Sample records for stalagmite oxygen isotope

  1. Carbon and oxygen isotope records and paleoclimate reconstruction (140-250 ka B.P.) from a stalagmite of Shuinan Cave, Guilin, China (United States)

    Meiliang, Zhang; Hai, Cheng; Daoxian, Yuan; Xiaoyan, Zhu; Yushi, Lin; Jiaming, Qin; Edwards, R. L.


    The time sequence of paleoclimatic changes from 245.2 to 147.9 ka B.P. has been established by high precision U-series dating by Thermal Ionization Mass Spectrometry and the analysis of the oxygen isotopes from a stalagmite of Shuinan Cave in Guilin. The oxygen isotope pattern is divided into three main intervals. The top part of the stalagmite (interval C) displays mainly relatively heavy oxygen isotopes, mostly -7 to -5‰VPDB, but at a depth of 86.5 cm below the top, there is a sharp change to values lighter than -8 ‰. This boundary, dated at 192.6 ±3.9 ka B.P. is correlated with the boundary between marine oxygen isotope stages 6 and 7. The underlying interval B has δ18O values consistently between -7.5 and -8.5‰ until 271 cm depth when there is a sharp rise in δ18O values towards values as heavy as -5‰. The upper position of this change is dated at 242.5±6.4 ka B.P. and is correlated with the boundary between marine isotope stages 7 and 8. Carbon isotope values lie between -8.5 and -11‰ and are not uniquely high or low in the three intervals, but also show rapid changes at the boundaries between intervals in the same sense as the shifts in δ18O. The pronounced shifts in δ18O are attributed to changes in the paleo-monsoon intensity which reflect major reorganizations of the climate system, but some regional characteristics are also present. The results are also consistent with previous studies of climate proxies from loess-palaesol sequences in northern China. These characteristics show that paleo-climate evolution since the late stage of the middle Pleistocene Epoch in the Guilin area not only follows the global characteristics, but also has the strong district or regional patterns.

  2. Comparison of Meteorological Data and Stable Isotope Time Series from an Indonesian Stalagmite (United States)

    Watanabe, Y.; Matsuoka, H.; Sakai, S.; Ueda, J.; Yamada, M.; Ohsawa, S.; Kiguchi, M.; Satomura, T.; Nakai, S.; Brahmantyo, B.; Maryunani, K. A.; Tagami, T.; Takemura, K.; Yoden, S.


    In the last decade, geochemical records in stalagmites have been widely recognized as a powerful tool for the elucidation of paleoclimate/environment of the terrestrial areas. The previous data are mainly reported from middle latitude. However, this study aims at reconstructing past climate variations in the Asian equatorial regions by using oxygen and carbon isotope ratios recorded in Indonesian stalagmites. Especially, we focused on the comparison of meteorological data and stable isotope time series from an Indonesia stalagmite, in order to check whether the geochemistry of stalagmite is influenced by local precipitation. We performed geological surveys in Buniayu limestone caves, Sukabumi, West Java, Indonesia, and collected a series of stalagmites/stalactites and drip water samples. A stalagmite sample was observed using thin sections to identify banding. Moreover, to construct the age model of the stalagmite, we also measured both (1) the number of bands and (2) uranium series disequilibrium ages using the MC-ICP-MS. These data suggest that each layer is annual banding dominantly. Oxygen and carbon isotope ratios were analyzed on the stalagmite for annual time scales. The carbon isotope ratio has a clear correlation with oxygen isotope ratios. Furthermore, the proxy data was compared with meteorological data set in the past 80 years, showing a good correlation between the temporal variation of oxygen/carbon isotope ratios and annual precipitation. These lines of evidence suggest that the isotopic variation is predominantly caused by kinetic mass fractionation driven by the degassing of carbon dioxide in the cave.

  3. Connection of the Oxygen Isotope in Stalagmites from East Asia with the Large Scale Atmospheric-Oceanic Patterns (United States)

    Li, S.; Jing, Y.; Luo, F.; Wan, J.


    Cave stalagmites δ18O is associated with climate, but the specific climatic meaning of East Asian stalagmites δ18O remains unclear. Several recent researches suggest that East Asian stalagmites δ18O represents neither surface air temperature nor precipitation, but an integral variation of Asian monsoon circulation systems. It reflects a ratio of different water vapor sources. Since large-scale atmospheric-oceanic patterns such as Atlantic Multidecadal Oscillation (AMO), Pacific Decadal Oscillation (PDO) and North Atlantic Oscillation (NAO) show significant effects on the Asian monsoon circulation systems, in this work we explored the relationships between these atmospheric-oceanic patterns and the East Asian stalagmites δ18O during the last three centuries by using several reconstructed dataets together with instrumental records. Considering the human activities exert extraordinary impacts on climate, we compared the two separated periods, before and after the industrial revolution. The results show significant lead-lag connections between the East Asian stalagmites δ18O and the large-scale atmospheric-oceanic patterns. One positive correlation peaks when PDO leads the East Asian stalagmites δ18O by 3 years. This PDO-stalagmite connection is robust through the whole recent centuries. In comparison, the relations between AMO, NAO and the East Asian stalagmites δ18O exhibit significant differences in the post-industrial period and the pre-industrial period. Thus, the East Asian stalagmites δ18O may be a reflector of the signals of PDO.

  4. Isotope hydrology of dripwaters in a Scottish cave and implications for stalagmite palaeoclimate research

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    L. Fuller


    Full Text Available Dripwater hydrology and hydrogeochemistry is particularly useful in constraining the meaning of speleothem palaeoclimate archives, for example using δ18O signatures. Here, we calibrate the relationship between δ18O in precipitation, percolation waters and contemporary calcite deposits, at Tartair cave, Sutherland, NW Scotland, an Atlantic site sensitive to regional changes both of temperature and precipitation. Monthly precipitation displayed a 7.1‰ range in δ18O, a negative linear relationship with rainfall amount, and no correlation with temperature. Autogenically-derived cave percolation waters show little variation in δ18O during the same period and their annual weighted mean is the same as that of the local precipitation. This evidence together with hydrological data and electroconductivity values indicates that percolation waters are well mixed and dominated by stored water. Calculated values of δ18O of calcite deposited in this cave environment indicate that the cave deposits are forming close to isotopic equilibrium and kinetic effects are negligible. Comparison of a high-resolution δ18O stalagmite record with the instrumental record of climate indicates that isotopically heavy values are reflective of relatively cold, dry conditions (and vice-versa for warm, wet condition and hence that stalagmite oxygen isotopes provide an appropriate means of investigating the palaeoclimate in this location.

  5. Climate and human impacts on vegetation changes in central Guizhou, China: Carbon and oxygen isotopic records in a stalagmite from Yelang Cave (United States)

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


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

  6. Peloponnesian Stalagmites and Soda Straw Stalactites as Climate Archives : Stable Isotopes in New Speleothem Material from Kapsia Cave, Peloponnese, Greece


    Haking, Linn


    This study presents results from stable isotope analyses of a modern stalagmite and three soda straw stalactites from Kapsia Cave, the Peloponnese, Greece. The resulting values from the stalagmite are put into context of local meteorological data, as well as previous research from Kapsia Cave. The potential for using soda straw stalactites as complementary climate archives on shorter time scales on the Peloponnese is also explored. The isotopic values in the stalagmite confirm a strong link t...

  7. Kinetic fractionation processes recorded in the stalagmites of some limestone caves in Korea (United States)

    Woo, K. S.; Jo, K.; Edwards, L. R.; Cheng, H.; Wang, Y.; Yoon, H.


    Stable isotope data (oxygen and carbon) of carbonate minerals (mostly calcite, but sometimes aragonite) in stalagmites have been the most commonly and widely used proxies for paleoclimatic research. This is based upon the assumption that carbonate minerals precipitated in isotopic equilibrium with dripping waters from stalactites, thus should reflect paleoclimatic variations. The state of equilibrium, so called "Hendy Test", has been commonly used. Hendy (1971) showed that during kinetic fractionation both oxygen and carbon isotopes behaves in a similar way due to faster degassing rate of cabon dioxide, resulting in the enrichment of both isotopes. The stalagmites from three limestone caves (Gwaneum, Eden and Daeya Caves) in Korea were investigated to understand the effects of kinetic fractionation during their growth. The stalagmites are mostly composed of columnar calcites, but contains the layers of cave coral that is composed of fibrous calcite. The cave coral layers should have grown when the supply rate of dripping water decreased significantly. Stable isotope pattern in three stalagmites do not show the same pattern of disequilibrium process. The cave corals in the Eden stalagmite show the enriched carbon and oxygen isotope values (15 and 5 per mil, respectively) that has the same bimodal pattern as suggested by Hendy (1971). However, the cave corals in the Gwaneum stalagmites show the enriched carbon, but depleted oxygen isotope values (3 and 1 per mil, respectively). Also, the calcite layer precipitated in disequilibrium in the Daeya stalagmite show more enriched carbon isotope values by up to 6 per mil, but show more or less the same oxygen isotopic values, compared to the columnar calcite which was precipitated in equilibrium. Therefore, caution should be made to determine the state of equilibrium precipitation of carbonate minerals in stalagmites. The "Hendy Test" may not be the only solution because other types of speleothems can be formed in

  8. Last glacial and Holocene stable isotope record of fossil dripwater from subtropical Brazil based on analysis of fluid inclusions in stalagmites

    NARCIS (Netherlands)

    Millo, Christian; Strikis, Nicolás M.; Vonhof, Hubert B.; Deininger, Michael; da Cruz, Francisco W.; Wang, Xianfeng; Cheng, Hai; Lawrence Edwards, R.


    The stable isotope composition of fossil dripwater preserved in stalagmites fluid inclusions is a promising tool to reconstruct paleopluviosity in the tropics and subtropics. Here we present δD and δ18O records of fossil dripwater from two stalagmites collected in Botuverá Cave (subtropical Brazil),

  9. New on-line method for water isotope analysis of fluid inclusions in speleothems using laser absorption spectroscopy: Application to stalagmites from Borneo and Switzerland (United States)

    Affolter, Stéphane; Fleitmann, Dominik; Nele Meckler, Anna; Leuenberger, Markus


    Speleothems are recognised as key continental archives for paleoclimate reconstructions. They contain fluid inclusions representing past drip water trapped in the calcite structure. Speleothem can be precisely dated and therefore the oxygen (δ18O) and hydrogen (δD) isotopes of fluid inclusions constitute powerful proxies for paleotemperature or to investigate changes in the moisture source over several interglacial-glacial cycles. To liberate fluid inclusion water and to analyse its isotopic composition, a new online extraction method developed at Bern is used. The principle can be summarised as follows: Prior to crushing, the sample is placed into a copper tube, fixed to the line previously heated to 140° C and flushed with a nitrogen and standard water mixture. Thereafter, the speleothem sample is crushed using a simple hydraulic crushing device and the released water from fluid inclusions is transferred by the nitrogen-standard water mixture flow to a Picarro L1102-i isotopic liquid water and water vapor analyser. The measuring principle is based on wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) technology that allows us to simultaneously monitor hydrogen and oxygen isotopes. Reproducibility of standard water measurements is typically better than 1.5 o for δD and 0.4 o for δ18O. With this method, we successfully analysed δD and δ18O isotopic composition of a stalagmite from Northern Borneo (tropical West Pacific) covering almost two glacial-interglacial cycles from MIS 12 to early MIS 9 (460-330 ka) as well as recent samples from Switzerland and Borneo. These results are used in combination with calcite δ18O to reconstruct paleotemperature. Currently, we are measuring a stalagmite from Milandre cave (Jura, Switzerland) covering the Bølling-Allerød, Younger Dryas cold phase and the Holocene.

  10. Stable isotope and trace element investigation of two contemporaneous annually-laminated stalagmites from northeastern China surrounding the "8.2 ka event"

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    J. Y. Wu


    Full Text Available The prominent "8.2 ka event" was well documented in the Greenland ice cores. It remains unclear, however, about its duration, structure and forcing mechanism at low- to mid-latitude regions. Here we use the physical and geochemical data of stalagmites from the Nuanhe Cave in Liaoning Province, northeastern China, to reconstruct a detailed history of East Asian monsoons covering the entire duration of the event. High-resolution chronologies of two contemporaneous stalagmites, each consisting of at least 770 yr annual growth bands, were established by calibrating and anchoring the floating band-counting ages against five high-precision 230Th dates. Two oxygen isotope profiles replicate each other on annual-decadal timescales despite their difference in growth rates, indicating that the δ18O variability has a climatic origin largely associated with changes in the rainfall δ18O from the West Pacific during summer season. A signal from the "8.2ka event" was faint in our δ18O records, not as significant as Indian monsoon dominated stalagmite δ18O records from Qunf in Oman and Dongge in Southern China. However, our δ13C and Ba/Ca profiles, as indicators of local environmental changes, provide strong support for a climate reversal centred at 8.2 ka BP, which is likely controlled by winter monsoon circulations via the westerly winds associated with North Atlantic climate. Therefore, we concluded that the winter- and summer-Asian monsoons responded independently to the high northern latitude climate.

  11. Paleoclimatological study using stalagmites from Java Island, Indonesia (United States)

    Watanabe, Y.; Matsuoka, H.; Ohsawa, S.; Yamada, M.; Kitaoka, K.; Kiguchi, M.; Ueda, J.; Yoshimura, K.; Kurisaki, K.; Nakai, S.; Brahmantyo, B.; Maryunani, K. A.; Tagami, T.; Takemura, K.; Yoden, S.


    In the last decade, decoding geochemical records in stalagmites has been widely recognized as a powerful tool for the elucidation of paleoclimate/environment of the terrestrial areas. The previous data are mainly reported from areas that are located in middle latitude. However, this study aims at reconstructing past climate variations in the Asian equatorial regions by using oxygen isotopes and other geochemical proxies recorded in Indonesian stalagmites.. Especially, we focus on the detection of the precipitation anomaly that reflects the El Niño Southern Oscillation (ENSO). We performed geological surveys in Buniayu limestone caves, Sukabumi, West Java, and Karangbolong, Central Java, Indonesia and collected a series of stalagmites/stalactites and drip water samples. Detailed textures of stalagmite samples were observed using thin sections to identify "annual" bandings. Moreover, we also measured both (1) annual luminescent banding that can be viewed by ultraviolet-light stimulation and (2) uranium series disequilibrium ages using the MC-ICP-MS for each stalagmite to construct the age model. We also carried out 3H-3He dating and stable isotope measurements of drip water samples to understand hydrogeology in study areas. Based on these frameworks, oxygen isotopes and other geochemical proxies will be analyzed for annual or sub-annual time scales. The proxy data will then be compared with meteorological data set, such as local precipitation, in the past 50 years. Finally, we will reconstruct for longer timescales the past climate, particularly the precipitation anomaly, in the region to detect ancient ENSO.

  12. Stalagmite δ18O Variability Records of ENSO-Controlled Rainfall From Niue Island, South Pacific (United States)

    Murgulet, V.; Aharon, P.


    Niue Island (19°00'S, 169°50'W), a large carbonate platform located at the edge of Pacific Warm Water Pool offers an ideal opportunity to reconstruct El Nino Southern Oscillation (ENSO) history by means of speleothems. Rainfall on Niue is primarily controlled by ENSO. Previously employed layer thickness proxy revealed that ENSO phenomenon is archived in stalagmites from Niue (Rasbury et al., 2006). Here we present a high resolution (sub-annual) δ18O profile from a stalagmite (ASM1) sampled in 2002 in a active growing position from a flank margin cave on Niue Island in order to test whether oxygen isotope composition of Niue stalagmites is a reliable proxy tool for detecting rainfall and ENSO variability. The stalagmite contains approximately 150 years of deposition and consists of sub-annual couplets alternating between thick, light calcite bands deposited during the austral summer and thin, dark calcite layers deposited during the austral dry winter. Comparison of ASM1 stalagmite δ18O with Niue annual rainfall generally shows an inverse relationship between oxygen isotope ratios and the amount of precipitation, with 18O depleted values reflecting higher rainfall. Conversely, 18O enriched values usually correspond with low rainfall. Because ENSO results in severe droughts on the island, Southern Oscillation Index (SOI) was also evaluated against ASM1 stalagmite δ18O. Not surprisingly, low SOI phases (ENSO events) coincide with more positive δ18O values. Thus, stalagmite δ18O of ASM1 represents a proxy tool for the amount of rainfall on Niue and ENSO variability. Ongoing research aims to derive an additional δ18 high resolution profile from a coeval stalagmite. Power spectra analysis of the δ18O profiles will be presented at the meeting. Reference: Rasbury, M., and P. Aharon (2006), ENSO-controlled rainfall variability records archived in tropical stalagmites from the mid-ocean island of Niue, South Pacific, Geochem. Geophys. Geosyst., 7, Q07010, doi:10

  13. Stalagmite water content as a proxy for drip water supply in tropical and subtropical areas

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    N. Vogel


    Full Text Available In this pilot study water was extracted from samples of two Holocene stalagmites from Socotra Island, Yemen, and one Eemian stalagmite from southern continental Yemen. The amount of water extracted per unit mass of stalagmite rock, termed "water yield" hereafter, serves as a measure of its total water content. Based on direct correlation plots of water yields and δ18Ocalcite and on regime shift analyses, we demonstrate that for the studied stalagmites the water yield records vary systematically with the corresponding oxygen isotopic compositions of the calcite (δ18Ocalcite. Within each stalagmite lower δ18Ocalcite values are accompanied by lower water yields and vice versa. The δ18Ocalcite records of the studied stalagmites have previously been interpreted to predominantly reflect the amount of rainfall in the area; thus, water yields can be linked to drip water supply. Higher, and therefore more continuous drip water supply caused by higher rainfall rates, supports homogeneous deposition of calcite with low porosity and therefore a small fraction of water-filled inclusions, resulting in low water yields of the respective samples. A reduction of drip water supply fosters irregular growth of calcite with higher porosity, leading to an increase of the fraction of water-filled inclusions and thus higher water yields. The results are consistent with the literature on stalagmite growth and supported by optical inspection of thin sections of our samples. We propose that for a stalagmite from a dry tropical or subtropical area, its water yield record represents a novel paleo-climate proxy recording changes in drip water supply, which can in turn be interpreted in terms of associated rainfall rates.

  14. Evolution of the isotope composition of C and O in the DIC in a water film during precipitation of calcite to the surface of a stalagmite in the presence of isotope exchange with the CO2 of the cave atmosphere and evaporation of the water (United States)

    Dreybrodt, Wolfgang; Romanov, Douchko


    In a thin water layer, super saturated with respect to calcite with pH of about 8, where the aqueous CO2 is in equilibrium with the pCO2 of the cave atmosphere, the following processes determine the temporal evolution of the isotope composition of carbon and oxygen in the dissolved inorganic carbon ( DIC). a) Precipitation of calcite driven by super saturation, whereby deposition rates Between the heavy and light isotopes are slightly different. b) Evaporation of water reducing the depth of the water layer and changing the isotope composition of oxygen in the water by Rayleigh-distillation. c) Isotope exchange between the CO2 in the cave atmosphere and the DIC for both carbon and oxygen. d) Isotope exchange between the oxygen in the water molecules and that in the DIC. All these processes can be described by a differential equation, which can be solved numerically. For small times a simple solution can be given. Δ_DIC(T_drip) = [ ( (⪉mbda + ɛ) C_eq/C0 - ɛ ) T_drip/τ + (δ^atm_eq - δ0 ) T_drip/τ^atm + (δ^water_eq-δ_0-ɛ_wT_drip/T_ev) T_drip/τ^water] Δ_DIC(T_drip) is the change of the δ13C and δ18O (given here as small numbers and not in the ‰ notation) after the drip time T_drip. ⪉mbda, ɛ are kinetic parameters of precipitation on the order of 10-2 and τ is the time scale of precipitation, typically about 1000 s. (δ^atm_eq - δ_0) and (δ^water_eq - δ_0) are the differences between the corresponding initial δ-value and that when DIC is in isotope equilibrium with the atmosphere or in the case of oxygen with the water. τ^atm and τ^water, both on the order of 10,000 s, are the time scales of the exchange reactions to approach isotope equilibrium. For carbon the last term (exchange with water) must be deleted. C_eq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. T_ev is the time needed to fully evaporate the water layer and

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

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    A. Wackerbarth


    Full Text Available Interpreting stable oxygen isotope18O records from stalagmites is still one of the complex tasks in speleothem research. Here, we present a novel model-based approach, where we force a model describing the processes and modifications of δ18O from rain water to speleothem calcite (Oxygen isotope Drip water and Stalagmite Model – ODSM with the results of a state-of-the-art atmospheric general circulation model enhanced by explicit isotope diagnostics (ECHAM5-wiso. The approach is neither climate nor cave-specific and allows an integrated assessment of the influence of different varying climate variables, e.g. temperature and precipitation amount, on the isotopic composition of drip water and speleothem calcite.

    First, we apply and evaluate this new approach under present-day climate conditions using observational data from seven caves from different geographical regions in Europe. Each of these caves provides measured δ18O values of drip water and speleothem calcite to which we compare our simulated isotope values. For six of the seven caves modeled δ18O values of drip water and speleothem calcite are in good agreement with observed values. The mismatch of the remaining caves might be caused by the complexity of the cave system, beyond the parameterizations included in our cave model.

