecting evolved volatiles in a liquid nitrogen cold trap. Water was selectively converted to molecular oxygen, the oxygen isotopic composition of which was then measured on a double collecting isotope ratio mass spectrometer. Results: Our stepwise heating experiments indicate NWA 7034 contains 3330ppm water, and this water has an average oxygen isotopic composition of Δ17O = 0.330 ± 0.011‰. The oxygen isotopic composition of water in NWA 7034 is unlike that of the silicates from which it is extracted (Δ17O = 0.56 ± 0.06 ‰) but is comparable to the average SNC silicate composition (Δ17O ≈ 0.3 ‰). However, there is no consensus on the oxygen isotopic composition of water in SNCs because aliquots of water extracted from different samples (separate pieces of a single meteorite or from different meteorites) have different oxygen isotopic compositions [3]. Furthermore, carbonates and sulfates extracted from SNCs also possess distinct oxygen isotopic compositions [4]. The variation in oxygen isotopic composition among these phases most likely results from the existence of isotopically distinct oxygen reservoirs on Mars that were not equilibrated. On Earth, interaction of ozone (O3) and carbon dioxide (CO2) leads to a mass independent oxygen

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

    PubMed

    Schoell, M; Schouten, S; Damsté, J S; de Leeuw, J W; Summons, R E

    1994-02-25

    The difference in carbon-13 ((13)C) contents of hopane and sterane biomarkers in the Monterey formation (Naples Beach, California) parallels the Miocene inorganic record of the change in (18)O (delta(18)O), reflecting the Miocene evolution from a well-mixed to a highly stratified photic zone (upper 100 meters) in the Pacific. Steranes (delta(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(35) hopanes (likely derived from bacterial plankton living at the base of the photic zone) have systematically decreasing (13)C concentrations in Middle and Late Miocene samples (delta(13)C = -29.5 to -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. PMID:17831625

  8. 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.

  9. The reduction and oxidation of ceria: A natural abundance triple oxygen isotope perspective

    NASA Astrophysics Data System (ADS)

    Hayles, Justin; Bao, Huiming

    2015-06-01

    Ceria (CeO2) is a heavily studied material in catalytic chemistry for use as an oxygen storage medium, oxygen partial pressure regulator, fuel additive, and for the production of syngas, among other applications. Ceria powders are readily reduced and lose structural oxygen when subjected to low pO2 and/or high temperature conditions. Such dis-stoichiometric ceria can then re-oxidize under higher pO2 and/or lower temperature by incorporating new oxygen into the previously formed oxygen site vacancies. Despite extensive studies on ceria, the mechanisms for oxygen adsorption-desorption, dissociation-association, and diffusion of oxygen species on ceria surface and within the crystal structure are not well known. We predict that a large kinetic oxygen isotope effect should accompany the release and incorporation of ceria oxygen. As the first attempt to determine the existence and the degree of the isotope effect, this study focuses on a set of simple room-temperature re-oxidation experiments that are also relevant to a laboratory procedure using ceria to measure the triple oxygen isotope composition of CO2. Triple-oxygen-isotope labeled ceria powders are heated at 700 °C and cooled under vacuum prior to exposure to air. By combining results from independent experimental sets with different initial oxygen isotope labels and using a combined mass-balance and triangulation approach, we have determined the isotope fractionation factors for both high temperature reduction in vacuum (⩽10-4 mbar) and room temperature re-oxidation in air. Results indicate that there is a 1.5‰ ± 0.8‰ increase in the δ18O value of ceria after being heated in vacuum at 700 °C for 1 h. When the vacuum is broken at room temperature, the previously heated ceria incorporates 3-19% of its final structural oxygen from air, with a δ18O value of 2.1-4.1+7.7 ‰ for the incorporated oxygen. The substantial incorporation of oxygen from air supports that oxygen mobility is high in vacancy

  10. Gradients in seasonality and seawater oxygen isotopic composition along the early Permian Gondwanan coast, SE Australia

    NASA Astrophysics Data System (ADS)

    Beard, J. Andrew; Ivany, Linda C.; Runnegar, Bruce

    2015-09-01

    Oxygen isotope compositions of marine carbonates are commonly employed for understanding ancient temperatures, but this approach is complicated in the very distant past due to uncertainties about the effects of diagenesis and the isotopic composition of seawater, both locally and globally. Microsampled accretionary calcite from two species of the fossil bivalve Eurydesma Sowerby and Morris 1845 collected from sediments of Cisuralian age in high latitude marine sediments along the SE coast of Australia records cyclic seasonal fluctuations in shell δ18O values during growth, demonstrating the primary nature of the isotope signal and thus allowing investigation of early Permian seawater isotopic composition and water temperature in the high southern latitudes. The mean and seasonal range of δ18Ocarb decreases poleward across about 10° of paleolatitude (∼67°S-77°S). The presence of co-occurring dropstones and stratigraphically associated glendonites constrains winter temperatures across the region to near-freezing, thus permitting calculation of realistic estimates of water composition and summer temperatures. Summer δ18Ocarb values indicate water temperatures between 5 °C and 12 °C, with warmer values at lower latitudes. The decrease in both mean sea surface temperature and seasonal amplitude with increasing latitude on the Gondwanan coast is much like that observed along high-latitude coastlines today. Calculated δ18Owater decreases toward the pole, likely associated with an increasing contribution of isotopically light fresh water derived from summer snow-melt. The gradient in δ18Owater is similar to that documented over a similar span of latitude on the modern SE Greenland coast. We infer the presence of a north-flowing coastal current of cold, O18-depleted water that entrains progressively greater amounts of more typical seawater as it moves away from the pole. δ18O values in SE Australia, however, are about 3‰ lower than those off Greenland

  11. Distinguishing phosphate from fertilizers and wastewater treatment plant effluents in Western Canada using oxygen isotope measurements

    NASA Astrophysics Data System (ADS)

