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Sample records for oxygen isotope variations

  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-isotope variations in post-glacial Lake Ontario

    NASA Astrophysics Data System (ADS)

    Hladyniuk, Ryan; Longstaffe, Fred J.

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Brookman, Tom H.; Ambrose, Stanley H.

    2012-09-01

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

  4. Carbon and oxygen isotope variations in Precambrian cherts

    SciTech Connect

    Robert, F. )

    1988-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

  7. Oxygen Isotope Variations 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.

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

    Sato, Tomohiro; Kasai, Yasuko; Yoshida, Naohiro

    2016-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Levin, N. E.; Li, S.

    2014-12-01

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

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

    PubMed

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

    2006-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1997-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Yuan, F.; Miyamoto, S.

    2006-12-01

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

  16. Oxygen Isotopes in Meteorites

    NASA Astrophysics Data System (ADS)

    Clayton, R. N.

    2003-12-01

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

  17. Oxygen 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

  18. 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

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

    PubMed Central

    Gehler, Alexander; Tütken, Thomas; Pack, Andreas

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    SciTech Connect

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

    2012-11-01

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

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

    USGS Publications Warehouse

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

    1985-01-01

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

  4. Small-scale oxygen isotope variations and petrochemistry of ultradeep (>300 km) and transition zone xenoliths

    NASA Astrophysics Data System (ADS)

    Deines, Peter; Haggerty, Stephen E.

    2000-01-01

    The oxygen isotopic composition of 6 xenoliths for which an origin between 310 to 450 km has been deduced was analyzed. An eclogite from Koidu, Sierra Leone, is composed of garnet with δ 18O gt = 5.67‰ vs SMOW (standard mean ocean water) ± 0.06‰ SEM (standard error of the mean) and clinopyroxene with δ 18O cpx = 5.52 ± 0.18. Results for xenoliths from Jagersfontein, South Africa, are; harzburgite: garnet δ 18O gt = 5.78 ± 0.16, clinopyroxene δ 18O cpx = 5.24 ± 0.27, orthopyroxene δ 18O opx = 4.39 ± 0.21, olivine δ 18O ol = 5.69 ± 0.08; lherzolite: δ 18O gt = 5.63 ± 0.07, δ 18O cpx = 4.3, δ 18O opx = 5.62 ± 0.27; a bimineralic gt/cpx xenolith with minor opx: δ 18O gt = 5.08 ± 0.13, δ 18O cpx = 4.32 ± 0.08, δ 18O opx = 4.21 ± 0.31. Two single crystal garnets with minor associated pyroxenes and in one case, olivine, gave the following results: #1 δ 18O gt = 5.62 ± 0.05, δ 18O cpx = 5.09 ± 0.07, δ 18O opx = 5.62 ± 0.12, δ 18O ol = 5.59; #2 δ 18O gt = 5.62 ± 0.09. While evidence for isotopic equilibrium is observed between some gt/ol, gt/opx and cpx/opx pairs, the 18O/ 16O fractionation between garnet and clinopyroxene tends to be out of equilibrium. Based on the observed oxygen isotope variability, a diffusion model for the data, and published radiogenic isotope data for the samples, it is concluded that these xenoliths experienced a series of metasomatic alterations, including an event which lowered the 18O content of the pyroxenes a few Ma prior to the eruption of the kimberlite.

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

    SciTech Connect

    Peter, J.M. ); Shanks, W.C. III )

    1992-05-01

    Sulfur, carbon, and oxygen isotope values were measured in sulfide, sulfate, and carbonate from hydrothermal chimney, spire, and mound samples in the southern trough of Guaymas Basin, Gulf of California, USA. {delta}{sup 34}S values of sulfides range from {minus}3.7 to 4.5{per thousand} and indicate that sulfur originated from several sources: (1) dissolution of O{per thousand} sulfide contained within basaltic rocks, (2) thermal reduction of seawater sulfate during sediment alteration reactions in feeder zones to give sulfide with positive {delta}{sup 34}S, and (3) entrainment or leaching of isotopically light (negative-{delta}{sup 34}S) bacteriogenic sulfide from sediments underlying the deposits. Oxygen isotope temperatures calculated for chimney calcites are in reasonable agreement with measured vent fluid temperatures and fluid inclusion trapping temperatures. Hydrothermal fluids that formed calcite-rich chimneys in the southern trough of Guaymas Basin were enriched in {sup 18}O with respect to seawater by about 2.4{per thousand} due to isotopic exchange with sedimentary and/or basaltic rocks. Carbon isotope values of calcite range from {minus}9.6 to {minus}14.0{per thousand} {delta}{sup 13}C{sub PDB}, indicating that carbon was derived in approximately equal quantities from the dissolution of marine carbonate minerals and the oxidation of organic matter during migration of hydrothermal fluid through the underlying sediment column. Statistically significant positive, linear correlations of {delta}{sup 34}S, {delta}{sup 13}C, and {delta}{sup 18}O of sulfides and calcites with geographic location within the southern trough of Guaymas Basin are best explained by variations in water/rock (w/r) ratios or sediment reactivity within subsurface alteration zones.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  8. 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.

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

    USGS Publications Warehouse

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

    1992-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2013-10-29

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

  13. 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

  14. Biogeochemical controls on seasonal variations of the stable isotopes of dissolved oxygen and dissolved inorganic carbon in Castle Lake, CA

    NASA Astrophysics Data System (ADS)

    Brown, J. M.; Poulson, S. R.

    2010-12-01

    The purpose of this project is to perform a seasonal dissolved oxygen (DO) and dissolved inorganic carbon (DIC) stable isotope (δ18O, δ13C) study to assess the fluctuations in biogeochemical processes with depth in a lake. DO and DIC concentrations and stable isotope compositions (δ18O-DO, δ13C-DIC) have been used as a technique to study the systematics of diurnal freshwater biogeochemical processes, primarily photosynthesis, respiration, and gas-exchange (e.g. Quay et al. 1995, Trojanowska et al. 2008). For example, photosynthesis produces DO isotopically identical to the host water, typically light relative to atmospheric oxygen (+23.5‰), while respiration preferentially consumes isotopically light DO. Diel δ18O-DO and δ13C-DIC studies in rivers (e.g. Parker et al. 2005, Parker et al. 2010, Poulson & Sullivan 2010) have been used to determine the rates of biogeochemical processes over a 24h time scale. However, similar studies in lakes are rare, for either diel or seasonal time scales. The focus of this project is Castle Lake, 12km southwest of Mt. Shasta, CA, at an elevation of 1660m. Castle Lake is an alpine, meso-oligotrophic lake with a 19ha surface area and a maximum depth of up to 35m. This project consists of sampling profiles, 2-3 weeks apart, throughout the 2010 field season for monitoring seasonal depth trends, with measurements of DO concentration, temperature, pH, alkalinity, specific conductivity, PAR, chlorophyll concentration, δ18O-DO, δ13C-DIC, δ18O-H2O, and δD-H2O. Diel measurements of DO concentration, temperature, pH, specific conductivity, PAR, and chlorophyll concentration have also been performed at various depths. To date, the profile data collected at Castle Lake show various seasonal changes, starting after ice-out (late June 2010) through mid-August 2010. DO profiles display a positive heterograde trend with a maximum of 11.33mg/L at 12m in mid-August and minima of ≤0.12mg/L near the lake bottom. DIC concentrations increase

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

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

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

  16. 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

  17. Simulation of the diurnal variations of the oxygen isotope anomaly (Δ17O) of reactive atmospheric species

    NASA Astrophysics Data System (ADS)

    Morin, S.; Sander, R.; Savarino, J.

    2010-12-01

    The isotope anomaly (Δ17O) of secondary atmospheric species such as nitrate (NO3-) or hydrogen peroxyde (H2O2) has potential to provide useful constrains on their formation pathways. Indeed, the Δ17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero Δ17O in the atmosphere. Interpreting variations of Δ17O in secondary species requires an in-depth understanding of the Δ17O of their precursors taking into account non-linear chemical regimes operating under various environmental settings. We present results from numerical simulations carried out using the atmospheric chemistry box model (CAABA/MECCA) to explicitly compute the diurnal variations of the isotope anomaly of short-lived species such as NOx and HOx. Δ17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the classical mass-balance equation, through the implementation of various sets of hypotheses pertaining to the transfer of Δ17O during chemical reactions. The model confirms that diurnal variations in Δ17O of NOx are well predicted by the photochemical steady-state relationship during the day, but that at night a different approach must be employed (i.e. "fossilization" of the Δ17O of NOx as soon as the photolytical lifetime of NOx drops below ca. 5 min). We quantify the diurnally-integrated isotopic signature (DIIS) of sources of atmospheric nitrate and H2O2 under the various environmental conditions analyzed, which is of particular relevance to larger-scale implementations of Δ17O where high computational costs cannot be afforded.

  18. Simulation of the diurnal variations of the oxygen isotope anomaly (Δ17O) of reactive atmospheric species

    NASA Astrophysics Data System (ADS)

    Morin, S.; Sander, R.; Savarino, J.

    2011-04-01

    The isotope anomaly (Δ17O) of secondary atmospheric species such as nitrate (NO3-) or hydrogen peroxide (H2O2) has potential to provide useful constrains on their formation pathways. Indeed, the Δ17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero Δ17O in the atmosphere. Interpreting variations of Δ17O in secondary species requires an in-depth understanding of the Δ17O of their precursors taking into account non-linear chemical regimes operating under various environmental settings. This article reviews and illustrates a series of basic concepts relevant to the propagation of the Δ17O of ozone to other reactive or secondary atmospheric species within a photochemical box model. We present results from numerical simulations carried out using the atmospheric chemistry box model CAABA/MECCA to explicitly compute the diurnal variations of the isotope anomaly of short-lived species such as NOx and HOx. Using a simplified but realistic tropospheric gas-phase chemistry mechanism, Δ17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the mass-balance equations, through the implementation of various sets of hypotheses pertaining to the transfer of Δ17O during chemical reactions. The model results confirm that diurnal variations in Δ17O of NOx predicted by the photochemical steady-state relationship during the day match those from the explicit treatment, but not at night. Indeed, the Δ17O of NOx is "frozen" at night as soon as the photolytical lifetime of NOx drops below ca. 10 min. We introduce and quantify the diurnally-integrated isotopic signature (DIIS) of sources of atmospheric nitrate and H2O2, which is of particular relevance to larger-scale simulations of Δ17O where high computational costs cannot be afforded.

  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. 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.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

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

    PubMed

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

    2016-03-01

    In Amazonian non-flooded forests with a moderate dry season, many trees do not form anatomically definite annual rings. Alternative indicators of annual rings, such as the oxygen (δ(18)Owc) and carbon stable isotope ratios of wood cellulose (δ(13)Cwc), have been proposed; however, their applicability in Amazonian forests remains unclear. We examined seasonal variations in the δ(18)Owc and δ(13)Cwc of three common species (Eschweilera coriacea, Iryanthera coriacea, and Protium hebetatum) in Manaus, Brazil (Central Amazon). E. coriacea was also sampled in two other regions to determine the synchronicity of the isotopic signals among different regions. The annual cyclicity of δ(18)Owc variation was cross-checked by (14)C dating. The δ(18)Owc showed distinct seasonal variations that matched the amplitude observed in the δ(18)O of precipitation, whereas seasonal δ(13)Cwc variations were less distinct in most cases. The δ(18)Owc variation patterns were similar within and between some individual trees in Manaus. However, the δ(18)Owc patterns of E. coriacea differed by region. The ages of some samples estimated from the δ(18)Owc cycles were offset from the ages estimated by (14)C dating. In the case of E. coriacea, this phenomenon suggested that missing or wedging rings may occur frequently even in well-grown individuals. Successful cross-dating may be facilitated by establishing δ(18)Owc master chronologies at both seasonal and inter-annual scales for tree species with distinct annual rings in each region. PMID:26621690

  4. 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.

  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. Oxygen isotope geochemistry of zircon

    NASA Astrophysics Data System (ADS)

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

    1994-09-01

    The high-temperature and small sample size of an I.R. laser system has allowed the first detailed study of oxygen isotope ratios in zircon. Low-magnetism zircons that have grown during metamorphism in the Adirondack Mts., N.Y. preserve primary delta (O-18) values and low magnetism igneous zircons are likewise primary, showing no significant affect due to subsequent granulite facies metamorphism. The measured fractionation between zircon and garnet is delta (Gt-Zrc) = 0.0 + or - 0.2/mil (1(sigma)) for most low-magnetism zircons in meta-igneous rocks. The consistency of this value indicates equilibration at temperatures of 700 - 1100 C and little or no change in the equilibrium fractionation over this temperature range. In contrast, detrital low-magnetism zircons in quartzite preserve igneous compositions, up to 4/mil out of equilibrium with host quartz, in spite of granulite facies metamorphism. The oxygen isotope composition of zircon can be linked to U-Pb ages and can `see through' metamorphism, providing a new tool for deciphering complex igneous, metamorphic and hydrothermal histories. Zircons separated by magnetic susceptibility show a consistent correlation. Low-magnetism zircons have the lowest uranium contents, the most concordant U-Pb isotopic compositions, and primary delta (O-18) values. In contrast, high-magnetism zircons are up to 2/mil lower in delta (O-18) than low-magnetism zircons from the same rock. The resetting of oxygen isotope ratios in high-magnetism zircons is caused by radiation damage which creates microfractures and enhances isotopic exchange. Zircons from the metamorphosed anorthosite-mangerite-charnocite-granite (AMCG) suite of adirondacks have previously been dated (1125-1157 Ma) and classified as igneous, metamorphic or disturbed based on their physical and U-Pb isotopic characteristics. Low-magnetism zircons from the AMCG suite have high, nearly constant values of delta (O-18) that average 8.1 + or - 0.4/mil(1 sigma) for samples

  7. 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.

  8. Variation in the oxygen isotope ratio of phloem sap sucrose from castor bean. Evidence in support of the Péclet effect.

    PubMed

    Barbour, M M; Schurr, U; Henry, B K; Wong, S C; Farquhar, G D

    2000-06-01

    Theory suggests that the level of enrichment of (18)O above source water in plant organic material (Delta) may provide an integrative indicator of control of water loss. However, there are still gaps in our understanding of the processes affecting Delta. One such gap is the observed discrepancy between modeled enrichment of water at the sites of evaporation within the leaf and measured enrichment of the leaf water as a whole (Delta(L)). Farquhar and Lloyd (1993) suggested that this may be caused by a Péclet effect. It is also unclear whether organic material formed in the leaf reflects enrichment of water at the sites of evaporation within the leaf or Delta(L). To investigate this question castor bean (Ricinus communis L.) leaves, still attached to the plant, were sealed into a controlled-environment gas exchange chamber and subjected to a step change in leaf-to-air vapor pressure difference. Sucrose was collected from a cut on the petiole of the leaf in the chamber under equilibrium conditions and every hour for 6 h after the change in leaf-to-air vapor pressure difference. Oxygen isotope composition of sucrose in the phloem sap (Delta(suc)) reflected modeled Delta(L). A model is presented describing Delta(suc) at isotopic steady state, and accounts for 96% of variation in measured Delta(suc). The data strongly support the Péclet effect theory. PMID:10859197

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kazuyuki; Asami, Ryuji; Iryu, Yasufumi

    2010-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  13. 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.

  14. 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.

  15. Neodymium isotopic variations in seawater

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

  16. 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.

  17. 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

  18. 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

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    SciTech Connect

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

    1991-02-01

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

  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. 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.