    We then examine the response of the cave system to mid-Holocene (6000 yr before present, 6 ka climate conditions by forcing the ODSM with ECHAM5-wiso results from 6 ka simulations. For a set of twelve European caves, we compare the modeled mid-Holocene-to-modern difference in speleothem calcite δ18O to available measurements. We show that the general European changes are simulated well. However, local discrepancies are found, and might be explained either by a too low model resolution, complex local soil-atmosphere interactions affecting evapotranspiration or by cave specific factors

  16. Oxygen isotopes implanted in the LDEF spacecraft (United States)

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


    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.

  17. A Test of Fidelity from Century-Long Instrumental and Stalagmite Proxy Climate Records from Niue Island, South Pacific (United States)

    Aharon, P.; Pulehetoa, S.


    Niue Island, located in the tropical South Pacific (19°00'S, 169°50'W), offers exceptional opportunities to test the fidelity of stalagmite proxy climate records vis-à-vis instrumental records for the following reasons: (i) the former coral-atoll is uplifted and heavily karstified thus containing a large variety of highly decorated caves; (ii) reliable instrumental records of rainfall are available since 1905 and air temperature records since 1931; (iii) the island is located in the path of the South Pacific Convergence Zone (SPCZ), one of the most extensive global atmospheric feature linking the "warm pool" in the northwest to the "rain pool" in the southeast, and (iv) the isolation from major continental masses renders the island climate free of artifacts. Three coeval, actively forming, stalagmites were sampled from an isolated nook in the lowest chamber of the Avaiki flank-margin cave on the leeward site of Niue Island. The chronology of the calcite stalagmites was established on the basis of multiple counting of the growth bands and confirmed by multiple radiocarbon dates. Stable oxygen and carbon isotope analyses were performed at a subannual resolution of 0.25 yr. The longest stalagmite contains a 150 yrs record since 1853 thus overlapping with the island instrumental climate record for the last century. SPCZ position relates to El-Niño/Southern Oscillation (ENSO) on interannual time scale and to the Interdecadal Pacific Oscillation (IPO) on interdecadal time scale (15-30 yrs). Niue monthly rainfall anomaly (NMRA) and stalagmite-based oxygen isotopes time series (1906-2006) exhibit an excellent match with the South Pacific Index (SPI) describing the temporal shifts in SPCZ, and are coherent with the IPO warm (1978-1998) and cold (1958-1975) phases and importantly with the IPO prominent changeover that occurred in 1976-1977. The NMRA data show excellent agreement with the Southern Oscillation Index (SOI) periodicity of 3 to 6 yrs. Analysis of the

  18. Oxygen isotopic anomaly and solar nebular photochemistry

    International Nuclear Information System (INIS)

    Kitamura, Y.; Shimizu, M.


    At the cool periphery of the solar nebula, oxygen could photochemically be formed from water. The mixing of 17 O and 18 O enriched by the self-shielding effect of 16 O 2 to the dust grain melted by the shock waves there would explain the oxygen isotopic anomaly in the high-temperature mineral of the carbonaceous meteorites. (Auth.)

  19. Noble gas paleotemperatures and water contents of stalagmites - a new extraction tool and a new paleoclimate proxy (United States)

    Vogel, N.; Scheidegger, Y.; Brennwald, M. S.; Fleitmann, D.; Figura, S.; Wieler, R.; Kipfer, R.


    Stalagmites represent excellent multi-proxy paleoclimate archives as they cover long timescales and can be dated with high precision [e.g., 1]. The absolute temperature at which a stalagmite grew, can be deduced from the amounts of atmospheric noble gases dissolved in the stalagmite's fluid inclusion water (= noble gas temperature, NGT) [2-4]. We present technical advances towards more robust NGT determinations and also propose a new paleoclimate proxy, namely the stalagmite's water content, which is a "by-product" of NGT determination. Water contents and oxygen isotope records of two Holocene stalagmites from Socotra Island (Yemen) were found to vary systematically: progressively lighter oxygen is accompanied by decreasing water contents and vice versa. Via the oxygen isotope records [5] the stalagmites' water contents are linked to the amounts of precipitation on Socotra Island. High precipitation, i.e., high drip rates lead to homogeneous calcite growth with low porosity and therefore a small number of water-filled inclusions, i.e. low water contents. A reduction of drip water supply fosters irregular crystal growth with higher porosity, leading to higher water contents of the calcite (see also [6]). Therefore the stalagmites' water contents seem to record changes in drip water supply and, under favourable conditions, changes in regional precipitation. The current method to extract water and noble gases from stalagmite samples is experimentally challenging and subject to certain limitations (e.g., time-consuming sample preparation in a glove box, temperature restrictions for water extraction, and the often inadequate correction for air from residual air-filled inclusions [3, 4]). To overcome these limitations we have developed a new type of crusher directly attached to our noble gas line. It not only allows crushing and separating the samples into different grain size fractions in vacuo, but the separates can be individually heated to significantly higher

  20. Oxygen isotopic fractionation during bacterial sulfate reduction (United States)

    Balci, N.; Turchyn, A. V.; Lyons, T.; Bruchert, V.; Schrag, D. P.; Wall, J.


    Sulfur isotope fractionation during bacterial sulfate reduction (BSR) is understood to depend on a variety of environmental parameters, such as sulfate concentration, temperature, cell specific sulfate reduction rates, and the carbon substrate. What controls oxygen isotope fractionation during BSR is less well understood. Some studies have suggested that carbon substrate is important, whereas others concluded that there is a stoichiometric relationship between the fractionations of sulfur and oxygen during BSR. Studies of oxygen fractionation are complicated by isotopic equilibration between sulfur intermediates, particularly sulfite, and water. This process can modify the isotopic composition of the extracellular sulfate pool (δ18OSO4 ). Given this, the challenge is to distinguish between this isotopic equilibration and fractionations linked to the kinetic effects of the intercellular enzymes and the incorporation of sulfate into the bacterial cell. The δ18OSO4 , in concert with the sulfur isotope composition of sulfate (δ34SSO4), could be a powerful tool for understanding the pathways and environmental controls of BSR in natural systems. We will present δ18OSO4 data measured from batch culture growth of 14 different species of sulfate reducing bacteria for which sulfur isotope data were previously published. A general observation is that δ18OSO4 shows little isotopic change (kinetic effect during BSR and/or equilibration between sulfur intermediates and the isotopically light water (~-5‰) of the growth medium. Our present batch culture data do not allow us to convincingly isolate the magnitude and the controlling parameters of the kinetic isotope effect for oxygen. However, ongoing growth of mutant bacteria missing enzymes critical in the different steps of BSR may assist in this mission.

  1. Stable Oxygen-18 and Deuterium Isotopes

    DEFF Research Database (Denmark)

    Müller, Sascha

    The application of stable Oxygen-18 (18O) and Deuterium (2H) isotopes, as a tracer for fluxes between different compartments of the water cycle was subject of the present PhD-thesis. During a three year period, temporal data from a wide range of water cycle constituents was collected from...... the Skjern River catchment, Denmark. The presented applications focused on studying the isotopic 'input signal' to the hydrosphere in the form of precipitation, the isotopic 'output signal' with its related dynamic processes at a coastal saltwater-freshwater interface (groundwater isotopes) and the temporal...... development within a given lowland headwater catchment (stream water isotopes). Based on our investigations on the precipitation isotopic composition a local meteoric water line (LMWL) was constructed and expressed as: δ2H=7.4 δ18O + 5.36‰. Moreover, we showed that under maritime temperature climate influence...

  2. Major events in Neogene oxygen isotopic records

    International Nuclear Information System (INIS)

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


    Changes in oxygen isotopic ratios of foraminiferal calcite during the cainozoic have been one of the primary tools for investigating the history of Arctic and Antarctic glaciation, although interpretations of the oxygen isotopic record differ markedly. The ambiguity in interpretation results mainly from the partitioning of temperature from ice volume effects in delta 18 O changes. Oxygen isotopic records for the Cainozoic show an increase in delta 18 O values towards the present, reflecting gradual cooling and increased glaciation of the Earth's climate since the late Cretaceous. A variety of core material from the South Atlantic and South-west Pacific oceans are investigated. This composite data represents one of the most complete available with which to evaluate the evolution of glaciation during the Neogene. Expansion of ice shelves in Antarctica undoubtedly accompanied the increased glaciation of the northern hemisphere, since eustatic sea-level lowering would positively reinforce ice growth on Antarctica

  3. Oxygen isotope fractionation in double carbonates. (United States)

    Zheng, Yong-Fei; Böttcher, Michael E


    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.

  4. Isotopic Composition of Oxygen in Lunar Zircons (United States)

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


    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.

  5. Oxygen isotope studies of ordinary chondrites (United States)

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


    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.

  6. Isotope chemistry and molecular structure. Carbon and oxygen isotope chemistry

    International Nuclear Information System (INIS)

    Bigeleisen, J.; Hom, R.C.; Ishida, T.


    The relationships between force constants and the isotope chemistry of carbon and oxygen are calculated for H 2 O, CO 2 , CH 2 O, CH 4 , C 2 H 4 , C 2 H 6 , and C 6 H 6 . Significant differences are found from the general features of protium--deuterium isotope chemistry. These are shown to be associated with a structural effect. Hydrogen is always an end atom except for hydrogen bonded moleules. Carbon is generally tetrahedrally bonded and its isotope chemistry shows significant contributions from the interaction between stretching and bending modes. These interactions lead to deviations in additivity of the total isotope effect from the contributions of the individual force constants. Stretching forces dominate the isotope chemistry of carbon and oxygen as they do in hydrogen. They account for 70%--90% of the reduced partition function ratios. Correlations are made between the stretching force contributions and molecular structure. It is shown that while significant differences exist between the specific contributions calculated from different force fields for methane, ethane, and benzene, the absolute value of ln(s/s') f is rather insensitive to the detailed structures of the F matrices studied

  7. A stalagmite-inferred high-resolution hydroclimate record at 6-7.5 ka in Okinawa, Japan (United States)

    Omine, K.; Uemura, R.; Masaka, K.; Asami, R.; Lone, M. A.; Chou, Y. C.; Shen, C. C.


    Holocene Asian summer monsoon was influenced by solar activity in Middle East and mainland China. However, this relationship is still unclear in the maritime margin of East Asian monsoon territory. In this study, we measured a Holocene stalagmite, HSN1, 246 mm in length, collected in Minami daito island, from Okinawa, Japan, to evaluate this solar forcing on regional monsoon intensity in the western Pacific region. Carbonate oxygen isotope ratios and H/O isotopic compositions of fluid-inclusion water were measured. A robust age model was established with precise U-Th ages from 6 to 7.5 thousand years ago. The growth rate was 180 μm/yr. In the presentation, we will compare our stalagmite proxy records with other marine, terrestrial, and also high-latitude paleoclimate records to clarify different forcings.

  8. Isotopic evidence for oxygenated Mesoarchaean shallow oceans (United States)

    Eickmann, Benjamin; Hofmann, Axel; Wille, Martin; Bui, Thi Hao; Wing, Boswell A.; Schoenberg, Ronny


    Mass-independent fractionation of sulfur isotopes (MIF-S) in Archaean sediments results from photochemical processing of atmospheric sulfur species in an oxygen-depleted atmosphere. Geological preservation of MIF-S provides evidence for microbial sulfate reduction (MSR) in low-sulfate Paleoarchaean (3.8-3.2 billion years ago (Ga)) and Neoarchaean (2.8-2.5 Ga) oceans, but the significance of MSR in Mesoarchaean (3.2-2.8 Ga) oceans is less clear. Here we present multiple sulfur and iron isotope data of early diagenetic pyrites from 2.97-Gyr-old stromatolitic dolomites deposited in a tidal flat environment of the Nsuze Group, Pongola Supergroup, South Africa. We identified consistently negative Δ33S values in pyrite, which indicates photochemical reactions under anoxic atmospheric conditions, but large mass-dependent sulfur isotope fractionations of 30‰ in δ34S, identifying active MSR. Negative pyrite δ56Fe values (-1.31 to -0.88‰) record Fe oxidation in oxygen-bearing shallow oceans coupled with biogenic Fe reduction during diagenesis, consistent with the onset of local Fe cycling in oxygen oases 3.0 Ga. We therefore suggest the presence of oxygenated near-shore shallow-marine environments with ≥5 μM sulfate at this time, in spite of the clear presence of an overall reduced Mesoarchaean atmosphere.

  9. Borneo stalagmites reveal climatic excursions associated with Toba ash layers prior to Greenland Stadial 20 (United States)

    Cobb, K. M.; Orland, I. J.; Carolin, S.; Adkins, J. F.; Valley, J. W.; Jersild, A.; LeGrande, A. N.; Colose, C.


    The Toba super-eruption occurred in close association with an abrupt climate transition from Greenland Interstadial (GI-) 20 to Greenland Stadial (GS-) 20, roughly 74 thousand years ago. However, recent attempts to characterize either the regional or global climate response to Toba have been limited by a lack of age control, geographic proximity, and/or convincing marker of the major eruption in most high-resolution paleoclimate archives. Here, we use a suite of micro-scale analytical techniques to evaluate the oxygen isotopic and geochemical composition of multiple stalagmites that grew across the Toba interval in Gunung Mulu National Park, northern Borneo. New timeseries of stalagmite d18O at 50-micron scales across the Toba horizon revleal a large (>1‰), rapid (segments across the Toba horizon in two well-dated stalagmites previously published in Carolin et al., 2013 and Caroline et al., 2014. The SIMS d18O data reveal high-frequency d18O excursions of +2 and -2 per mil during the transition from GI-20 (warm conditions) to Greenland Stadial GS-20 (cool conditions), suggesting that this period was characterized by large fluctuations in regional hydroclimate in the western tropical Pacific, with potentially profound impacts on global atmospheric circulation. We also present results from synchrotron analyses of ash-related elements (S, P, Si, and Al) to resolve the number and relative magnitude of Toba-related eruptions as recorded in several different stalagmites from Borneo, where ash layers likely exceeded 2cm on the overlying terrain. Together, these results indicate that large, rapid ( 10yr-long) environmental changes with marked effects on both the vegetation and hydroclimate above the cave may have been triggered by discrete eruptions of the Toba caldera. We investigate the regional hydroclimate responses to the Toba super-eruption in the isotope-equipped NASA-GISS coupled climate model across a range of eruption sizes, number, and duration.

  10. Oxygen Isotope Systematics of Almahata Sitta (United States)

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


    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

  11. Potential of Stable Carbon and Oxygen Isotope Variations of Speleothems from Andaman Islands, India, for Paleomonsoon Reconstruction

    Directory of Open Access Journals (Sweden)

    Amzad H. Laskar


    Full Text Available The Indian monsoon activity, coinciding with the Inter-Tropical Convective Zone (ITCZ, progresses from the southern Indian Ocean during the boreal summer and withdraws towards the south in winter. Islands situated to the south of India receive, therefore, the first and last showers of the monsoon; speleothems in such islands have not yet been explored for their potential to reconstruct past monsoon rainfall. Here, we present the first measurements of stable carbon and oxygen isotopic compositions (δ13C and δ18O of a stalagmite collected from the Baratang Island of Andamans, along with new data on δ18O of modern monsoon precipitation (May to July 2010. The aim was to detect (i whether these samples are amenable to dating using 14C, (ii whether their oxygen isotopes indicate precipitation under isotopic equilibrium, and (iii if (i and (ii above are true, can we reconstruct monsoon activity during the past few millennia? Our results indicate that while δ18O of speleothem does show evidence for precipitation under isotopic equilibrium; dating by 14C shows inversions due to varying contributions from dead carbon. The present work highlights the problems and prospects of speleothem paleomonsoon research in these islands.

  12. A Stalagmite record of Holocene Indonesian-Australian summer monsoon variability from the Australian tropics (United States)

    Denniston, Rhawn F.; Wyrwoll, Karl-Heinz; Polyak, Victor J.; Brown, Josephine R.; Asmerom, Yemane; Wanamaker, Alan D.; LaPointe, Zachary; Ellerbroek, Rebecca; Barthelmes, Michael; Cleary, Daniel; Cugley, John; Woods, David; Humphreys, William F.


    Oxygen isotopic data from a suite of calcite and aragonite stalagmites from cave KNI-51, located in the eastern Kimberley region of tropical Western Australia, represent the first absolute-dated, high-resolution speleothem record of the Holocene Indonesian-Australian summer monsoon (IASM) from the Australian tropics. Stalagmite oxygen isotopic values track monsoon intensity via amount effects in precipitation and reveal a dynamic Holocene IASM which strengthened in the early Holocene, decreased in strength by 4 ka, with a further decrease from ˜2 to 1 ka, before strengthening again at 1 ka to years to levels similar to those between 4 and 2 ka. The relationships between the KNI-51 IASM reconstruction and those from published speleothem time series from Flores and Borneo, in combination with other data sets, appear largely inconsistent with changes in the position and/or organization of the Intertropical Convergence Zone (ITCZ). Instead, we argue that the El Niño/Southern Oscillation (ENSO) may have played a dominant role in driving IASM variability since at least the middle Holocene. Given the muted modern monsoon rainfall responses to most El Niño events in the Kimberley, an impact of ENSO on regional monsoon precipitation over northwestern Australia would suggest non-stationarity in the long-term relationship between ENSO forcing and IASM rainfall, possibly due to changes in the mean state of the tropical Pacific over the Holocene.

  13. Anomalous oxygen isotopic charge state distribution in ECRIS : New evidence

    NARCIS (Netherlands)

    Drentje, AG; Girard, A; Hitz, D; Melin, G

    The highly performing Electron Cyclotron Resonance Ion Source CAPRICE in Grenoble was operated with a mixture of three oxygen isotopes. The summed currents per charge state show a distribution almost identical to that of natural oxygen. However, the distributions per isotope are distinctly and

  14. Oxygen isotopic composition of the Luna 20 soil. (United States)

    Clayton, R. N.


    Comparison of the oxygen isotopic composition in the Luna 20 soil sample with the oxygen isotopic abundances of the Apollo 11, 12, 14, and 15 lunar soil samples. The Luna 20 soil is found to have a relatively low delta 0-18 content (0.57%) in comparison to the other lunar soils (0.58 to 0.63%).


    NARCIS (Netherlands)


    The performance of the KVI ECRIS-2 for a mixture of O-18, O-17, and O-16 isotopes is-as expected-very much the same as for natural oxygen gas, i.e., the sum of the currents of given charge states of the isotopes equals that of the same charge state of the natural oxygen. However, it is found that

  16. Simulated European stalagmite record and its relation to a quasi-decadal climate mode

    Directory of Open Access Journals (Sweden)

    G. Lohmann


    Full Text Available A synthetic stalagmite δ18O record for the Bunker Cave (51° N, 7° E is constructed using a combined climate–stalagmite modelling approach where we combine an atmospheric circulation model equipped with water isotopes and a model simulating stalagmite calcite δ18O values. Mixing processes in the soil and karst above the cave represent a natural low-pass filter of the speleothem climate archive. Stalagmite δ18O values at Bunker Cave lag the regional surface climate by 3–4 yr. The power spectrum of the simulated speleothem calcite δ18O record has a pronounced peak at quasi-decadal time scale, which is associated with a large-scale climate variability pattern in the North Atlantic. Our modelling study suggests that stalagmite records from Bunker Cave are representative for large-scale teleconnections and can be used to obtain information about the North Atlantic and its decadal variability.

  17. U/Th dating and pollen analysis of a stalagmitic sequence of the isotopic stage 5 (''Galerie des Vervietois, Grotte de Han'' Belgium). Datation uranium/thorium et analyse pollinique d'une sequence stalagmitique du stade isotopique 5 (Galerie des Vervietois, Grotte de Han-sur-Lesse, Belgique)

    Energy Technology Data Exchange (ETDEWEB)

    Quinif, Y. (Faculte Polytechnique de Mons (Belgium)); Bastin, B. (Louvain Univ., Louvain-la-Neuve (Belgium). Unite de Physique Nucleaire)


    The stalagmitic body of the 'Galerie des Vervietois' ('Grotte de Han', Belgium) has been sampled by numerous drillings. We present here two series studied by lithostratigraphy, palynology and absolute dating by the uranium series disequilibrium. These series allow one to date and reconstitute the palaeoclimatic sequence from isotopic substage 5.5 to isotopic substage 5.3, emphasizing the climatic deterioration of the isotopic substage 5.4 (Melisey I in the 'Grande Pile' sequence). (authors).

  18. Relationship between modern rainfall variability, cave dripwater, and stalagmite geochemistry in Guam, USA (United States)

    Partin, Judson W.; Jenson, John W.; Banner, Jay L.; Quinn, Terrence M.; Taylor, Frederick W.; Sinclair, Daniel; Hardt, Benjamin; Lander, Mark A.; Bell, Tomoko; Miklavič, Blaž; Jocson, John M. U.; TaborošI, Danko


    Modern rainwater, cave dripwater and cave stalagmite geochemical time series from a cave in Guam (13°38'N, 144°53'E) are used to better understand how changes in cave stalagmite geochemistry relate to aboveground changes in rainfall at a tropical location. A scientific field team based in Guam collects ˜monthly samples from multiple sites for geochemical analyses at a cave and aboveground rainfall from a nearby location. We compute a transfer function between rainfall amount and oxygen isotopic composition (δ18O) of a decrease (increase) of 0.94 ± 0.3 m/year for every 1‰ increase (decrease) in rainfall δ18O, based on data extracted from the International Atomic Energy Agency (IAEA) Global Networks of Isotopes in Precipitation (GNIP) database and from data generated in this study. Dripwater δ18O and Mg/Ca ratios show annual cyclicity at some, but not all sites, accentuating the complex nature of cave hydrology. A stalagmite δ18O record for the last ˜160 years indicates the existence of droughts of decadal length, when rainfall is estimated to be ˜0.65 ± 0.3 m/year less than average conditions. This estimate of rainfall reduction most likely refers to wet season months, as these months preferentially contribute to groundwater recharge. The proxy-based climate record at Guam provides new evidence highlighting how a rainy site in the Western Pacific Warm Pool today can experience considerable changes in rainfall on decadal timescales.