    Fau, Veronique; Nightingale, Michael; Tamburini, Frederica; Mayer, Bernhard

    2014-05-01

    The successful application of oxygen isotope ratios as a tracer for phosphate in aquatic ecosystems requires that different sources of phosphate are isotopically distinct. The objective of this study was to determine whether the oxygen isotope ratios of phosphate from fertilizers and effluents from wastewater treatment plants in Western Canada are isotopically distinct. Therefore, we carried out oxygen isotope analyses on phosphate in effluent from five different wastewater treatment plants (WWTP) in the Bow River watershed of Alberta, Canada. Samples were collected directly from the final effluent (post-UV) in Banff and Canmore upstream of Calgary, and from effluents of Calgary's WWTPs at Bonnybrook, Fish Creek and Pine Creek. We also carried out oxygen isotope analyses on a variety of phosphate-containing fertilizers that are widely used in Western Canada. Historically, most of the phosphate contained in manufactured fertilizers sold in Alberta came from two distinct deposits: 1) a weathered Pliocene igneous carbonatite located in eastern Canada, and 2) the Permian Phosphoria Formation in the western USA. Phosphate (PO43-) contained in the water or the fertilizer was concentrated and quantitatively converted to pure silver phosphate (Ag3PO4). The silver phosphate was then reduced with carbon in an oxygen free environment using a TC/EA pyrolysis reactor linked to a mass spectrometer where 18O/16O ratios of CO were measured in continuous flow mode. Preparation of samples for δ18OPO4 analyses was conducted using the Magnesium Induced Coprecipitation (MAGIC) method. Expected oxygen isotope ratios for phosphate in equilibrium with water (δ18Oeq) were calculated using the Longinelli and Nuti equation: T (° C) = 111.4 - 4.3 (δ18Oeq - δ18Owater). Measured δ18O values of phosphate for fertilizer samples varied from 8 to 25 oÈ®n average, fertilizer samples of sedimentary origin had higher δ18O values (15.8) than those of igneous origin (11.5). Phosphate isotopic

  12. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  14. 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.

  15. 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

  16. Isotope dilution study of exchangeable oxygen in premium coal samples

    SciTech Connect

    Finseth, D.

    1987-01-01

    A difficulty with improving the ability to quantitate water in coal is that truly independent methods do not always exist. The true value of any analytical parameter is always easier to determine if totally independent methods exist to determine that parameter. This paper describes the possibility of using a simple isotope dilution technique to determine the water content of coal and presents a comparison of these isotope dilution measurements with classical results for the set of Argonne coals from the premium coal sample program. Isotope dilution is a widely used analytical method and has been applied to the analysis of water in matrices as diverse as chicken fat, living humans, and coal. Virtually all of these applications involved the use of deuterium as the diluted isotope. This poses some problems if the sample contains a significant amount of exchangeable organic hydrogen and one is interested in discriminating exchangeable organic hydrogen from water. This is a potential problem in the coal system. To avoid this potential problem /sup 18/O was used as the diluted isotope in this work.

  17. Timing and extent of early marine oxygen isotope stage 2 alpine glaciation in Skagit Valley, Washington

    NASA Astrophysics Data System (ADS)

    Riedel, Jon L.; Clague, John J.; Ward, Brent C.

    2010-03-01

    Twenty-two new radiocarbon ages from Skagit valley provide a detailed chronology of alpine glaciation during the Evans Creek stade of the Fraser Glaciation (early marine oxygen isotope stage (MIS) 2) in the Cascade Range, Washington State. Sediments at sites near Concrete, Washington, record two advances of the Baker valley glacier between ca. 30.3 and 19.5 cal ka BP, with an intervening period of glacier recession about 24.9 cal ka BP. The Baker valley glacier dammed lower Skagit valley, creating glacial Lake Concrete, which discharged around the ice dam along Finney Creek, or south into the Sauk valley. Sediments along the shores of Ross Lake in upper Skagit valley accumulated in glacial Lake Skymo after ca. 28.7 cal ka BP behind a glacier flowing out of Big Beaver valley. Horizontally laminated silt and bedded sand and gravel up to 20 m thick record as much as 8000 yr of deposition in these glacially dammed lakes. The data indicate that alpine glaciers in Skagit valley were far less extensive than previously thought. Alpine glaciers remained in advanced positions for much of the Evans Creek stade, which may have ended as early as 20.8 cal ka BP.

  18. 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

  19. Culture Studies of Nitrogen and Oxygen Isotope Effects Associated with Nitrate Assimilation and Denitrification

    NASA Astrophysics Data System (ADS)

    Sigman, D. M.; Granger, J.; Lehmann, M. F.; Difiore, P. J.; Tortell, P. D.

    2007-12-01

    The isotope effects of nitrate-consuming reactions such as nitrate assimilation and denitrification are potential indicators of the physiological state of the organisms carrying out these reactions. Moreover, an understanding of these isotope effects is needed to use the stable isotopes to investigate the fluxes associated with these reactions in modern and ancient environments. We have used batch cultures to investigate the nitrogen (N) and oxygen (O) isotope effects of (1) nitrate assimilation by eukaryotic and prokaryotic algae and by heterotrophic bacteria, and (2) nitrate reduction by denitrifying bacteria. We observe intra- and inter-specific variation in isotope effect amplitudes and, in the case of denitrifiers, indications of isotope effect decreases during individual nitrate drawdown experiments. However, the measured N and O isotope effect ratio is close to 1 for all studied organisms, with the exception of an unusual denitrifier (Rhodobacter sphaeroides) that possesses only periplasmic (non-respiratory) nitrate reductase. This observation and other findings are consistent with nitrate reductase being the predominant source of isotope fractionation and with most isotope effect amplitude variability arising from variable degrees to which nitrate imported into the cell is reduced versus effluxed back into the environment; the more efflux, the more complete the expression of the fractionation imparted by nitrate reduction. If this is the case, then isotope effect amplitudes in the field should be related to physiological conditions in the environment, a prediction that, we argue, is supported by recent studies of (1) nitrate assimilation in the polar ocean and (2) denitrification in sediment porewaters.

  20. 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.