  4. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  9. Oxygen isotope variations in rainfall, drip-water and speleothem calcite from a well-ventilated cave in Texas, USA: Assessing a new speleothem temperature proxy

    NASA Astrophysics Data System (ADS)

    Feng, Weimin; Casteel, Richard C.; Banner, Jay L.; Heinze-Fry, Ayla

    2014-02-01

    Measurements of the oxygen isotopic composition (δ18O value) of rainfall, drip-water and associated calcite (grown on artificial substrates and in a natural speleothem) at multiple drip sites in a well-ventilated cave in central Texas were conducted to investigate the potential use of speleothem δ18O for quantitative temperature reconstructions. From 2009 to 2011, rainfall δ18O varied by 11.5‰ (-10.5‰ to 1.0‰, V-SMOW), whereas drip-waters had a much narrower range of 0.3‰ (-4.7‰ to -4.4‰, V-SMOW). This contrast indicates that mixing processes along flow paths in the vadose zone above the cave produce a well-homogenized water reservoir that supplies drip-water to the cave. The δ18O values for calcite grown on substrates over the same time period show seasonal variations (summer: ˜-6‰; winter: ˜-3‰) that are strongly correlated with surface air temperatures (ta) at all three monitored sites (r2 = 0.88-0.96; p < 0.001). These results indicate that the dominant control on calcite δ18O is temperature. An empirical relationship was established for one monitored site: ta = -9.1 (±0.9) × δ18O × 103 - 20.6 (±4.1); r2 = 0.88, and applied to a δ18O time series of the top 6.7 mm of a stalagmite that grew at this drip site. This yields a temperature record that appears to reflect seasonal variations for the period 2005-2009. This speleothem-derived temperature record is offset to lower values (by 0-8 °C) compared to the instrumental temperature record. This offset may be a result of differences between substrate and speleothem calcite in terms growth mechanism, extent of non-equilibrium isotopic effects, or temporal shifts in drip-water δ18O values. Despite this offset, the speleothem-derived record reconstructs the amplitudes of seasonal variations and changes in inter-annual summer peak temperatures in the instrumental record. Results of this study have implications for reconstructing past temperatures, and for establishing a speleothem

  10. 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.

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

    USGS Publications Warehouse

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

    2011-01-01

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

  12. Variation in Atmospheric Helium Isotopes

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

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

    SciTech Connect

    Bennett, V.C.

    1989-01-01

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

  14. Oxygen isotope fractionation in double carbonates.

    PubMed

    Zheng, Yong-Fei; Böttcher, Michael E

    2016-01-01

    Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60 °C and 100 °C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in (18)O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0-1200 °C. The calculated fractionation factors for double carbonate-water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2 and CaMg[CO3]2 against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2 and CO2 are much closer to theoretical predictions for the cerussite-CO2 system than for the magnesite-CO2 system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates. PMID:25393769

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  16. 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.

  17. 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

    }-(0.30±0.03)·S-(4.7±1.2) where S is the salinity, R is the gas constant, pH0 is the pH difference between free scale and the scale used to calculate the concentration of DIC species. Quantitative evaluation of these two extreme cases using our model suggests that oxygen isotope fractionation between aragonite and water varies significantly with a pH change between 7.5 and 10 (e.g., ˜4‰ at 25 °C), but little with a salinity change between 5‰ and 35‰ (<0.1‰ at 25 °C) during extremely fast precipitation, whereas during slow precipitation little variation occurs with pH varying between 7.5 and 10 at a given salinity (<0.3‰ in δ18O at T = 0-55 °C). This model connects aragonite precipitation kinetics with oxygen isotope fractionation between aragonite and water, and provides a framework to reconcile the discrepancy among experimental calibrations of aragonite-water fractionation in different labs and empirical calibrations using biogenic aragonites by variations in precipitation conditions (including pH, salinity and precipitation rate).

  18. 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.

  19. 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

  20. 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

    the oxygen-isotope composition of atmospheric water vapour in the chamber. Measured plant water oxygen-isotope values displayed variations of up to 37 ‰ along the length of a single Equisetum plant, and average plant water oxygen-isotope values for this species varied up to 10 ‰ over the growing season. Because the transpiring tissues of most plants produce the largest amount of phytoliths, which are ultimately preserved in the underlying soil, it is imperative to understand the how the variability of the oxygen-18 enrichment in the water of transpiring tissues is reflected in the oxygen-isotope composition of the phytoliths in order to use this method for successful paleoclimate reconstruction.

  1. Oxygen Isotope Systematics of Almahata Sitta

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  2. 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.

  3. 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.

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

    USGS Publications Warehouse

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

    2002-01-01

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

  5. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  7. 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.

  8. 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

  9. 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.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

    Webb, Elizabeth A.; Longstaffe, Fred J.

    2002-06-01

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

  12. Temporal variations of the anomalous oxygen component

    NASA Technical Reports Server (NTRS)

    Cummings, A. C.; Webber, W. R.

    1983-01-01

    Data from the cosmic ray experiment on Voyagers 1 and 2 was used to examine anomalous oxygen in the time period from launch in 1977 to the end of 1981. Several time periods were found where large periodic (typically 26 day) temporal variations of the oxygen intensity between approximately 5 - 15 MeV/nuc are present. Variations in intensity by up to a factor of 10 are observed during these periods. Several characteristics of these variations indicate that they are not higher energy extensions of the low energy particle (approximately 1 MeV/nuc) increases found in many corotating interaction regions (CIR's). Many of these periodic temporal variations are correlated with similar, but much smaller, recurrent variations in the 75 MeV proton rate. Voyager 1 and Voyager 2 counting rates were compared to estimate the local radial gradient for both the protons and the oxygen. The proton gradients during periods of both maximum and minumum fluxes are consistent with the overall positive radial gradients reported by others from Pioneer and near-Earth observations, supporting the view that these variations are due to local modulation of a source outside the radial range of project measurements. In contrast, the oxygen gradients during periods of maximum proton flux differ in sign from those during minimum proton fluxes, suggesting that the origin of the oxygen variations is different from that of the protons.

  13. 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.

  14. 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

  15. 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

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

    NASA Astrophysics Data System (ADS)

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

    2001-05-01

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

  17. Spatial Variations in Vitreous Oxygen Consumption

    PubMed Central

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

    2016-01-01

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

  18. 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

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

    PubMed

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

    1990-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1990-01-01

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

  1. 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

  2. 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.

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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).

  18. 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

  19. 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

  20. 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.

  1. 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.

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

    PubMed

    Yurimoto, Hisayoshi; Kuramoto, Kiyoshi

    2004-09-17

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

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  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. 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.

  3. 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.

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  5. 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

  6. 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.

  7. 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

  8. 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...

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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

  14. 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

  15. 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

  16. 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.

  17. 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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

    Price, Gregory; Grimes, Stephen

    2015-04-01

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

  20. Sr isotopic variations along the Juan de Fuca Ridge.

    USGS Publications Warehouse

    Eaby, J.; Clague, D.A.; Delaney, J.R.

    1984-01-01

    The Sr isotopic ratios of 39 glass and microcrystalline basalt samples along the Juan de Fuca Ridge and one glass sample from Brown Bear Seamount are at the lower end of the range for normal MORB; the average 87Sr/86Sr ratio is 0.70249 + or - 0.00014 (2sigma ). Although subtle variations exist along the strike of the ridge, the Sr isotopic data do not show systematic variation relative to the proposed Cobb hotspot. The isotopic data are inconsistent with an enriched mantle-plume origin for the Cobb-Eikelberg Seamount chain.-W.H.B.

  1. 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

  2. Pristine extraterrestrial material with unprecedented nitrogen isotopic variation

    PubMed Central

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

    2009-01-01

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

  3. Pristine extraterrestrial material with unprecedented nitrogen isotopic variation.

    PubMed

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

    2009-06-30

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

  4. 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

  5. Cadmium isotope variations in the Southern Ocean

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  6. 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

  7. 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.

  8. 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.

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

    SciTech Connect

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

    1981-01-01

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

  10. 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.

  11. 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.

  12. 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.

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  15. Variation of Benthic Foraminiferal Assemblage and Carbon and Oxygen Isotopic Composition for the Last 30000 Years on gas-hydrate-bearing Umitaka Spur, Joetsu, Eastern Margin of Japan Sea

    NASA Astrophysics Data System (ADS)

    Takeuchi, E.; Nakagawa, H.; Hiruta, A.; Matsumoto, R.

    2006-12-01

    Umitaka spur off Joetsu, eastern margin of Japan Sea, is characterized by large pockmarks, mounds and gas hydrate BSRs. Numerous gas plumes, about 600m height, were identified on the spur and sea water have high methane concentration. Moreover massive gas hydrates have been recovered from the seafloor of the spur. The environment around the spur is assumed to have been influenced methane. But active methane phenomena are only observed adjacent to pockmarks, not inside of them. If pockmarks have been made by large methane-release events, when and why did these events occur? To solve these questions, we conducted studies on foraminifer assemblages and Carbon-14 age determinations. Carbon and oxygen isotopic analyses of benthic foraminifera were carried out on three piston cores which were recovered during the KY06-08 cruise in 2005. Sediments and depositional environments Carbon-14 ages were measured by planktonic foraminifera (Globigerina. umbilicata) at 4 horizons of PC01 which recovered 7 m long sediment core. PC01 were dated as 22ka cal. BC at 3.9 m, and 3.2ka cal. BC at 6.4 m. The sediments are composed of bioturbated massive units (0-1.5m), which indicate oxidative conditions on the seafloor, and laminated unit (1.5-7.0m), which indicates reductive conditions on the seafloor. Benthic foraminifera At about 28kyr, the benthic foraminifera abundance and proportion of Stainforthia. rotundata increased. Afterwards, very little benthic foraminifera occurred. According to Akimoto (1996), Ruthefordoides corunuta (same as S. rotundata) occur with Calyptogena communities which are related to methane seeps. It is suggested that the methane flux in this area were more active than at present and the sea floor environment was oxygen-free and enriched in methane. Carbon and oxygen isotopic anomalies The delta13C of benthic foraminifera decreased at 24ka~27ka. At the same time, S. rotundte increased, so this suggests that delta13C-depleted dissolved inorganic carbon was made

  16. Helium isotopic abundance variation in nature

    SciTech Connect

    Holden, N.E.

    1993-08-01

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

  17. Secular changes in the oxygen isotopic composition of Devonian biogenic apatite

    NASA Astrophysics Data System (ADS)

    Breisig, S.; Joachimski, M. M.; Buggisch, W.

    2003-04-01

    Oxygen isotopes are a key tool for quantifying temperature and salinity of ancient sea water. Initially, pristine skeletal carbonates (preferentially LMC) have been utilized to monitor variations in the oxygen isotopic composition of past oceans. A high preservation potential of the primordial isotopic signature may also be awarded to conodonts. These microfossils consist of fluor-apatite (francolite) with a dense microcrystalline structure and therefore are comparatively insensitive with regard to diagenetic overprinting. Because conodonts are frequent in Devonian rocks and widely used as index fossils, their application for oxygen isotope analysis is espe-cially promising for this specific geological time interval. Laser-based microsampling or high-temperature combustion techniques (TC/EA) allows us to analyse microsamples of conodont apatite (0.5 to 1 mg). The oxygen isotope measurements are performed on trisilverphosphate after dissolving conodont apatite (0.5 to 1 mg) in nitric acid and precipitating the phosphate group as Ag_3PO_4. Conodont samples from different locations in Germany (Rheinisches Schieferge-birge) and the Czech Republic (Prague Basin) as well as from the United States (Iowa) and Morocco (Anti-Atlas) have been analysed. δ18Oapatite values are presented for the Lochkovian, Middle and Late Devonian. δ18Oapatite values for the Lochkovian (Prague Basin) vary between 18.5 and 19.0 ppm (δ18Oapatite values given in V-SMOW). Assuming an oxygen isotopic composition for Devonian seawater of -1 ppm (ice-free world), the δ18Oapatite values translate into tem-peratures of 26^o to 28^oC for the tropical Lochkovian ocean. Eifelian to Givetian conodonts (Rheinisches Schiefergebirge, Prague Basin) show δ18Oapatite values from 18.5 to 20.4 ppm, corresponding to paleotemperatures of 20 to 28^o C. The Middle to Late Devonian transition is mainly documented by conodonts from Iowa with δ18Oapatite values of 18 to 20 ppm (21-30^o C). Conodont δ18Oapatite

  18. 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

  19. 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

  20. Isotopic study of oxygen diffusion in oxide coatings

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  1. A mechanistic model for interpretation of hydrogen and oxygen isotope ratios in tree-ring cellulose

    NASA Astrophysics Data System (ADS)

    Roden, John S.; Lin, Guanghui; Ehleringer, James R.

    2000-01-01

    A mechanistic model is presented to quantify both the physical and biochemical fractionation events associated with hydrogen and oxygen isotope ratios in tree-ring cellulose. The model predicts the isotope ratios of tree-rings, incorporating both humidity and source water environmental information. Components of the model include (1) hydrogen and oxygen isotope effects associated with leaf water enrichment; (2) incorporation of leaf water isotope ratio values into photosynthetic carbohydrates along with the biochemical fractionation associated with autotrophic synthesis; (3) transport of exported carbohydrates (such as sucrose) from leaves to developing xylem in shoots and stems where cellulose is formed; (4) a partial exchange of oxygen and hydrogen isotopes in carbohydrates with xylem sap water during conversion into cellulose; and (5) a biochemical fractionation associated with cellulose synthesis. A modified version of the Craig-Gordon model for evaporative enrichment adequately described leaf water δD and δ 18O values. The leaf water model was robust over a wide range of leaf waters for both controlled experiments and field studies, far exceeding the range of values to be expected under natural conditions. The isotopic composition of cellulose was modeled using heterotrophic and autotrophic fractionation factors from the literature as well as the experimentally derived proportions of H and O that undergo exchange with xylem water during cellulose synthesis in xylem cells of tree-rings. The fraction of H and O from carbohydrates that exchange with xylem sap water was estimated to be 0.36 and 0.42, respectively. The proportions were based on controlled, long-term greenhouse experiments and field studies where the variations in the δD and δ 18O of tree-ring cellulose were measured under different source water isotopic compositions. The model prediction that tree-ring cellulose contains information on environmental water source and atmospheric vapor pressure

  2. 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.

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

    USGS Publications Warehouse

    Bullen, T.D.; Walczyk, T.

    2009-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2005-12-01

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

  6. Hafnium isotope variations in oceanic basalts

    NASA Technical Reports Server (NTRS)

    Patchett, P. J.; Tatsumoto, M.

    1980-01-01

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

  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. 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.

  12. 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.

  13. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  15. 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.

  16. 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.

  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. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  20. 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

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

    USGS Publications Warehouse

    Hitchon, B.; Friedman, I.

    1969-01-01

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2016-03-01

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

  4. 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.

  5. 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

  6. 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.

  7. 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.

  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. 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.

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. pH control on oxygen isotopic composition of symbiotic corals

    NASA Astrophysics Data System (ADS)

    Rollion-Bard, Claire; Chaussidon, Marc; France-Lanord, Christian

    2003-10-01

    Boron, carbon and oxygen isotopic compositions were determined at the micrometre scale by high-resolution ion microprobe in a sample of modern coral (massive hermatypic coral, Porites lutea). The ion probe data show for B and O much larger isotopic variations at the micrometre scale than those measured at the millimetre scale by conventional techniques: δ 18O PDB values range from -10.6±0.9‰ to -0.2±0.5‰ and δ 11B values range from +18.6±1.5‰ to +30.6±1.6‰. By contrast, δ 13C values show the same range of variations, from -4.6±0.65‰ to -2.2±0.67‰ at the micrometre and millimetre scales. The range of δ 11B values indicates that significant pH variations, from ≈7.1 to ≈9.0, are present at the sites of calcification. The largest δ 18O variations correspond to the highest δ 11B values, i.e. to the highest pHs. This measurement of pH allows modelling the oxygen isotopic fractionation occurring during aragonite precipitation. Taking into account the rate of O isotopic equilibrium between dissolved carbonate species (H 2CO 3, HCO 3- and CO 32-) and water via the two reactions of hydration and hydroxylation, the full range of δ 18O values measured at the micrometre scale can be modelled for residence times of dissolved carbonates in the calcifying fluid ranging between ≈1 h and at maximum ≈12 h. The pH controls the δ 18O of the growing carbonate through the relative fractions of dissolved carbonate species and through the kinetics of their isotopic equilibration with water via hydration and hydroxylation. The so-called 'vital effect' systematically observed for δ 18O in corals can thus be understood as representing an average of rapid pH variations due to coral biology during coral growth. Selectively measuring δ 18O values in the zones of coral skeletons that have low δ 11B values (i.e. formed at low pH) should significantly improve the quality of palaeoclimatic reconstructions based on δ 18O values.