  19. Oxygen isotopic compositions of chondrules in Allende and ordinary chondrites (United States)

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


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

  20. Oxygen exchange with water alters the oxygen isotopic signature of nitrate in soil ecosystems.

    NARCIS (Netherlands)

    Kool, D.M.; Wrage, N.; Oenema, O.; Kessel, van C.; Groenigen, van J.W.


    Combined oxygen (O) and nitrogen (N) stable isotope analyses are commonly used in the source determination of nitrate . The source and fate of are studied based on distinct O and N isotopic signatures (d18O and d15N) of various sources and isotopic effects during transformation processes, which

  1. Oxygen Isotope Fractionation between Coexisting Calcite and Dolomite. (United States)

    Weber, J N


    The oxygen isotopic composition of calcite from carbonate rocks of the lower unit of the Flagstaff formation (Paleocene) exposed along the western margin of the Wasatch Plateau, Utah, is about 7 per mil lower than that of coexisting dolomite, suggesting that isotopic equilibration of these two minerals can occur at relatively low temperatures. Unlike recent isotopic evidence presented by Degens and Epstein, the data do not preclude a primary chemical origin for the dolomite.

  2. The oxygen isotopic composition of water extracted from carbonaceous chondrites


    Baker, L.; Franchi, Ian; Wright, Ian; Pillinger, Colin


    The oxygen isotopic composition of water from carbonaceous chondrites suggests that close to isotopic equilibrium was attained on CI and CM parent bodies. This is more consistent with a closed system than one with fluid flow. Tagish Lake does not display such equilibrium.

  3. Chemical production of chondrule oxygen isotopic composition (United States)

    Thiemens, M. H.


    Defining the source of observed meteoritic O isotopic anomalies remains a fundamental challenge. The O isotopic composition of chondrules are particularly striking. There are at least three types of chemical processes that produce the isotopic compositions observed in chondrules and Ca-Al-rich inclusions (CAI's). The processes are rather general, viz, they require no specialized processes and the processes associated with chondrule production are likely to produce the observed compositions.

  4. What does the oxygen isotope composition of rodent teeth record? (United States)

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


    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).

  5. Carbon and oxygen isotope fractionation in scleractinian corals: a review

    Energy Technology Data Exchange (ETDEWEB)

    Swart, P.K. (Miami Univ., FL (USA). Comparative Sedimentology Lab.)


    The present theories on the fractionation of stable isotopes in scleractinian corals are critically discussed in the light of data available on primary productivity, respiration and stable isotope chemistry. These data support a model of fractionation in which the carbon and oxygen isotopes are decoupled. Calcification occurs from a reservoir of carbon dioxide derived from both organic and inorganic sources. Photosynthesis preferentially fixes /sup 12/C and thereby leaves behind /sup 13/C. Increases in the rate of photosynthesis therefore also enrich the carbon isotope ratio of the skeleton. From theoretical considerations, photosynthesis has little effect on the oxygen isotope ratio of the skeleton, a fact confirmed by available data. The process of respiration adds depleted carbon and oxygen to the calcification reservoirs. The varying correlations between carbon and oxygen isotopes seen in hermatypic corals are caused by changes in the relationship between photosynthesis and respiration at different geographical localities. The isotopic compositions in the skeletons of non-zooxanthellate corals, which show a consistent positive correlation, can also be explained by the above scenario.

  6. Oxygen isotopic fractionation in the condensation of refractory smokes (United States)

    Nelson, R.; Thiemens, M.; Nuth, J.; Donn, B.


    This paper reports preliminary measurements of the oxygen isotopic fractionation that occurs during the condensation of refractory metal oxide smokes. Fractionation occurred at temperatures in excess of 500 K during and/or subsequent to reaction of SiH4, Fe(CO)5, Al(CH3)3, and O2 in a H2 carrier gas. Observed isotopic fractionation was as high as -15 per mil/amu. The magnitude of the isotopic fractionation suggests that the process is kinetically controlled since the effect is greatly in excess of that expected for equilibrium isotopic exchange.

  7. A latitudinal study of oxygen isotopes within horsehair (United States)

    Thompson, E.; Bronk Ramsey, C.; McConnell, J. R.


    This study aims to explore the hypothesis that 'if oxygen isotope ratios deplete with decreasing temperature then a study of oxygen isotope ratios within horsehair from Oxfordshire to Iceland will show a latitudinal depletion gradient'. By looking at oxygen isotope values at different geographical positions, we can track the relationship with latitude and with different regional climate features. This will provide a firmer understanding of how to compare climate records from different locations. Additionally, a comparison of the horse breeds from this study to those analysed within previous studies will create an even better understanding of the intra-species variation within the δ18O values of horsehair. A total of 24 horses were sampled on the 7th March from Thordale Stud in Shetland, the Icelandic Food And Veterinary Authority in Iceland, the Exmoor Pony Centre in Exmoor and the Pigeon House Equestrian Centre in Oxfordshire. By starting the sampling process from the most recent growth at the follicle, the sampling date becomes a chronological marker, temporally fixing the first sample within a sequential set of data points extending for one year or longer, depending on the length of each individual hair. The samples were analysed for oxygen isotope values using an IRMS coupled within a Sercon HTEA. Preliminary results show a latitudinal gradient is evident on comparison between the locations, consistent with the findings of Darling and Talbot's study of fresh water isotopes in the British Isles (2003). These results support the hypothesis, showing that a study of oxygen isotope ratios within horse hair from Oxfordshire to Iceland showing a latitudinal depletion gradient, consistent with a depletion of oxygen isotope ratios due to decreasing temperatures. Darling, W. and Talbot, J. (2003). The O and H stable isotope composition of freshwaters in the British Isles. 1. Rainfall. Hydrol. Earth System Science, 7(2), pp.163-181.

  8. Oxygen-isotope fractionation between marine biogenic silica and seawater (United States)

    Matheney, Ronald K.; Knauth, L. Paul


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

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


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


    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicat...

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


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


    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicatio...

  11. Multiple-turnover isotopic labeling of Fmoc- and Boc-protected amino acids with oxygen isotopes. (United States)

    Seyfried, Martin S; Lauber, Birgit S; Luedtke, Nathan W


    An efficient method for the selective isotopic labeling of carboxylic acids is reported. By reacting an amino acid with excess carbodiimide and (18)OH(2), a kinetically enhanced multiple turnover reaction provides the (18)O-labeled product in high yield and excellent isotopic enrichment. This reaction is fully compatible with standard Fmoc, Boc, Trt, and OtBu protecting groups and provides a means to selectively label the alpha-carboxylic acids of functionalized amino acids with stable oxygen isotopes.

  12. Carbon and Oxygen isotopic composition in paleoenvironmental determination

    International Nuclear Information System (INIS)

    Silva, J.R.M. da.


    This work reports that the carbon and oxygen isotopic composition separate the mollusks from marine environment of the mollusks from continental environment in two groups isotopically different, making the biological control outdone by environment control, in the isotopic fragmentation mechanisms. The patterns from the continental environment are more rich in O 16 than the patterns from marine environments. The C 12 is also more frequent in the mollusks from continental environments. The carbon isotopic composition in paterns from continental environments is situated betwen - 10.31 and - 4,05% and the oxygen isotopic composition is situated between - 6,95 and - 2,41%. To the marine environment patterns the carbon isotopic composition is between - 2,08 and + 2,65% and the oxigen isotopic composition is between - 2,08 and + 0,45%. Was also analysed fossil marine mollusks shells and their isotopic composition permit the formulation of hypothesis about the environment which they lived. (C.D.G.) [pt

  13. Oxygen Isotope Speleothem record of Decadal and Multidecadal Atlantic Oscillations over the last millennium in Southwestern Morocco (United States)

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


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

  14. Study of oxygen isotope ratio in accessory zircons

    International Nuclear Information System (INIS)

    Bibikova, E.V.; Ustinov, V.I.; Gracheva, T.V.; Kiselevskij, M.A.; Shukolyukov, Yu.A.


    The isotope ratio of oxygen has been studied in accessory zircons of ores predominantly of granite composition, of different age with a known contents and distribution of radioactive elements in the grain volume, which enabled one to calculate the integral dose of the mineral structure irradiation by alpha-particles. The degree of zircon structure metamict character has been also calculated from the data obtained with the use of infrared spectroscopy. It is shown that for the totally metamictous zircons the exchange between the structural oxygen and the oxygen of water is characteristic, the water easily penetrating into broken structure of the mineral and washing out the radiogenic lead. The prevailing role of the chemical processes is confirmed, but not of the diffusion ones resulting in the lead carry-over, break of the U-Pb isotope system, and appearance of discordant ages. The isotopically light zircon proves to be less suitable for geochronological studies

  15. Caves in caves: Post depositional holes in stalagmites (United States)

    Shtober Zisu, Nurit; Schwarcz, Henry P.; Chow, Tom; Konyer, Norman B.; Noseworthy, Michael D.


    Previous studies of speleothems for the purposes of isotopic analysis and U-series dating have resulted in preparation of stalagmites by sectioning longitudinally along the growth axis. We frequently observe holes in such sections, both along the growth axis, and laterally to it, ranging in size up to several mm in diameter. Our initial supposition was that these holes are produced during the growth of the stalagmite under constant dripping conditions, but it was found that two kinds of holes exist within the stalagmites. "Axial holes" were formed syngenetically as is shown by the depression of growth layers into the holes and the persistence of the axial hole over many cm of the growth history. Some cut the active growth surface of the stalagmite. "Off-axis holes" are seen in many stalagmites (as well as stalactites); they cut discordantly through growth layers, and never terminate at a growth surface. They range in size from a few mm to several cm in maximum dimension, and may not be coaxially oriented. They are lined with micron-sized, randomly oriented calcite crystals and under which lies an organic-rich coating. We used CT (Computed Tomography) and MRI (Magnetic Resonance Imaging) scanning in order to locate holes, and to search for water trapped in these macro-inclusions. These methods, allow us to visualize the holes without destruction of the stalagmite, the holes and the surrounding calcite. To our best knowledge, the present paper is the first to combine CT and MRI methods in the study of fluid inclusions in rocks, or in visualizing the distribution of holes in speleothems. CT scans reveal abundant off-axis holes in some speleothems, while most display at least a few holes. MRI scans shows that, in uncut speleothems, these holes never contain water (although Genty et al. [2002] found water-filled holes in some stalagmites). Off-axis holes may be a result of bioerosion, possibly bacterial, followed by partial refilling of the hole with calcite which is

  16. Rate of oxygen isotope exchange between selenate and water. (United States)

    Kaneko, Masanori; Poulson, Simon R


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

  17. Oxygen Isotopic Compositions of Olivine and Pyroxene from CI Chondrites (United States)

    Leshin, L. A.; Rubin, A. E.; McKeegan, K. D.


    The oxygen isotopic compositions of carbonaceous chondrites are complicated since individual components of these meteorites have distinct isotopic compositions that have been affected, to varying degrees, by both nebular and parent body processes. We present the first measurements of oxygen isotopic compositions of rare olivine and pyroxene in the CI chondrites. By combining these data with oxygen isotopic analyses of secondary minerals in these rocks previously reported by Clayton and co-workers, we hope to place quantitative constraints on the physical processes that occurred during formation of these meteorites. The oxygen isotopic composition of separated olivine and pyroxene grains from Orgueil and Ivuna were measured using SIMS. The delta ^(18)O values of the olivines range from ~+3 to +13 and the delta^(17)O values range from ~+1 to +7. The delta^(18)O values of the pyroxenes range from ~+4 to +10 and the delta^(17)O values range from ~+2 to +5. Observations that will be explained in the interpretation of the data are: (1) CI pyroxene and olivine grains have essentially identical oxygen isotopic compositions which are distinct from those measured in other carbonaceous chondrites. (2) All data points except two are indistinguishable from terrestrial values at the one sigma level, and the two exceptions fall only slightly below the terrestrial fractionation line. We consider the data taken as a whole to be consistent with terrestrial values, as well as the slightly positive delta^(17)O values reported previously for matrix and magnetite in CI chondrites. (3) Due to the small range in d values observed relative to the uncertainties, it is not possible to distinguish whether these data fall on a line of approximately slope 1 or slope 1/2.

  18. An oxygen isotope record from Lake Xiarinur in Inner Mongolia since the last deglaciation and its implication for tropical monsoon change (United States)

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


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

  19. Atmospheric odd oxygen production due to the photodissociation of ordinary and isotopic molecular oxygen (United States)

    Omidvar, K.; Frederick, J. E.


    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.

  20. Carbon and oxygen isotope compositions of the carbonate facies in ...

    Indian Academy of Sciences (India)

    The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleopro- terozoic to the Neoproterozoic period.Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies.However,the ...

  1. Carbon and oxygen isotope compositions of the carbonate facies

    Indian Academy of Sciences (India)

    The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleopro- terozoic to the Neoproterozoic period.Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies.However,the ...

  2. WAIS Divide WDC06A Oxygen Isotope Record, Version 1 (United States)

    National Aeronautics and Space Administration — This data set contains complete low resolution (0.25 to 100 cm) oxygen isotope data from the WAIS Divide Ice Core WDC06A, 0 to 3404.7 m depth. Also included is the...

  3. Carbon and oxygen isotope compositions of the carbonate facies in ...

    Indian Academy of Sciences (India)

    The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleopro- terozoic to the Neoproterozoic period. Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies. However, the ...

  4. Carbon and oxygen isotopic compositions and diagenesis of the ...

    African Journals Online (AJOL)

    Carbon and oxygen isotopic compositions and diagenesis of the Ewekoro formation in the eastern Dahomey Basin, southwestern Nigeria. OA Adekeye, SO Akande, RB Bale, BD Erdtmann. Abstract. No Abstract. Journal of Mining and Geology 2005, Vol. 41(1): 87-95. Full Text: EMAIL FULL TEXT EMAIL FULL TEXT

  5. Nitrogen and Oxygen Isotopic Studies of the Marine Nitrogen Cycle. (United States)

    Casciotti, Karen L


    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.

  6. Oxygen isotope analysis of plant water without extraction procedure

    International Nuclear Information System (INIS)

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


    Isotopic analyses of plant water (mainly xylem, phloem and leaf water) are gaming importance as the isotopic signals reflect plant-environment interactions, affect the oxygen isotopic composition of atmospheric O 2 and CO 2 and are eventually incorporated into plant organic matter. Conventionally, such isotopic measurements require a time-consuming process of isolating the plant water by azeotropic distillation or vacuum extraction, which would not complement the speed of isotope analysis provided by continuous-flow IRMS (Isotope-Ratio Mass Spectrometry), especially when large data sets are needed for statistical calculations in biological studies. Further, a substantial amount of plant material is needed for water extraction and leaf samples would invariably include unenriched water from the fine veins. To measure sub-microlitre amount of leaf mesophyll water, a new approach is undertaken where a small disc of fresh leaf is cut using a specially designed leaf punch, and pyrolysed directly in an IRMS. By comparing with results from pyrolysis of the dry matter of the same leaf, the 18 O content of leaf water can be determined without extraction from fresh leaves. This method is validated using a range of cellulose-water mixtures to simulate the constituents of fresh leaf. Cotton leaf water δ 18 O obtained from both methods of fresh leaf pyrolysis and azeotropic distillation will be compared. The pyrolysis technique provides a robust approach to measure the isotopic content of water or any volatile present in a homogeneous solution or solid hydrous substance

  7. Oxygen isotope fractionation in phosphates: the role of dissolved complex anions in isotope exchange. (United States)

    Zheng, Yong-Fei


    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.

  8. How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate (United States)

    Price, Gregory; Grimes, Stephen


    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.

  9. Planetary Accretion, Oxygen Isotopes and the Central Limit Theorem (United States)

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


    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.

  10. Defining uncertainty and error in planktic foraminiferal oxygen isotope measurements (United States)

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


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

  11. Carbon and Oxygen Isotope Ratios in Rona Limestone, Romania

    Directory of Open Access Journals (Sweden)

    Stela Cuna


    Full Text Available The carbon and oxygen isotopic compositions of limestones provide criteria for the evaluation of the depositional environment. For Jurassic and younger samples, the best discrimination between marine and fresh-water limestones is given by Z parameter, calculated as a linear correlation between δ13C and δ18O (‰ PDB. Rona Limestone (Upper Paleocene - Lower Eocene, outcropping on a small area in NW Transylvania (Meseş area is a local lacustrine facies. There, it divides Jibou Formation into the Lower Red Member and the Upper Variegated Member, respectively. Recently, a sequence containing a marine nannoplankton assemblage was identified in the base of Rona deposits. The main goal of our study was to characterize, based on the isotopic record, the primary environment of formation of the deposit, as well as that in which some diagenetic processes (the formation of dolomite and of green clay around the siliceous chert nodules took place. Ten samples representing limestones, dolomitic limestone, marls and the green carbonate-rich clay were studied from petrographical and mineralogical points of view, and the carbon and oxygen isotopic ratios from the carbonate (calcite component were measured. In conclusion, it was found that the procedure of extraction of CO2 we used enabled the discrimination between the isotopic prints of calcite vs. dolomite. This pleads for considering our results as a primary isotopic pattern in the bulk rock. The oxygen and carbon isotope data indicate a fresh-water depositional environment with Z<120. The δ13C mean value (-4.96 ‰ PDB is, generally, representative for fresh-water carbonates of the Tertiary period. The same environment characterized also the formation of carbonates within the green clay.

  12. Oxygen isotopic signature of CO2 from combustion processes

    Directory of Open Access Journals (Sweden)

    W. A. Brand


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

  13. Oxygen-isotope exchange rates for three isostructural polyoxometalate ions. (United States)

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


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

  14. Oxygen isotopic exchange probes of ATP hydrolysis by RNA helicases. (United States)

    Hackney, David D


    It is often possible to obtain a detailed understanding of the forward steps in ATP hydrolysis because they are thermodynamically favored and usually occur rapidly. However, it is difficult to obtain the reverse rates for ATP resynthesis because they are thermodynamically disfavored and little of their product, ATP, accumulates. Isotopic exchange reactions provide access to these reverse reactions because isotopic changes accumulate over time due to multiple reversals of hydrolysis, even in the absence of net resynthesis of significant amounts of ATP. Knowledge of both the forward and reverse rates allows calculation of the free energy changes at each step and how it changes when coupled to an energy-requiring conformational step such as unwinding of an RNA helix. This chapter describes the principal types of oxygen isotopic exchange reactions that are applicable to ATPases, in general, and helicases, in particular, their application and their interpretation. Copyright © 2012 Elsevier Inc. All rights reserved.

  15. Iron isotope fractionation and the oxygen fugacity of the mantle. (United States)

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


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

  16. Deuterium and oxygen-18 isotope dilution spaces in normal adults

    International Nuclear Information System (INIS)

    Wong, W.; Cochran, W.; Lee, L.; Klish, W.; Klein, P.


    In light of the limited series of published comparison the authors have determined the deuterium and oxygen-18 isotope dilution spaces in 10 normal subjects, 5 males and 5 females. Labeled water was administered orally at doses of 40 mg deuterium oxide and 60 mg oxygen-18 per kg of body weight. One predose blood sample and six hourly postdose blood samples were collected from each subject. Aliquots of plasma water were reduced directly to hydrogen gas with zinc shot in individual quartz reaction vessels and 2 H/ 1 H isotope ratios were determined by gas-isotope-ratio mass spectrometry (GIRMS). 18 O/ 16 O isotope ratios were determined after plasma samples were equilibrated with CO 2 in an isotope exchange system. Both 2 H- and 18 O-labeled water attained isotopic equilibrium in plasma within 3 hr after administration. The deuterium dilution spaces in males and females were 56.4 +/- 2.1% (mean +/- SD) and 55.9 +/- 0.9% of body weight, respectively, while the 18 O dilution spaces constituted 54.1 +/- 1.85% and 53.30 +/- 1.30%. The deuterium spaces were larger than the 18 O spaces by 4.55 +/- 0.56% in men and 4.78 +/- 1.63% in women and were significant at P < 0.01. These results compare with values of 3.81 +/- 2.66% for males (n = 6) and 1.10 +/- 2.67% for females (n = 2) previously reported by Schoeller et al

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

    DEFF Research Database (Denmark)

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


    , the mechanisms underlying the extreme mobility enhancement remain elusive. Herein, we used 18O isotope exchanged SrTi18O3 as substrates to create 2DEG at room temperature with and without the LSMO buffer layer. By mapping the oxygen profile across the interface between STO18 and disordered LaAlO3 or yttria...