  1. 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

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

    SciTech Connect

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

    1998-07-01

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

  3. Oxygen and Sulfur Isotope Composition of Dissolved Sulfate in Interstitial Waters of the Great Australian Bight, ODP Leg 182.

    NASA Astrophysics Data System (ADS)

    Bernasconi, S. M.; Böttcher, M. E.; Wormann, U. G.

    2005-12-01

    We measured the sulfur and oxygen isotope composition of dissolved sulfides and sulfate at ODP Sites 1129, 1130, 1131 and 1132 in the Great Australian Bight (GAB). At all Sites, a saline brine is present in the subsurface as indicated by increasing chloride concentrations with depth to reach contents up to 3 times seawater. Sulfate also increases with depth but the concentrations are reduced by intense microbial sulfate reduction. The sulfur isotope fractionation between coexisting dissolved sulfate and sulfide is very large and reaches up to 70 ‰ at all studied Sites. Due to the high sulfide concentrations and the lack of a significant source of oxidants we consider that the large sulfur isotope fractionations are induced by sulfate reducing bacteria alone without a significant contribution of elemental sulfur disproportionation and sulfide oxidation processes. The oxygen isotope composition of dissolved sulfate reaches maximum values of approximately +27 ‰ vs. VSMOW at all sites, close to the equilibrium isotope fractionation between sulfate and water. The oxygen isotope composition of dissolved sulfate positively correlates with the sulfur isotope fractionation between sulfate and sulfide. These oxygen isotope data thus support the hypothesis that that the high sulfur isotope fractionation are related to a single step fractionation by sulfate reducing bacteria and do not involve significant sulfide oxidation reactions and/or elemental sulfur disproportionation. Sulfide oxidation processes would lead to a lowering of the oxygen isotope composition of residual sulfate. Elemental sulfur disproportionation has been shown to increase the oxygen isotope composition of sulfate but to a smaller extent than that that observed in the GAB. The patterns of the oxygen isotope increase with progressive sulfate reduction indicate a predominant influence of isotope exchange rather than a kinetic isotope fractionation controlling the oxygen isotope composition of sulfate

  4. Oxygen Isotope Composition of Evapotranspiration and its Relation to C4 Photosynthetic Discrimination

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

    The oxygen isotope composition (δ18O) of atmospheric water vapor (H2O) and carbon dioxide (CO2) is an important signal of global change and has been used to diagnose the palaeoclimate record, elucidate plant-water relations, and constrain regional carbon sinks/sources. At the present time there is very limited capacity to quantify the δ18O of H2O and CO2 exchange between the land and atmosphere. Of particular interest to carbon cycle studies that use δ18O as a tracer is the need to determine the isotope composition of leaf water at the sites of evaporation (δL,e). δL,e can not be measured directly, but represents a critical boundary condition for determining C18O16O discrimination. Here we use simultaneous observations of the δ18O composition of water vapor and carbon dioxide exchange using a combination of eddy covariance (EC), automated chambers, and tunable diode laser spectroscopy to investigate the relation between canopy leaf water enrichment and photosynthetic discrimination in a C4 (Zea mays L.) ecosystem. The objectives of the study were to: 1) present new results of isotopic water vapor flux measurements based on the EC methodology; 2) examine the influence of evapotranspiration on the isotopic composition of the atmosphere (isoforcing); 3) evaluate the extent of H218O-C18O16O equilibration at the canopy scale; and 4) refine our understanding regarding the role of C4 ecosystems in the budgets of C18O16O and H218O. Data and analyses are presented from experiments that were conducted in the laboratory and in the field at the University of Minnesota over the period August 8, 2008 to August 31, 2009. Our preliminary results indicate that the oxygen isotope composition of evapotranspiration (δET) ranged from about -20‰ (VSMOW scale) in the early morning to -5‰ after midday. These values were used to estimate δL,e and to evaluate the steady state/non-steady behavior of C4 vegetation. δL,e showed a strong diurnal pattern with typical values ranging

  5. 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

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1985-12-01

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

  8. 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.

  9. 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

  10. Oxygen Isotopic and Petrological Constraints on the Origin and Relationship of IIE Iron Meteorites and H Chondrites

    NASA Astrophysics Data System (ADS)

    McDermott, K. H.; Greenwood, R. C.; Franchi, I. A.; Anand, M.; Scott, E. R. D.

    2011-03-01

    New oxygen isotopic measurements of IIEs and H chondrites are indistinguishable — strengthening a possible common origin for these groups. Combining oxygen results with mineralogy, the nature of their parent body or bodies can be explored.

  11. 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

  12. Uranium and molybdenum isotope evidence for an episode of widespread ocean oxygenation during the late Ediacaran Period

    NASA Astrophysics Data System (ADS)

    Kendall, Brian; Komiya, Tsuyoshi; Lyons, Timothy W.; Bates, Steve M.; Gordon, Gwyneth W.; Romaniello, Stephen J.; Jiang, Ganqing; Creaser, Robert A.; Xiao, Shuhai; McFadden, Kathleen; Sawaki, Yusuke; Tahata, Miyuki; Shu, Degan; Han, Jian; Li, Yong; Chu, Xuelei; Anbar, Ariel D.