  15. Spatially Controlled Fe Isotope Variations at Torres del Paine

    NASA Astrophysics Data System (ADS)

    Gajos, N.; Lundstrom, C.

    2013-12-01

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

  16. 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

  17. Geographic variation of stable isotopes in African elephant ivory

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  18. 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

  19. Triple Oxygen Isotope Measurement of Nitrate to Analyze Impact of Aircraft Emissions

    NASA Astrophysics Data System (ADS)

    Chan, Sharleen

    With 4.9% of total anthropogenic radiative forcing attributed to aircraft emissions, jet engines combust copious amounts of fuel producing gases including: NOx (NO + NO2), SOx, VOC's and fine particles [IPCC (1999), IPCC (2007), Lee et al., 2009]. The tropospheric non-linear relationships between NOx, OH and O3 contribute uncertainties in the ozone budget amplified by poor understanding of the NOx cycle. In a polluted urban environment, interaction of gases and particles produce various new compounds that are difficult to measure with analytical tools available today [Thiemens, 2006]. Using oxygen triple isotopic measurement of NO3 to investigate gas to particle formation and chemical transformation in the ambient atmosphere, this study presents data obtained from aerosols sampled at NASA's Dryden Aircraft Operations Facility (DAOF) in Palmdale, CA during January and February, 2009 and Los Angeles International Airport (LAX) during Fall 2009, Winter 2010, and Spring 2010. The aerosols collected from jet aircraft exhaust in Palmdale exhibit an oxygen isotope anomaly (Delta17O =delta 17O -0.52 delta18O) increase with photochemical age of particles (-0.22 to 26.41‰) while NO3 concentration decreases from 53.76 - 5.35ppm with a radial distance from the jet dependency. Bulk aerosol samples from LAX exhibit seasonal variation with Delta17 O and NO3 concentration peaking in winter suggesting multiple sources and increased fossil fuel burning. Using oxygen triple isotopes of NO3, we are able to distinguish primary and secondary nitrate by aircraft emissions allowing new insight into a portion of the global nitrogen cycle. This represents a new and potentially important means to uniquely identify aircraft emissions on the basis of the unique isotopic composition of jet aircraft emissions.

  20. 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.

  1. Nd isotopic variations in Precambrian banded iron formations

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

  2. 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

  3. 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.

  4. Exploring antimony isotope ratio variations for provenancing purposes

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  5. 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.

  6. Oxygen isotopic and chemical zoning of melilite crystals in a type A Ca-Al-rich inclusion of Efremovka CV3 chondrite

    NASA Astrophysics Data System (ADS)

    Kawasaki, Noriyuki; Sakamoto, Naoya; Yurimoto, Hisayoshi

    2012-12-01

    Different oxygen isotopic reservoirs have been recognized in the early solar system. Fluffy type A Ca-Al-rich inclusions (CAIs) are believed to be direct condensates from a solar nebular gas, and therefore, have acquired oxygen from the solar nebula. Oxygen isotopic and chemical compositions of melilite crystals in a type A CAI from Efremovka CV3 chondrite were measured to reveal the temporal variation in oxygen isotopic composition of surrounding nebular gas during CAI formation. The CAI is constructed of two domains, each of which has a core-mantle structure. Reversely zoned melilite crystals were observed in both domains. Melilite crystals in one domain have a homogeneous 16O-poor composition on the carbonaceous chondrite anhydrous mineral (CCAM) line of δ18O = 5-10‰, which suggests that the domain was formed in a 16O-poor oxygen isotope reservoir of the solar nebula. In contrast, melilite crystals in the other domain have continuous variations in oxygen isotopic composition from 16O-rich (δ18O = -40‰) to 16O-poor (δ18O = 0‰) along the CCAM line. The oxygen isotopic composition tends to be more 16O-rich toward the domain rim, which suggests that the domain was formed in a variable oxygen isotope reservoir of the solar nebula. Each domain of the type A CAI has grown in distinct oxygen isotope reservoir of the solar nebula. After the domain formation, domains were accumulated together in the solar nebula to form a type A CAI.

  7. Oxygen isotopes and emerald trade routes since antiquity

    PubMed

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

    2000-01-28

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

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1986-09-01

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

  12. Temporal variation of the oxygen flux in the inner magnetosphere

    NASA Astrophysics Data System (ADS)

    Beaujean, R.

    1995-01-01

    The intensity of oxygen ions in the inner magnetosphere was studied by several experiments using track detectors. This report combines the measurements on Soviet COSMOS satellites of the period 1985-1988 with earlier results from the SL-1 mission (1983). The evident temporal variation supports the conclusion that the orgin for these particles is trapping of the anomalous component.

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

    SciTech Connect

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

    1985-01-01

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

  14. 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.

  15. 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

  16. 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

  17. Daily Variation of Isotope Ratios in Mars Atmospheric Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Livengood, Timothy A.; Kostiuk, Theodor; Kolasinski, John R.; Hewagama, Tilak; Henning, Wade G.; Sornig, Manuela; Stangier, Tobias; Krause, Pia; Sonnabend, Guido; Mahaffy, Paul R.

    2014-11-01

    The atmosphere of Mars has been shown by ground based high-resolution infrared spectroscopy and in situ measurements with the Phoenix lander and Mars Science Laboratory Curiosity rover to be enriched in C and O heavy isotopes, consistent with preferential loss of light isotopes in eroding Mars’ primordial atmosphere. The relative abundance of heavy isotopes, combined with contemporary measurements of loss rates to be obtained with MAVEN, will enable estimating the primordial atmospheric inventory on Mars. IR spectroscopy of Mars collected in May 2012 as well as in March and May of 2014 from the NASA IRTF has resolved transitions of all three singly-substituted minor isotopologues of carbon dioxide in addition to the normal isotope, enabling remote measurements of all the carbon and oxygen isotope ratios as a function of latitude, longitude, and time of day. Earlier measurements obtained in October 2007 demonstrated that the relative abundance of O-18 increased linearly with increasing surface temperature over a relatively warm early-afternoon temperature range, but did not extend far enough to inspect the effect of late-afternoon cooling. These results imply that isotopically enriched gas is sequestered overnight when surface temperature is minimum and desorbs through the course of the day as temperature increases. Current spectroscopic constants indicate that the peak isotopic enrichment could be significantly greater than what has been measured in situ, apparently due to sampling the atmosphere at different time of day and surface temperature. The observing runs in 2012 and 2014 measured O-18 enrichment at several local times in both morning and afternoon sectors as well as at the subsolar, equatorial, and anti-subsolar latitudes. The two runs in 2014 have additionally observed O-17 and C-13 transitions in the morning sector, from local dawn to noon. These observations include a limited sampling of measurements over Gale Crater, which can be compared with

  18. 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

  19. Unexpected hydrogen isotope variation in oceanic pelagic seabirds.

    PubMed

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

    2014-08-01

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

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

    SciTech Connect

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

    1991-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  2. 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.

  3. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  5. 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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    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.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

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

    PubMed

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

    2014-08-01

    The condition of water cycles in Tibet Plateau is a complex process, and the hydrogen and oxygen isotopes contain important information of this process. Based on the analysis of isotopic composition of freshwater lake, saltwater lake and geothermal water in the southern Tibetan Plateau, this study investigated water cycling, composition and variation of hydrogen and oxygen isotopes and the influencing factors in the study area. The study found that the mean values of delta18O and deltaD in Daggyaima lake water (-17.0 per thousand for delta18O and -138. 6 per thousand for deltaD), Langcuo lake water (-6.4 per thousand for delta18O and -87.4 per thousand for deltaD) and Dagejia geothermal water (-19.2 per thousand for delta18 and -158.2 per thousand for deltaD) all showed negative delta18O and deltaD values in Tibetan Plateau by the influence of altitude effects. Lake water and geothermal water were influenced by evaporation effects in inland arid area, and the slope of evaporation line was less than 8. Deuterium excess parameters of lake water and geothermal water were all negative. The temperature of geothermal reservoirs in Dagejia geothermal field was high,and oxygen shift existed in the relationship of hydrogen and oxygen isotopes. PMID:25338365

  10. A preliminary assessment of oxygen isotope fractionation and growth increment periodicity in the estuarine clam Rangia cuneata

    NASA Astrophysics Data System (ADS)

    Andrus, C. Fred T.; Rich, Kelley Whatley

    2008-10-01

    Rangia cuneata is an upper estuarine clam common in the coastal regions of the Gulf of Mexico. Limited data exist regarding oxygen isotope fractionation and microstructural increment periodicity in this species. As these clams were recently identified as an invasive species in other regions, such data may be useful for environmental management purposes. Additionally, the shell of this clam is common in archeological middens, and thus may serve as a paleoenvironmental proxy. In order to assess these aspects of the species' natural history, samples were collected from the upper Mobile Bay, Alabama, USA. A stable oxygen isotope profile was generated from one of these valves, and compared to growth increments seen in thin section. Time-series water temperature data from near the collection site were used to construct idealized models of oxygen isotope variation, assuming equilibrium fractionation, constant shell growth, and stable water δ18O values. Comparison of the modeled and measured data suggest the shell was precipitated in, or near oxygen isotope equilibrium with ambient water, and that the microstructural increments in the shell were precipitated in response to tidal cycles.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. Thallium isotope variations in anthropogenically-affected soils

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

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

    USGS Publications Warehouse

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

    1980-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2001-11-01

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

  2. 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

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

    SciTech Connect

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

    2008-09-03

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

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

    NASA Astrophysics Data System (ADS)

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

    1996-10-01

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

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  7. 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

  8. 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

  9. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  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. 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.

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

    PubMed Central

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

    2015-01-01

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

  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. Oxygen isotopic constraints on the origin of magnesian chondrules and on the gaseous reservoirs in the early Solar System

    NASA Astrophysics Data System (ADS)

    Chaussidon, Marc; Libourel, Guy; Krot, Alexander N.

    2008-04-01

    We report in situ ion microprobe analyses of the oxygen isotopic composition of the major silicate phases (olivine, low-Ca pyroxene, silica, and mesostasis) of 37 magnesian porphyritic (type I) chondrules from CV (Vigarano USNM 477-2, Vigarano UH5, Mokoia, and Efremovka) and CR (EET 92042, EET 92147, EET 87770, El Djouf 001, MAC 87320, and GRA 95229) carbonaceous chondrites. In spite of significant variations of the modal proportions of major mineral phases in CR and CV chondrules, the same isotopic characteristics are observed: (i) olivines are isotopically homogeneous at the ‰ level within a chondrule although they may vary significantly from one chondrule to another, (ii) low-Ca pyroxenes are also isotopically homogeneous but systematically 16O-depleted relative to olivines of the same chondrule, and (iii) all chondrule minerals analyzed show 16O-enrichments relative to the terrestrial mass fractionation line, enrichments that decrease from olivine (±spinel) to low-Ca pyroxene and to silica and mesostasis. The observation that, in most of the type I chondrules studied, the coexisting olivine and pyroxene crystals and glassy mesostasis have different oxygen isotopic compositions implies that the olivine and pyroxene grains are not co-magmatic and that the glassy mesostasis is not the parent liquid of the olivine. The δ 18O and δ 17O values of pyroxene and olivine appear to be strongly correlated for all the studied CR and CV chondrules according to:

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

    PubMed

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

    2013-01-01

    In the present study, controlled laboratory column experiments were conducted to understand the biogeochemical changes during the microbial sulfate reduction. Sulfur and oxygen isotopes of sulfate were followed during sulfate reduction in zero valent iron incubated flow through columns at a constant temperature of 20±1°C for 90 d. Sulfur isotope signatures show considerable variation during biological sulfate reduction in our columns in comparison to abiotic columns where no changes were observed. The magnitude of the enrichment in δ(34)S values ranged from 9.4‰ to 10.3‰ compared to initial value of 2.3‰, having total fractionation δS between biotic and abiotic columns as much as 6.1‰. Sulfur isotope fractionation was directly proportional to the sulfate reduction rates in the columns. Oxygen isotopes in this experiment seem less sensitive to microbial activities and more likely to be influenced by isotopic exchange with ambient water. A linear relationship is observed between δ(34)S and δ(18)O in biotic conditions and we also highlight a good relationship between δ(34)S and sulfate reduction rate in biotic columns. PMID:23000047

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

    PubMed

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

    1991-01-01

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

  19. Study of oxygen isotopes and N=8 isotones with an extended cluster-orbital shell model

    NASA Astrophysics Data System (ADS)

    Masui, H.; Katō, K.; Ikeda, K.

    2006-03-01

    We attempt to obtain a unified description of the bound and unbound states of multivalence nucleons of a core system in the framework of the cluster-orbital shell model (COSM). In this framework, the interaction between the core and a valence nucleon (the core-N interaction) is treated microscopically, and the changes in both the core structure and the core-N interaction are discussed on the same basis. Furthermore, the center-of-mass motion of every nucleon is completely eliminated, and higher shell configurations, including unbound continuum components, are appropriately taken into account by applying a stochastic variational approach. To examine the reliability of this approach and to discuss how the dynamics of the core reflects to the total system, we study oxygen isotopes and N=8 isotones, which are described by O16 + Xn and O16 + Xp models, respectively.

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

    PubMed

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

    2015-01-01

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

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  3. 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.

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

    NASA Astrophysics Data System (ADS)

    Shima, M.

    1986-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2006-11-01

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

  6. 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.

  7. 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

  8. 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

  9. 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

  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. 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.

  12. 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.

  13. 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

  14. 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

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

    SciTech Connect

    Kolodny, Y.; Kaplan, I. R.

    1981-04-01

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

  16. 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...

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  19. Carbon and Oxygen Isotopic Measurements of K/T Boundary Spherules from Haiti

    NASA Astrophysics Data System (ADS)

    Hough, R. M.; Sigurdsson, H.; Franchi, I. A.; Wright, I. P.; Pillinger, C. T.; Gilmour, I.

    1993-07-01

    formation for the spherules and will also clarify the effect of the internal bubbles upon the compositions. Dark brown spherules selected for oxygen isotope measurements were broken into fragments to allow repeat analyses on the same spherule. Due to the smaller size of the yellow spherules they were analyzed whole. The dark brown spherules yield a delta^17O of 4.97 to 3.65 per mil and a delta^18O between 9.47 to 7.15 per mil. The yellow spherules yield a delta^17O of 6.77 per mil and a delta^18O of 13.02 per mil. Both closely follow the terrestrial fractionation line for Delta^17O with only a slight deviation and the delta^18O values agree with those previously measured by [3]. Heterogeneity's seen in the carbon data for the dark brown spherules seem to be reflected in the oxygen data with variations between fragments of the same spherule and between whole spherules. The yellow spherules appear to be homogeneous in terms of their oxygen isotopic compositions. References: [1] Koeberl C. and Sigurdsson H. (1992) GCA, 56, 2113-2119. [2] Gilmour I. et al. (1992) Science, 258, 1624-1625. [3] Sigurdsson H. et al. (1991) Nature, 349, 482-486.

  20. 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

  1. 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

  2. Temporal variations of the anomalous oxygen component, 1977 - 1984

    NASA Technical Reports Server (NTRS)

    Mason, G. M.; Klecker, B.; Galvin, A. B.; Hovestadt, D.; Ipavich, F. M.

    1985-01-01

    A survey is of the long term temporal variations of 6.6 to 12 MeV/nucleon anomalous oxygen at 1 AU covering the period 1977 to 1984. This time interval included the recent solar maximum, with the recovery at neutron monitor energies beginning in 1982. During this time interval, 6.6 to 12 MeV/nucleon 0 fluxes decreased by at least a factor of 50, and indeed remained below the instrumental detection threshold after 1979. By late 1984, neutron monitors had recovered to roughly 1979 levels from the 1982 solar maximum, and anomalous O still remained below the detection threshold.

  3. Trace element and oxygen isotope composition of Hawaiian hotspot zircon

    NASA Astrophysics Data System (ADS)

    Vazquez, J. A.; Bindeman, I. N.; Shamberger, P. J.; Hammer, J. E.