  18. Hydrogen and oxygen isotope ratios in body water and hair: modeling isotope dynamics in nonhuman primates. (United States)

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


    The stable isotopic composition of drinking water, diet, and atmospheric oxygen influence the isotopic composition of body water ((2)H/(1)H, (18)O/(16)O expressed as δ(2) H and δ(18)O). In turn, body water influences the isotopic composition of organic matter in tissues, such as hair and teeth, which are often used to reconstruct historical dietary and movement patterns of animals and humans. Here, we used a nonhuman primate system (Macaca fascicularis) to test the robustness of two different mechanistic stable isotope models: a model to predict the δ(2)H and δ(18)O values of body water and a second model to predict the δ(2)H and δ(18)O values of hair. In contrast to previous human-based studies, use of nonhuman primates fed controlled diets allowed us to further constrain model parameter values and evaluate model predictions. Both models reliably predicted the δ(2)H and δ(18)O values of body water and of hair. Moreover, the isotope data allowed us to better quantify values for two critical variables in the models: the δ(2)H and δ(18)O values of gut water and the (18)O isotope fractionation associated with a carbonyl oxygen-water interaction in the gut (α(ow)). Our modeling efforts indicated that better predictions for body water and hair isotope values were achieved by making the isotopic composition of gut water approached that of body water. Additionally, the value of α(ow) was 1.0164, in close agreement with the only other previously measured observation (microbial spore cell walls), suggesting robustness of this fractionation factor across different biological systems. © 2012 Wiley Periodicals, Inc.

  19. Isotopic study of oxygen diffusion in oxide coatings (United States)

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


    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.

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

    DEFF Research Database (Denmark)

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


    Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce...... such long-lived consistency was most easily established by mixing in a terrestrial magma ocean. The measured identical oxygen isotope mass fractionation lines for Earth and Moon suggest that oxygen isotope reservoirs of both bodies were homogenized at the same time during a giant moon-forming impact...

  1. Oxygen isotopic composition of carbon dioxide in the middle atmosphere. (United States)

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


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

  2. Oxygen isotopic constraints on the composition of the moon (United States)

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


    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.

  3. Lightning and Mass Independent Oxygen Isotopic Fractionation in Nebular Silicates (United States)

    Nuth, Joseph A.


    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.

  4. Hydrogen and oxygen isotope values in hydrogen peroxide. (United States)

    Barnette, Janet E; Lott, Michael J; Howa, John D; Podlesak, David W; Ehleringer, James R


    Hydrogen peroxide (H(2)O(2)) is a widely used oxidizer with many commercial applications; unfortunately, it also has terrorist-related uses. We analyzed 97 hydrogen peroxide solutions representing four grades purchased across the United States and in Mexico. As expected, the range of hydrogen (δ(2)H, 230‰) and oxygen (δ(18)O, 24‰) isotope values of the H(2)O(2) solutions was large, reflecting the broad isotopic range of dilution waters. This resulted in predictable linear relationships of δ(2)H and δ(18)O values of H(2)O(2) solutions that were near parallel to the Meteoric Water Line (MWL), offset by the concentration of H(2)O(2) in the solution. By grade, dilute (3 to 35%) H(2)O(2) solutions were not statistically different in slope. Although the δ(2)H values of manufactured H(2)O(2) could be different from those of water, rapid H(2)O(2)-H(2)O exchange of H atoms eliminated any distinct isotope signal. We developed a method to measure the δ(18)O value of H(2)O(2) independent of dilution water by directly measuring O(2) gas generated from a catalase-induced disproportionation reaction. We predicted that the δ(18)O values of H(2)O(2) would be similar to that of atmospheric oxygen (+23.5‰), the predominant source of oxygen in the most common H(2)O(2) manufacturing process (median disproportionated δ(18)O=23.8‰). The predictable H-O relationships in H(2)O(2) solutions make it possible to distinguish commercial dilutions from clandestine concentration practices. Future applications of this work include synthesis studies that investigate the chemical link between H(2)O(2) reagents and peroxide-based explosive products, which may assist law enforcement in criminal investigations. Copyright © 2011 John Wiley & Sons, Ltd.

  5. Triple oxygen isotope systematics of structurally bonded water in gypsum (United States)

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


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

  6. The oxygen isotopic composition of water extracted from unequilibrated ordinary chondrites


    Baker, L.; Franchi, I.A.; Wright, I.P.; Pillinger, C.T.


    The oxygen isotopic composition of water extracted from the unequilibrated ordinary chondrites Semarkona and Bishunpur reveals differences in alteration mineralogy and levels of isotopic enrichment – reflecting key parameters in the alteration process.

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

    Digital Repository Service at National Institute of Oceanography (India)

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

    The variation of stable isotopes between individual shells of planktic foraminifera of a given species and size may provide short-term seasonal insight on Paleoceanography. In this context, oxygen isotope analyses of individual Globigerinoides...

  8. Oxygen isotope fractionation between human phosphate and water revisited

    DEFF Research Database (Denmark)

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


    to investigate the impact of solid food consumption on the oxygen isotope composition of the total ingested water (drinking water+solid food water). The results, along with those from three, smaller published data sets, can be considered as random estimates of a unique delta18OW/delta18OP linear relationship......-dominated and cereal-free diets, which may have been the diets of some of our early ancestors, the shift is a little higher and the application of the regression equation would slightly overestimate delta18OW in these cases....

  9. Oxygen isotopic compositions of asteroidal materials returned from Itokawa by the Hayabusa mission. (United States)

    Yurimoto, Hisayoshi; Abe, Ken-ichi; Abe, Masanao; Ebihara, Mitsuru; Fujimura, Akio; Hashiguchi, Minako; Hashizume, Ko; Ireland, Trevor R; Itoh, Shoichi; Katayama, Juri; Kato, Chizu; Kawaguchi, Junichiro; Kawasaki, Noriyuki; Kitajima, Fumio; Kobayashi, Sachio; Meike, Tatsuji; Mukai, Toshifumi; Nagao, Keisuke; Nakamura, Tomoki; Naraoka, Hiroshi; Noguchi, Takaaki; Okazaki, Ryuji; Park, Changkun; Sakamoto, Naoya; Seto, Yusuke; Takei, Masashi; Tsuchiyama, Akira; Uesugi, Masayuki; Wakaki, Shigeyuki; Yada, Toru; Yamamoto, Kosuke; Yoshikawa, Makoto; Zolensky, Michael E


    Meteorite studies suggest that each solar system object has a unique oxygen isotopic composition. Chondrites, the most primitive of meteorites, have been believed to be derived from asteroids, but oxygen isotopic compositions of asteroids themselves have not been established. We measured, using secondary ion mass spectrometry, oxygen isotopic compositions of rock particles from asteroid 25143 Itokawa returned by the Hayabusa spacecraft. Compositions of the particles are depleted in (16)O relative to terrestrial materials and indicate that Itokawa, an S-type asteroid, is one of the sources of the LL or L group of equilibrated ordinary chondrites. This is a direct oxygen-isotope link between chondrites and their parent asteroid.

  10. Stalagmite Survival: 500kyr of Cyclical Growth and Natural Attrition of Stalagmites in Sulawesi (United States)

    Scroxton, N.; Gagan, M. K.; Dunbar, G. B.; Ayliffe, L. K.; Hantoro, W. S.; Shen, C. C.; Hellstrom, J. C.; Zhao, J. X.; Cheng, H.; Edwards, R. L.; Sun, H.; Rifai, H.


    Numerous speleothem studies have analysed the age distribution of stalagmites harvested from multiple caves and inferred important changes in paleoclimates to explain stalagmite growth phases. However, stalagmites take tens to hundreds of thousands of years to grow, and thus the twin desires to preserve the cave condition for future generations and advance palaeoclimate science are often in conflict. In this study we use U/Th ages from low impact mini-cores extracted in situ from the bases of stalagmites, thus keeping the intrinsic value of the cave intact. Our case study is based on 77 individual stalagmites drilled in situ in thirteen caves located in and around Bantimurung-Bulusaraung National Park, South Sulawesi, Indonesia. The stalagmites grew during discrete time intervals within the last ~530,000 years, and analysis of their age distribution shows an exponential decrease in the number of older stalagmites surviving to the present day. The age distribution indicates that the rate of natural attrition of stalagmites is approximately constant through time, probably in response to a number of natural processes, including downward erosion of the karst terrain, cave collapse, in-cave erosional processes and in-cave sedimentation covering stalagmites. Natural attrition of stalagmites is likely to be a general cave phenomenon, and has important implications for cave conservation because it highlights that random removal of stalagmites without prior knowledge of their ages will result in unnecessary replication and a failure to sample the full length of the available paleoclimate record. Departure from this "normal" exponential profile can be used to infer palaeoclimate information: significant deviations are produced by periods of more frequent stalagmite growth, inferred here to reflect increases in monsoon rainfall over Sulawesi (345-340, 75-70 and 10-5 kyr BP). By adjusting the record to account for stalagmite attrition, more statistically robust paleoclimate

  11. Oxygen Isotope Variability within Nautilus Shell Growth Bands.

    Directory of Open Access Journals (Sweden)

    Benjamin J Linzmeier

    Full Text Available 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.

  12. Oxygen Isotope Variability within Nautilus Shell Growth Bands (United States)


    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

  13. Oxygen isotope fractionation between bird bone phosphate and drinking water (United States)

    Amiot, Romain; Angst, Delphine; Legendre, Serge; Buffetaut, Eric; Fourel, François; Adolfssen, Jan; André, Aurore; Bojar, Ana Voica; Canoville, Aurore; Barral, Abel; Goedert, Jean; Halas, Stanislaw; Kusuhashi, Nao; Pestchevitskaya, Ekaterina; Rey, Kevin; Royer, Aurélien; Saraiva, Antônio Álamo Feitosa; Savary-Sismondini, Bérengère; Siméon, Jean-Luc; Touzeau, Alexandra; Zhou, Zhonghe; Lécuyer, Christophe


    Oxygen isotope compositions of bone phosphate (δ18Op) were measured in broiler chickens reared in 21 farms worldwide characterized by contrasted latitudes and local climates. These sedentary birds were raised during an approximately 3 to 4-month period, and local precipitation was the ultimate source of their drinking water. This sampling strategy allowed the relationship to be determined between the bone phosphate δ18Op values (from 9.8 to 22.5‰ V-SMOW) and the local rainfall δ18Ow values estimated from nearby IAEA/WMO stations (from -16.0 to -1.0‰ V-SMOW). Linear least square fitting of data provided the following isotopic fractionation equation: δ18Ow = 1.119 (±0.040) δ18Op - 24.222 (±0.644); R 2 = 0.98. The δ18Op-δ18Ow couples of five extant mallard ducks, a common buzzard, a European herring gull, a common ostrich, and a greater rhea fall within the predicted range of the equation, indicating that the relationship established for extant chickens can also be applied to birds of various ecologies and body masses. Applied to published oxygen isotope compositions of Miocene and Pliocene penguins from Peru, this new equation computes estimates of local seawater similar to those previously calculated. Applied to the basal bird Confuciusornis from the Early Cretaceous of Northeastern China, our equation gives a slightly higher δ18Ow value compared to the previously estimated one, possibly as a result of lower body temperature. These data indicate that caution should be exercised when the relationship estimated for modern birds is applied to their basal counterparts that likely had a metabolism intermediate between that of their theropod dinosaur ancestors and that of advanced ornithurines.

  14. Oxygen isotope studies of the Salton Sea geothermal field

    International Nuclear Information System (INIS)

    Olson, E.R.


    Interbedded shales and sandstones were drilled to a depth of 1588 metres in Sinclair Number Four Well, Salton Sea Geothermal Field. Bottom hole temperatures are approximately 290 0 C. The oxygen dels of hydrothermal and detrital calcite have a systematic relationship at any depth in the geothermal reservoir. Typical values are: vein calcite, +6 0 / 00 ; calcite in white sandstone, +10 0 / 00 ; calcite in dark gray shale, +11 0 / 00 ; calcite in light gray shale, +17 0 / 00 ; calcite in red-brown shale, +20 0 / 00 . This succession represents decreasing water-rock interaction that is also indicated by the clay mineralogy of the shales. Permeability has a marked effect on the equilibration of water and rocks at any given temperature. Original differences in permeability have resulted in partial preservation of original detrital sedimentary compositions. The fluids in the Salton Sea Geothermal Field are probabaly partially evaporated Colorado River water, and their oxygen del values vary as much as 4 0 / 00 throughout the field. Truesdell's (1974) data suggest that dissolved salts may make the water oxygen activity del as much as 6 0 / 00 greater than the concentration del in the geothermal reservoir. Such an uncertainty is a serious impediment to precise isotope geothermometry in this system.(auth.)

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

    Directory of Open Access Journals (Sweden)

    Brooke eCrowley


    Full Text Available Stable isotope data provide insight into the foraging ecology of animals. Traditionally, carbon and nitrogen isotope values have been used to infer dietary and habitat preferences. Oxygen isotopes are used less frequently but may complement the ecological information provided by carbon and nitrogen, particularly in densely forested or arid environments. Additionally, because oxygen is preserved in both bioapatite and collagen, it is useful for paleoecological studies. To investigate the suitability of oxygen isotopes for complementing and building on ecological applications of carbon and nitrogen isotopes, we analyze all three isotopes in bone collagen for nearly identical assemblages of Costa Rican mammals in two ecologically distinct habitats - a evergreen rainforest and a seasonal dry forest. We assess the degree to which differences in habitat, activity pattern, diet, arboreality, and thermoregulation are revealed by each of the isotope systems. Our results highlight the potential of oxygen isotopes in modern and paleoecological contexts. In addition to reflecting habitat type, oxygen isotope values in collagen distinguish species on the basis of vertical habitat stratification and drinking behavior. Within a locality, individuals with low oxygen isotope values likely track meteoric water, whereas those with elevated values most likely consume evaporatively-enriched plant tissues, such as canopy leaves. These patterns will be useful in reconstructing paleoenvironments and interpreting ecological differences among taxa both extant and extinct.

  16. Oxygen isotope composition of mafic magmas at Vesuvius (United States)

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


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

  17. Thermophysiology of Tyrannosaurus rex: Evidence from Oxygen Isotopes. (United States)

    Barrick, R E; Showers, W J


    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.

  18. ISOL Beams of Neutron-Rich Oxygen Isotopes

    CERN Document Server

    Köster, U; Bergmann, U; Catherall, R; Cederkäll, J; Dillmann, I; Dubois, M; Durantel, F; Fraile-Prieto, L M; Franchoo, S; Gaubert, G; Gaudefroy, L; Hallmann, O; Huet-Equilbec, C; Jacquot, B; Jardin, P; Kratz, K L; Lecesne, N; Leroy, R; López, A; Maunoury, L; Pacquet, J Y; Pfeiffer, B; Saint-Laurent, M G; Stodel, C; Villari, A C C; Weissman, L


    ISOL beams of $19-22^$O were produced at ISOLDE and GANIL. At ISOLDE the neutron-rich oxygen isotopes are produced by 1.4GeV proton-induced reactionsin a UC_X/graphite target. The target is connected via a water-cooled transfer line (to retain all non-volatile isobars) to an ISOLDE type FEBIAD ion source wherethe released CO is dominantly ionized as CO^+, $^19-22$O beams were also produced at SPIRAL (GANIL). A 77.5 MeV/nucleon $^36$S beam was fragmented in a thick graphite target, coupled by a cold tranfer tube to an ECR ion source which ionizes the released CO dominantly as O^+ and CO+.

  19. The development of a completely automated oxygen isotope mass spectrometer

    International Nuclear Information System (INIS)

    Ahern, T.K.


    A completely automated mass spectrometer system has been developed to measure the oxygen isotope ratio of carbon dioxide samples. The system has an accuracy of 0.03 percent, and is capable of analyzing more than 100 samples a day. The system uses an Interdata minicomputer as the primary controller. The intelligence of the system is contained within hardware circuits, software within the minicomputer, and firmware written for a Motorola 6802 microprocessor. A microprocessor-based inlet system controller maximizes the throughput of carbon dioxide samples within the inlet system. The inlet system normally contains four different aliquots of carbon dioxide and introduces these samples to the mass spectrometer through a single admittance leak. The system has been used in the analysis of 111 samples of ice taken from the Steele glacier

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

    Directory of Open Access Journals (Sweden)

    Lisowska-Gaczorek Aleksandra


    Full Text Available The main objective of oxygen isotope analysis is to determine the probable place of origin of an individual or the reconstruction of migration paths. The research are methodologically based on referencing oxygen isotope ratios of apatite phosphates (δ18Op to the range of environmental background δ18O, most frequently determined on the basis of precipitation.

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

    Directory of Open Access Journals (Sweden)

    Hannah B Vander Zanden


    Full Text Available The measurement of stable carbon (δ13C and nitrogen (δ15N isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H and oxygen (δ18O isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applications using δ2H and, to a lesser extent, δ18O values have demonstrated potential for these elements to provide novel insights in modern food web studies. We explore the advantages and challenges associated with three applications of δ2H and δ18O values in food web studies. First, large δ2H differences between aquatic and terrestrial ecosystem end members can permit the quantification of energy inputs and nutrient fluxes between these two sources, with potential applications for determining allochthonous vs. autochthonous nutrient sources in freshwater systems and relative aquatic habitat utilization by terrestrial organisms. Next, some studies have identified a relationship between δ2H values and trophic position, which suggests that this marker may serve as a trophic indicator, in addition to the more commonly used δ15N values. Finally, coupled measurements of δ2H and δ18O values are increasing as a result of reduced analytical challenges to measure both simultaneously and may provide additional ecological information over single element measurements. In some organisms, the isotopic ratios of these two elements are tightly coupled, whereas the isotopic disequilibrium in other organisms may offer insight into the diet and physiology of individuals. Although a coherent framework for interpreting δ2H and δ18O data in the context of food web studies is emerging, many fundamental uncertainties remain. We highlight directions for targeted research that

  2. Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim (United States)

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


    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.

  3. Anatomy of the thriple oxygen isotope Terrestrial Fractionatoin Line (United States)

    Sharp, Z. D.; Pack, A.


    In the triple oxygen isotope system, it is well established that the δ17O value of nearly all terrestrial materials is approximately ½ that of the corresponding δ18O value. In triple isotope space then, all samples plot on a slope 1/2 line, termed the Terrestrial Fractionation Line (TFL). It has recently been recognized that subtle, but significant departures from the TFL exist, given by Δ'17O = δ'17O -λ× δ'18O + γ, where λ is the slope of the TFL (γ is the y-intercept and assumed to be zero in most studies). There have been many published λ values, ranging from 0.52 to 0.5305. λ values determined from a best-fit to rock and mineral samples range from 0.5244 to 0.5266. λ values from meteoric waters are 0.527 to 0.528 (γ = 0.007 to 0.034), explained by equilibrium and kinetic processes. Extreme polar glacial samples define a λ >0.53. As pointed out by Matsuhisia et al. (GCA, 1978), there is no single factor that controls the δ17O-δ18O slope, and clearly there is no `correct' TFL line. However, some generalities can be noted. 1) Meteoric waters generally plot with a λ = 0.528 with a Δ'17O = 0.033. At both high and low δ18O values, the Δ'17O values of meteoritic waters decrease. Mantle derived samples plot in a limited δ space, with δ18O values of 5-9‰ and a Δ'17O of -0.05‰. Rock and mineral samples falling outside this narrow range have undergone interaction with meteoric or ocean water at some point in their history, either by alteration or neoform mineral growth. The quartz-water triple isotope fractionation factor varies with temperatures, ranging from 0.5237 to 0.5266 at 0°C and 200°C, respective. A fit to published rock data gives an overall λ = 0.5237-0.5240. These results are most likely explained by the sum of hydrothermal and low-temperature mineral-water fractionations. Attempting to place any significance on a TFL from a set of data in unwarranted without understanding the processes controlling the isotopic compositions of

  4. Seasonality of Oxygen isotope composition in cow (Bos taurus) hair and its model interpretation (United States)

    Chen, Guo; Schnyder, Hans; Auerswald, Karl


    Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (panalysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

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

    International Nuclear Information System (INIS)

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


    Oxygen isotopic selectivity on infrared multiphoton dissociation of 2,3-dihydropyran has been studied by the examination of the effects of excitation frequency, laser fluence, and gas pressure on the dissociation probability of 2,3-dihydropyran and isotopic composition of products. Oxygen-18 was enriched in a dissociation product: 2-propenal. The enrichment factor of 18 O and the dissociation probability were measured at laser frequency between 1033.5 and 1057.3 cm -1 ; the laser fluence of 2.2 - 2.3 J/cm 2 ; and the 2,3-dihydropyran pressure of 0.27 kPa. The dissociation probability decreases as the laser frequency being detuned from the absorption peak of 2,3-dihydropyran around 1081 cm -1 . On the other hand, the enrichment factor increases with detuning the frequency. The enrichment factor of 18 O increases with increasing the 2,3-dihydropyran pressure at the laser fluence below 3 J/cm 2 and the laser frequency of 1033.5 cm -1 , whereas the yield of 2-propenal decreases with increasing the pressure. Very high enrichment factor of 751 was obtained by the irradiation of 0.53 kPa of 2,3-dihydropyran at 2.1 J/cm 2 . (author)

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

    International Nuclear Information System (INIS)

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


    Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition above and below its melting temperature have been studied and compared with the primary (PKIE) and secondary kinetic isotope effects (SKIE) of 13 C and 18 O, respectively, in the decarboxylation of other heterocyclic acids. The temperature dependence of the secondary oxygen-18 isotope effects is negative in the total 221-255 deg C temperature interval investigated initially. The 13 C KIE measured above melting point of N.A. (temperature interval 235-270 deg C) are located in the range 1.007-1.009. Below melting point of nicotinic acid the 13 C KIE are larger and reveal the negative temperature dependence ( 13 C KIE decreases with decreasing the reaction temperature from 1.013/at 230 deg C to 1.0114/at 221 deg C). A discussion of the above isotopic results is presented. (author)

  7. Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry (United States)

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


    Surface temperature is among the most important parameters describing planetary climate and habitability, and yet there remains considerable debate about the temperature evolution of the Earth's oceans during the Phanerozoic Eon (541 million years ago to present), the time during which complex metazoan life radiated on Earth. Here we critically assess the emerging record of Phanerozoic ocean temperatures based on carbonate clumped isotope thermometry of fossil brachiopod and mollusk shells, and we present new data that fill important gaps in the Late Paleozoic record. We evaluate and reject the hypothesis that solid-state reordering of 13C-18O bonds has destroyed the primary clumped isotope temperature signal of most fossils during sedimentary burial at elevated temperatures. The resulting Phanerozoic record, which shows a general coupling between tropical seawater temperatures and atmospheric carbon dioxide (CO2) levels since the Paleozoic, indicates that tropical temperatures during the icehouse climate of the Carboniferous period were broadly similar to present (∼25-30 °C), and suggests that benthic metazoans were able to thrive at temperatures of 35-40 °C during intervals of the early and possibly the latest Paleozoic when CO2 levels were likely 5-10× higher than present-day values. Equally important, there is no resolvable trend in seawater oxygen isotope ratios (δ18 O) over the past ∼500 million years, indicating that the average temperature of oxygen exchange between seawater and the oceanic crust has been high (∼270 °C) since at least the early Paleozoic, which points to mid-ocean ridges as the dominant locus of water-rock interaction over the past half-billion years.