    2015-05-01

    To improve estimates of the extent of ocean oxygenation during the late Ediacaran Period, we measured the U and Mo isotope compositions of euxinic (anoxic and sulfidic) organic-rich mudrocks (ORM) of Member IV, upper Doushantuo Formation, South China. The average δ238U of most samples is 0.24 ± 0.16‰ (2SD; relative to standard CRM145), which is slightly higher than the average δ238U of 0.02 ± 0.12‰ for restricted Black Sea (deep-water Unit I) euxinic sediments and is similar to a modeled δ238U value of 0.2‰ for open ocean euxinic sediments in the modern well-oxygenated oceans. Because 238U is preferentially removed to euxinic sediments compared to 235U, expanded ocean anoxia will deplete seawater of 238U relative to 235U, ultimately leading to deposition of ORM with low δ238U. Hence, the high δ238U of Member IV ORM points to a common occurrence of extensive ocean oxygenation ca. 560 to 551 Myr ago. The Mo isotope composition of sediments deposited from strongly euxinic bottom waters ([H2S]aq >11 μM) either directly records the global seawater Mo isotope composition (if Mo removal from deep waters is quantitative) or represents a minimum value for seawater (if Mo removal is not quantitative). Near the top of Member IV, δ98Mo approaches the modern seawater value of 2.34 ± 0.10‰. High δ98Mo points to widespread ocean oxygenation because the preferential removal of isotopically light Mo to sediments occurs to a greater extent in O2-rich compared to O2-deficient marine environments. However, the δ98Mo value for most Member IV ORM is near 0‰ (relative to standard NIST SRM 3134 = 0.25‰), suggesting extensive anoxia. The low δ98Mo is at odds with the high Mo concentrations of Member IV ORM, which suggest a large seawater Mo inventory in well-oxygenated oceans, and the high δ238U. Hence, we propose that the low δ98Mo of most Member IV ORM was fractionated from contemporaneous seawater. Possible mechanisms driving this isotope fractionation include

  13. Late Eocene Antarctic glacial events revealed by radiogenic isotope records from the Kerguelen Plateau

    NASA Astrophysics Data System (ADS)

    Smith, B. W.; Munn, G. H.; Bohaty, S. M.; Scher, H. D.

    2011-12-01

    Oxygen isotope measurements of benthic foraminifera in ODP Hole 738B (Kerguelen Plateau, Southern Ocean) show a 0.6% shift toward more positive values at ca. 37.1 Ma, near the middle/late Eocene boundary. The δ18O values during this cool event reach 2.2%, which may reflect a combination of both intermediate deep-water cooling and partial glaciation of East Antarctica. We conducted neodymium (Nd) isotope measurements of the terrigenous detrital fraction (i.e., decarbonated and leached) from the same samples used to construct the stable isotope record. Our results reveal a shift in the Nd isotope composition of fine-grained material deposited on Kerguelen Plateau that coincides with the δ18O excursion. The background ɛNd values (i.e., before and after the δ18O shift) are -12 ɛNd, consistent with regionally sourced sediment from along the East Antarctica margin (e.g., Wilkes Land, Prydz Bay). During the δ18O excursion at 37.1 Ma, there is transient decrease in ɛNd values to -15.5. These results strongly indicate that Kerguelen Plateau received an influx of detrital material from ancient sediment sources (i.e., with low ɛNd values), such as those found in nearby Prydz Bay. Our results support an increase in continental ice volume in East Antarctica during this event, resulting in enhanced rates of mechanical weathering. We have also documented a second cool event ca. 36.7 Ma, approximately 400 kyr after the 37 Ma event. Future efforts will focus on determining the timing of middle-to-late Eocene cooling episoides and further documenting changes in weathering during each of these events.

  14. The oxygen isotope signature of sulfate derived from abiotic sulfite oxidation under different pH conditions

    NASA Astrophysics Data System (ADS)

    Mueller, I.; Brunner, B.; Ferdelman, T. G.

    2011-12-01

    The oxygen isotope composition of sulfate serves as an archive of past oxidative sulfur cycling. It carries information about the oxidants as well as the biochemical pathway involved in the oxidation of reduced sulfur compounds, because oxygen sources can be traced by their distinct oxygen isotope composition. Studies on the aerobic oxidation of pyrite determined varying relative contributions of oxygen from dissolved molecular oxygen (O2) and water (H2O). These discrepancies were assumed to be due to slight differences in the production and consumption of sulfur intermediates which can exchange oxygen isotopes with water. Additionally, changing pH conditions influence the oxidation rate of sulfur intermediates to sulfate as well as the rate of oxygen exchange between sulfur intermediates and water. Consequently, this affects the oxygen isotope signature of produced sulfate. However, very little is known about the oxygen isotope effects during the oxidation of sulfur intermediates. We performed experiments to assess the abiotic oxidation of sulfite to sulfate under different pH conditions, as sulfite is assumed to be an intermediate during the oxidation of reduced sulfur compounds. Dissolved sulfite was oxidized with differently isotopically labeled O2, as well as in differently labeled H2O. The relative contribution of oxygen from O2 and water in produced sulfate was determined, along with the respective oxygen isotope fractionation. Our results provide a more detailed mechanistic understanding of the aerobic oxidation of reduced sulfur species.

  15. 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.

  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

    2013-07-01

    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

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

  20. 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.

  1. 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.

  2. 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.

  3. Climate Change During the Late Glacial and Early Holocene From Lough Monreagh, Western Ireland: Evidence From Carbon and Oxygen Isotope Values of Lacustrine Marl

    NASA Astrophysics Data System (ADS)

    Manchester, C. W.; Patterson, W. P.

    2008-12-01

    Lake sediment is an archive of climate variability reconstructed using proxy data such as stable isotope values and trace element chemistry. These proxy data permit reconstruction of temperature, precipitation, and terrestrial vegetation variability through time. Stable oxygen isotope values conflate temperature and water oxygen isotope variability, while carbon isotope values of marl provide a record of variability in dissolved inorganic carbon (DIC). An 8.67m core, obtained from Lough Monreagh, Western Ireland, contains marl ranging in age from about 17,300-7,894 cal yr B.P. Marl was analyzed at 1mm resolution for stable oxygen and carbon isotope values. Variation in sedimentation rate results in samples that represent up to five years at minimum resolution and as little as four months at highest resolution. Oxygen isotope values decrease at 13,500 yr B.P. from -3.5 to -5 per mil VPDB inferring a decrease in temperature followed by a warming period consistent with previous interpretations of the Older Dryas. Another decrease in oxygen isotope values (-3.9 to -7.0 per mil VPDB) occurs from 12,800-11,500 yr B.P. indicating a significant decrease in temperature consistent with the Younger Dryas. Carbon isotope values increase between 17,200-14,000 yr B.P. from 3.6 to 6.0 per mil VPDB suggesting high productivity is forcing the carbon isotope values of DIC higher than bedrock values, contrary to ostracod population data that suggest low productivity. Carbon isotope values decrease between 12,800-11,500 from 4.0 to 3.0 per mil VPDB coincident with the Younger Dryas clay layer, a time where marl was not produced in the lake. A 6 per mil decrease in carbon isotope values between 11,262-10860 yr B.P. from 4 to -2 per mil VPDB indicates a significant increase in terrestrial vegetation. Sample to sample variability nearing the top of the core is higher due to increased sedimentation rate and concomitantly the sample resolution increases. This study represents the highest

  4. 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.