    2010-12-01

    The trace element and isotopic compositions of zircon are increasingly used to delimit the provenance of detrital minerals in sedimentary rocks, as well as the dynamics and timescales of magmagenesis and metamorphism. Numerous studies document the characteristics of zircon hosted by continental and MORB-related rocks, but the characteristics of zircon generated in magmas from oceanic hotspots are relatively unknown. We present the trace element and O-isotope compositions of Hawaiian zircon from gabbroic and dioritic xenoliths sampled by Holocene basalts at Hualalai volcano. The plutonic zircon yield U-Pb and 238U-230Th ages of ca. 250 ka and 40 ka and grew from intrusions of highly fractionated alkalic magma lodged at >10 km depths (Shamberger & Hammer, 2006; Vazquez et al., 2007). Individual Hualalai zircon are euhedral to anhedral with inclusions of feldspars, pyroxenes, and trachytic glass. Zoning apparent in cathodoluminescence images is generally indistinct, but a significant minority of crystals has rims with relatively high luminescence. Ion microprobe analyses of individual zircon crystals reveal trace element zoning that generally correlates with luminescence. Up to 20-fold variation in HREE concentrations, with overall positive correlation between Eu/Eu* and Ti and inverse correlation between Hf and Ti, characterize Hualalai zircon. These relations are similar to those reported for zircon from some felsic suites related by cooling-induced fractionation. Luminescent rims have relatively low REE, Hf, and Y, but have Ti concentrations like their corresponding interiors. Ti-in-zircon thermometry yields temperatures between 800-1000°C after adjustments for sub-unity TiO2 and SiO2 activities using silicate-oxide equilibria. These temperatures are generally consistent with temperatures derived from two-feldspar and glass-pyroxene pairs included by single zircon crystals. Despite compositional differences, zircon interiors and luminescent rims yield 238U-230Th

  4. Stable Isotopic Variations of a Stalagmite from Belum Cave, India: Potential for Monsoon Reconstruction

    NASA Astrophysics Data System (ADS)

    Allu, N. C.; Tiwari, M.; Yadava, M. G.; Nguyen, D. C.; Shen, C.; Belangaonkar, S. P.; Ramesh, R.

    2011-12-01

    Speleothems, known to record environmental changes on land, are important palaeoclimatic archives for the terrestrial environment as they possess a remarkably accurate dating potential. The climatic proxies that can be deciphered from speleothems are stable isotope composition (δ18O, δ13C), organic (humic) matter, growth rate, and trace element composition, as well as luminescent laminae, which may display annual rhythms. In the present work, we have studied speleothems from a new semi-arid region in southern India for exploring their potential for reconstructing monsoon history during the last interglacial-glacial transition. The study area is the Belum caves, Andhra Pradesh. A 54 cm long fossil stalagmite was investigated for oxygen and carbon isotope (δ18O, δ13C) compositions. Results from radiocarbon dating method indicate that the stalagmite is older than 40 kyr. Its age interval obtained by U-Th dating method vary from 41 kyr to 158 kyr. Average values δ18O and δ13C, observed along the growth direction, are -5.8 and -5.3 %, respectively. The variations in δ13C are within ~-7.3 to -4.3 %, and for δ18O from -7.1 to -3.9 %. The isotopic values are unlike the other caves in Indian region. While δ18O values are similar, 13C is more enriched. This indicates that the dripping of water could be relatively slower during the growth of the Belum stalagmite and interactions between regional aquifers.

  5. 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.

  6. 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.

  7. Oxygen isotope systematics of gem corundum deposits in Madagascar: relevance for their geological origin

    NASA Astrophysics Data System (ADS)

    Giuliani, Gaston; Fallick, Anthony; Rakotondrazafy, Michel; Ohnenstetter, Daniel; Andriamamonjy, Alfred; Ralantoarison, Théogène; Rakotosamizanany, Saholy; Razanatseheno, Marie; Offant, Yohann; Garnier, Virginie; Dunaigre, Christian; Schwarz, Dietmar; Mercier, Alain; Ratrimo, Voahangy; Ralison, Bruno

    2007-02-01

    comparison with oxygen isotope data obtained on gem corundum from Eastern Africa, India, and Sri Lanka is presented. Giant placer deposits from Sri Lanka, Madagascar, and Tanzania have a large variety of colored sapphires and rubies with a large variation in δ18O due to mingling of corundum of different origin: mafic and ultramafic rocks for ruby, desilicated pegmatites for blue sapphire, syenite for yellow, green, and blue sapphire, and skarn in marbles for blue sapphire.

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

  10. Theoretical and Experimental Approaches to Understanding the Anomalous Distribution of Oxygen Isotopes in the Solar System

    NASA Astrophysics Data System (ADS)

    Dominguez, Gerardo; Christensen, Elizabeth; Boyer, Charisa; Park, Manesseh; Benitez, Ezra; Nunn, Morgan; Thiemens, Mark H.; Jackson, Terri

    2016-06-01

    Decades of careful laboratory analysis of primitive meteorites have revealed an intriguing and unexplained pattern in the distribution of oxygen isotopes in the solar system. With the recent analysis of solar wind oxygen by NASA’s Genesis mission, it appears that the Sun has a distinct oxygen isotopic composition from the terrestrial planets, asteroids, and comets. These differences cannot be explained by mass-dependent diffusion and require a physical-chemical mechanism or mechanisms that separate oxygen isotopes in a non-mass dependent manner.Several hypothesis have been proposed to explain the anomalous distribution. Photochemical self-shielding of CO may explain the anomalous distribution, however, this mechanism has key weaknesses including the requirement of a very fine tuned timescale to explain the isotopic differences between the Sun and bulk of the terrestrial planets. Recently, attention has been directed at understanding specific chemical reactions that occur on interstellar dust grains due to their similarities with non-equilibrium photochemical reactions believed to be responsible for the mass-independent isotopic fractionation patterns observed in Earth’s atmosphere. A specific focus has been directed towards understanding the formation of H2O because some of its precursor (HO2, and O3) are well-known to acquire mass-independent isotopic signatures when formed in the gas-phase.In this presentation, I describe a series of laboratory astrophysical experiments whose goal is to understand the distribution of oxygen isotopes in the solar system and perhaps, by extension, the distribution in other planetary systems. Preliminary results for the isotopic composition of O3 formed at 5K will be presented as well as the first, to our knowledge, measurements of the isotopic composition of H2O (18O/16O, 17O/16O, D/H) formed at 32K. We find that H2O formed in the astrophysical conditions we simulated acquired an anomalous isotopic composition with a triple-oxygen

  11. 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

  12. Atmospheric Oxygen Variation Over the Last 100 Million Years

    NASA Astrophysics Data System (ADS)

    Watson, A. J.; Mills, B.; Daines, S. J.; Lenton, T. M.; Belcher, C.

    2014-12-01

    There is no agreement over how atmospheric oxygen has varied over recent Earth history. Our knowledge of past O2 concentrations relies on biogeochemical modelling, constrained by geochemical data and proxies. There are however few direct indicators of oxygen concentrations, though the presence of fossil charcoal indicates that levels have not strayed outside the "fire window", say below 16% or above 35%, during the last hundred million years. Different model predictions encompass both decreasing and increasing trends over this period however. These predictions are sensitive to weathering of continental rocks, which provide a sink for O2, but also a supply of phosphorus and sediment to the ocean, both of which increase carbon burial and thereby provide an oxygen source. Here we update our COPSE model with a more detailed treatment than hitherto, incorporating new input data, seafloor weathering processes, and different compositions and weatherability of granites and basalts. Our model suggests a broadly declining O2 trend over the late Mesozoic to present. An alternative forcing uses the phosphorus deposition curve of Follmi (1995), which is constructed from P measurements in ocean cores, and indicates P fluxes to the oceans that have varied over time by two orders of magnitude. Used to drive the model this also results in a declining long-term trend for atmospheric O2 over the last hundred million years, but with dramatic shorter-term variations superposed on the trend. These however stay (just) within the "fire window" for oxygen concentrations, and can be tentatively related to the evolution of fire adaptations in plants.

  13. 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

  14. Oxygen and strontium isotopic studies of basaltic lavas from the Snake River plain, Idaho

    USGS Publications Warehouse

    Leeman, William P.; Whelan, Joseph F.

    1983-01-01

    The Snake Creek-Williams Canyon pluton of the southern Snake Range crops out over an area of about 30 km2, about 60 km southeast of Ely, Nev. This Jurassic intrusion displays large and systematic chemical and mineralogical zonation over a horizontal distance of 5 km. Major-element variations compare closely with Dalyls average andesite-dacite-rhyolite over an SiO2 range of 63 to 76 percent. For various reasons it was originally thought that assimilation played a dominant role in development of the Snake Creek-Williams Canyon pluton. However, based on modeling of more recently obtained trace element and isotopic data, we have concluded that the zonation is the result of in-situ fractional crystallization, with little assimilation at the level of crystallization. This report summarizes data available for each of the mineral species present in the zoned intrusion. Special attention has been paid to trends We present oxygen and strontium isotopic data for olivine tholeiites, evolved (that is, differentiated and (or) contaminated) lavas, rhyolites, and crustal- derived xenoliths from the Snake River Plain. These data show that the olivine tholeiites are fairly uniform in d80 (5.1 to 6.2) and 87Sr/86Sr (0.7056 to 0.7076) and reveal no correlation between these ratios. The tholeiites are considered representative of mantle-derived magmas that have not interacted significantly with crustal material or meteoric water. The evolved lavas display a wider range in d 80 (5.6 to 7.6) and 87Sr/86Sr (0.708 to 0.717) with positive correlations between these ratios in some suites but not in others. Crustal xenoliths have high and variable 8?Sr/86Sr (0.715 to 0.830) and d80 values that vary widely (6.7 to 9.2) and are a few permil greater than d80 values of the Snake River basalts. Thus, isotopic data for the evolved lavas are permissive of small degrees of contamination by crustal rocks similar to the most d80-depleted xenoliths. The d80 enrichments in some evolved lavas also are

  15. 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.

  16. 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.

  17. Astronomical Oxygen Isotopic Evidence for Supernova Enrichment of the Solar System Birth Environment

    NASA Astrophysics Data System (ADS)

    Young, Edward; Gounelle, M.; Smith, R. L.; Morris, M. R.; Pontoppidan, K. M.

    2010-01-01

    Ratios among [C16O], [C17O] and [C18O] from young stellar objects (YSOs) obtained by high-resolution infrared spectroscopy (CRIRES, NIRSPEC) suggest that the solar system is indeed unusual in its 18O/17O compared with the present-day Galaxy at a variety of scales of observation. Galactic chemical evolution (GCE) models suggest that 18O/17O is independent of time. A nearly constant Galactic 18O/17O with time is indicated by existing data showing a systematic variation in oxygen isotopologue ratios with distance from the Galactic center. In this context, we show that the disparity between present-day Galactic and solar 18O/17O is explained if the solar system was born in an environment enriched by type II supernovae from low-mass progenitors. Enrichment by ejecta from exploding B stars (not O stars) on the order of 1 % by mass can account for the enhancement in 18O/17O of the birth environment of the solar system compared with normal Galactic values. Analysis of the stochastic nature of star formation utilizing a well-known mass generation function shows that the parental molecular cloud complex that produced the solar system was proximal to a cluster composed of order 500 stars. Larger clusters produce SNe II with oxygen isotope ratios that are inconsistent with enhancement in 18O/17O. This cluster predated the solar system by approximately 10 to 30 Myrs. Enrichment by B star ejecta explains not only the anomalous 18O/17O of the solar system but also its anomalous Si isotopic composition and the former presence of extinct 60Fe.

  18. Strontium, Lead, and Oxygen Isotopic Signatures of Mid-Miocene Silicic Volcanism in Eastern Oregon

    NASA Astrophysics Data System (ADS)

    Hess, Emily Nancy

    Widespread, mid-Miocene rhyolite volcanism of eastern Oregon that are coeval or slightly postdate flood basalts of the Columbia River Basalt Province allows for mapping crustal domains using radiogenic and stable isotopes. Rhyolites are thought to be derived in large part by partial melting of the crust and thus yield direct information on the composition of the crust. Silicic volcanism is expressed in the form of numerous domes and tuffs exposed over a wide area (~300 km in N-S dimension and ~200 km in E-W dimension) west of the presumed craton boundary, which runs parallel but mostly east of the Oregon-Idaho state border as delineated by geophysical characteristics and isotopic transitions, including the 87Sr/86Sri =0.7060 line (MSL) and 87Sr/86Sri =0.7040 line (CSL). 87Sr/86Sri of twenty-seven silicic units are variable and some are high. Sr isotopic ratios are inconsistent with the location of the traditional MSL and CSL boundaries. A primary control on the 87Sr/86Sri isotope variations may reflect changes in the crustal make-up of Paleozoic accreted terranes of a particular area rather than arising from a westward-dipping decollement that moved cratonic lithosphere below accreted terranes in eastern Oregon. A secondary control on observed isotopic ratios may be related to the amount and composition of basalt involved in the generation of rhyolites. This could lead to higher or lower 87Sr/86Sri relative to the surrounding crust because de facto coeval mafic magmas of the Columbia River Basalt Group have a wide range of Sr isotopic signatures. While Pb isotope data is incomplete for all samples of this study, the available data indicate a significant range in Pb isotopes. Yet, data of individual regions tend to plot close to one another relative to the entire data distribution. Comparison of samples from this study in a more regional view indicates the samples generally fall within the previously defined lead isotope boundaries of the main-phase Columbia River

  19. 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.

  20. 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.

  1. 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

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    (Sus scrofa). Samples were analyzed between 5 and 7 times in order to reduce the analytical uncertainty to ±0.012-0.025‰. Our data confirm the prediction from mass balance that animals inherit a ∆17O signature from anomalous air O2. We have developed a detailed mass balance for mammals with respect to ∆17O. The mass balance considers the oxygen fluxes (drinking and food water, respired O2, metabolic water, excrements, evaporated water and exhaled CO2). The fractionation in δ18O and ∆17O (from associated β-value) was considered for each of the fluxes. The result is an allometric scaling model for ∆17O as function of log Mb. Predicted and measured data agree within the uncertainty of the model and the measurements, respectively. Small mammals with their high specific metabolic rate show the greatest portion of oxygen from air O2 in their body water and in their bones and teeth. With this approach, ∆17O of air O2 can be determined with an uncertainty in the range of 0.05-0.1‰. This is more precise than what can be obtained from analyses of terrigene sulfate. With well-preserved fossil material, it may be possible to determine ∆17O of air O2 beyond the time limit of ice core data. The high precision of our approach may allow identifying variations in ∆17O of air O2 between glacial and interglacial periods. With mammal material, we will construct a ∆17O-profile of tropospheric O2 back to the Palaeogene. Using the same approach with reptile apatite, we expect to be able to extend the database beyond the Cretaceous/Palaeogene boundary. Correct interpretation of ∆17O of biogenic apatite, however, requires knowledge of the metabolic parameters for the analyzed groups as well as the β-values for all isotope fractionation processes involved. [1] Luz B. et al. (1999) Nature, 400, 547-550. [2] Pack A. et al. (2007) Rapid Communications in Mass Spectrometry, 21, 3721-3728. [3] Rumble D. et al. (2007) Geochimica et Cosmochimica Acta, 71, 3592-3600. [4] Bao H

  3. Oxygen and carbon isotopic composition of limestones and dolomites, bikini and eniwetok atolls

    USGS Publications Warehouse

    Grant, Gross M.; Tracey, J.I., Jr.

    1966-01-01

    Aragonitic, unconxolidated sediments from the borings on the Eniwetok and Bikini atolls are isotopically identical with unaltered skeletal fragments, whereas the recrystallized limestones exhibit isotopic variations resulting from alteration in meteoric waters during periods of emergence. Dolomites and associated calcites are enriched in O18, perhaps because of interaction with hypersaline brines.

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Can isotopic variations in structural water of gypsum reveal paleoclimatic changes?

    NASA Astrophysics Data System (ADS)

    Gatti, E.; Bustos, D.; Coleman, M. L.