  8. Centennial-scale solar forcing of the South American Monsoon System recorded in stalagmites. (United States)

    Novello, Valdir F; Vuille, Mathias; Cruz, Francisco W; Stríkis, Nicolás M; de Paula, Marcos Saito; Edwards, R Lawrence; Cheng, Hai; Karmann, Ivo; Jaqueto, Plínio F; Trindade, Ricardo I F; Hartmann, Gelvam A; Moquet, Jean S


    The South American Monsoon System (SAMS) is generally considered to be highly sensitive to Northern Hemisphere (NH) temperature variations on multi-centennial timescales. The direct influence of solar forcing on moisture convergence in global monsoon systems on the other hand, while well explored in modeling studies, has hitherto not been documented in proxy data from the SAMS region. Hence little is known about the sensitivity of the SAMS to solar forcing over the past millennium and how it might compete or constructively interfere with NH temperature variations that occurred primarily in response to volcanic forcing. Here we present a new annually-resolved oxygen isotope record from a 1500-year long stalagmite recording past changes in precipitation in the hitherto unsampled core region of the SAMS. This record details how solar variability consistently modulated the strength of the SAMS on centennial time scales during the past 1500 years. Solar forcing, besides the previously recognized influence from NH temperature changes and associated Intertropical Convergence Zone (ITCZ) shifts, appears as a major driver affecting SAMS intensity at centennial time scales.

  9. Oxygen Isotopes Archived in Subfossil Chironomids: Advancing a Promising Proxy for Lake Water Isotopes (United States)

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


    Oxygen isotopes measured in subfossil chironomid head capsules (aquatic insect remains) in lake sediments are beginning to offer paleoclimate insights from previously under-studied areas of the world. Since the first published pilot study demonstrated the potential of chironomid δ18O to record lake water δ18O (Wooller et al., 2004), subsequent work has refined our understanding of this proxy: confirming via lab cultures that growth water controls head capsule δ18O (Wang et al., 2009), refining laboratory pretreatment protocols, and further validating the method by demonstrating strong agreement between carbonate and chironomid-derived paleo-isotope records (Verbruggen et al., 2009, 2010, 2011). However, outstanding questions remain, including the seasonality of chironomid growth, possible species-dependent vital effects, and diagenetic effects on the protein-chitin complex that comprise chironomid cuticles. To address some of these questions, we summarize available data from paired modern chironomid-lake water δ18O values from around the world and discuss climatic and environmental factors affecting chironomid isotopic signatures. We also present new data on the resistance of these subfossils to diagenesis and degradation throughout the late Quaternary using Fourier Transform Infrared Spectroscopy (FT-IR) and Pyrolysis Gas Chromatography Mass Spectrometry (Py-GC/MS) of chironomid remains up to >100,000 years old. As chironomids are nearly ubiquitous in lakes globally and, we argue, molecularly stable through glacial and interglacial cycles, this proxy has the potential to greatly expand the spatial and temporal resolution of Quaternary paleo-isotopes and thus climate records. In addition to reviewing and presenting new methodological advances, we also present applications of chironomid δ18O from millennial- to centennial-scale Holocene Greenland lake records.

  10. Mass-independent oxygen isotopic partitioning during gas-phase SiO2 formation. (United States)

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


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

  11. A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings. (United States)

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


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

  12. Oxygen isotope geochemistry of mafic magmas at Mt. Vesuvius (United States)

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


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

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

    International Nuclear Information System (INIS)

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


    The delta 18 O of mammalian bone-phosphate varies linearly with delta 18 O of environmental water, but is not in isotopic equilibrium with that water. This situation is explained by a model of delta 18 O in body water in which the important fluxes of exchangeable oxygen through the body are taken into account. Fractionation of oxygen isotopes between body and environmental drinking water is dependent on the rates of drinking and respiration. Isotopic fractionation can be estimated from physiological data and the estimates correlate very well with observed fractionation. Species whose water consumption is large relative to its energy expenditure is sensitive to isotopic ratio changes in environmental water. (author)

  14. Dating of a quaternary limestone cave by combining the SSNTD technique with paleodose measurements: application to the stalagmite and stalactite growth

    International Nuclear Information System (INIS)

    Misdaq, M.A.; Oufni, L.; Erramli, H.; Boudad, L.; Kabiri, L.


    Uranium ( 238 U) and thorium ( 232 Th) contents were evaluated in different stalagmite and stalactite samples belonging to a quaternary limestone cave by using a method based on determining mean critical angles of etching of the CR-39 and LR-115 II solid-state nuclear track detectors (SSNTDs). Annual absorbed α-, β- and γ-dose rates were determined in the stalagmite and stalactite materials. The stalagmite and stalactite samples were dated by exploiting data obtained for the total annual absorbed dose rates and measuring the corresponding paleodoses. Results obtained were compared with those obtained by classic thermoluminescence and U/Th disequilibrium methods. The studied speleothem began from about 121 kyr and continued to about 69 kyr, coinciding almost with the last interglaciation corresponding to the fourth and fifth isotope stages. The formation rates of the stalagmite and stalactite samples were found equal to 0.88 and 0.94 cm kyr -1 , respectively

  15. Near Surface CO2 Triple Oxygen Isotope Composition

    Directory of Open Access Journals (Sweden)

    Sasadhar Mahata


    Full Text Available The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000 - 0.516 × 1000 × ln(1 + δ18O/1000], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. Therefore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforementioned surface sources. We have analyzed Δ17O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation, in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could provide an additional tracer for constraining the carbon cycle.

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

    International Nuclear Information System (INIS)

    Yakir, D.; DeNiro, M.J.


    Lemna gibba L. B3 was grown under heterotrophic, photoheterotrophic, and autotrophic conditions in water having a variety of hydrogen and oxygen isotopic compositions. The slopes of the linear regression lines between the isotopic composition of water and leaf cellulose indicated that under the three growth conditions about 40, 70, and 100% of oxygens and carbon-bound hydrogens of cellulose exchanged with those of water prior to cellulose formation. Using the equations of the linear relationships, we estimated the overall fractionation factors between water and the exchanged oxygen and carbon bound-hydrogen of cellulose. At least two very different isotope effects must determine the hydrogen isotopic composition of Lemna cellulose. One reflects the photosynthetic reduction of NADP, while the second reflects exchange reactions that occur subsequent to NADP reduction. Oxygen isotopic composition of cellulose apparently is determined by a single type of exchange reaction with water. Under different growth conditions, variations in metabolic fluxes affect the hydrogen isotopic composition of cellulose by influencing the extent to which the two isotope effects mentioned above are recorded. The oxygen isotopic composition of cellulose is not affected by such changes in growth conditions

  17. A model predicting hydrogen and oxygen isotopes of mammalian hair at the landscape scale (United States)

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


    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.

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

    National Oceanic and Atmospheric Administration, Department of Commerce — Ras Umm Sidd bimonthly coral oxygen isotope data (coral core RUS-95). Notes on the data: File (Ras Umm Sidd d18O.txt.) includes columns for Year AD (bimonthly...

  19. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil (United States)

    National Aeronautics and Space Administration — This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest canopy...

  20. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil (United States)

    National Aeronautics and Space Administration — ABSTRACT: This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest...

  1. Palmyra Island Monthly Oxygen Isotope Data (delta 18O) for 1886-1998 (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Palmyra Island Monthly Coral Oxygen Isotope Data. 112-yr, monthly-resolved coral record from Palmyra Island (5 deg 52 min N, 162 deg 8 min W). The coral was drilled...

  2. LBA-ECO CD-02 Oxygen Isotopes of Plant Tissue Water and Atmospheric Water Vapor (United States)

    National Aeronautics and Space Administration — This data set reports the oxygen isotope signatures of water extracted from plant tissue (xylem from the stems and leaf tissue) and of atmospheric water vapor from...

  3. LBA-ECO CD-02 Oxygen Isotopes of Plant Tissue Water and Atmospheric Water Vapor (United States)

    National Aeronautics and Space Administration — ABSTRACT: This data set reports the oxygen isotope signatures of water extracted from plant tissue (xylem from the stems and leaf tissue) and of atmospheric water...

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

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


    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

  5. U-Series Dates for Stalagmitic Flowstone E (Riss/Würm Interglaciation) at Grotte du Lazaret, Nice, France


    Falguères, Christophe; De Lumley, Henry; James.L, Bischoff


    Publication : University of Washington; Several samples of stalagmitic flowstone (Ensemble E) at Grotte du Lazaret (Nice, France) were dates by U-series isotopes. The results show that this speleothem began to grow about 130 000 yr BP and continued to about 70 000 yr BP coinciding almost exactly with the last interglaciation (isotope stage 5). Even though Ensemble E is not in direct stratigraphic relation with the cave deposits, this study shows that the Acheulian artifacts industry and fauna...

  6. The use of oxygen isotopes of dissolved oxygen as an innovative tool for water quality parameter estimation

    International Nuclear Information System (INIS)

    Tasneem, M.A.; Sajjad, M.I.; Khan, I.H.; Latif, Z.; Butt, S.; Afzal, M.; Ali, M.


    The water samples were collected from Rawal lake near Islamabad for seasonal studies of physiochemical and isotopic parameters of water and dissolved oxygen. Optimum experimental conditions for /sup 18/O analysis of dissolved oxygen of aqueous samples were determined. Stratification of dissolved oxygen was observed in Rawal Lake Before rainy season in summer. The water quality deteriorates with depth, because the respiration exceeds the photosynthesis and gas exchange. The concentration and /sup 18/O of dissolved oxygen show no variation with depth in winter, 1998 sampling. (author)

  7. Heterogeneities in the solar nebula. [oxygen isotopic composition in carbonaceous chondrites (United States)

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


    Oxygen isotopic compositions of the high-temperatue phases in carbonaceous chondrites define a mixing line with an O-16 rich component and show little superimposed chemical isotope fractionation. Within a single inclusion in Allende, variations of delta O-18 and delta O-17 of 39% are found. The ordinary chondrites are slightly displaced from the terrestrial fractionation trend, implying that at least 0.2% of the oxygen in terrestrial rocks was derived from the O-16 rich component.

  8. Spatial and Temporal Trends in Stable Carbon and Oxygen Isotope Ratios of Juvenile Winter Flounder (United States)

    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...

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

    Digital Repository Service at National Institute of Oceanography (India)

    Oba, T.; Banakar, V.K.

    9.3 is greater than 11.3 is greater than 1 is greater than 7.5. This rating of interglacial warming is closely comparable with the standard oxygen isotope curve of deep-sea sediment cores and also to the hydrogen isotope curve of the EP1CA Dome C ice...

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

    CSIR Research Space (South Africa)

    Waterhouse, JS


    Full Text Available Annual oxygen and hydrogen isotope ratios in the alpha-cellulose of the latewood of oak (Quercus robur L.) growing on well-drained ground in Norfolk, UK have been measured. The authors have compared the observed values of isotope ratios with those...

  11. Phosphate oxygen isotopes within aquatic ecosystems: Global data synthesis and future research priorities

    International Nuclear Information System (INIS)

    Davies, Ceri L.; Surridge, Ben W.J.; Gooddy, Daren C.


    The oxygen isotope ratio of dissolved inorganic phosphate (δ 18 O p ) represents a novel and potentially powerful stable isotope tracer for biogeochemical research. Analysis of δ 18 O p may offer new insights into the relative importance of different sources of phosphorus within natural ecosystems. Due to the isotope fractionations that occur alongside the metabolism of phosphorus, δ 18 O p could also be used to better understand the intracellular and extracellular reaction mechanisms that control phosphorus cycling. In this review focussed on aquatic ecosystems, we examine the theoretical basis to using stable oxygen isotopes within phosphorus research. We consider the methodological challenges involved in accurately determining δ 18 O p , given aquatic matrices in which potential sources of contaminant oxygen are ubiquitous. Finally, we synthesise the existing global data regarding δ 18 O p in aquatic ecosystems, concluding by identifying four key areas for future development of δ 18 O p research. Through this synthesis, we seek to stimulate broader interest in the use of δ 18 O p to address the significant research and management challenges that continue to surround the stewardship of phosphorus. - Highlights: • Oxygen isotope ratio in dissolved inorganic phosphate a novel stable isotope tracer. • Theoretical basis for application of this tracer in aquatic ecosystems reviewed. • Protocols for determining phosphate oxygen isotope ratio summarised. • Synthesis of global data from marine and freshwater ecosystems reported. • Priorities for future research in this rapidly evolving field identified

  12. Phosphate stable oxygen isotope variability within a temperate agricultural soil. (United States)

    Granger, Steven J; Harris, Paul; Peukert, Sabine; Guo, Rongrong; Tamburini, Federica; Blackwell, Martin S A; Howden, Nicholas J K; McGrath, Steve


    In this study, we conduct a spatial analysis of soil total phosphorus (TP), acid extractable phosphate (PO 4 ) and the stable oxygen (O) isotope ratio within the PO 4 molecule (δ 18 O PO 4 ) from an intensively managed agricultural grassland site. Total P in the soil was found to range from 736 to 1952 mg P kg - 1 , of which between 12 and 48% was extractable using a 1 M HCl (HCl PO 4 ) solution with the two variables exhibiting a strong positive correlation. The δ 18 O PO 4 of the extracted PO 4 ranged from 17.0 to 21.6‰ with a mean of 18.8‰ (± 0.8). While the spatial variability of Total P has been researched at various scales, this is the first study to assess the variability of soil δ 18 O PO 4 at a field-scale resolution. We investigate whether or not δ 18 O PO 4 variability has any significant relationship with: (i) itself with respect to spatial autocorrelation effects; and (ii) HCl PO 4 , elevation and slope - both globally and locally. Results indicate that δ 18 O PO 4 was not spatially autocorrelated; and that δ 18 O PO 4 was only weakly related to HCl PO 4 , elevation and slope, when considering the study field as a whole. Interestingly, the latter relationships appear to vary in strength locally. In particular, the δ 18 O PO 4 to HCl PO 4 relationship may depend on the underlying soil class and/or on different field managements that had operated across an historical north-south field division of the study field, a division that had been removed four years prior to this study.

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

    International Nuclear Information System (INIS)

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


    The paper gives data on isotope composition of interstitial and near-bottom waters sampled in a region of gas-hydrate formation in the Sea of Okhotsk. The studies show that heavy isotopes of oxygen and hydrogen is used in gas-hydrate formation, with the result that isotope composition of its constitution water constitutes δ 18 O=+1.99per mille, δD=+23per mille relatively to SMOW. Formation of autogenic carbonates leads to isotope exchange with interstitial water wich, in turn, changes its primary isotope composition in the direction of increasing of O-18 content. The near-bottom waters are isotope-light relatively to the SMOW standard and to the mean isotope composition of interstitial water in the studied region of gas-hydrate spreading. (orig.) [de

  14. Stable carbon and oxygen isotope study on benthic foraminifera ...

    Indian Academy of Sciences (India)

    The present study is pursued on isotopic values of different pairs of benthic foraminifera from the Krishna–Godavari basin and Peru offshore to understand habitat-wise isotopic variation and ... Department of Applied Geology, Indian Institute of Technology (Indian School of Mines), Dhanbad, Jharkhand 826 004, India.

  15. Stable carbon and oxygen isotope study on benthic foraminifera ...

    Indian Academy of Sciences (India)

    Ajoy K Bhaumik


    Jul 24, 2017 ... Stable isotopes of benthic foraminifera have widely been applied in micropalaeontological research to understand vital effects in foraminifera. Isotopic fractionations are mainly controlled by ontogeny, bottom/pore water chemistry, habitat preference, kinetic effect and respiration. Discontinuous abundance.

  16. Sources of Holocene variability of oxygen isotopes in paleoclimate archives

    Directory of Open Access Journals (Sweden)

    A. N. LeGrande


    Full Text Available Variability in water isotopes has been captured in numerous archives and used to infer past climate changes. Here we examine water isotope variability over the course of the Holocene using the water-isotope enabled, coupled atmosphere-ocean general circulation model, GISS ModelE-R. Eight Holocene time slices, ~1000 years apart are simulated and driven by estimated changes in orbital configuration, greenhouse gases, and ice sheet extent. We find that simulated water isotope archives match well with those seen in ice cores, ocean sediment cores, and speleothems. The climate changes associated with the water isotope changes, however, are more complex than simple modern spatial slope interpretations might suggest. In particular, water isotope variability in Asian speleothems is linked to alterations in landward water vapor transport, not local precipitation, and ice sheet changes over North America lead to the masking of temperature signals in Summit, Greenland. Salinity-seawater isotope variability is complicated by inter-ocean basin exchanges of water vapor. Water isotopes do reflect variability in the hydrology, but are better interpreted in terms of regional hydrological cycle changes rather than as indicators of local climate.

  17. Oxygen isotope signatures of transpired water vapor: the role of isotopic non-steady-state transpiration under natural conditions. (United States)

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


    The oxygen isotope signature of water is a powerful tracer of water movement from plants to the global scale. However, little is known about the short-term variability of oxygen isotopes leaving the ecosystem via transpiration, as high-frequency measurements are lacking. A laser spectrometer was coupled to a gas-exchange chamber directly estimating branch-level fluxes in order to evaluate the short-term variability of the isotopic composition of transpiration (δE ) and to investigate the role of isotopic non-steady-state transpiration under natural conditions in cork-oak trees (Quercus suber) during distinct Mediterranean seasons. The measured δ(18) O of transpiration (δE ) deviated from isotopic steady state throughout most of the day even when leaf water at the evaporating sites was near isotopic steady state. High agreement was found between estimated and modeled δE values assuming non-steady-state enrichment of leaf water. Isoforcing, that is, the influence of the transpirational δ(18) O flux on atmospheric values, deviated from steady-state calculations but daily means were similar between steady state and non-steady state. However, strong daytime isoforcing on the atmosphere implies that short-term variations in δE are likely to have consequences for large-scale applications, for example, partitioning of ecosystem fluxes or satellite-based applications. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

  18. Oxygen isotopic composition of fulgurites from the Egyptian Sahara and other locations. (United States)

    Longinelli, Antonio; Serra, Romano; Sighinolfi, Giampaolo; Selmo, Enricomaria; Sgavetti, Maria


    Fulgurites are glassy crusts or hollow glassy tubes formed by the impact of a lightning strike on a target material on the Earth's surface. The oxygen isotopic composition of fulgurites has never been measured and, consequently, it is unknown whether or not isotopic fractionations take place between the target material and the fulgurite glass during the lightning event which is an excellent natural example of extremely fast melting process. Following well-established procedures (high-temperature reaction of the fulgurite material with BrF(5), conversion into CO(2) of the evolved O(2) and measurement of the(18)O/(16)O ratio on a Finnigan Delta S mass spectrometer) we measured for the first time the oxygen isotopic composition of sets of fulgurites coming from various locations on the Earth's surface. The range of isotopic values is quite large, probably reflecting the oxygen isotopic values of the target materials. In the case of fulgurites from the Sahara Desert the isotopic values obtained from the bulk material, quartz crystals sticking to the fulgurite body, tiny samples of loose sand coming from fulgurite bubbles, and sand samples collected near the fulgurites, are very close to one another. Although we do not have indisputable evidence, we conclude that, at least in the case of oxygen, the fusion process of the material struck by lightning, as well as all the extremely fast high-temperature fusion processes, probably take place without any isotopic fractionation effect. Copyright © 2012 John Wiley & Sons, Ltd.