  5. 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).

  6. Determining terrestrial paleotemperatures using the oxygen isotopic composition of pedogenic carbonate

    NASA Astrophysics Data System (ADS)

    Dworkin, S. I.; Nordt, L.; Atchley, S.

    2005-08-01

    Quantifying terrestrial paleotemperatures has proven to be a challenging endeavor. This paper explores the use of the oxygen isotopic composition of pedogenic calcite for terrestrial paleotemperature reconstructions. We generate three paleotemperature equations, two of them derived by simultaneous solution of equations that describe the fractionation of oxygen isotopes in the exogenic cycle, while the third equation is derived using a linear regression through modern δ18Occ / MAT (oxygen isotopic composition of pedogenic calcite versus mean annual temperature) data. We use the paleotemperature equations to evaluate climate change across the K-T boundary by analyzing the oxygen isotopic composition of pedogenic carbonates from a series of stacked paleosols in west Texas. The fabrics in the calcite nodules were evaluated in order to identify soil carbonate components that have the best chance of containing isotopic information that represents ancient pedogenic conditions. The average temperature for West Texas during the time period studied is 18+ / - 0.5 °C. Two temperature excursions are recognized prior to the K-T boundary in which terrestrial temperatures increase by about 4 °C for relatively short periods of time. These short greenhouse events documented in west Texas correlate with changes in marine temperatures as well as terrestrial temperatures in North Dakota during the same time period. Latitudinal temperature gradients generated using the West Texas and North Dakota data indicate that the spatial simultaneous solution yields the most reliable temperature reconstructions of the three equations considered in this study.

  7. Geologic implications of the oxygen isotope profile of the Toa Baja drill hole, Puerto Rico

    SciTech Connect

    Smith, B.M. )

    1991-03-01

    The whole-rock O-isotopic compositions of volcanic and volcaniclastic samples from the Toa Baja drill hole demonstrate that low-temperature (< 200C) processes have strongly enriched the island arc materials in {sup 18}O. Subsequent to eruption, processes such as subaerial weathering, alteration during transport and deposition in volcaniclastic aprons, submarine weathering, burial diagenesis, and prograde regional metamorphism through the beginning of the prehnite-pumpellyite facies have raised average whole-rock {delta}{sup 18}O values by {approximately}4% for basalt and andesite lava flows, and by {approximately}8% for volcaniclastic sandstones. These O-isotopic disturbances were probably caused by oxygen exchange with regionally circulating seawater under rather high-water/rock conditions. The processes associated with ageing' of volcanic and volcaniclastic materials in the oceanic environment are probably more important to the global budgets of the oxygen isotopes than has been assumed in the past. Integration of these results into global models for the oxygen isotopes awaits analysis of more varied oceanic terranes, to determine the generality of the O-isotopic conclusions proferred here, and to more carefully evaluate the relative sizes of volcanic, volcaniclastic, and oceanic oxygen reservoirs and their variabilities in time.

  8. 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. "

  9. 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. PMID:26823426

  10. 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.

  11. 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.

  12. Intercolony variability of skeletal oxygen and carbon isotope ratios of corals: temperature-controlled tank experiment and field observation

    NASA Astrophysics Data System (ADS)

    Suzuki, A.; Omata, T.; Kawahata, H.

    2005-12-01

    We conducted tank experiments in which we grew Porites spp. colonies in thermostated seawater at five temperature settings under moderate light intensity. A skeletal isotope microprofiling technique applied along the major growth axis of each colony revealed that the oxygen isotope ratios of newly deposited skeleton in most colonies remained almost constant during tank incubation. However, the oxygen isotope ratios displayed a surprisingly large intercolony variability (~1‰ at each temperature setting) although the mean slope obtained for the temperature - skeletal oxygen isotope ratio relationship was close to previous results. The variations in the oxygen isotope ratios were apparently caused by kinetic isotope effects related to variations in the skeletal growth rate rather than by species-specific variability or genetic differences within species. Carbon isotope ratios showed significantly inverse correlation with linear growth rates, suggesting a kinetic isotope control at low growth rates. We also examined oxygen and carbon isotope ratios of Porites corals collected from coral reefs of southern Ryukyu Islands, Japan. In shallow faster-growing corals, oxygen and carbon isotope ratios showed out-of-phase annual fluctuations. In contrast, in deep slower growing corals (mean annual linear extension < 4.8 mm yr1), oxygen and carbon isotope fluctuations were in phase, which has been identified as a pattern influenced by kinetic isotope effects. The slower growing corals were strongly influenced, and the faster growing corals weakly influenced, by kinetic isotope effects over metabolic isotope effects. Growth-rate-related kinetic isotope effects found in both the cultured corals and the deep slower-growing corals may be, at least partly, attributed to low light condition.

  13. 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.

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

    SciTech Connect

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

    1995-11-10

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

  15. Changes in Oxygen Isotopes Composition of Precipitation over Tibetan Plateau during Cenozoic

    NASA Astrophysics Data System (ADS)

    Botsyun, S.; Sepulchre, P.; Donnadieu, Y.; Risi, C. M.; Fluteau, F.

    2014-12-01

    Despite the increasing role of the stable oxygen isotopes measurements for reconstructing mountains belts paleoelevation, some issues remain that lead to a large uncertainty in paleoelevation estimationes. Among them, the use of modern isotopic lapse rate with no account of climate change linked to lower topography can lead to misinterpretation of uplift rates. In this study, we use the atmospheric general circulation model LMDZ-iso to simulate changes in isotopic composition of precipitation due to uplift of the Himalayas and Tibetan plateau. Various scenarios of TP growth have been applied together with Paleocene, Eocene, Oligocene and Miocene boundary conditions. Our simulations allow us to estimate the magnitude of precipitation, temperature and wind field changes related to the spatial and temporal evolution of the Tibetan Plateau and Himalayas. Such changes affected the isotopic composition of precipitation during the Cenozoic.We investigate the impact of these changes on the isotopic lapse rate and the implications for paleoelevation estimates.