    2015-12-01

    Water of crystallization in gypsum can be used as paleo-environmental proxy to study large scale climatic variability in arid areas. This is because changes in the isotopic composition of water of crystallization are due to isotopic variations in the mother brine from which the mineral precipitated, and the brine isotopic composition is linked to evaporation processes and humidity. This is particularly important when the salts are the only traces left of the original water, i.e. in modern arid areas. This study aims to prove that the 2-D/18-O compositions of the water of crystallization extracted from successive precipitates or even different growth zones of natural gypsum (CaSO4·H2O) can reconstruct the evaporation history and paleo-humidity of the source water basin. The method was tested in a laboratory experiment that evaporated CaSO4 brines under controlled temperature and humidity conditions. The brine was left to evaporate for five days at two different humidities (45 and 75 RH%); subsequently, brines and precipitated gypsum were sampled at 24 hour intervals. In this way we simulated zoned growth of gypsum. The samples were then analyzed for oxygen and hydrogen isotopic composition using a Thermo Scientific TC/EA with modified column, coupled to a MAT 253 Thermo Finnigan mass spectrometer at JPL. If preliminary results validate the novel hypothesis that changes in mineral composition can reveal details of paleo-environmental conditions the theory will be tested on natural gypsum collected from selected areas in White Sands National Monument, New Mexico. The study is currently ongoing but the full dataset will be presented at the conference.

  13. Coupled variations in helium isotopes and fluid chemistry: Shoshone Geyser Basin, Yellowstone National Park

    SciTech Connect

    Hearn, E.H.; Kennedy, B.M. ); Truesdell, A.H. )

    1990-11-01

    Early studies of {sup 3}He/{sup 4}He variations in geothermal systems have generally attributed these fluctuations to either differences in the source of the magmatic {sup 3}He-rich helium or to local differences in the deep flux of magmatic {sup 3}He-rich helium. Kennedy et al, however, show that near-surface processes such as boiling and dilution may also drastically affect {sup 3}He/{sup 4}He ratios of geothermal vapors. Helium isotope ratios were determined for several hot springs at Shoshone Geyser Basin of Yellowstone National Park for this study, along with other noble gas data. Stable isotope data and water and gas chemistry data for each spring were also compiled. The water chemistry indicates that there is one deep, hot thermal water in the area which is mixing with dilute meteoric water that has entered the system at depth. Spring HCO{sub 3}{sup {minus}} concentrations correlate with {sup 3}He/{sup 4}He values, as in nearby Lower Geyser Basin. This correlation is attributed to variable amounts of deep dilution of thermal waters with a relatively cool water that inhibits boiling at depth, thus preventing the loss of CO{sub 2} and magmatic He in the most diluted samples. Oxygen and hydrogen isotope data also support a boiling and dilution model, but to produce the observed fractionations, the boiling event would have to be extensive, with steam loss at the surface, whereas the boiling that affected the helium isotope ratios was probably a small scale event with steam loss at depth. It is possible that deep boiling occurred in the basin and that small amounts of steam escaped along fractures at about 500 m below the surface while all subsequently produced steam was lost near or at the surface.

  14. Coupled variations in helium isotopes and fluid chemistry: Shoshone Geyser Basin, Yellowstone National Park

    USGS Publications Warehouse

    Hearn, E.H.; Kennedy, B.M.; Truesdell, A.H.

    1990-01-01

    Early studies of 3He/4He variations in geothermal systems have generally attributed these fluctuations to either differences in the source of the magmatic 3He-rich helium or to local differences in the deep flux of magmatic 3He-rich helium. Kennedy et al. (1987), however, show that near-surface processes such as boiling and dilution may also drastically affect 3He 4He ratios of geothermal vapors. Helium isotope ratios were determined for several hot springs at Shoshone Geyser Basin of Yellowstone National Park for this study, along with other noble gas data. Stable isotope data and water and gas chemistry data for each spring were also compiled. The water chemistry indicates that there is one deep, hot thermal water in the area which is mixing with dilute meteoric water that has entered the system at depth. Spring HCO3- concentrations correlate with 3He 4He values, as in nearby Lower Geyser Basin. This correlation is attributed to variable amounts of deep dilution of thermal waters with a relatively cool water that inhibits boiling at depth, thus preventing the loss of CO2 (and therefore HCO3-) and magmatic He in the most diluted samples. Oxygen and hydrogen isotope data also support a boiling and dilution model, but to produce the observed fractionations, the boiling event would have to be extensive, with steam loss at the surface, whereas the boiling that affected the helium isotope ratios was probably a small scale event with steam loss at depth. It is possible that deep boiling occurred in the basin and that small amounts of steam escaped along fractures at about 500 m below the surface while all subsequently produced steam was lost near or at the surface. ?? 1990.

  15. 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

  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. Seasonal variation of oxygen-18 in precipitation and surface water of the Poyang Lake Basin, China.

    PubMed

    Hu, Chunhua; Froehlich, Klaus; Zhou, Peng; Lou, Qian; Zeng, Simiao; Zhou, Wenbin

    2013-06-01

    Based on the monthly δ(18)O value measured over a hydrology period in precipitation, runoff of five tributaries and the main lake of the Poyang Lake Basin, combined with hydrological and meteorological data, the characteristics of δ(18)O in precipitation (δ(18)OPPT) and runoff (δ(18)OSUR) are discussed. The δ(18)OPPT and δ(18)OSUR values range from-2.75 to-14.12 ‰ (annual mean value=-7.13 ‰ ) and from-2.30 to-8.56 ‰, respectively. The seasonal variation of δ(18)OPPT is controlled by the air mass circulation in this region, which is dominated by the Asian summer monsoon and the Siberian High during winter. The correlation between the wet seasonal averages of δ(18)OSUR in runoff of the rivers and δ(18)OPPT of precipitation at the corresponding stations shows that in the Poyang Lake catchment area the river water consists of 23% direct runoff (precipitation) and 77% base flow (shallow groundwater). This high proportion of groundwater in the river runoff points to the prevalence of wetland conditions in the Poyang Lake catchment during rainy season. Considering the oxygen isotopic composition of the main body of Poyang Lake, no isotopic enrichment relative to river inflow was found during the rainy season with maximum expansion of the lake. Thus, evaporation causing isotopic enrichment is a minor component of the lake water balance in the rainy period. During dry season, a slight isotopic enrichment has been observed, which suggests a certain evaporative loss of lake water in that period. PMID:23473021

  18. 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

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

    PubMed Central

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

    2013-01-01

    The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth’s system are intricately linked to planetary scale processes, and precise characterization of the overall process requires a detailed understanding of the linkage between climate dynamics and the chemistry leading to the product sulfate. This paper reports a high-resolution, 22-y (1980–2002) record of the oxygen-triple isotopic composition of sulfate (SO4) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO4 aerosol is linked to the ozone variation in the tropical upper troposphere/lower stratosphere via the Ozone El-Niño Southern Oscillations (ENSO) Index (OEI). Higher ∆17O values (3.3‰, 4.5‰, and 4.2‰) were observed during the three largest ENSO events of the past 2 decades. Volcanic events inject significant quantities of SO4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and ∆17O = 3.3‰, OEI = 11 and ∆17O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that ∆17O of sulfate aerosols can record extreme phases of naturally occurring climate cycles, such as ENSOs, which couple variations in the ozone levels in the atmosphere and the hydrosphere via temperature driven changes in relative humidity levels. A longer term, higher resolution oxygen-triple isotope analysis of sulfate aerosols from ice cores, encompassing more ENSO periods, is required to reconstruct paleo-ENSO events and paleotropical ozone variations. PMID:23447567

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

    PubMed

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

    2013-10-29

    The ability of sulfate aerosols to reflect solar radiation and simultaneously act as cloud condensation nuclei renders them central players in the global climate system. The oxidation of S(IV) compounds and their transport as stable S(VI) in the Earth's system are intricately linked to planetary scale processes, and precise characterization of the overall process requires a detailed understanding of the linkage between climate dynamics and the chemistry leading to the product sulfate. This paper reports a high-resolution, 22-y (1980-2002) record of the oxygen-triple isotopic composition of sulfate (SO4) aerosols retrieved from a snow pit at the South Pole. Observed variation in the O-isotopic anomaly of SO4 aerosol is linked to the ozone variation in the tropical upper troposphere/lower stratosphere via the Ozone El-Niño Southern Oscillations (ENSO) Index (OEI). Higher (17)O values (3.3‰, 4.5‰, and 4.2‰) were observed during the three largest ENSO events of the past 2 decades. Volcanic events inject significant quantities of SO4 aerosol into the stratosphere, which are known to affect ENSO strength by modulating stratospheric ozone levels (OEI = 6 and (17)O = 3.3‰, OEI = 11 and (17)O = 4.5‰) and normal oxidative pathways. Our high-resolution data indicated that (17)O of sulfate aerosols can record extreme phases of naturally occurring climate cycles, such as ENSOs, which couple variations in the ozone levels in the atmosphere and the hydrosphere via temperature driven changes in relative humidity levels. A longer term, higher resolution oxygen-triple isotope analysis of sulfate aerosols from ice cores, encompassing more ENSO periods, is required to reconstruct paleo-ENSO events and paleotropical ozone variations. PMID:23447567

  1. 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

  2. A nebula setting as the origin for bulk chondrule Fe isotope variations in CV chondrites

    NASA Astrophysics Data System (ADS)

    Hezel, Dominik C.; Needham, Andrew W.; Armytage, Ros; Georg, Bastian; Abel, Richard L.; Kurahashi, Erika; Coles, Barry J.; Rehkämper, Mark; Russell, Sara S.

    2010-08-01

    We combined micro computer tomography with Fe and Si isotope measurements of Mokoia, Allende and Grosnaja chondrules. Ten Mokoia chondrules contain 0.9 to 11.8 vol.% opaque phases (metal + sulfide), and 6 Allende chondrules contain 0.0 to 6.6 vol.% opaque phases. Hence, the Fe isotope composition of many chondrules is dominated by the Fe isotope composition of their opaque phases. We studied Fe isotopes of 35 bulk chondrules. The range is different for each of the three meteorites studied and largest for Allende with δ56Fe ranging from - 0.82 to + 0.37‰. Six out of seven chondrules analysed for their Si isotope composition in Mokoia and Grosnaja have similar δ29Si of around - 0.12‰. One anomalous chondrule in Mokoia has a δ29Si of + 0.58‰. We exclude isotopically heterogeneous chondrule precursors and different isotopic chondrule reservoirs as the source of the observed Fe isotope variation among bulk chondrules. We conclude that the observed bulk chondrule Fe isotope variation is the result of evaporation and re-condensation processes in a nebula setting with high dust densities, required to explain the comparatively low isotope fractionations. Subsequent parent body alteration slightly overprinted this pre-accretionary Fe isotope variation.

  3. Deep drilling at the Siljan Ring impact structure: oxygen-isotope geochemistry of granite

    USGS Publications Warehouse

    Komor, S.C.; Valley, J.W.

    1990-01-01

    The Siljan Ring is a 362-Ma-old impact structure formed in 1700-Ma-old I-type granites. A 6.8-km-deep borehole provides a vertical profile through granites and isolated horizontal diabase sills. Fluid-inclusion thermometry, and oxygen-isotope compositions of vein quartz, granite, diabase, impact melt, and pseudotachylite, reveal a complex history of fluid activity in the Siljan Ring, much of which can be related to the meteorite impact. In granites from the deep borehole, ??18O values of matrix quartz increase with depth from near 8.0 at the surface to 9.5??? at 5760 m depth. In contrast, feldspar ??18O values decrease with depth from near 10 at the surface to 7.1??? at 5760 m, forming a pattern opposite to the one defined by quartz isotopic compositions. Values of ??18O for surface granites outside the impact structure are distinct from those in near-surface samples from the deep borehole. In the deep borehole, feldspar coloration varies from brick-red at the surface to white at 5760 m, and the abundances of crack-healing calcite and other secondary minerals decrease over the same interval. Superimposed on the overall decrease in alteration intensity with depth are localized fracture zones at 4662, 5415, and 6044 m depth that contain altered granites, and which provided pathways for deep penetration of surface water. The antithetic variation of quartz and feldspar ??18O values, which can be correlated with mineralogical evidence of alteration, provides evidence for interaction between rocks and impact-heated fluids (100-300?? C) in the upper 2 km of the pluton. Penetration of water to depths below 2 km was restricted by a general decrease in impact-fracturing with depth, and by a 60-m-thick diabase sill at 1500 m depth that may have been an aquitard. At depths below 4 km in the pluton, where water/rock ratios were low, oxygen isotopic compositions preserve evidence for limited high-temperature (>500?? C) exchange between alkali feldspar and fluids. The high

  4. Carbon, hydrogen, and oxygen isotope studies of the regional metamorphic complex at Naxos, Greece

    USGS Publications Warehouse

    Rye, R.O.; Schuiling, R.D.; Rye, D.M.; Jansen, J.B.H.

    1976-01-01

    At Naxos, Greece, a migmatite dome is surrounded by schists and marbles of decreasing metamorphic grade. Sillimanite, kyanite, biotite, chlorite, and glaucophane zones are recognized at successively greater distances from the migmatite dome. Quartz-muscovite and quartz-biotite oxygen isotope and mineralogie temperatures range from 350 to 700??C. The metamorphic complex can be divided into multiple schist-rich (including migmatites) and marblerich zones. The ??18O values of silicate minerals in migmatite and schist units and quartz segregations in the schist-rich zones decrease with increase in metamorphic grades. The calculated ??18OH2O values of the metamorphic fluids in the schist-rich zones decrease from about 15??? in the lower grades to an average of about 8.5??? in the migmatite. The ??D values of OH-minerals (muscovite, biotite, chlorite, and glaucophane) in the schist-rich zones also decrease with increase in grade. The calculated ??DH2O values for the metamorphic fluid decrease from -5??? in the glaucophane zone to an average of about -70??? in the migmatite. The ??D values of water in fluid inclusions in quartz segregations in the higher grade rocks are consistent with this trend. The??18O values of silicate minerals and quartz segregations in marble-rich zones are usually very large and were controlled by exchange with the adjacent marbles. The ??D values of the OH minerals in some marble-rich zones may reflect the value of water contained in the rocks prior to metamorphism. Detailed data on 20 marble units show systematic variations of ??18O values which depend upon metamorphic grade. Below the 540??C isograd very steep ??18O gradients at the margins and large ??18O values in the interior of the marbles indicate that oxygen isotope exchange with the adjacent schist units was usually limited to the margins of the marbles with more exchange occurring in the stratigraphic bottom than in the top margins. Above the 540??C isograd lower ??18O values occur in

  5. 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.

  6. Carbon Isotopic Composition Of Earlydiagenetic Methane: Variations With Sediments Depth

    NASA Astrophysics Data System (ADS)

    Jędrysek, Mariusz Orion; Hałas, Stanisław; Pieńkos, Tomasz

    2015-03-01

    We demonstrate the annual cycle of methane in fresh sediments of two lakes - Moszne (E Poland) and Skrzynka (W Poland). The vertical gradient in δ13C(CH4) values varied widely from about -4.5‰/(-1 m) in late summer 1993 to about +2.5‰/(-1 m) in late winter, in the uppermost sediment profiles of about 3-meters in length. These vertical variations apparently are not due to oxidation or temperature changes, but rather to the higher gradient of the downward decrease of production rates via the acetic acid fermen-tation pathway rather than via the CO2-H2 pathway. The production of methane and δ13C(CH4) values are the highest during summer while the lowest during winter, reflect-ed especially during surface sampling. The downward gradient of δ13C in winter, late autumn and, at greater depths, in late summer results from isotope enrichment of the residual pool of precursors of methane, predominantly CO2.