  19. Characteristics of multi-stage AGMD-DCMD cascade system for oxygen isotope production

    International Nuclear Information System (INIS)

    Kim, Jae Woo; Choi, Hwa Rim; Chang, Dae Sik; Kim, Taek Soo; Lim, Gwon; Jeong, Do Young


    Membrane distillation (MD) appears to be useful for the separation of the light isotopes such as oxygen and hydrogen isotopes contained in water, because membrane permeation units are compact and simple, and more importantly its energy consumption is low compared to conventional water fractional distillation.1-4 Permeation fluxes and the degree of oxygen isotope separation of AGMD (Air Gap Membrane Distillation) and VEMD (Vacuum Enhanced Membrane Distillation) processes were measured by using the hot water feed. Even though VEMD shows slightly higher isotopic separation degree with higher permeation flux, it is very difficult to apply VEMD to multi-stage cascade system. Since local oxygen isotope separation coefficient for a single membrane unit is low, multi-stage membrane cascade system is required to increase isotopic concentration further in product. Although AGMD is suitable for constructing the membrane cascading system, permeation flux for AGMD is still too low to apply to the isotope production system. In this investigation, we increased permeation flux of AGMD using AGMD-DCMD (Direct Contact Membrane Distillation) combined process. Permeation flux and degree of isotope separation of AGMD-DCMD combined process were measured by using 10 stages cascade system

  20. Simultaneous determination of stable carbon, oxygen, and hydrogen isotopes in cellulose. (United States)

    Loader, N J; Street-Perrott, F A; Daley, T J; Hughes, P D M; Kimak, A; Levanič, T; Mallon, G; Mauquoy, D; Robertson, I; Roland, T P; van Bellen, S; Ziehmer, M M; Leuenberger, M


    A technological development is described through which the stable carbon-, oxygen-, and nonexchangeable hydrogen-isotopic ratios (δ(13)C, δ(18)O, δ(2)H) are determined on a single carbohydrate (cellulose) sample with precision equivalent to conventional techniques (δ(13)C 0.15‰, δ(18)O 0.30‰, δ(2)H 3.0‰). This triple-isotope approach offers significant new research opportunities, most notably in physiology and medicine, isotope biogeochemistry, forensic science, and palaeoclimatology, when isotopic analysis of a common sample is desirable or when sample material is limited.

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

    International Nuclear Information System (INIS)

    Torquato, J.R.F.


    Samples of carbonated rocks of precambrian age are studied. The stable carbon and oxygen isotopes are applied to the study of terrestrial materials considering the variations of some element isotopic composition in function of the environment of sedimentation. The isotopic analysis was done using mass spectrometers. The analytical results and the description of region geology of the site of each sample are presented. The isotopic data are interpreted aiming to the environment of sedimentation. New techniques for better improvement of carbon and oxygen ratios, are proposed, such as: to use the analysis of surface trend and the isotopic logging in mapping of surface and subsurface. A new method for approximated determination of the ages of precambrian carbonated rocks, considering the limitations of their new technique, is also presented. (M.C.K.) [pt

  2. Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature (United States)

    Hayles, J.; Shen, B.; Homann, M.; Yeung, L.


    One point of contention among geoscientists is whether the 18O/16O ratio of seawater is roughly constant, or if it varies considerably throughout geologic time. On one hand, the oxygen isotope composition of the ocean is thought to be well buffered by high- and low-temperature interactions between seawater and seafloor rocks. If these interactions do not vary on billion-year timescales, the oxygen-isotope compositions of marine sedimentary rocks mostly relate to changes in seawater temperature and global ice volume. On the other hand, long-term cooling of the planetary interior would alter these water-rock interactions leading to a secular change in the oxygen isotope composition of seawater. Models suggest that this secular change would enrich seawater with heavy oxygen isotopes over time. In this study, we present new, high precision, triple-oxygen-isotope (18O/16O, 17O/16O) analyses of marine chert samples from 3.45 Ga to 460Ma. The results of these analyses are paired with a new theoretical quartz-water equilibrium curve and a simplified seawater model to provide possible pairings of δ'18O and Δ'17O for the water which these samples could have formed in equilibrium with. Analysis of the new sample data, in addition to published chert triple oxygen isotope compositions, shows a general trend of older chert samples being progressively incompatible with waters possessing a modern-like seawater triple oxygen isotope composition. Implications on constraining the secular evolution of seawater δ18O and temperature will be discussed.

  3. Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides (United States)

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


    Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be

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

    International Nuclear Information System (INIS)

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


    Techniques of low-temperature isotopic-spectral determination of impurities of hydrogen, nitrogen, oxygen and carbon in semiconductor materials Bi, Ge, Pb tellurides are developed. The techniques include selection into special vessel with the known volume (exchanger) of sample analyzed, dosed introduction into exchanger of rare isotope of the element determined ( 2 H, 15 N, 18 O, 13 C) in the form of isotope-containing gas, balancing of the determined element isotopes in the system sample-isotope, containing gas, spectroscopic, determination of its isotope composition in gaseous phase of the system and calculation of the amount of the element determined in the sample. The lower boundaries of the amounts determined constitute 10 -7 , 10 -7 , 10 -6 and 10 -5 mass % respectively when sample of 20 g are used [ru

  5. Oxygen isotopic ratios of primordial water in carbonaceous chondrites (United States)

    Fujiya, Wataru


    In this work, I estimate the δ18 O and δ17 O values of primordial water in CM chondrites to be 55 ± 13 and 35 ± 9‰, respectively, based on whole-rock O and H data. Also, I found that the O and/or H data of Antarctic meteorites are biased, which is attributed to terrestrial weathering. This characteristic O isotopic ratio of water together with corresponding water abundances in CM chondrites are consistent with the origin of water as ice processed by photochemical reactions at the outer regions of the solar nebula, where mass-independent O isotopic fractionation and water destruction may have occurred. Another possible mechanism to produce the inferred O isotopic ratio of water would be O isotopic fractionation between water vapor and ice, which likely occurred near the condensation front of H2O (snow line) in the solar nebula. The inferred O isotopic ratio of water suggests that carbonate in CM chondrites formed at low temperatures of <150 °C. The O isotopic ratios of primordial water in chondrites other than CM chondrites are not well constrained.

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

    International Nuclear Information System (INIS)

    Chiba, H.; Sakai, H.


    Oxygen isotope exchange rate between dissolved sulfate and water was experimentally determined at 100, 200 and 300 deg C. The isotope exchange rate is strongly dependent on temperature and pH of the solution. Combining the temperature and pH dependence of the reaction rate, the exchange reaction was estimated to be first-order with respect to sulfate. The logarithm of apparent rate constant of exchange reaction at a given temperature is a function of the pH calculated at the experimental temperatures. From the pH dependence of the apparent rate constant, it was deduced that the isotope exchange reaction between dissolved sulfate and water proceeds through collision between H 2 SO 4 0 and H 2 O at low pH, and between HSO 4 - and H 2 O at intermediate pH. The isotope exchange rate obtained indicates that oxygen isotope geothermometry utilizing the studied isotope exchange is suitable for temperature estimation of geothermal reservoirs. The extrapolated half-life of this reaction to oceanic temperature is about 10 9 years, implying that exchange between oceanic sulfate and water cannot control the oxygen isotope ratio of oceanic sulfates. (author)

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

    International Nuclear Information System (INIS)

    Longinelli, A.


    The purpose of this study is to try to establish quantitative relationships between the average oxygen isotopic composition of local meteoric water, the oxygen isotopic composition of mammal body water and the oxygen isotopic composition of phosphate in mammal bones. These relationships, after calibration of the method on living specimens, would allow quantitative paleoclimatological research based on the measurement of delta 18 O(PO 4 3- ) of fossil mammal bones

  8. In vacuo reduction of silver orthophosphate with graphite for high-precision oxygen isotope analysis. (United States)

    Pelc, Andrzej; Halas, Stanislaw


    The reduction of silver phosphate with graphite under vacuum conditions was studied at final reaction temperatures varying from 430 to 915°C to determine: (i) the CO(2) extraction yield, and (ii) the oxygen isotopic composition of CO(2). The CO(2) yield and oxygen isotopic composition were determined on a calibrated dual inlet and triple collector isotope ratio mass spectrometer. We observed the following three stages of the reduction process. (1) At temperatures below 590°C only CO(2) is formed, while silver orthophosphate decays to pyrophosphate. (2) At higher temperatures, 590-830°C, predominantly CO is formed from silver pyrophosphate which decays to metaphosphate; this CO was always converted into CO(2) by the glow discharge method. (3) At temperatures above 830°C the noticeable sublimation of silver orthophosphate occurs. This observation was accompanied by the oxygen isotope analysis of the obtained CO(2). The measured δ(18)O value varied from -11.93‰ (at the lowest temperature) to -20.32‰ (at the highest temperature). The optimum reduction temperature range was found to be 780-830°C. In this temperature range the oxygen isotopic composition of CO(2) is nearly constant and the reaction efficiency is relatively high. The determined difference between the δ(18)O value of oxygen in silver phosphate and that in CO(2) extracted from this phosphate is +0.70‰. Copyright © 2010 John Wiley & Sons, Ltd.

  9. Hydrogen and oxygen isotope ratios of geothermal waters in the southern hachimantai area

    International Nuclear Information System (INIS)

    Matsubaya, Osamu; Etchu, Hiroshi; Takenaka, Teruo; Yoshida, Yutaka.


    Geothermal waters from the Matsukawa and Kakkonda Geothermal Plants, wells at Amihari-Motoyu, and Nyuto and Tazawako areas were isotopically studied. The geothermal waters from Mutsukawa, Kakkonda and Amihari-Motoyu have hydrogen isotope ratios similar to the local meteoric waters, while have higher oxygen isotope ratios than the local meteoric waters. This relationship of hydrogen and oxygen isotope ratios, that is called ''oxygen shift'', means that these geothermal waters are meteoric waters undergone the oxygen isotope exchange with rocks at high temperature of underground. The exygen shifts are 2 -- 3 per mil in Matsukawa and Kakkonda, and 7 per mil in Amihari-Motoyu. This difference may be important to understand the processe of water-rock interaction in this area. The geothermal waters at Nyuto and Tazawako areas also show 2 -- 3 per mil oxygen shift. The steam from the Tazawako-cho well and the hot spring water form the Tsurunoyu are estimated to be vapor and liquid phases separated form a single geothermal water of NaCl type, though the hot water from the Tsurunoyu is diluted with shallow meteoric water. (author)

  10. Temperature and Oxygen Isotope Composition of The Ediacaran Ocean: Constraints From Clumped Isotope Carbonate Thermometry (United States)

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


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

  11. A chemical exchange system for isotopic feed to a nitrogen and oxygen isotope separation plant

    International Nuclear Information System (INIS)

    Mills, T.R.; Garcia, M.G.; Vandervoort, R.C.; McInteer, B.B.


    A process has been developed to provide isotopic feed to a nitric oxide isotope distillation plant. Central to the process is the isotopic chemical exchange of NO and nitric acid in countercurrent flows in a 3-in. diameter packed column. An isotopically depleted stream of NO is reenriched to natural isotopic abundances by the exchange and is recycled as feed back to the distillation columns. Makeup NO is generated in another column from sulfur dioxide and nitric acid. Multistage gas purifiers reduce condensible impurities in the nitric oxide below 10 ppm. The process operates unattended at flow rates of 0.5 to 2 mol/min. The new NO recycle-enrichment and generation processes have successfully provided the feedstock for the NO isotope separation columns for over 6 years. 19 refs., 2 figs

  12. Oxygen-18 Isotopic Studies of HOOO and DOOO. (United States)

    Barreau, Lou; Martinez, Oscar; Crabtree, Kyle N; Womack, Caroline C; Stanton, John F; McCarthy, Michael C


    Owing to questions that still persist regarding the length of the O-H and central O-O bond, and large-amplitude torsional motion of trans hydridotrioxygen HOOO, a weakly bound complex between OH and O 2 , new 18 O isotopic measurements of HOOO and DOOO were undertaken using Fourier transform microwave and microwave-millimeter-wave double resonance techniques. Rotational lines from three new 18 O species of DOOO (D 18 OOO, DO 18 O 18 O, and D 18 O 18 O 18 O) were detected, along with the two singly substituted 18 O isotopic species of HOOO (HO 18 OO and HOO 18 O) that were not measured in the previous isotopic investigation. From a least-squares fit, spectroscopic constants, including the three rotational constants, were precisely determined for all five species. The inertial defect of DOOO and its 18 O species is uniformly negative: of order -0.04 amu Å 2 , regardless of the number or location of the 18 O atoms, in contrast to that found for HOOO or its 18 O isotopic species. A reanalysis of the molecular structure was performed using either normal HOOO and its four singly substituted isotopic species, the new DOOO data, or all the isotopic species (10 in total). The differences between the purely experimental (r 0 ) structures are generally quite small, of order ±0.01 Å for the bond lengths and ±1° for the bond angle. The length of the O-H bond remains unrealistically short compared to free OH, and the central O-O bond length is consistently very close to 1.68 Å. On the basis of the effective O-H bond length derived from the experimental structure, the average displacement of the large amplitude torsional motion from planarity is estimated to be ∼22°.

  13. Glacial meltwater input to the Alaska Coastal Current: Evidence from oxygen isotope measurements (United States)

    Kipphut, George W.


    Results of a study of the oxygen isotopic composition of coastal, pelagic, and fresh waters from the northern Gulf of Alaska region are presented. This study was undertaken to investigate whether isotopic tracers could be of use in determining the important freshwater inputs to the Alaska Coastal Current (ACC) and whether they could confirm the presence of the ACC in coastal waters west of Kodiak Island. The Alaska Coastal Current, the major coastal circulation feature of the northern Gulf of Alaska, can be distinguished from oceanic waters on the basis of its lower salinity at least as far west as Kodiak Island. This study adds significantly to the small amount of oxygen isotopic information available for the waters of this region. The isotopic results suggest that in late summer, glacial meltwater may provide a substantial portion of the total freshwater runoff into the ACC, and that the ACC does extend as far to the west as Unimak Pass.

  14. Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater (United States)

    Hermoso, Michaël; Horner, Tristan J.; Minoletti, Fabrice; Rickaby, Rosalind E. M.


    In this study, we show that there are independent controls of 18O/16O and 13C/12C fractionation in coccolithophore and dinoflagellate calcite due to the contrasting kinetics of each isotope system. We demonstrate that the direction and magnitude of the oxygen isotope fractionation with respect to equilibrium is related to the balance between calcification rate and the replenishment of the internal pool of dissolved inorganic carbon (DIC). As such, in fast growing cells, such as those of Emiliania huxleyi and Gephyrocapsa oceanica (forming the so-called ;heavy group;), calcification of the internal carbon pool occurs faster than complete isotopic re-adjustment of the internal DIC pool with H2O molecules. Hence, coccoliths reflect the heavy oxygen isotope signature of the CO2 overprinting the whole DIC pool. Conversely, in large and slow growing cells, such as Coccolithus pelagicus ssp. braarudii, complete re-equilibration is achieved due to limited influx of CO2 leading to coccoliths that are precipitated in conditions close to isotopic equilibrium (;equilibrium group;). Species exhibiting the most negative oxygen isotope composition, such as Calcidiscus leptoporus (;light group;), precipitate coccolith under increased pH in the coccolith vesicle, as previously documented by the ;carbonate ion effect;. We suggest that, for the carbon isotope system, any observed deviation from isotopic equilibrium is only ;apparent;, as the carbon isotopic composition in coccolith calcite is controlled by a Rayleigh fractionation originating from preferential incorporation of 12C into organic matter. Therefore, species with low PIC/POC ratios as E. huxleyi and G. oceanica are shifted towards positive carbon isotope values as a result of predominant carbon fixation into the organic matter. By contrast, cells with higher PIC/POC as C. braarudii and C. leptoporus maintain, to some extent, the original negative isotopic composition of the CO2. The calcareous dinoflagellate

  15. Examining cross-equatorial precipitation variability in the western Indian Ocean using stalagmites from Madagascar (United States)

    Scroxton, N.; Burns, S. J.; McGee, D.; Hardt, B. F.; Godfrey, L.; Ranivoharimanana, L.; Faina, P.


    The behavior of the world's monsoon systems and the position of the Inter Tropical Convergence Zone (ITCZ) resulting from large global climatic changes is reasonably well understood at orbital and millennial timescales. However, under the boundary conditions and relatively modest forcing of the last 2000 years it is not yet clear how tropical monsoon systems changed and why. The traditional schema of north-south translation of the ITCZ is being challenged by new theories relating to meridional expansion and contraction of the tropical rain belt, and/or to changes in zonal circulation patterns resembling modern El-Niño Southern Oscillation end members. Located at a hotspot of zonal and meridional climate forcing, stalagmites from the western Indian Ocean can provide new insights into past rainfall variability and uncover the driving mechanisms. Here, we present results from a new southern hemisphere speleothem record from Anjohibe cave, northwestern Madagascar, covering the last 1,700 years. We demonstrate that our quasi-annual, precisely dated, stable oxygen isotope record serves as a proxy for the strength of the northwestern Madagascan monsoon. The record shows a multi-decadal, in-phase relationship with its northern hemisphere monsoon counterpart from Oman - contrary to the expected antiphase relationship that would result from north-south ITCZ translation. At the centennial scale, the Madagascan record correlates well with precipitation records from Eastern Africa. We discuss the potential causes of western Indian Ocean precipitation coherency, and how it relates to either symmetrical changes in continental sensible heating, or to a low frequency zonal sea-surface temperature mode.

  16. Isotopic composition of the anomalous low energy cosmic ray nitrogen and oxygen (United States)

    Mewaldt, R. A.; Stone, E. C.; Vidor, S. B.; Vogt, R. E.


    The isotopic composition of the enhanced fluxes of cosmic ray nitrogen and oxygen observed below 30 MeV/nuc is of interest, whether the nuclei are a sample from some nearby galactic source region that is underabundant in carbon, or a sample of the neutral interstellar medium. Enhanced fluxes in the 6 to 12 MeV/nuc energy interval were measured over a two year period with the Caltech Electron/Isotope Spectrometer on IMP-7. The observed low-energy nitrogen and oxygen nuclei are predominantly N-14 and O-16, with upper limits (84% confidence level) of N-15/N below 0.26, O-17/0 below 0.13, and O-18/0 below 0.12 for other isotopes in the 6-12 MeV/nuc energy interval. The implications of these results for the origin of the enhanced nitrogen and oxygen fluxes are discussed.

  17. Phosphate oxygen isotopes within aquatic ecosystems: Global data synthesis and future research priorities

    Energy Technology Data Exchange (ETDEWEB)

    Davies, Ceri L. [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Surridge, Ben W.J., E-mail: [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Gooddy, Daren C. [British Geological Survey, Maclean Building, Wallingford, Oxfordshire OX10 8BB (United Kingdom)


    The oxygen isotope ratio of dissolved inorganic phosphate (δ{sup 18}O{sub p}) represents a novel and potentially powerful stable isotope tracer for biogeochemical research. Analysis of δ{sup 18}O{sub p} may offer new insights into the relative importance of different sources of phosphorus within natural ecosystems. Due to the isotope fractionations that occur alongside the metabolism of phosphorus, δ{sup 18}O{sub p} could also be used to better understand the intracellular and extracellular reaction mechanisms that control phosphorus cycling. In this review focussed on aquatic ecosystems, we examine the theoretical basis to using stable oxygen isotopes within phosphorus research. We consider the methodological challenges involved in accurately determining δ{sup 18}O{sub p}, given aquatic matrices in which potential sources of contaminant oxygen are ubiquitous. Finally, we synthesise the existing global data regarding δ{sup 18}O{sub p} in aquatic ecosystems, concluding by identifying four key areas for future development of δ{sup 18}O{sub p} research. Through this synthesis, we seek to stimulate broader interest in the use of δ{sup 18}O{sub p} to address the significant research and management challenges that continue to surround the stewardship of phosphorus. - Highlights: • Oxygen isotope ratio in dissolved inorganic phosphate a novel stable isotope tracer. • Theoretical basis for application of this tracer in aquatic ecosystems reviewed. • Protocols for determining phosphate oxygen isotope ratio summarised. • Synthesis of global data from marine and freshwater ecosystems reported. • Priorities for future research in this rapidly evolving field identified.

  18. Oxygen isotopic signature of CO2 from combustion processes

    NARCIS (Netherlands)

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


    For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (C-13 and O-18) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the delta O-18

  19. Nucleosynthesis in AGB Stars Traced by Oxygen Isotopic Ratios

    NARCIS (Netherlands)

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


    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

  20. Ground Based Observation of Isotopic Oxygen in the Martian Atmosphere Using Infrared Heterodyne Spectroscopy (United States)

    Smith, R. L.; Kostiuk, T.; Livengood, T. A.; Fast, K. E.; Hewagama, T.; Delgado, J. D.; Sonnabend, G.


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

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


    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

  2. High Precision Oxygen Three Isotope Analysis of Wild-2 Particles and Anhydrous Chondritic Interplanetary Dust Particles (United States)

    Nakashima, D.; Ushikubo, T.; Zolensky, Michael E.; Weisberg, M. K.; Joswiak, D. J.; Brownlee, D. E.; Matrajt, G.; Kita, N. T.


    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 (isotope analyses of Wild-2 particles and anhydrous chondritic IDPs, and discuss the relationship between the cometary dust and carbonaceous chondrite chondrules.

  3. Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite (United States)

    Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne


    The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical

  4. Changes in Oxygen Isotopes Composition of Precipitation over Tibetan Plateau during Cenozoic (United States)

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


    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.