  16. Potential use of Oxygen Isotopes From α -Cellulose in Tree Rings to Examine Climate Trends, El Malpais National Monument, New Mexico, USA

    NASA Astrophysics Data System (ADS)

    Kocis, W. N.; Mora, C. I.; Grissino-Mayer, H.; Uhle, M.

    2003-12-01

    The development of high-resolution geological proxies is key to understanding long-term climate variability. Tree-ring studies have shown the potential to provide a uniquely high resolution, precisely dated record of climate change. The oxygen isotope composition of α -cellulose in tree rings may provide a high resolution, dateable proxy for examining precipitation source, variability, and other long-term climate trends and parameters. We are examining the potential of tree ring α -cellulose oxygen isotopes to record changes in precipitation activity in the southwestern United States, at a site within El Malpais National Monument. Here, more than half of the annual precipitation is derived from the North American Monsoon (NAM). It has been previously suggested that the precipitation sources for the NAM may change on long-term scales. Tree rings from El Malpais that have already been subject to a 2129 -year precipitation reconstruction and are absolutely dated in time are the basis of this study. We hypothesize that a change in the precipitation source should be reflected in the oxygen isotope composition of the α -cellulose within the tree rings. Intra-annual latewood and earlywood α -cellulose samples were extracted and analyzed by pyrolysis-IRMS for the period 1992-1964. The oxygen isotope analysis revealed δ 18O values ranging from ˜ 33-37‰ for the earlywood and ˜ 33-38‰ for the latewood. Latewood samples are generally 0.5 to 2‰ heavier than earlywood. Inter-annual trends are also observed, in particular, the average δ 18O values are ˜ 2‰ heavier after the mid-1970's. Numerous other proxies, including tree-ring width analysis, show changes in the mid-1970's that are inferred to be related to a shift in the Pacific Decadal Oscillation. While further work must be done to better understand the factors influencing the tree ring oxygen isotopes, they appear to record a major change coincident with that shift.

  17. Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

    USGS Publications Warehouse

    Thurston, R.S.; Mandernack, K.W.; Shanks, Wayne C., III

    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.

  18. Preliminary results on the oxygen isotopic composition of the lower crust, Kilbourne Hole Maar, New Mexico

    NASA Astrophysics Data System (ADS)

    James, David E.; Padovani, Elaine R.; Hart, Stanley R.

    1980-05-01

    18O/16O ratios measured in deep crustal xenoliths from Kilbourne Hole maar, New Mexico show that the oxygen isotopic composition of the lower crust of that region is grossly heterogeneous. Xenoliths derived from similar crustal depths vary in δ18O by nearly 6‰, although the xenoliths are individually in internal oxygen isotopic equilibrium. Mafic granulites (including charnockite), probably of mantle origin, have δ18O of about 6.2 to 6.3‰ and correspondingly low 87Sr/86Sr ratios (0.703 to 0.707). Garnet granulites, apparently the residue of partial fusion of pelitic sedimentary rock, have δ18O ranging from about 9‰ to 12‰ and correspondingly high 87Sr/86Sr ratios (0.71 to 0.78). No evidence is found for extensive oxygen exchange over large distances in the anhydrous lower crust beneath Kilbourne Hole. Absence of regional isotopic equilibrium indicates that even at melting or near melting temperatures the oxygen isotopic identity of the protolith can be preserved over long periods of time. We conclude that there is little reason to postulate that massive oxygen exchange with a mantle-like reservoir is a general phenomenon of the lower crust.

  19. Kinetic isotope effect in CO2 degassing: Insight from clumped and oxygen isotopes in laboratory precipitation experiments

    NASA Astrophysics Data System (ADS)

    Affek, Hagit P.; Zaarur, Shikma

    2014-10-01

    Laboratory precipitation experiments provide the basis for the common calibration of both the oxygen isotope and the clumped isotope thermometers. These focus on CaCO3 crystals that form deep in the bulk of the solution, often by the bubbling of N2(g) through a saturated Ca(HCO3)2 solution, following the classic experiments on McCrea (1950). Here we examine oxygen and clumped isotopes in CaCO3 that was precipitated at the surface of a solution that undergoes passive CO2 degassing. This CaCO3 is affected by enhanced disequilibrium that is associated with degassing, and has therefore higher δ18O and lower Δ47 values than those of the accepted thermometer calibrations. These offsets from the common thermometers calibrations increase with decreasing temperature for Δ47 but decrease with decreasing temperature for δ18O. The Δ47-δ18O co-variance is therefore strongly temperature dependent, in contrast to theoretical predictions. This suggests an influence of additional fractionation in fast growing minerals, between DIC and calcite, that affects δ18O and counteracts some of the degassing related enrichment. This effect seems not to influence Δ47. The physical setup of CaCO3 minerals growing at the solution surface is analogous to the degassing and precipitation processes that occur in stalagmites, such that these laboratory experiments may help shed light on the isotopic disequilibrium that is observed in speleothems.

  20. 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.