  7. Seasonal Variation in Stable Carbon and Nitrogen Isotope Values of Bats Reflect Environmental Baselines

    PubMed Central

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

    2015-01-01

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

  8. Partitioning evapotranspiration - Testing the Craig and Gordon model with field measurements of oxygen isotope ratios of evaporative fluxes

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

    Stable oxygen isotopes of water provide a valuable tracer for water movements within ecosystems and are used to estimate the contribution of transpiration to total ecosystem evapotranspiration (ft). We tested the Craig and Gordon equation against continuous field measurements of isotopic composition of evaporation and assessed the impact for partitioning evapotranspiration. Therefore, evaporation (E) and its isotopic signature (δ18OE) on bare soil plots, as well as evapotranspiration (ET) and its corresponding isotopic composition of (δ18OET) of an herbaceous layer was measured with a cavity ring-down spectrometer connected to a soil chamber on a field site in central Portugal. We quantified the variation in δ18OE arising from uncertainties in the determination of environmental input variables to the Craig and Gordon equation: the isotope signature (δ18Oe) and the temperature at the evaporating site (Te), and the kinetic fractionation factor (αk). We could hence quantify ft based on measured δ18OET, modeled δ18OE from observed soil water isotopic composition at the evaporating site (δ18Oe), and modeled δ18O of transpiration (δ18OT) from observed total soil water isotopic composition. Our results demonstrate that predicting δ18OE using the Craig and Gordon equation leads to good agreement with measured δ18OE given that the temperature and 18O isotope profiles of the soil are thoroughly characterized. However, modeled δ18OE is highly sensitive to changes in Te and δ18Oe as well as αk. This markedly affected the partition results of transpiration and evaporation from the total ET flux: The fraction of transpiration (ft) varied strongly using different formulations for αk and assuming steady or non-steady state transpiration. These findings provide a first comparison of laser-based and modeled isotopic compositions of evaporation based on the Craig and Gordon equation under field conditions. This is of special interest for studies using stable isotopes

  9. 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.

  10. 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

  11. 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.

  12. 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

  13. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    : (1) inadequate dissolved sulfide for quantitative thiomolybdate formation and capture of a seawater-like δ98Mo signature in sediments or (2) delivery of isotopically light Mo to sediments via a particulate Fe-Mn oxyhydroxide shuttle. A compilation of Mo isotope data from euxinic ORM suggests that there were transient episodes of extensive ocean oxygenation that break up intervals of less oxygenated oceans during late Neoproterozoic and early Paleozoic time. Hence, Member IV does not capture irreversible deep ocean oxygenation. Instead, complex ocean redox variations likely marked the transition from O2-deficient Proterozoic oceans to widely oxygenated later Phanerozoic oceans.

  15. 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.

  16. 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.

  17. Impact of Tibetan Plateau uplift on Asian climate and stable oxygen isotopes in precipitation

    NASA Astrophysics Data System (ADS)

    Botsyun, Svetlana; Sepulchre, Pierre; Risi, Camille; Donnadieu, Yannick

    2016-04-01

    Surface elevation provides crucial information for understanding both geodynamic mechanisms of Earth's interior and influence of mountains growth on climate. Stable oxygen isotopes paleoaltimetry is considered to be a very efficient technic for reconstruction of the elevation history of mountains belts, including Tibetan Plateau and the Himalayas. This method relies on the difference between δ18O of paleo-precipitation reconstructed using the natural archives, and modern measured values for the point of interest. However, stable-isotope paleoaltimetry is potentially hampered by the fact that the presumed constancy of altitude-δ18O relationships through time might not be valid and climate changes affects δ18O in precipitation. We use the isotope-equipped atmospheric general circulation model LMDZ-iso for modeling Asia climate variations and associated δ18O in precipitation linked with Himalayas and Tibetan Plateau uplift. Experiments with reduced height over the Tibetan Plateau and the Himalayas have been designed. For the purpose of understanding where and how simulated complex climatic changes linked with the growth of mountains affect δ18O in precipitation we develop a theoretical expression for the precipitation composition. Our results show that modifying Tibetan Plateau height alters large-scale atmospheric dynamics including monsoon circulation and subsidence and associated climate variables, namely temperature, precipitation, relative humidity and cloud cover. In turn, δ18O signal decomposition results show that the isotopic signature of rainfall is very sensitive to climate changes related with the growth of the Himalayas and Tibetan Plateau, notably changes in relative humidity and precipitation amount. Topography appears to be the main controlling factor for only 40{%} of the sites where previous paleoelevation studies have been performed. Change of moisture sources linked with Asian topography uplift is shown to be not sufficient to yield a strong

  18. Coupled Trace Element and Isotope Variations in Oceanic Basalts: Recycling Re-examined

    NASA Astrophysics Data System (ADS)

    Salters, V. J.

    2005-12-01

    In 1982 Hofmann and White (Nature, 295, p.363). proposed that the enriched mantle components found their origin in recycled crustal material and this theory had found wide acceptance. However, our recent Hf-isotope data in combination with Nd- and Pb-isotopes and trace element variations shows that in detail many variations are not consistent with the origin of the enriched endmembers being related to recycled crustal materials. Although the addition of the Hf-isotopes did not result in the recognition of additional mantle endmembers, the Hf-isotopes do test their modes of origin and now question whether crustal recycling is the dominant process that causes the enriched mantle endmembers. Hf-isotopes on the enriched basalts from the Koolau volcano on Hawaii have shown that the enriched Koolau endmember contains an ancient depleted lithosphere component and indicate that a recycled crustal component is not a dominant component. The existence of this depleted component is confirmed by the recognition of this component in the Os-Hf-isotope variations in the peridotite xenoliths. Hf-isotopes on Samoan basalts (EMII endmember) have confirmed the presence of depleted lithosphere in the source and the combined trace element and isotope variation also shows the recycling of crustal material is not the dominant process causing enriched mantle signatures. Walvis Ridge is the "type" locality for Enriched Mantle I compositions. We have determined the trace element and isotopic compositions of Walvis Ridge basalts to better determine the geochemical characteristics of the enriched mantle endmember which is thought to include a significant contribution from recycled pelagic sediments. Characteristic for pelagic sediment contribution is a shallow slope on a Hf-Nd isotope correlation diagram. However, Walvis forms one the steepest slopes being inconsistent with pelagic sediments. Furthermore, Walvis Ridge basalts have some of the highest La/Nb ratios, up to 1.6, which has been

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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).

  4. 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.

  5. 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.

  6. Lake Louise Water (USGS47): A new isotopic reference water for stable hydrogen and oxygen isotope measurements

    USGS Publications Warehouse

    Qi, Haiping; Lorenz, Jennifer M.; Coplen, Tyler B.; Tarbox, Lauren V.; Mayer, Bernhard; Taylor, Steve

    2014-01-01

    RESULTS: The δ2H and δ18O values of this reference water are –150.2 ± 0.5 ‰ and –19.80 ± 0.02 ‰, respectively, relative to VSMOW on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. CONCLUSION: This isotopic reference material, designated as USGS47, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and stable oxygen isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. "

  7. Multiple stable oxygen isotopic studies of atmospheric sulfate: A new quantitative way to understand sulfate formation processes in the atmosphere

    NASA Astrophysics Data System (ADS)

    Lee, Charles Chi-Woo

    2000-11-01

    Sulfate is an important trace species in the Earth's atmosphere because of its roles in numerous atmospheric processes. In addition to its inherent light-scattering properties, sulfate can serve as cloud condensation nucleus (CCN), affecting cloud formation as well as microphysical properties of clouds. Consequently, atmospheric sulfate species influence the global radiative energy balance. Sulfate is known to increase acidity of rainwater with negative consequences in both natural and urban environments. In addition, aerosol sulfate (<=2.5 μm) is respirable and poses a threat to human health as a potential carrier of toxic pollutants through the respiratory tract. Despite intense investigative effort, uncertainty regarding the relative significance of gas and aqueous phase oxidation pathways still remains. Acquisition of such information is important because the lifetime and transport of S(IV) species and sulfate aerosols are influenced by the oxidative pathways. In addition, sulfate formation processes affect the aerosol size distribution, which ultimately influences radiative properties of atmospheric aerosols. Therefore, the budgetary information of the sulfur cycle, as well as the radiative effects of sulfate on global climate variation, can be attained from better quantitative understanding of in situ sulfate formation processes in the atmosphere. Multiple stable oxygen isotopic studies of atmospheric sulfate are presented as a new tool to better comprehend the atmospheric sulfate formation processes. Coupled with isotopic studies, 35S radioactivity measurements have been utilized to assess contribution of sulfate from high altitude air masses. Atmospheric sulfate (aerosols and rainwater) samples have been collected from diverse environments. Laboratory experiments of gas and aqueous phase S(IV) oxidation by various oxidants, as well as biomass burning experiments, have also been conducted. The main isotopic results from these studies are as follows: (1

  8. 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

  9. 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.

  10. 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.

  11. 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.

  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. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Individual variation of isotopic niches in grazing and browsing desert ungulates.

    PubMed

    Lehmann, D; Mfune, J K E; Gewers, E; Brain, C; Voigt, C C

    2015-09-01

    Ungulates often adjust their diet when food availability varies over time. However, it is poorly understood when and to what extent individuals change their diet and, if they do so, if all individuals of a population occupy distinct or similar dietary niches. In the arid Namibian Kunene Region, we studied temporal variations of individual niches in grazing gemsbok (Oryx gazella gazella) and predominantly browsing springbok (Antidorcas marsupialis). We used variation in stable C and N isotope ratios of tail hair increments as proxies to estimate individual isotopic dietary niches and their temporal plasticity. Isotopic dietary niches of populations of the two species were mutually exclusive, but similar in breadth. Isotopic niche breadth of gemsbok was better explained by within-individual variation than by between-individual variation of stable isotope ratios, indicating that gemsbok individuals were facultative specialists in using isotopically distinct local food resources. In contrast, inter- and intra-individual variations contributed similarly to the isotopic niche breadth of the springbok population, suggesting a higher degree of individual isotopic segregation in a more generalist ungulate. In both species, between-individual variation was neither explained by changes in plant primary productivity, sex, geographical position nor by group size. Within species, individual dietary niches overlapped partially, suggesting that both populations included individuals with distinct isotopic dietary niches. Our study provides the first evidence for isotopic dietary niche segregation in individuals of two distinct desert ungulates. Similar, yet isotopically distinct dietary niches of individuals may facilitate partitioning of food resources and thus individual survival in desert ecosystems. PMID:25953117

  18. 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.

  19. Geochemical Variations in Paleoseeps Over Short Time Scales: Stable Isotope Results From the Panoche-Tumey Hills Paleoseep (PTHP), California

    NASA Astrophysics Data System (ADS)

    Sample, J. C.; Csar, A.; Schwartz, H.

    2007-12-01

    Fluctuations in fluids compositions over varying time scales are widely recognized from modern cold seep deposits. We present results from a detailed study of carbonate mineral proxies for fluid flow from the PTHP. This cold seep deposit extends for 20 km along strike and was fed by a system of sandstone injectites during its mid- Paleocene lifespan. We sampled carbonate-bearing portions of the seep horizons both laterally and vertically over an area of approximately 5 km2. We analyzed the elemental and stable isotopic chemistry to examine temporal variations. Carbonate occurrences include dolomite to low-Mg calcite mineralogies in matrix cements, cemented pipe structures, laminated carbonates (fossilized bacterial mats?), and carbonate veins. In all cases the direction of carbonate mineral growth can be determined. Previous work on bulk samples has yielded a range of δ13C of --54 to +3 ‰ and δ18O of --7 to +7 ‰ (all values VPDB). Our more detailed sampling shows a smaller range, but significant variation of isotopic results over mm's to cm's (δ13C values vary in individual features from as much as --28.19 to +3.58 ‰; δ18O values from --8.68 to +4.71 ‰). Sequential sampling by micromilling of transects across carbonate infill show the greatest range in carbon isotopes. Individual transects show ranges in carbon isotopes minimum and maximum of 4.8 and 29.7 ‰, respectively. Oxygen isotopes vary less - from 4.1 to 10.1 ‰ for different transects. The influence of meteoric diagenesis on the oxygen is difficult to constrain well. Coupled with carbonate and sulfate/sulfide mineralogy, the variations in isotopic compositions can be related to fine-scale variations in microchemical environments, perhaps due to repeated changes in the chemistry of fluids fluxing through the features examined. Given the age range of the seep horizon, and the size of individual carbonate features, we estimate that total cementation times of individual features, and hence fluid

  20. High resolution Early Jurassic (Sinemurian-Early Pliensbachian) isotope variation, Dorset UK

    NASA Astrophysics Data System (ADS)

    Price, Gregory; Baker, Sarah; VanDeVelde, Justin; Clemence, Marie-Emilie

    2016-04-01

    We present a high-resolution carbon and oxygen isotope record for the Early Jurassic based on well-preserved marine molluscs (belemnites) from Dorset, UK. Our new data show a number of carbon isotope excursions, starting with the Sinemurian-Pliensbachian boundary Event followed by lesser negative excursions showing in the Polymorphous, Jamesoni and Masseanum-Valdani Subzones. The recognition of the Sinemurian-Pliensbachian boundary Event in this study and elsewhere suggests that observed carbon-isotope trends are likely to represent a supra regional or global perturbation of the carbon cycle. A prominent positive carbon isotope event is also seen within the Pliensbachian Ibex Zone. This event is also clearly evident in the data from belemnites from Spain, but rather puzzlingly not within carbon isotope records derived from bulk carbonate from Portugal. This carbon isotope excursion is not, however, coincident with inferred peak temperatures. The oxygen isotope and Mg/Ca data allows the determination of 2 pronounced Pliensbachian cool events within the Taylori and Brevispina Subzones. From the low point in the Brevispina Subzone, oxygen isotopes become more negative coupled with an increase in Mg/Ca values culminating in an Early Pliensbachian thermal maximum during the Davoei Zone. Taken with existing data it appears that the Pliensbachian is characterised by 2 major warmings, firstly within the Davoei Zone followed by warming beginning in the latest Pliensbachian and peaking in the Early Toarcian.

  1. Oxygen and strontium isotope studies of K-rich volcanic rocks from the Alban Hills, Italy

    NASA Astrophysics Data System (ADS)

    Ferrara, G.; Laurenzi, M. A.; Taylor, H. P.; Tonarini, S.; Turi, B.

    1985-09-01

    18O/ 16O and 87Sr/ 86Sr ratios and major and trace element contents were measured for 33 leucite-bearing lavas from the Alban Hills, located just south of Rome. Petrologically, this volcanic center is the least complex of all the Pleistocene to Holocene volcanoes in the Roman Comagmatic Province, and the 87Sr/ 86Sr uniformity reflects this (0.71024-0.71091). Whole-rock δ 18O = +5.6 to +9.8, but many samples were enriched in 18O by post-eruption hydration, evidenced by the good correlation between H 2O content (up to 5 wt. %) and δ 18O . Correcting for these effects, we obtain a δ 18O range of +5.6 to +7.8 for the original magmas. No other volcanic center in the Roman Province displays such uniform strontium and oxygen isotopic compositions; thus, this volcano provides special insight into the origin of the High-K Series magma end-member in Central Italy. Three groups of lavas are recognized on 87Sr/ 86Sr-1/Sr, δ 18O- 87Sr/ 86Sr , and K 2O-SiO 2 graphs; all of these groups, as well as the major caldera-forming eruption (Villa Senni Tuff), are derived from a very uniform, LIL-enriched, metasomatized source in the upper mantle. This source had δ 18O = +6.5 ± 1.0 and 87Sr/ 86Sr= 0.71030 ± 0.00010 . The δ 18O values correlate positively with 87Sr/ 86Sr , indicating minor interaction with the continental crust. Essentially all chemical and isotopic variations in the primitive (low-SiO 2, high-Ca, high-Sr) potassic lavas in Italy can be explained by mixing in the upper mantle between this Alban Hills end-member and a Low-K Series Roccamonfina-type end-member.

  2. Multiple oxygen and sulfur isotope compositions of atmospheric sulfate in Baton Rouge, LA, USA

    NASA Astrophysics Data System (ADS)

    Jenkins, Kathryn A.; Bao, Huiming

    Secondary atmospheric sulfates (SAS) is the ultimate oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. Their presence in the atmosphere as aqueous or solid phases contributes to acid rain and climate change, thus, understanding SAS formation pathways is pertinent. There has been extensive measurement of δ34S values for SAS, which mainly aimed at source identification. Relatively fewer oxygen isotope compositions ( δ18O, Δ 17O), which are most useful for resolving competing oxidation pathways, were available, however. This study represents the first effort to characterize the Δ 17O, δ18O, and δ34S simultaneously for SAS in a tropospheric air shed. We measured a total of 20 samples collected in Baton Rouge (LA, USA) during a 600-day period. The isotope compositions for atmospheric sulfate range from +0.25‰ to +1.43‰ for Δ 17O, +11.8‰ to +19.3‰ for δ18O, and -1.4‰ to +3.8‰ for δ34S. No apparent correlation is found among Δ 17O, δ18O, or δ34S values. The Δ 17O has no seasonal variation and its values are consistent with an oxidation pathway dominated by aqueous H 2O 2. The δ18O and δ34S are within the range of those observed in other sites around the world and are not characteristic for Baton Rouge. Despite the huge variability in atmospheric condition among mid-latitude sites, the long-term average Δ 17O value for SAS appears to fall within a fairly narrow range from +0.6‰ to +0.8‰, which is ˜1‰ to 2‰ lower than those in polar sites.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  4. Analysis of the hydrogen and oxygen stable isotope ratios of beverage waters without prior water extraction using isotope ratio infrared spectroscopy.