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

    International Nuclear Information System (INIS)

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


    The nature and systematics of impurities such as carbonates need to be established in order to understand their provenance in coal seams with reference to mining, beneficiation and ultimately their elimination or reduction. To this end, mineralogical and carbon-13 and oxygen-18 isotopic studies were undertaken on carbonate occurrences in coal from the eastern Transvaal highveld. Isotopic variations of considerable amplitude and individual values of extreme ''lightness'' are to be found in the carbonates in coal of the Witbank and adjacent basins. The observed isotopic ratios have a clear bearing on the nature and origins of the carbonates. 1 tab., 1 fig

  6. Investigating the Direct Meltwater Effect in Terrestrial Oxygen-Isotope Paleoclimate Records Using an Isotope-Enabled Earth System Model (United States)

    Zhu, Jiang; Liu, Zhengyu; Brady, Esther C.; Otto-Bliesner, Bette L.; Marcott, Shaun A.; Zhang, Jiaxu; Wang, Xianfeng; Nusbaumer, Jesse; Wong, Tony E.; Jahn, Alexandra; Noone, David


    Variations in terrestrial oxygen-isotope reconstructions from ice cores and speleothems have been primarily attributed to climatic changes of surface air temperature, precipitation amount, or atmospheric circulation. Here we demonstrate with the fully coupled isotope-enabled Community Earth System Model an additional process contributing to the oxygen-isotope variations during glacial meltwater events. This process, termed "the direct meltwater effect," involves propagating large amounts of isotopically depleted meltwater throughout the hydrological cycle and is independent of climatic changes. We find that the direct meltwater effect can make up 15-35% of the δ18O signals in precipitation over Greenland and eastern Brazil for large freshwater forcings (0.25-0.50 sverdrup (106 m3/s)). Model simulations further demonstrate that the direct meltwater effect increases with the magnitude and duration of the freshwater forcing and is sensitive to both the location and shape of the meltwater. These new modeling results have important implications for past climate interpretations of δ18O.

  7. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions (United States)

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


    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.

  8. Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia (United States)

    Brookman, Tom H.; Ambrose, Stanley H.


    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.

  9. Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate. (United States)

    Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky


    Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

  10. Lake Louise water (USGS47): a new isotopic reference water for stable hydrogen and oxygen isotope measurements. (United States)

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


    Because of the paucity of isotopic reference waters for daily use, a new secondary isotopic reference material has been prepared from Lake Louise water from Alberta, Canada, for international distribution. This water was filtered, homogenized, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule. The δ(2)H and δ(18)O 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 δ(2)H and δ(18)O 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% probability of encompassing the true value. 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. Published in 2013. This article is a U.S. Government work and is in the public domain in the USA. Published in 2013. This article is a U.S. Government work and is in the public domain in the USA.

  11. Detection of phosphohydrolytic enzyme activity through the oxygen isotope composition of dissolved phosphate (United States)

    Colman, A. S.


    Phosphohydrolytic enzymes play an important role in phosphorus remineralization. As they release phosphate (Pi) from various organophosphorus compounds, these enzymes facilitate the transfer of oxygen atoms from water to the phosphoryl moieties. Most such enzymatic reactions impart a significant isotopic fractionation to the oxygen transferred. If this reaction occurs within a cell, then the resultant oxygen isotope signal is overprinted by continued recycling of the Pi. However, if this reaction occurs extracellularly, then the isotopic signal will be preserved until the Pi is transported back into a cell. Thus, the oxygen isotope composition of Pi (δ18Op) in an aquatic ecosystem can serve as a useful indicator of the mechanisms by which P is remineralized. We develop a time-dependent model illustrating the sensitivity of the δ18O of dissolved phosphate to various modes of P remineralization. The model is informed by cell lysis experiments that reveal the relative proportions of P­i that are directly liberated from cytosol vs. regenerated from co-liberated dissolved organic phosphorus compounds via extracellular hydrolysis. By incorporating both cellular uptake and release fluxes of P, we show that the degree of isotopic disequilibrium in an aquatic ecosystem can be a strong indicator of P remineralization mode. Apparent oxygen isotope equilibrium between Pi and water arises in this model as a steady-state scenario in which fractionation upon cellular uptake of Pi counterbalances the hydrolytic source flux of disequilibrated Pi. Low and high rates of extracellular phosphohydrolase activity are shown to produce steady-state δ18Op values that are respectively above or below thermodynamic equilibrium compositions.

  12. Analytical techniques for determination of framework oxygen isotope ratio of wairakite

    International Nuclear Information System (INIS)

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


    Dehydration techniques were developed for the analysis of isotopic ratios of framework oxygen of wairakite, one of calcium zeolites often encountered in geothermal systems. Channel water in wairakite were separated from aluminosilicate framework by dehydration in vacuum at 300 deg, 400 deg, 450 deg, 500 deg, 550 deg, 650 deg, 750 deg, 850 deg, and 950 degC, and by stepwise heating at temperatures from 300 deg to 700 degC. The oxygen isotopic analyses of the separated channel water and the residual aluminosilicate framework of wairakite indicated that dehydration at temperatures higher than 400 degC is accompanied by isotopic exchang between the framework oxygen and dehydrating water vapor. The isotopic exchange during the high temperature dehydration makes the δ 18 O of framework oxygen lower and that of channel water higher than those obtained by dehydration at 300 degC. These results are consistent with dehydration behavior of wairakite under vacuum that the maximum rate of dehydration of channel water is attained at about 400 degC. Consequently it is recommended to dehydrate wairakite at a temperature as low as possible in order to avoid the effect of the isotopic exchange. Time required to attain complete dehydration becomes longer with lowering the temperature of dehydration. To compromise these conflicting effects, the optimum conditions of dehydration have been found that most of the channel water is dehydrated at 300 degC for 24 hours, followed by stepwise heating for additional 17 hours up to 700 degC. We obtained a better than ± 0.1 reproducibility for the framework oxygen isotopic determinations with this technique. (author)

  13. Oxygen isotopic fractionation of O₂ during adsorption and desorption processes using molecular sieve at low temperatures. (United States)

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


    Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in

  14. Grain-scale stable carbon and oxygen isotopic variations of the international reference calcite, IAEA-603. (United States)

    Nishida, Kozue; Ishimura, Toyoho


    The new international reference material IAEA-603 (calcite) for stable carbon and oxygen isotopes (δ 13 C and δ 18 O values) was released in 2016 to replace the previous reference material, NBS19 (exhausted). We examined the grain-scale isotopic variations in IAEA-603 for application to microscale isotopic analysis of carbonate samples. Individual grains of IAEA-603 were analyzed with an IsoPrime100 isotope ratio mass spectrometer with a customized continuous-flow gas preparation system (MICAL3c). The individual grains of IAEA-603 were observed by optical and scanning electron microscopy, and their observational characteristics (grain color and size) were compared with their stable isotope compositions. Translucent grains (main component of IAEA-603; grain weight, 4-132 μg) had homogeneous isotopic ratios, comparable with the grain-scale isotopic homogeneity of NBS 19. Their average δ 13 C and δ 18 O values were the same as the recommended values determined by the IAEA. Opaque (whitish) grains (1-2 per 100 grains; grain weight, 8-63 μg) were significantly more depleted in 13 C and 18 O than the translucent grains. Low-abundance opaque grains (1-2 grains out of 100 grains) have lower δ 13 C and δ 18 O values, suggesting that these grains should be eliminated when using IAEA-603 for single-grain (microscale) isotope analysis. Copyright © 2017 John Wiley & Sons, Ltd.

  15. Uncertainties in the oxygen isotopic composition of barium sulfate induced by coprecipitation of nitrate. (United States)

    Michalski, Greg; Kasem, Michelle; Rech, Jason A; Adieu, Sabine; Showers, William S; Genna, Bernie; Thiemens, Mark


    Coprecipitation of nitrate and sulfate by barium has probably resulted in significant error in numerous studies dealing with the oxygen isotopic composition of natural sulfates using chemical/thermal conversion of BaSO(4) and analysis by isotope ratio mass spectrometry. In solutions where NO(3) (-)/SO(4) (2-) molar ratios are above 2 the amount of nitrate coprecipitated with BaSO(4) reaches a maximum of approximately 7% and decreases roughly linearly as the molar ratio decreases. The fraction of coprecipitated nitrate appears to increase with decreasing pH and is also affected by the nature of the cations in the precipitating solution. The size of the oxygen isotope artifact in sulfate depends both on the amount of coprecipitated nitrate and the delta(18)O and Delta(17)O values of the nitrate, both of which can be highly variable. The oxygen isotopic composition of sulfate extracted from atmospheric aerosols or rain waters are probably severely biased because photochemical nitrate is usually also present and it is highly enriched in (18)O (delta(18)O approximately 50-90 per thousand) and has a large mass-independent isotopic composition (Delta(17)O approximately 20-32 per thousand). The sulfate delta(18)O error can be 2-5 per thousand with Delta(17)O artifacts reaching as high as 4.0 per thousand.

  16. Evaluation of Perchlorate Sources in the Rialto-Colton and Chino California Subbasins using Chlorine and Oxygen Isotope Ratio Analysis (United States)


    4) isotopic exchange between O2 and CO2 in the reaction tubes (both O2-DI-IRMS methods); and (5) analytical artifact of elevated CO2 in the ion...FINAL REPORT Evaluation of Perchlorate Sources in the Rialto-Colton and Chino California Subbasins using Chlorine and Oxygen Isotope Ratio...0061 RIALTO-COLTON AND CHINO CALIFORNIA SUBBASINS USING 5b. GRANT NUMBER CHLORINE AND OXYGEN ISOTOPE RATIO ANALYSIS NA 5c. PROGRAM ELEMENT NUMBER

  17. A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee, Switzerland

    NARCIS (Netherlands)

    Teranes, J.L.; McKenzie, J.A.; Bernasconi, S.M.; Lotter, A.F.; Sturm, M.


    Abstract—In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in

  18. A Quantitative, Time-Dependent Model of Oxygen Isotopes in the Solar Nebula: Step one (United States)

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


    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,

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

    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...

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

    International Nuclear Information System (INIS)

    Olausson, E.


    Oxygen and carbon isotope analyses have been carried out on samples from a core of the Angola Basin (6 0 50'S, 10 0 45'E, depth 2100 m). The pelagic foraminifer Globigerinoides ruber, a species with a shallow water habitat, and two benthic species Uvigerina peregrina and Bulimina aculeata have been analysed. The data are given relative to PDB. (Auth.)

  1. N=14 and 16 shell gaps in neutron-rich oxygen isotopes

    Czech Academy of Sciences Publication Activity Database

    Stanoiu, M.; Azaiez, F.; Dombrádi, Zs.; Sorlin, O.; Brown, A.; Belleguic, M.; Sohler, D.; Saint Laurent, M. G.; Lopez-Jimenez, M. J.; Penionzhkevich, Y. E.; Sletten, G.; Achouri, N. L.; Angélique, J. C.; Becker, F.; Borcea, C.; Bourgeois, C.; Bracco, A.; Daugas, J. M.; Dlouhý, Zdeněk; Donzaud, C.; Duprat, J.; Fülöp, Zs.; Guillemaud-Mueller, D.; Grévy, S.; Ibrahim, F.; Kerek, A.; Krasznahorkay, A.; Lewitowicz, M.; Leenhardt, S.; Lukyanov, S.; Mayet, P.; Mandal, S.; van der Marel, H.; Mittig, W.; Mrázek, Jaromír; Negoita, F.; de Oliveira Santos, F.; Podolyák, Zs.; Pouhgeon, F.; Porquet, M. G.; Roussel-Chomaz, P.; Savajols, H.; Sobolev, Y.; Stodel, C.; Timár, J.; Yamamoto, A.

    -, č. 69 (2004), 034312 ISSN 0556-2813 R&D Projects: GA AV ČR IAA1048102 Institutional research plan: CEZ:AV0Z1048901 Keywords : shell gaps * neutron-rich nuclei * oxygen isotopes Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 3.125, year: 2004

  2. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream. (United States)

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


    Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of

  3. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream (United States)

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


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

  4. Measurement of infiltration rates in urban sewer systems by use of oxygen isotopes. (United States)

    De Bénédittis, J; Bertrand-Krajewski, J L


    The paper presents the principle of a method to measure infiltration rates in sewer systems based on the use of oxygen isotopes and its application in Lyon (France). In the urban area of Lyon, significant differences in delta 18O that can reach 3 per thousand are observed between the oxygen isotopic compositions of groundwater originating from Rhone, Saone and from their associated alluvial aquifers. Drinking water supplying Lyon results mainly from pumping in the Rhone alluvial aquifer. Therefore, in some areas, the difference of isotopic composition between wastewater resulting from the consumption of drinking water and local groundwater can be used to measure infiltration in sewer systems. The application in the catchment of Ecully shows that the infiltration flow rate presents strong fluctuations at an hourly scale: it varies between 15 and 40 m3/h. This variability could be explained by non-constant discharges of pumping and by variations of the water level in the sewer.

  5. The oxygen isotopic composition of the Sun inferred from captured solar wind. (United States)

    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


    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.

  6. Stable hydrogen and oxygen isotope ratios of bottled waters of the world. (United States)

    Bowen, Gabriel J; Winter, David A; Spero, Howard J; Zierenberg, Robert A; Reeder, Mathew D; Cerling, Thure E; Ehleringer, James R


    Bottled and packaged waters are an increasingly significant component of the human diet. These products are regulated at the regional, national, and international levels, and determining the authenticity of marketing and labeling claims represents a challenge to regulatory agencies. Here, we present a dataset of stable isotope ratios for bottled waters sampled worldwide, and consider potential applications of such data for regulatory, forensic and geochemical standardization applications. The hydrogen and oxygen isotope ratios of 234 samples of bottled water range from -147 per thousand to +15 per thousand and from -19.1 per thousand to +3.0 per thousand, respectively. These values fall within and span most of the normal range for meteoric waters, indicating that these commercially available products represent a source of waters for use as laboratory working standards in applications requiring standardization over a large range of isotope ratios. The measured values of bottled water samples cluster along the global meteoric water line, suggesting that bottled water isotope ratios preserve information about the water sources from which they were derived. Using the dataset, we demonstrate how bottled water isotope ratios provide evidence for substantial evaporative enrichment of water sources prior to bottling and for the marketing of waters derived from mountain and lowland sources under the same name. Comparison of bottled water isotope ratios with natural environmental water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, suggesting that in many cases bottled water need not be considered as an isotopically distinct component of the human diet. Our findings suggest that stable isotope ratios of bottled water have the power to distinguish ultimate (e.g., recharge) and proximal (e.g., reservoir) sources of bottled water and constitute a potential

  7. Paleoclimate Reconstruction of Guangxi in SW China during the Past 2000-Year: Stalagmite Records from Two Caves (United States)

    Lien, W. Y.; Li, H. C.; Mii, H. S.


    Paleoclimate reconstructions help us to understand the role of the East Asian Summer Monsoon (EASM) on local precipitation and controlling factor of EASM variability, and to improve our climatic prediction. This study presents two stalagmite records from Jinlun Cave (23.553oN, 108.265oE) and Yilingyan Cave (23.041oN, 108.297oE) which are only 60 km apart in Guangxi Province, China. The 35-cm long stalagmite JL12 from Jinlun Cave and 10-cm long stalagmite YLY12 from Yilingyan Cave reveal 1500-year and 2000-year continuous growth respectively based on AMS 14C dating. Data points of the AMS 14C dates with the least dead carbon fraction (DCF) are used to build up the age model. Although dead carbons influence the 14C dating results, it is a feasible dating method for the stalagmites as 230Th/U dating on both stalagmites was not successful due to low U contents. A total of 1586 samples from JL12 and 948 samples from YLY12 have been done for stable isotopes analyses to serve as paleoclimate proxies. Comparison of the d18O records with the local rainfall records and the dry-wetness historic records shows the stalagmite d18O records as a rainfall proxy. The JL12 d18O record resembles the YLY12 d18O record in general, though some differences exist, which confirms the d18O records representing the local climate. The relatively lighter (lower) d18O values of the JL12 and YLY12 records during the Medieval Warm Period (MWP, AD900-1200) indicate stronger EASM. In the first phase of Little Ice Age (LIA), from AD1300 to AD1560, the d18O fluctuate drastically and the average during this period was lower, while the d18O was higher in the second phase of Little Ice Age (AD1560-AD1760), exhibiting a drier and stable climate in the second phase. Furthermore, the DCF varies through the stalagmite records, ascending during the LIA, descending during the MWP, which informs dry condition during the LIA and a moist climate in the MWP. Spectral analysis of the high-resolution d18O records

  8. Holocene moisture changes in western China, Central Asia, inferred from stalagmites (United States)

    Cai, Yanjun; Chiang, John C. H.; Breitenbach, Sebastian F. M.; Tan, Liangcheng; Cheng, Hai; Edwards, R. Lawrence; An, Zhisheng


    Central Asia lies at the convergence between the Mediterranean and Asian monsoon climates, and there is a complex interaction between the westerlies with the monsoon to form the climate of that region and its variability. The region is highly vulnerable to changes in rainfall, highlighting the need to understand the underlying controls. We present a stalagmite-based δ18O record from Kesang Cave in western China, using MC-ICP-MS U-series dating and stable isotope analysis. Stalagmite calcite δ18O largely documents changes in the δ18O of precipitation. δ18O in stalagmites was low during the early and middle Holocene (10.0-3.0 ka BP), and shifted to higher values between 3.0 and 2.0 ka BP. After 2.0 ka BP, δ18O fluctuates with distinct centennial-scale variations. Drawing from results of state-of-the-art atmospheric general circulation model simulations for the preindustrial period and 9 ka BP, we propose that changes in moisture source regions and the wetter climate both contributed to the isotopic depletion of precipitation during the early and middle Holocene. Multiple records from surrounding regions indicate a generally wetter climate during the early and mid- Holocene, supporting our interpretation on the speleothem δ18O. Changes in precipitation seasonality do not appear to be a viable explanation for the observed changes, nor increased penetration of monsoonal moisture to the study site. We speculate that the climatic regime shifted around 3.0-2.0 ka BP towards a drier climate, resulting in temperature having dominant control on precipitation δ18O. The demise of three settlements around 500AD at the margin of Tarim Basin coincided with a period of decreased precipitation and increased temperature that likely affected local water resources, underscoring the potential impact of climate on human habitation in this region.

  9. Oxygen isotope exchange between metabolites and water during biochemical reactions leading to cellulose synthesis

    International Nuclear Information System (INIS)

    Sternberg, L. da S.L.; DeNiro, M.J.; Savidge, R.A.


    Cellulose was produced heterotrophically from different carbon substrates by carrot tissue cultures and Acetobacter xylinum (a cellulose-producing bacterium) and by castor bean seeds germinated in the dark, in each case in the presence of water having known concentration of oxygen-18 ( 18 O). We used the relationship between the amount of 18 O in the water and in the cellulose that was synthesized to determine the number and 18 O content of the substrate oxygens that exchanged with water during the reactions leading to cellulose synthesis. Our observations support the hypothesis that oxygen isotope ratios of plant cellulose are determined by isotopic exchange occurring during hydration of carbonyl groups of the intermediates of cellulose synthesis. (author)

  10. Determination of nitrate isotopic signature in waters of different sources by analysing the nitrogen and oxygen isotopic ratio. (United States)

    Koszelnik, Piotr; Gruca-Rokosz, Renata


    A reference study on both the nitrogen content in waters and nitrogen and oxygen isotopic signatures characterising nitrate from different sources was conducted within the San River catchment area. Three kinds of catchments were studied: (1) forested and uncultivated; (2) artificially fertilised with nitrate; and (3) fertilised with manure and sewage. Moreover, atmospheric water was studied. The obtained values were found to be similar to others in the literature, with the exception of nitrate from the atmosphere, in regard to which influence reflecting the local conditions was to be noted. The isotopic signature of nitrate in the studied water results from the biogeochemical transformation of nitrogen compounds rather than from the mixing of different sources. The obtained results were statistically distinct and can be used as end-member values in further modelling studies connected with the management of nitrate in river waters, especially under middle-eastern European conditions.

  11. Modeling the oxygen-isotopic composition of the North American Ice Sheet and its effect on the isotopic composition of the ocean during the last glacial cycle

    NARCIS (Netherlands)

    Sima, A.; Paul, A.; Schulz, M.; Oerlemans, J.


    We used a 2.5-dimensional thermomechanical icesheet model including the oxygen-isotope ratio 18O/16O as a passive tracer to simulate the isotopic composition (d18O) of the North American Ice Sheet (NAIS) during the last glacial cycle. This model allowed us to estimate the NAIS contribution to the

  12. Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites (United States)

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


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

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

    International Nuclear Information System (INIS)

    Buchardt, B.; Hansen, H.J.


    In order to investigate possible isotopic fractionations due to algal symbiosis the oxygen and carbon isotope compositions of shell carbonate from symbiont-free and symbiont-bearing benthic foraminifera have been compared to that of molluscs living at the same locality. The material was collected over a depth profile in the Gulf of Elat (Aqaba), Israel, covering the interval from 4 to 125 metres. After corrections variations for temperature with depth, characteristic 18 O-depletions were observed in the foraminiferal shell carbonate when compared to the molluscs. These depletions are interpreted as 1) a constant vital effect seen in all the foraminifera studied and 2) an additional, light-dependent vital effect observed in the symbiont-bearing forms only, caused by incorporation of photosynthetic oxygen formed by the symbiotic algae. This additional vital effect emphasizes the difficulties in applying foraminifera to oxygen isotope palaeotemperature analyses. No well-defined differences in carbon isotope compositions are observed between symbiont-bearing and symbiont-free foraminifera. (author)

  14. Oxygen Isotopes in Tree Rings: A 345 Year Record of Precipitation in Amazonia (United States)

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


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

  15. Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters (United States)

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


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

  16. Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts. (United States)

    Michalski, Greg; Kolanowski, Michelle; Riha, Krystin M


    Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ(15)N values of synthetic and natural nitrates were 0 ± 2 ‰ similar to the air N2 from which they are derived. The δ(18)O values of synthetic nitrates were 23 ± 3 ‰, similar to air O2, and natural nitrate fertilizer δ(18)O values (55 ± 5 ‰) were similar to those observed in atmospheric nitrate. The Δ(17)O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ(17)O values of 18 ± 2 ‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.