  1. Oxygen isotopic ratios toward molecular clouds in the Galactic disk

    NASA Astrophysics Data System (ADS)

    Li, Hai-Kun; Zhang, Jiang-Shui; Liu, Zhi-Wei; Lu, Deng-Rong; Wang, Min; Wang, Jin

    2016-03-01

    We present our observations of the J = 1 - 0 rotation transitions in molecular isotopes C18O and C17O toward a sample of molecular clouds with different galactocentric distances, using the Delingha 13.7m (DLH 13.7 m) telescope, administered by Purple Mountain Observatory, and its 9-beam SIS receiver. Complementary observations toward several sources with large galactocentric distance are obtained with the IRAM 30m and Mopra 22m telescopes. C18O/C17O abundance ratios reflecting the 18O/17O isotope ratios are obtained from integrated intensity ratios of C18O and C17O. We derived the ratio value for 13 sources covering a galactocentric distance range of 3kpc to 16kpc. In combination with our mapping results that provide a ratio value of 3.01±0.14 in the Galactic center region, it shows that the abundance ratio tends to increase with galactocentric distance, i.e., it supports a radial gradient along the Galactic disk for the abundance ratio. This is consistent with the inside-out formation scenario of our Galaxy. However, our results may suffer from small samples with large galactocentric distance. Combining our data with multi-transition lines of C18O and C17O will be helpful for constraining opacities and abundances and further confirming the Galactic radial gradient shown by the isotope ratio 18O/17O.

  2. Lateglacial and Holocene climatic changes in south-eastern Patagonia inferred from carbonate isotope records of Laguna Potrok Aike (Argentina)

    NASA Astrophysics Data System (ADS)

    Oehlerich, M.; Mayr, C.; Gussone, N.; Hahn, A.; Hölzl, S.; Lücke, A.; Ohlendorf, C.; Rummel, S.; Teichert, B. M. A.; Zolitschka, B.

    2015-04-01

    First results of strontium, calcium, carbon and oxygen isotope analyses of bulk carbonates from a 106 m long sediment record of Laguna Potrok Aike, located in southern Patagonia are presented. Morphological and isotopic investigations of μm-sized carbonate crystals in the sediment reveal an endogenic origin for the entire Holocene. During this time period the calcium carbonate record of Laguna Potrok Aike turned out to be most likely ikaite-derived. As ikaite precipitation in nature has only been observed in a narrow temperature window between 0 and 7 °C, the respective carbonate oxygen isotope ratios serve as a proxy of hydrological variations rather than of palaeotemperatures. We suggest that oxygen isotope ratios are sensitive to changes of the lake water balance induced by intensity variations of the Southern Hemisphere Westerlies and discuss the role of this wind belt as a driver for climate change in southern South America. In combination with other proxy records the evolution of westerly wind intensities is reconstructed. Our data suggest that weak SHW prevailed during the Lateglacial and the early Holocene, interrupted by an interval with strengthened Westerlies between 13.4 and 11.3 ka cal BP. Wind strength increased at 9.2 ka cal BP and significantly intensified until 7.0 ka cal BP. Subsequently, the wind intensity diminished and stabilised to conditions similar to present day after a period of reduced evaporation during the "Little Ice Age". Strontium isotopes (87Sr/86Sr ratio) were identified as a potential lake-level indicator and point to a lowering from overflow conditions during the Glacial (∼17 ka cal BP) to lowest lake levels around 8 ka cal BP. Thereafter the strontium isotope curve resembles the lake-level curve which is stepwise rising until the "Little Ice Age". The variability of the Ca isotope composition of the sediment reflects changes in the Ca budget of the lake, indicating higher degrees of Ca utilisation during the period with

  3. 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.

  4. Nitrite isotope dynamics in coastal sediments: An intricate link between nitrogen and oxygen cycling

    NASA Astrophysics Data System (ADS)

    Charoenpong, C.; Buchwald, C.; Ziebis, W.; Wankel, S. D.

    2014-12-01

    Marine sediments often exhibit strong redox gradients, hosting a range of important nitrogen transformation processes. While the interplay among these microbially catalyzed nitrogen transformations has been well studied in the water column, the sharp redox transition in sediments often makes it far more difficult to unravel the complexity underpinning the cycling of nitrogen. Although often low in concentration, nitrite represents an important 'crossroad' in the nitrogen cycle as a reactive intermediate of both reductive and oxidative N transformations, including nitrification, dissimilatory nitrate reduction to ammonium and denitrification. Here we focus on the dual isotopic composition of nitrite (δ15N and δ18O), in concert with nitrate and ammonium data, as a means for constraining the sedimentary N cycling. Intact flow-through core incubations were performed on sediments collected from intertidal flats on the island of Sylt, Germany. Three types of substrate (i.e., sand, silt, and clay) were collected and subjected to different oxygen (i.e., ambient vs depleted) and nitrogen (i.e., ambient vs highly loaded) regimes. In addition to the measurement of natural abundance N and O stable isotopes, we also amended cores with nitrate having a positive ∆17O in our high nitrogen treatment, which offers yet an additional tracer to further constrain these transformations. While the concentration and isotopic composition (δ15N and δ18O) of nitrite act to integrate the influence of major N redox reactions, the N and O isotope systematics are decoupled. Although nitrogen atoms are generally conserved among these transformations, oxygen isotopes of nitrite are subject to a different set of processes. For example, the loss of an oxygen atom during the reductive processes of NO3- and NO2- reduction, the gain of oxygen atoms from O2 and water during nitrification, and oxygen isotopic equilibration between nitrite and water are all reflected in the δ18O of NO2-. Thus, the

  5. Oxygen isotope fractionation between synthetic aragonite and water: Influence of temperature and Mg 2+ concentration

    NASA Astrophysics Data System (ADS)