    PubMed

    Chesson, Lesley A; Bowen, Gabriel J; Ehleringer, James R

    2010-11-15

    Hydrogen (δ(2)H) and oxygen (δ(18)O) stable isotope analysis is useful when tracing the origin of water in beverages, but traditional analytical techniques are limited to pure or extracted waters. We measured the isotopic composition of extracted beverage water using both isotope ratio infrared spectroscopy (IRIS; specifically, wavelength-scanned cavity ring-down spectroscopy) and isotope ratio mass spectrometry (IRMS). We also analyzed beer, sodas, juices, and milk 'as is' using IRIS. For IRIS analysis, four sequential injections of each sample were measured and data were corrected for sample-to-sample memory using injections (a) 1-4, (b) 2-4, and (c) 3-4. The variation between δ(2)H and δ(18)O values calculated using the three correction methods was larger for unextracted (i.e., complex) beverages than for waters. The memory correction was smallest when using injections 3-4. Beverage water δ(2)H and δ(18)O values generally fit the Global Meteoric Water Line, with the exception of water from fruit juices. The beverage water stable isotope ratios measured using IRIS agreed well with the IRMS data and fit 1:1 lines, with the exception of sodas and juices (δ(2)H values) and beers (δ(18)O values). The δ(2)H and δ(18)O values of waters extracted from beer, soda, juice, and milk were correlated with complex beverage δ(2)H and δ(18)O values (r = 0.998 and 0.997, respectively) and generally fit 1:1 lines. We conclude that it is possible to analyze complex beverages, without water extraction, using IRIS although caution is needed when analyzing beverages containing sugars, which can clog the syringe and increase memory, or alcohol, a known spectral interference. PMID:20941769

  5. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia.

    PubMed

    Baur, M E; Hayes, J M; Studley, S A; Walter, M R

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron. PMID:11539027

  6. Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

    NASA Technical Reports Server (NTRS)

    Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

    1985-01-01

    Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

  7. 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

  8. 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

  9. 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].

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

    NASA Astrophysics Data System (ADS)

    Yde, Jacob C.; Knudsen, Niels T.; Steffensen, Jørgen P.; Carrivick, Jonathan L.; Hasholt, Bent; Ingeman-Nielsen, Thomas; Kronborg, Christian; Larsen, Nicolaj K.; Mernild, Sebastian H.; Oerter, Hans; Roberts, David H.; Russell, Andrew J.

    2016-03-01

    Analysis of stable oxygen isotope (δ18O) characteristics is a useful tool to investigate water provenance in glacier river systems. In order to attain knowledge on the diversity of δ18O variations in Greenlandic rivers, we examined two contrasting glacierised catchments disconnected from the Greenland Ice Sheet (GrIS). At the Mittivakkat Gletscher river, a small river draining a local temperate glacier in southeast Greenland, diurnal oscillations in δ18O occurred with a 3 h time lag to the diurnal oscillations in run-off. The mean annual δ18O was -14.68 ± 0.18 ‰ during the peak flow period. A hydrograph separation analysis revealed that the ice melt component constituted 82 ± 5 % of the total run-off and dominated the observed variations during peak flow in August 2004. The snowmelt component peaked between 10:00 and 13:00 local time, reflecting the long travel time and an inefficient distributed subglacial drainage network in the upper part of the glacier. At the Kuannersuit Glacier river on the island Qeqertarsuaq in west Greenland, the δ18O characteristics were examined after the major 1995-1998 glacier surge event. The mean annual δ18O was -19.47 ± 0.55 ‰. Despite large spatial variations in the δ18O values of glacier ice on the newly formed glacier tongue, there were no diurnal oscillations in the bulk meltwater emanating from the glacier in the post-surge years. This is likely a consequence of a tortuous subglacial drainage system consisting of linked cavities, which formed during the surge event. Overall, a comparison of the δ18O compositions from glacial river water in Greenland shows distinct differences between water draining local glaciers and ice caps (between -23.0 and -13.7 ‰) and the GrIS (between -29.9 and -23.2 ‰). This study demonstrates that water isotope analyses can be used to obtain important information on water sources and the subglacial drainage system structure that is highly desired for understanding glacier hydrology.

  11. 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.

  12. Zn isotopes in the suspended load of the Seine River, France: Isotopic variations and source determination

    NASA Astrophysics Data System (ADS)

    Chen, JiuBin; Gaillardet, Jérôme; Louvat, Pascale; Huon, Sylvain

    2009-07-01

    We report Zn isotopic ratios (δ 66Zn) of river suspended particulate matter (SPM) and floodplain deposits (FD) from the Seine basin, France, with a precision ⩽0.05‰. A decrease in δ 66Zn from 0.30‰ to 0.08‰ is observed in SPM from the upstream to downstream parts of the fluvial system, associated with an increase in Zn concentration from 100 ppm to 400 ppm. The Zn/Al of SPM at the river mouth is up to five times greater than the Zn/Al of the natural background, and by normalizing to the later value we define a Zn enrichment factor. Suspended sediments from a temporal series of samples collected in Paris display a similar variation in δ 66Zn of between 0.08‰ and 0.26‰, while showing an inverse relationship between the Zn enrichment factor and δ 66Zn. The amount of Zn transported as suspended load varies from 10% to 90%, as a function of increasing discharge. The δ 66Zn of SPM and the dissolved load are correlated, suggesting that adsorption processes are probably not the dominant process by which the Zn enrichment of SPM takes place. Instead, we interpret our data as reflecting the mixture of two main populations of suspended particles with distinct δ 66Zn. The first is characteristic of natural silicate particles transported by erosion processes to the river, while the second likely represents anthropogenic particles derived from wastewater treatment plants or combined sewer overflows. Based on isotopic ratios, we calculate that 70% of Zn in SPM of the Seine River in Paris is of anthropogenic origin.

  13. Lead isotope variation with growth zoning in a galena crystal

    USGS Publications Warehouse

    Cannon, R.S., Jr.; Pierce, A.P.; Delevaux, M.H.

    1963-01-01

    A large crystal of lead sulfide from Picher, Oklahoma, has significant differences in isotopic composition of lead in successive growth zones. Lead isotope ratios in the parent ore-fluid evidently changed with time during crystal growth. The growth history of this crystal, interpreted quantitatively, points to a tentative hypothesis of genesis of Mississippi Valley deposits of lead and zinc.

  14. Chlorine isotope variations across the Izu-Bonin-Mariana arc

    NASA Astrophysics Data System (ADS)

    Barnes, Jaime D.; Sharp, Zachary D.; Fischer, Tobias P.

    2008-11-01

    Chlorine isotope ratios were determined for volcanic gas, geothermalwell, ash, and lava samples along the Izu-Bonin-Mariana volcanicfront, serpentinite clasts and muds from serpentine seamounts(Conical, South Chamorro, Torishima), basalts from the Guguancross-chain, and sediments from Ocean Drilling Program (ODP)Sites 800, 801, 802, and 1149. There is no systematic variationin {delta}37Cl values along the volcanic front in either gas or ashsamples. In contrast, distinct variations occur across the arc,implying variations in the fluid source at different depthswithin the subduction zone. Serpentinite clasts and serpentinemuds from the seamounts tap a source of 30 km depth and have{delta}37Cl values of structurally bound chloride of +0.4{per thousand} ±0.4{per thousand} (n = 24), identical to most seafloor serpentinites, suggestinga serpentinite (chrysotile and/or lizardite to antigorite transition)fluid source. Tapping deeper levels of the subduction zone ( 115-130km depth), volcanic gases and ashes have {delta}37Cl values averaging-1.1{per thousand} ± 1.0{per thousand} (n = 29), precisely overlapping therange measured in sediments from ODP cores (-1.1{per thousand} ±+0.7{per thousand}, n = 11) and limited altered oceanic crust (AOC). Bothsediments and AOC are possible Cl sources in the volcanic front.The Guguan cross-chain basalts come from the greatest depthsand have an average {delta}37Cl value of +0.2{per thousand} ± 0.2{per thousand</p>
      </li>

      <li>
      <p><a target=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.

  15. Intraseasonal isotopic variation associated with the Madden-Julian Oscillation

    NASA Astrophysics Data System (ADS)

    Kurita, Naoyuki; Noone, David; Risi, Camille; Schmidt, Gavin A.; Yamada, Hiroyuki; Yoneyama, Kunio

    2011-12-01

    The Madden-Julian Oscillation (MJO) is the dominant mode of intraseasonal variability in the tropical atmosphere. This study examines the evolution of the hydrologic regime from before the onset of the MJO (pre-onset period) to the MJO onset period, using deuterated water vapor (HDO) measurements from the Tropospheric Emission Spectrometer (TES) and from ground-based stations. Ground-based observations reveal a clear transition between high HDO/H2O isotope ratios during the pre-onset period to a period of repeated abrupt decreases in the HDO/H2O isotope ratio associated with intense convection. Each observed minimum in the HDO/H2O ratio corresponded to a maximum in stratiform rainfall fraction, which was derived independently from radar precipitation coverage area. The ground-based observations are consistent with the satellite observations of the HDO/H2O ratio. In order to attribute the mechanisms that bring about the isotopic changes within the MJO convection, an isotope-enabled general circulation model (GCM) constrained by observed meteorological fields was used to simulate this MJO period. The GCM reproduced many of the observed isotopic features that accompanied the onset of an MJO. After the development of deep convection, large-scale stratiform cloud cover appears, and isotope ratios respond, as a consequence of diffusive exchange between stratiform raindrops and the surrounding vapor. In this diffusive exchange process, heavy isotopes tend to become enriched in precipitation and depleted in the surrounding vapor, and thus successive stratiform rainfall results in decreasing isotope values in the middle and lower troposphere. On the basis of these characteristics, isotope tracers can be used to partition stratiform and convective rainfall from observed isotope data and to validate the simulated proportions of convective/stratiform rainfall.

  16. 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.

  17. ODP Site 1063 (Bermuda Rise) revisited: Oxygen isotopes, excursions and paleointensity in the Brunhes Chron

    NASA Astrophysics Data System (ADS)

    Channell, J. E.; Hodell, D. A.

    2011-12-01

    An age model for the Brunhes Chron for Ocean Drilling Program (ODP) Site 1063 (Bermuda Rise) is based on the tandem correlation of oxygen isotope and relative paleointensity data to calibrated reference templates. Four intervals in the Brunhes Chron where component inclinations are negative, for both u-channel samples and discrete samples, are correlated to the following magnetic excursions with Site 1063 ages in brackets: Laschamp (41 ka), Blake (116 ka), Iceland Basin (190 ka), Pringle Falls (239 ka). These ages are consistent with current age estimates for these excursion, other than for "Pringle Falls" which has an apparent age older than current estimates by ~20-30 kyrs. For each of these excursions, virtual geomagnetic poles (VGPs) reach high southerly latitudes implying paired polarity reversals in a brief time span (<2 kyr in each case) that is several times shorter than the observed duration of long-lived polarity transitions at mid-latitudes. Several intervals of low component inclinations, that are low and negative in one case, are observed both in u-channel and discrete samples at ~318 ka (MIS 9), ~413 ka (MIS 11) and in the 500-600 ka interval (MIS14-15). These may constitute inadequately recorded excursions, or high amplitude secular variation.

  18. ODP Site 1063 (Bermuda Rise) revisited: Oxygen isotopes, excursions and paleointensity in the Brunhes Chron

    NASA Astrophysics Data System (ADS)

    Channell, J. E. T.; Hodell, D. A.; Curtis, J. H.

    2012-02-01

    An age model for the Brunhes Chron of Ocean Drilling Program (ODP) Site 1063 (Bermuda Rise) is constructed by tandem correlation of oxygen isotope and relative paleointensity data to calibrated reference templates. Four intervals in the Brunhes Chron where paleomagnetic inclinations are negative for both u-channel samples and discrete samples are correlated to the following magnetic excursions with Site 1063 ages in brackets: Laschamp (41 ka), Blake (116 ka), Iceland Basin (190 ka), Pringle Falls (239 ka). These ages are consistent with current age estimates for three of these excursions, but not for "Pringle Falls" which has an apparent age older than a recently published estimate by ˜28 kyr. For each of these excursions (termed Category 1 excursions), virtual geomagnetic poles (VGPs) reach high southerly latitudes implying paired polarity reversals of the Earth's main dipole field, that apparently occurred in a brief time span (<2 kyr in each case), several times shorter than the apparent duration of regular polarity transitions. In addition, several intervals of low paleomagnetic inclination (low and negative in one case) are observed both in u-channel and discrete samples at ˜318 ka (MIS 9), ˜412 ka (MIS 11) and in the 500-600 ka interval (MIS 14-15). These "Category 2" excursions may constitute inadequately recorded (Category 1) excursions, or high amplitude secular variation.

  19. Oxygen and hydrogen isotopes in thermal waters at Zunil, Guatemala

    SciTech Connect

    Fournier, R.O.; Hanshaw, B.B.; Urrutia Sole, J.F.

    1982-10-01

    Enthalpy-chloride relations suggest that a deep reservoir exists at Zunil with a temperature near 300/sup 0/C. Water from that reservoir moves to shallower and cooler local reservoirs, where it mixes with diluted water and then attains a new water-rock chemical equilibrium. This mixed water, in turn, generally is further diluted before being discharged from thermal springs. The stable-isotopic composition of the thermal water indicates that recharge for the deep water at Zunil comes mainly from local sources. The presence of measurable tritium, which suggests that the deep water has been underground about 20 to 30 years, also indicates a local source for the recharge.

  1. Enzymatic Glucose Sensor Compensation for Variations in Ambient Oxygen Concentration

    PubMed Central

    Collier, Bradley B.; McShane, Michael J.

    2014-01-01

    Due to the increasing prevalence of diabetes, research toward painless glucose sensing continues. Oxygen sensitive phosphors with glucose oxidase (GOx) can be used to determine glucose levels indirectly by monitoring oxygen consumption. This is an attractive combination because of its speed and specificity. Packaging these molecules together in “smart materials” for implantation will enable non-invasive glucose monitoring. As glucose levels increase, oxygen levels decrease; consequently, the luminescence intensity and lifetime of the phosphor increase. Although the response of the sensor is dependent on glucose concentration, the ambient oxygen concentration also plays a key role. This could lead to inaccurate glucose readings and increase the risk of hyper- or hypoglycemia. To mitigate this risk, the dependence of hydrogel glucose sensor response on oxygen levels was investigated and compensation methods explored. Sensors were calibrated at different oxygen concentrations using a single generic logistic equation, such that trends in oxygen-dependence were determined as varying parameters in the equation. Each parameter was found to be a function of oxygen concentration, such that the correct glucose calibration equation can be calculated if the oxygen level is known. Accuracy of compensation will be determined by developing an overall calibration, using both glucose and oxygen sensors in parallel, correcting for oxygen fluctuations in real time by intentionally varying oxygen, and calculating the error in actual and predicted glucose levels. While this method was developed for compensation of enzymatic glucose sensors, in principle it can also be implemented with other kinds of sensors utilizing oxidases. PMID:26257458

  2. Cryogenic separation of oxygen-argon mixture in natural air samples for isotopic and molecular ratios

    NASA Astrophysics Data System (ADS)

    Habeeb Rahman, Keedakkadan; Abe, Osamu

    2014-05-01

    The discovery of mass independent isotope fractionation in oxygen during the formation of ozone in the stratosphere has initiated a wide application in isotope geochemistry field. Separation of oxygen-argon mixture has become the foundation of high precision analysis of Δ17O and δ(O2/Ar) for geochemical applications. Here we present precise and simplified cryogenic separation of argon oxygen mixture from the atmospheric and dissolved air using 30/60 mesh 5A molecular sieve zeolite. A pioneer study of this method was conducted by Thiemens and Meagher in 1984. The column which is made of glass tube contains about 1.1 grams of molecular sieve zeolite and both ends of column was filled with glass wools. The experimental set up was tested for different combination of molecular sieves and slurry temperatures. We found the most efficient condition for the separation was at a column temperature of -103°C. For complete transfer of O2 and Ar mixture usually takes in 15-20 minutes time. The isotopic ratios of oxygen were analyzed using mass spectrometer (Thermo Fischer Delta Plus) relative to reference oxygen-argon mixture at 3V of m/z 32 for both sample and reference side. The signals of m/z 28, 32, and 40 were measured by dynamically to determine oxygen -argon ratio and to check nitrogen contamination. Repeated measurements of atmospheric air yielded a reproducibility (SE n=80) of 0.006, 0.004 and 0.19‰ for δ17O, δ18O and δO2/Ar respectively. The isotopic and molecular fractionation of argon- oxygen mixture during gas adsorption and desorption while using molecular sieve under liquid nitrogen temperature was studied. We have established a linear relationship governing the effect of 13X and 5A molecular sieves on molecular fractionation. And suggested the use of single 1/8" pellet 13X molecular sieve provided a negligible fractionation.