    Kim, Sang-Tae; O'Neil, James R.; Hillaire-Marcel, Claude; Mucci, Alfonso

    2007-10-01

    Aragonite was precipitated in the laboratory at 0, 5, 10, 25, and 40 °C to determine the temperature dependence of the equilibrium oxygen isotope fractionation between aragonite and water. Forced CO 2 degassing, passive CO 2 degassing, and constant addition methods were employed to precipitate aragonite from supersaturated solutions, but the resulting aragonite-water oxygen isotope fractionation was independent of the precipitation method. In addition, under the experimental conditions of this study, the effect of precipitation rate on the oxygen isotope fractionation between aragonite and water was almost within the analytical error of ±˜0.13‰ and thus insignificant. Because the presence of Mg 2+ ions is required to nucleate and precipitate aragonite from Na-Ca-Cl-HCO 3 solutions under these experimental conditions, the influence of the total Mg 2+ concentration (up to ˜0.9 molal) on the aragonite-water oxygen isotope fractionation was examined at 25 °C. No significant Mg 2+ ion effect, or oxygen isotope salt effect, was detected up to 100 mmolal total Mg 2+ but a noticeable isotope salt effect was observed at ˜0.9 molal total Mg 2+. On the basis of results of the laboratory synthesis experiments, a new expression for the aragonite-water fractionation is proposed over the temperature range of 0-40 °C: 1000lnα=17.88±0.13(103/T)-31.14±0.46 where αaragonite-water is the fractionation factor between aragonite and water, and T is in kelvins. Given the analytical and statistical errors associated with this and previous determinations, the new relation reveals that many biogenic aragonites are precipitated at and or very near oxygen isotope equilibrium with their ambient water. When the new aragonite-water expression is combined with the calcite-water calibration published by Kim and O 'Neil [Kim S. -T., and O'Neil J. R. (1997) Equilibrium and nonequilibrium oxygen isotope effects in synthetic carbonates. Geochim. Cosmochim. Acta61, 3461-3475], a positive

  6. 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].

  7. 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.

  8. 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.

  9. 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. PMID:25561552

  10. 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

  11. Paleotemperatures versus sea level: Oxygen isotope signal from fish bone phosphate of the Miocene Calvert Cliffs, Maryland

    NASA Astrophysics Data System (ADS)

    Barrick, Reese E.; Fischer, Alfred G.; Bohaska, David J.

    1993-12-01

    The use of skeletal oxygen isotopic records for use in paleotemperature reconstruction has been hampered by the lack of independent evidence for ocean water oxygen isotopic composition. The δ18O record from homeothermic cetaceans has provided an independent estimate of ocean δ18O values represented by the Calvert and Choptank formations of Maryland. Fish teeth and bones (especially shark and ray teeth) were also collected from these sediments and provide the basis for paleotemperature estimates for represented time slices of the middle Miocene. Trends in δ18O values of the fish phosphate throughout the Calvert Formation are of opposite polarity to the trends from the cetacean bone phosphate. Paleotemperatures calculated using the cetacean proxies for ocean δ18O values sharpen the already present trend, indicating that ocean temperatures increased during episodes of greater glaciation and decreased during periods of lesser or no glaciation. When using modern average ocean values of 0‰ SMOW in the paleotemperature calculation, however, corrected paleotemperatures for the Choptank Formation do not alter the existing pattern of temperatures.

  12. Nitrogen cycling in shallow low-oxygen coastal waters off Peru from nitrite and nitrate nitrogen and oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Hu, Happy; Bourbonnais, Annie; Larkum, Jennifer; Bange, Hermann W.; Altabet, Mark A.

    2016-03-01

    O2 deficient zones (ODZs) of the world's oceans are important locations for microbial dissimilatory nitrate (NO3-) reduction and subsequent loss of combined nitrogen (N) to biogenic N2 gas. ODZs are generally coupled to regions of high productivity leading to high rates of N-loss as found in the coastal upwelling region off Peru. Stable N and O isotope ratios can be used as natural tracers of ODZ N-cycling because of distinct kinetic isotope effects associated with microbially mediated N-cycle transformations. Here we present NO3- and nitrite (NO2-) stable isotope data from the nearshore upwelling region off Callao, Peru. Subsurface oxygen was generally depleted below about 30 m depth with concentrations less than 10 µM, while NO2- concentrations were high, ranging from 6 to 10 µM, and NO3- was in places strongly depleted to near 0 µM. We observed for the first time a positive linear relationship between NO2-δ15N and δ18O at our coastal stations, analogous to that of NO3- N and O isotopes during NO3- uptake and dissimilatory reduction. This relationship is likely the result of rapid NO2- turnover due to higher organic matter flux in these coastal upwelling waters. No such relationship was observed at offshore stations where slower turnover of NO2- facilitates dominance of isotope exchange with water. We also evaluate the overall isotope fractionation effect for N-loss in this system using several approaches that vary in their underlying assumptions. While there are differences in apparent fractionation factor (ɛ) for N-loss as calculated from the δ15N of NO3-, dissolved inorganic N, or biogenic N2, values for ɛ are generally much lower than previously reported, reaching as low as 6.5 ‰. A possible explanation is the influence of sedimentary N-loss at our inshore stations which incurs highly suppressed isotope fractionation.

  13. 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

  14. Daily atmospheric circulation patterns from the North Atlantic region as recorded in high-resolution stable isotope records from Greenland ice cores

    NASA Astrophysics Data System (ADS)

    Rimbu, N.; Lohmann, G.

    2009-04-01

    We investigate the relationship between decadal variability of several stable isotope (deuterium and oxygen 18) high-resolution records from Greenland ice cores and the frequency of daily circulation patterns from the North Atlantic realm. Daily circulation patterns as well as their seasonal frequencies for the period 1850-2003 used in this study were published by Philipp et al. (2007). The main source of stable isotopes is the world ocean. During their path from the oceans to the Greenland ice sheet the concentration of heavy relative to light stable isotopes is modified by different fractionation processes. The fractionation depends on the moisture source locations and conditions, temperature of condensation, rain-out effect, amount effect, altitude effect, re-evaporation and kinetic processes. A correlation analysis reveals that a large part of stable isotopes decadal variability from Greenland ice cores is controlled by a summer atmospheric circulation pattern (pattern 2 according to Philipp's et al. classification). Analysis of the moisture transport using NCEP/NCAR reanalysis fields suggests a strong rain-out effect associated with this circulation pattern. This may explain the strong correlation between the frequency of this pattern and stable isotope variability from Greenland ice cores. We argue that high-resolution stable isotope records from Greenland can be used to reconstruct the frequency of certain daily circulation patterns during past periods. This helps to put the decadal variations of the daily circulation patterns as identified from analysis of observed data into a long-term context. Reference Philipp A, Della-Marta PM, Jacobeit J, Fereday DR, Jones PD, Moberg A, Wanner H. 2007: Long-term variability of daily North Atlantic-European pressure patterns since 1850 classified by simulated annealing clus