  3. Oxygen and carbon isotope geochemistry of the Krivoy rog iron formation, Ukranian SSR

    NASA Astrophysics Data System (ADS)

    Perry, E. C.; Ahmad, S. N.

    1981-04-01

    Oxygen and carbon isotope analyses of samples from three mines in the Krivoy Rog iron formation, Ukranian SSR, are reported here. Maximum and minimum quartz-magnetite fractionation values ( Δ QM) and inferred temperature range in degrees centrigrade for each mine are:

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

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

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

  6. Stable Carbon and Oxygen Isotope Ratios of Otoliths Differentiate Winter Flounder (Pseudopleuonectes americanus) Habitats

    EPA Science Inventory

    Stable carbon (13C) and oxygen (18O) isotope ratios were measured in otoliths of juvenile winter flounder (Pseudopleuronectes americanus) collected from 18 nursery areas along the coast of Rhode Island, USA. Samples were obtained during June and July of 2002 from locations tha...

  7. OXYGEN ISOTOPES IN ATMOSPHERIC SULFATES, SULFUR DIOXIDE, AND WATER VAPORS FIELD MEASUREMENTS, JULY 1975

    EPA Science Inventory

    Oxygen isotope ratios were determined for atmospheric samples of sulfate aerosols, sulfur dioxide, and water vapor collected simultaneously during a six-day period in July, 1975, at St. Louis, MO; Auburn, IL; and Glasgow, IL. The collection sites were located about 100km apart. C...

  8. Stabel Carbon and Oxygen Isotope Ratios of Otoliths from Juvenile and Adult Winter Flounder

    EPA Science Inventory

    This study was designed to determine if stable carbon (13C) and oxygen (18O) isotope ratios in otoliths could be used to differentiate the locations that serve as important nursery areas for winter flounder along the Rhode Island, USA coastline. In recent years the populations ...

  9. 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

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

    NASA Technical Reports Server (NTRS)

    Kaye, J. A.

    1986-01-01

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

  11. Oxygen isotope composition of sulfate produced during microbial sulfur oxidation: A pathway-specific fingerprint?

    NASA Astrophysics Data System (ADS)

    Pjevac, P.; Brunner, B.; Mußmann, M.

    2012-04-01

    The oxidation of zero-valent sulfur such as elemental sulfur (S0) is an important energy source in many marine habitats including deep-sea vents, pelagic redox-clines and coastal surface sediments. Many microorganisms oxidize elemental sulfur to sulfate to gain reducing power. This transformation is catalyzed by a few known enzymatic pathways such as the reverse dissimilatory sulfite reductase (rDSR)-aprAB/Sor pathway or the Sox multienzyme pathway. The isotopic composition of oxygen and sulfur in produced sulfate (δ34S and δ18O) is determined by the isotope composition of the reactants, the ratio between forward and backward fluxes of enzymatically catalyzed reaction steps, and by kinetic and equilibrium isotopic fractionation. We hypothesize that the activity of distinct oxidation pathways is reflected in different δ34S and particularly, in unique δ18O isotopic fingerprints in the produced sulfate. To test our hypothesis we grew pure cultures of photo- and chemoautotrophic sulfur-oxidizing microorganisms of different phylogenetic origin with S0 as sole source of reducing power and determined the sulfur and oxygen isotope composition of the produced sulfate. The identification of characteristic isotope fingerprints for each sulfur oxidation pathway could serve as a tool to estimate and deduce the importance of certain enzymatic pathways and sulfur-oxidizing microorganisms in the environment.

  12. Radii and Binding Energies in Oxygen Isotopes: A Challenge for Nuclear Forces.

    PubMed

    Lapoux, V; Somà, V; Barbieri, C; Hergert, H; Holt, J D; Stroberg, S R

    2016-07-29

    We present a systematic study of both nuclear radii and binding energies in (even) oxygen isotopes from the valley of stability to the neutron drip line. Both charge and matter radii are compared to state-of-the-art ab initio calculations along with binding energy systematics. Experimental matter radii are obtained through a complete evaluation of the available elastic proton scattering data of oxygen isotopes. We show that, in spite of a good reproduction of binding energies, ab initio calculations with conventional nuclear interactions derived within chiral effective field theory fail to provide a realistic description of charge and matter radii. A novel version of two- and three-nucleon forces leads to considerable improvement of the simultaneous description of the three observables for stable isotopes but shows deficiencies for the most neutron-rich systems. Thus, crucial challenges related to the development of nuclear interactions remain. PMID:27517768

  13. Oxygen isotope composition of modern pedogenic carbonate from the southern margin of the Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Breecker, D.; Sharp, Z.; Newell, D.; Jessup, M.; Cottle, J.

    2007-12-01

    Oxygen-isotope paleoelevation estimates of large plateaus provide important geodynamic constraints on the teconic evolution of orogenic systems as well as offering insight into the dynamic feedbacks between surface uplift and regional- to global-scale climate systems. If the isotopic lapse rate (δ18O vs elevation) is known, then the oxygen isotope composition of ancient meteoric water can be used to estimate paleoelevation. The oxygen isotope composition of pedogenic carbonate preserved in paleosols has been used as a proxy for the oxygen isotope composition of soil water in order to reconstruct paleoelevation in a number of settings. Isotopic equilibrium between carbonate and water is assumed in order to calculate the δ18O value of soil water from measured δ18O values of pedogenic carbonate (δ18Opc). Uncertainties surrounding the temperature of isotopic equilibrium and the degree of evaporation of soil water limit the precision of elevation estimates from pedogenic carbonate. In this study, measurements of the oxygen isotope composition of pedogenic carbonate forming in modern soils from the Mt. Everest Region of Tibet are compared with modern meteoric water δ18O values (δ18Omw) to calibrate δ18Opc as a proxy for elevation. Pedogenic carbonate samples coating the underside of clasts were collected along depth profiles in soils at different elevations ranging from 3750 - 5200m on the southern margin of the Tibetan Plateau. Incipient soils developing in the lowest and presumably youngest river terraces were chosen for δ18Opc measurements because these are the most likely to have formed under the influence of modern precipitation. The oxygen isotope composition of modern spring and stream waters along the Bhote Kosi and Arun River were also measured in this study and agree well with previously published elevation- δ18Omw relationships for the Himalayas. Average δ18Opc values below 50 cm in the modern soils were used to calculate equilibrium δ18Omw values

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

    PubMed

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

    2011-06-24

    All planetary materials sampled thus far vary in their relative abundance of the major isotope of oxygen, (16)O, such that it has not been possible to define a primordial solar system composition. We measured the oxygen isotopic composition of solar wind captured and returned to Earth by NASA's Genesis mission. Our results demonstrate that the Sun is highly enriched in (16)O relative to the Earth, Moon, Mars, and bulk meteorites. Because the solar photosphere preserves the average isotopic composition of the solar system for elements heavier than lithium, we conclude that essentially all rocky materials in the inner solar system were enriched in (17)O and (18)O, relative to (16)O, by ~7%, probably via non-mass-dependent chemistry before accretion of the first planetesimals. PMID:21700868

  15. 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

  16. Radii and Binding Energies in Oxygen Isotopes: A Challenge for Nuclear Forces

    NASA Astrophysics Data System (ADS)

    Lapoux, V.; Somà, V.; Barbieri, C.; Hergert, H.; Holt, J. D.; Stroberg, S. R.

    2016-07-01

    We present a systematic study of both nuclear radii and binding energies in (even) oxygen isotopes from the valley of stability to the neutron drip line. Both charge and matter radii are compared to state-of-the-art ab initio calculations along with binding energy systematics. Experimental matter radii are obtained through a complete evaluation of the available elastic proton scattering data of oxygen isotopes. We show that, in spite of a good reproduction of binding energies, ab initio calculations with conventional nuclear interactions derived within chiral effective field theory fail to provide a realistic description of charge and matter radii. A novel version of two- and three-nucleon forces leads to considerable improvement of the simultaneous description of the three observables for stable isotopes but shows deficiencies for the most neutron-rich systems. Thus, crucial challenges related to the development of nuclear interactions remain.

  17. The oxygen isotopic compositions of silica phytoliths and plant water in grasses: implications for the study of paleoclimate

    NASA Astrophysics Data System (ADS)

    Webb, Elizabeth A.; Longstaffe, Frederick J.

    2000-03-01

    Information about climatic conditions during plant growth is preserved by the oxygen-isotope composition of biogenic silica (phytoliths) deposited in grasses. The oxygen-isotope composition of phytolith silica is dependent on soil-water δ 18O values, relative humidity and evapotranspiration, and temperature during plant growth. Phytolith and plant-water δ 18O values for C3 ( A. breviligulata) and C4 ( C. longifolia) grasses from natural and greenhouse sites in southwestern Ontario were used to compare the isotopic fractionation between biogenic silica and water in various parts of these living plants. For non or weakly transpiring tissues (rhizomes, stems, sheaths) in both grass species, the Δ 18O silica-plant water remained constant at ˜34‰, and the δ 18O and δD values of plant water collected from pre-dawn and mid-day samplings showed little variation. These plant waters were only slightly enriched in 18O and D relative to water provided to the grasses. Isotopic temperatures calculated from the silica and plant-water isotopic data matched measured growing temperatures for the region. By comparison, the upper leaf water was extremely enriched in oxygen-18 and deuterium at maximum rates of transpiration relative to water from non-transpiring tissues, as were the calculated, steady-state values for leaf-water δ 18O and δD. Silica produced in the transpiring tissues (leaf, inflorescence) has higher δ 18O values than silica from non-transpiring tissues, but the enrichment is modest compared to upper leaf water under mid-day conditions. Leaf phytoliths have formed from plant water typical of average conditions in the lower leaf, where the extreme 18O-enrichment is not encountered. C. longifolia was also collected from Alberta and Nebraska, where growing conditions are different from southwestern Ontario. Phytoliths at all three sites have a similar pattern of δ 18O values within the plants, but the isotopic separation between leaf and stem silica increases

  18. 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

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

    NASA Technical Reports Server (NTRS)

    Yurimoto, H; Abe, M.; Ebihara, M.; Fujimura, A.; Hashizume, K.; Ireland, T. R.; Itoh, S.; Kawaguchi, K.; Kitajima, F.; Mukai, T.; Nagao, K.; Nakamura, T.; Naraoka, H.; Noguchi, T.; Okazaki, R.; Sakamoto, N.; Seto, Y.; Tsuchiyama, A.; Uesugi, M.; Yada, T.; Yoshikawa, M.; Zolensky, M.

    2011-01-01

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

  20. Oxygen and carbon isotopic study on the genesis of the Steirischer Erzberg siderite deposit (Austria)

    NASA Astrophysics Data System (ADS)

    Laube, N.; Frimmel, H. E.; Hoernes, S.

    1995-06-01

    The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The δ 18O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6‰ (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in δ 18O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average δ 13C-value of the carbonate host is +0.5 ± 1.2‰ (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower δ 13C-values, on average -1.4 ± 0.8‰ (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower δ 13C-values of -4.2 ± 0.6‰ and-4.7 ± 0.7‰, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average δ 13C-value of -2.9 ± 0.7‰, and matrix siderite/ankerite an average value of-4.1 ± 0.4‰. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.

  1. Oxygen Isotopic Analyses of Water in Bjurböle Matrix and Chondrules

    NASA Astrophysics Data System (ADS)

    Nunn, M.; Thiemens, M. H.

    2011-12-01

    Past oxygen isotopic analyses of the Bjurböle meteorite have been limited to whole rock and chondrule studies. We present here the first oxygen isotopic measurements of water contained in the matrix and chondrules of the L4 equilibrated ordinary chondrite Bjurböle. Water was extracted by vacuum pyrolysis from samples of separated matrix and chondrules from Bjurböle. A new, low volume, ultra low blank system was built specifically for these measurements. Each fraction was pumped overnight on a vacuum line to remove as much adsorbed terrestrial water as possible before heating step-wise to 150, 350, 600 and 1000°C. While heating, evaporated volatiles were collected in a liquid nitrogen cold trap. Water was quantitatively converted to molecular oxygen with bromine pentafluoride. Isotopic abundances were measured on a double-collecting isotope ratio mass spectrometer. The Δ 17O values obtained from direct fluorination of Bjurböle chondrules and whole rock and UV laser probe analyses of individual Bjurböle chondrules all cluster around one [1, 2]. Compared to these data, water extracted from the Bjurböle matrix and chondrules is isotopically light (Δ 17O = 0.5 and 0.7, respectively), presumably reflecting different equilibration histories of water and oxygen-bearing minerals in each component. Additionally, the proximity of Δ 17O values of water extracted at lower temperatures to zero indicates low-temperature heating is necessary to remove all adsorbed terrestrial water and obtain the true isotopic signature of extraterrestrial water.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    PubMed Central

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

    2013-01-01

    To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003−2005 at Alert station, Canada (82°30′N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ17O and δ18O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λMDF(H2O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003−2005. An oxygen isotopic anomaly of Δ17O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ17O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930−1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ17O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l'Environnement, Gif sur Yvette, France, had 17Oexcess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water. PMID:24009339

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

    PubMed

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

    2013-09-24

    To identify the possible anomalous oxygen isotope signature in stratospheric water predicted by model studies, 25 water vapor samples were collected in 2003-2005 at Alert station, Canada (82°30'N), where there is downward transport of stratospheric air to the polar troposphere, and were analyzed for δ(17)O and δ(18)O relative to Chicago local precipitation (CLP). The latter was chosen as a reference because the relatively large evaporative moisture source should erase any possible oxygen isotope anomaly from the stratosphere. A mass-dependent fractionation coefficient for meteoric waters, λMDF(H2O) = 0.529 ± 0.003 [2σ standard error (SE)], was determined from 27 CLP samples collected in 2003-2005. An oxygen isotopic anomaly of Δ(17)O = 76 ± 16 ppm (2σ SE) was found in water vapor samples from Alert relative to CLP. We propose that the positive oxygen isotope anomalies observed at Alert originated from stratospheric ozone, were transferred to water in the stratosphere, and subsequently mixed with tropospheric water at high latitudes as the stratospheric air descended into the troposphere. On the basis of this ground signal, the average Δ(17)O in stratospheric water vapor predicted by a steady-state box model is ∼40‰. Seven ice core samples (1930-1991) from Dasuopu glacier (Himalayas, China) and Standard Light Antarctic Precipitation did not show an obvious oxygen isotope anomaly, and Vienna Standard Mean Ocean Water exhibited a negative Δ(17)O relative to CLP. Six Alert snow samples collected in March 2011 and measured at Laboratoire des Sciences du Climat et de l'Environnement, Gif sur Yvette, France, had (17)Oexcess of 45 ± 5 ppm (2σ SE) relative to Vienna Standard Mean Ocean Water. PMID:24009339