  17. In situ SIMS oxygen isotope analysis of olivine in the Tibetan mantle xenoliths (United States)

    Zhao, Zhidan; Zhu, Di-Cheng; Liu, Dong; Mo, Xuanxue


    Although the mantle-derived xenoliths from Lhasa terrane provide a means of directly investigating the mantle underlying the southern part of the plateau, they were rarely found in the region. The only case of mantle xenoliths came from the Sailipu ultrapotassic volcanic rocks, erupted at ˜17 Ma, which have indicated that the subcontinental mantle of southern Tibetan Plateau is hot and strongly influenced by metasomatism (Zhao et al., 2008a, b; Liu et al., 2011). A further study by Liu et al.(2014) of in-situ oxygen isotope of olivine crystals in Sailipu mantle xenoliths identify a metasomatized mantle reservoir that interpreted as the sub-arc lithospheric mantle, with anomalously enriched oxygen isotopes (δ18O=8.03). Here we present oxygen isotopes data on the Sailipu mantle xenolith olivines, using different method of sample preparation. Mantle xenoliths (less than 1 cm in diameter) together originally with their host volcanic rocks were prepared in epoxy adjacent to grains of a San Carlos olivine intralaboratory standard and then polished to a flat and smooth surface. Oxygen isotope compositions of olivines occurs both in mantle xenolith and as phenocryst in the host rock, were analyzed in situ using CAMECA SIMS-1280 ion microprobe at the Institute of Geology and Geophysics, Chinese Academy of Sciences. We also performed traditional oxygen isotope analysis on three olivine phenocrysts separates from the host lava. Our new data show: (1) The mantle xenolith olivines have typical mantle oxygen isotopic composition (δ18O=4.8-8.0‰ with average of 5.5±0.2‰ n=105) with variety Fo#(78-90), (2) Oxygen isotopes of situ olivine phenocrysts in the Sailipu lavas (δ18O=7.1-9.2‰ Fo#=70-84, n=66), are similar to that of the whole rock (δ18O=7.0-9.4‰ Fo#=64-74, n=8, Zhao et al., 2009), and three olivine phenocryst grains (δ18O=7.2-7.8); (3) The intralaboratory standard of San Carlos olivine can be a suitable standard using for analyzing olivines with Fo not only

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

    Energy Technology Data Exchange (ETDEWEB)

    Sandy, Edward H. [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Department of Chemistry, University of Sierra Leone, Freetown (Sierra Leone); Blake, Ruth E., E-mail: [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Chang, Sae Jung [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Jun, Yao, E-mail: [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Yu, Chan [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China)


    Highlights: • Phosphonate (phon) hydrolysis by UVR (1.2 kW) attained ≥90% completion in 84 h. • Isotope study reveals both ambient H{sub 2}O and O{sub 2} involvements in phon C-P bond cleavage. • Mechanistic models proposed for phon C-P bond cleavage based on O-isotope analysis. • Model equations used to calculate δ{sup 18}O{sub P-org} of original phon P-moiety-useful as a tracer. • Study shows relevance in tracing phon sources and cycling in the environment. -- Abstract: The degradation of phosphonates in the natural environment constitutes a major route by which orthophosphate (Pi) is regenerated from organic phosphorus and recently implicated in marine methane production, with ramifications to environmental pollution issues and global climate change concerns. This work explores the application of stable oxygen isotope analysis in elucidating the C-P bond cleavage mechanism(s) of phosphonates by UV photo-oxidation and for tracing their sources in the environment. The two model phosphonates used, glyphosate and phosphonoacetic acid were effectively degraded after exposure to UV irradiation. The isotope results indicate the involvement of both ambient water and atmospheric oxygen in the C-P bond cleavage and generally consistent with previously posited mechanisms of UV-photon excitation reactions. A model developed to calculate the oxygen isotopic composition of the original phosphonate P-moiety, shows both synthetic phosphonates having distinctly lower values compared to naturally derived organophosphorus compounds. Such mechanistic models, based on O-isotope probing, are useful for tracing the sources and reactions of phosphonates in the environment.

  19. Method-Dependent Variations in Oxygen Isotope Compositions Obtained for Structural Carbonate in Bone Bioapatite (United States)

    Metcalfe, J. Z.; Longstaffe, F. J.; White, C. D.


    The carbon and oxygen isotope compositions of structural carbonate contained in bioapatite can be obtained by reaction with ortho-phosphoric acid at various temperatures and reaction times, using off-line or automated sample preparation, and continuous-flow or dual-inlet isotope-ratio mass spectrometry (IRMS). Here, we compare the isotopic compositions obtained for structural carbonate in bone bioapatite using (1) conventional off- line gas extraction (25°C) and dual-inlet IRMS, (2) GasBench automated sampling (50°C) and continuous-flow IRMS, and (3) MultiPrep automated sampling (50°C, 90°C) and dual-inlet IRMS. On average, the stable carbon isotope compositions obtained for the same sample using different methods are within ±0.33 per mil (n=29). The reproducibility of oxygen isotope compositions using the different methods is much poorer (±3.18 per mil; n=29). The differences among these methods were most pronounced for samples analyzed using the MultiPrep at 90°C and dual-inlet IRMS. In the latter case, some samples consistently had extremely low oxygen isotope compositions, and also yielded a contaminant gas containing masses 47, 48, and 49, which was not separated from the normal reaction product (carbon dioxide) during cryogenic processing. Normal and anomalous samples do not systematically differ in their crystallinity indices, C/P ratios, gas yields, or total organic content. Anomalous samples have an additional peak in their deconvoluted FTIR spectra at 866 cm-1 and their ignition products lack β-TCP. They also contain slightly more Al and Si cations, and slightly fewer Na cations. It is not clear how these subtle structural and chemical differences relate to the production of the contaminant gas.

  20. Triple oxygen isotope composition of leaf waters in Mpala, central Kenya (United States)

    Li, Shuning; Levin, Naomi E.; Soderberg, Keir; Dennis, Kate J.; Caylor, Kelly K.


    Variations in triple oxygen isotopes have been used in studies of atmospheric photochemistry, global productivity and increasingly in studies of hydroclimate. Understanding the distribution of triple oxygen isotopes in plant waters is critical to studying the fluxes of oxygen isotopes between the atmosphere and hydrosphere, in which plants play an important role. In this paper we report triple oxygen isotope data for stem and leaf waters from Mpala, Kenya and explore how Δ17 O, the deviation from an expected relationship between 17O /16O and 18O /16O ratios, in plant waters vary with respect to relative humidity and deuterium excess (d-excess). We observe significant variation in Δ17 O among waters in leaves and stems from a single plant (up to 0.16‰ range in Δ17 O in leaf water in a plant over the course of a signal day), which correlates to changes in relative humidity. A steady state model for evaporation in leaf water reproduces the majority of variation in Δ17 O and d-excess we observed in leaf waters, except for samples that were collected in the morning, when relative humidity is high and the degree of fractionation in the system is minimal. The data and the steady state model indicate that the slope, λtransp, that links δ17 O and δ18 O values of stem and leaf waters and characterizes the fractionation during transpiration, is strongly influenced by the isotopic composition of ambient vapor when relative humidity is high. We observe a strong, positive relationship between d-excess and Δ17 O, with a slope 2.2 ± 0.2 per meg ‰-1, which is consistent with the observed relationship in tropical rainfall and in water in an evaporating open pan. The strong linear relationship between d-excess and Δ17 O should be typical for any process involving evaporation or any other fractionation that is governed by kinetic effects.

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

    International Nuclear Information System (INIS)

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


    The results of an investigation of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen (E approx. 80 to 230 MeV/amu) made using the U.C. Berkeley HKH instrument aboard the ISEE-3 spacecraft are reported. The combination of high mass resolution and a large statistical sample makes possible a precise determination of the relative isotopic abundances for these elements. In local interplanetary space we find: 13 C/C = 0.067 +- 0.008, 15 N/N = 0.54 +- 0.03, 17 O/O 18 O/O = 0.019 +- 0.003

  2. A measurement of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen (United States)

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


    The paper reports the results of an investigation of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen (80-230 MeV/amu) made using the U.C. Berkeley HKH instrument aboard the ISEE-3 spacecraft. The combination of high mass resolution and a large statistical sample makes possible a precise determination of the relative isotopic abundances for these elements. In local interplanetary space the following values are found: C-13/C = 0.067 + or - 0.008, N-15/N = 0.54 + or - 0.03, O-17/O less than 0.027, and O-18/O - 0.019 + or - 0.003.

  3. Self-shielding in O2 - A possible explanation for oxygen isotopic anomalies in meteorites? (United States)

    Navon, O.; Wasserburg, G. J.


    The production of isotopic effects in oxygen due to self-shielding of photolysing radiation by the Schumann-Runge bands of (O-16)2 is investigated. The model studied is the simple case of incoming radiation falling on a gaseous medium of uniform composition. The enhancement of O-17 and O-18 production upon photodissociation of O2 is calculated for various column densities, and its dependence on temperature and the presence of other molecules is examined. The issue of whether the products of photolysis can be trapped and thus preserve a peculiar isotopic composition is discussed.

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

    International Nuclear Information System (INIS)

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


    Full text: The carbon isotope ratio of phloem sap sugars has been previously observed to correlate strongly with the phloem sap sugar concentration in Eucalyptus globulus. We hypothesized that the correspondence between these two parameters results from co-linearity in their responses to variation in plant water potential. Carbon isotope discrimination is expected to decrease with decreasing plant water potential due to the influence of stomatal conductance on the ratio of intercellular to ambient CO 2 , concentrations (c 1 /c a ). Conversely, we expected the phloem sap sugar concentration to increase with decreasing plant water potential, thereby maintaining positive turgor pressure within the sieve tubes. The study comprised 40 individual Eucalyptus globulus trees growing in three plantations situated on opposing ends of a rainfall gradient in southwestern Australia. A strong correlation was observed between the carbon isotope ratio in phloem sap sugars and phloem sap sugar concentration. Carbon isotope discrimination correlated positively with shoot water potential, whereas phloem sap sugar concentration correlated negatively with shoot water potential. The relationship between carbon isotope discrimination measured in phloem sap sugars collected from the stem and c 1 /c a measured instantaneously on subtending leaves was close to that theoretically predicted. Accordingly, a strong, negative relationship was observed between instantaneous c 1 /c a and the phloem sap sugar concentration. Oxygen isotope discrimination in phloem sap sugars also correlated strongly with phloem sap sugar concentration. A theoretical model suggested that the observed variation in stomatal conductance was sufficient to account for the variation observed in oxygen isotope discrimination across the study. Results strongly support the contention that water relations form a mechanistic link between phloem sap sugar concentration and both instantaneous and integrated measures of the

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

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


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

  6. Oxygen isotope fractionation in the CaCO3-DIC-H2O system (United States)

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


    The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

  7. Stable isotope records for the last 10 000 years from Okshola cave (Fauske, northern Norway and regional comparisons

    Directory of Open Access Journals (Sweden)

    H. Linge


    Full Text Available The sensitivity of terrestrial environments to past changes in heat transport is expected to be manifested in Holocene climate proxy records on millennial to seasonal timescales. Stalagmite formation in the Okshola cave near Fauske (northern Norway began at about 10.4 ka, soon after the valley was deglaciated. Past monitoring of the cave and surface has revealed stable modern conditions with uniform drip rates, relative humidity and temperature. Stable isotope records from two stalagmites provide time-series spanning from c. 10 380 yr to AD 1997; a banded, multi-coloured stalagmite (Oks82 was formed between 10 380 yr and 5050 yr, whereas a pristine, white stalagmite (FM3 covers the period from ~7500 yr to the present. The stable oxygen isotope18Oc, stable carbon isotope13Cc, and growth rate records are interpreted as showing i a negative correlation between cave/surface temperature and δ18Oc, ii a positive correlation between wetness and δ13Cc, and iii a positive correlation between temperature and growth rate. Following this, the data from Okshola show that the Holocene was characterised by high-variability climate in the early part, low-variability climate in the middle part, and high-variability climate and shifts between two distinct modes in the late part.

    A total of nine Scandinavian stalagmite δ18Oc records of comparable dating precision are now available for parts or most of the Holocene. None of them show a clear Holocene thermal optimum, suggesting that they are influenced by annual mean temperature (cave temperature rather than seasonal temperature. For the last 1000 years, δ18Oc values display a depletion-enrichment-depletion pattern commonly interpreted as reflecting the conventional view on climate development for the last millennium. Although the δ18

  8. Speleothem isotopic evidence for rapid human-induced expansion of grasslands in Madagascar at 890 CE (United States)

    Burns, S. J.; Godfrey, L.; Faina, P.; McGee, D.; Hardt, B. F.; Ranivoharimanana, L.; Randrianasy, J.


    The degree to which human activity impacted the landscape, vegetation and fauna of Madagascar remains under debate. Since the early 1920's, the prevailing hypothesis has been that the savannah grasslands that now cover 70% of Madagascar were the result of deforestation, which has also been tied to the disappearance of much of the island's endemic megafauna. Other studies suggest that Madagascar's grasslands are largely natural and that megafaunal extinctions may be climatically induced, leading some authors to question the entire narrative of extensive alteration of the landscape by early human activity. We collected two stalagmites, M14-AB2 and M14-AB3, from Anjohibe Cave in northwestern Madagascar (15.55°S, 46.89°E, 100 masl). Age models were constructed using 8 U/Th age determinations from AB2 and 10 from AB3. The samples began to grow at ~500 CE and were active at the time of collection. Carbon and oxygen stable isotope ratios were measured on 266 samples from AB2 and 173 samples from AB3, yielding sub-decadal temporal resolution. A rapid, more than 10 per mil increase in stalagmite carbon stable isotope ratios documents an almost complete transformation of the landscape from one with a flora dominated by C3 plants to a C4 grassland system. This transformation, well replicated in both stalagmites, occurred at approximately 890 +/- 20 CE and was complete in 100 years. Further, relatively constant oxygen isotope ratios across the carbon isotope transition demonstrate that landscape alteration was not related to changes in climate. We hypothesize that the transformation was caused primarily by expansion of the use of fire by early inhabitants of Madagascar to promote agriculture and the growth of grass as fodder for cattle. The resulting loss of forest habitat very likely increased environmental pressures on Madagascar's megafauna and accelerated their disappearance.

  9. U-Series dates for stalagmitic flowstone E (Riss/Würm interglaciation) at Grotte du Lazaret, Nice, France (United States)

    Falgueres, Christophe; de Lumley, Henry; Bischoff, James L.


    Several samples of stalagmitic flowstone (Ensemble E) at Grotte du Lazaret (Nice, France) were dated by U-series isotopes. The results show that this speleothem began to grow about 130,000 yr B.P. and continued to about 70,000 yr B.P., coinciding almost exactly with the last interglaciation (isotope stage 5). Even though Ensemble E is not in direct stratigraphic relation with the cave deposits, this study shows that the Acheulian artifacts industry and fauna within Lazaret are older than the Riss/Wurm interglaciation.

  10. Assessment of renal function by the stable oxygen and hydrogen isotopes in human blood plasma.

    Directory of Open Access Journals (Sweden)

    Tai-Chih Kuo

    Full Text Available Water (H(2O is the most abundant and important molecule of life. Natural water contains small amount of heavy isotopes. Previously, few animal model studies have shown that the isotopic composition of body water could play important roles in physiology and pathophysiology. Here we study the stable isotopic ratios of hydrogen (δ(2H and oxygen (δ(18O in human blood plasma. The stable isotopic ratio is defined and determined by δ(sample = [(R(sample/R(STD-1] * 1000, where R is the molar ratio of rare to abundant, for example, (18O/(16O. We observe that the δ(2H and the δ(18O in human blood plasma are associated with the human renal functions. The water isotope ratios of the δ(2H and δ(18O in human blood plasma of the control subjects are comparable to those of the diabetes subjects (with healthy kidney, but are statistically higher than those of the end stage renal disease subjects (p<0.001 for both ANOVA and Student's t-test. In addition, our data indicate the existence of the biological homeostasis of water isotopes in all subjects, except the end stage renal disease subjects under the haemodialysis treatment. Furthermore, the unexpected water contents (δ(2H and δ(18O in blood plasma of body water may shed light on a novel assessment of renal functions.

  11. Source determination of nitrous oxide based on nitrogen and oxygen isotope tracing dealing with oxygen exchange. (United States)

    Kool, Dorien M; Van Groenigen, Jan Willem; Wrage, Nicole


    Source determination of nitrous oxide (N(2)O) from soils has so far been complicated by methodological constraints: the frequently used (15)N tracer method could not differentiate between pathways related to nitrification, that is, nitrifier nitrification (NN), nitrifier denitrification (ND), and nitrification-coupled denitrification (NCD). To overcome this problem, a dual isotope method using both (15)N and (18)O was proposed. However, O exchange between nitrogen oxides and water has been found to disturb such a method. We here explain in detail a novel dual isotope method that allows to quantify O exchange in denitrification and to differentiate N(2)O production from NN, ND, NCD, and fertilizer denitrification (FD). The method has already been applied to a range of soils with good success. Potential of and scope for further improvement of the method are discussed. Copyright © 2011 Elsevier Inc. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    J. Kaiser


    Full Text Available Oxygen triple isotope measurements can be used to calculate aquatic gross oxygen production rates. Past studies have emphasised the appropriate definition of the 17O excess and often used an approximation to derive production rates from the 17O excess. Here, I show that the calculation can be phrased more consistently and without any approximations using the relative 17O/16O and 18O/16O isotope ratio differences (delta values directly. I call this the "dual delta method". The 17O excess is merely a mathematical construct and the derived production rate is independent of its definition, provided all calculations are performed with a consistent definition. I focus on the mixed layer, but also show how time series of triple isotope measurements below the mixed layer can be used to derive gross production.

    In the calculation of mixed layer productivity, I explicitly include isotopic fractionation during gas invasion and evasion, which requires the oxygen supersaturation s to be measured as well. I also suggest how bubble injection could be considered in the same mathematical framework. I distinguish between concentration steady state and isotopic steady state and show that only the latter needs to be assumed in the calculation. It is even possible to derive an estimate of the net production rate in the mixed layer that is independent of the assumption of concentration steady state.

    I review measurements of the parameters required for the calculation of gross production rates and show how their systematic uncertainties as well as the use of different published calculation methods can cause large variations in the production rates for the same underlying isotope ratios. In particular, the 17O excess of dissolved O2 in equilibrium with atmospheric O2 and the 17O excess of photosynthetic O2 need to

  13. Assessment of nitrogen and oxygen isotopic fractionation during nitrification and its expression in the marine environment. (United States)

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


    Nitrification is a microbially-catalyzed process whereby ammonia (NH(3)) is oxidized to nitrite (NO(2)(-)) and subsequently to nitrate (NO(3)(-)). It is also responsible for production of nitrous oxide (N(2)O), a climatically important greenhouse gas. Because the microbes responsible for nitrification are primarily autotrophic, nitrification provides a unique link between the carbon and nitrogen cycles. Nitrogen and oxygen stable isotope ratios have provided insights into where nitrification contributes to the availability of NO(2)(-) and NO(3)(-), and where it constitutes a significant source of N(2)O. This chapter describes methods for determining kinetic isotope effects involved with ammonia oxidation and nitrite oxidation, the two independent steps in the nitrification process, and their expression in the marine environment. It also outlines some remaining questions and issues related to isotopic fractionation during nitrification. Copyright © 2011 Elsevier Inc. All rights reserved.

  14. From Mars Meteorites to Laboratory Investigations: Understanding Heterogeneous Photochemical Transformations Using Oxygen Triple Isotope Anomalies of Carbonates (United States)

    Shaheen, R.; Smirnova, V.; Jackson, T. L.; Mang, L.; Thiemens, M. H.


    The planet Mars is unique in our solar system with a positive O-isotope anomaly observed in its bulk silicate and carbonates minerals ranging from 0.3 to 0.6 ‰. The carbonate isotopic signature can be used to reveal its origin, past history and atmosphere-hydrosphere-geosphere-interactions. Ozone is a powerful natural tracer of photochemical processes in Earth's atmosphere. It possess the highest enrichment in heavy isotopes δ17O ≈ δ18O (70-150‰) and oxygen isotopic anomaly (Δ17O = 30-40‰). The oxygen isotopic anomaly from ozone is transferred to other oxygen carrying molecules in the atmosphere through different mechanisms. Laboratory experiments were conducted with the JSC-Mars Simulant and iron oxide to investigate how this anomaly can be transferred to water and minerals under conditions similar to present day Mars. Three sets of laboratory experiments (O3-H2O-UV-minerals; O2-H2O-UV-minerals; O3-H2O-minerals) were performed. The oxygen triple isotopic analysis of product mineral carbonates formed from adsorbed CO2 reaction showed an oxygen isotopic anomaly (Δ17O = 0.4-3‰). The oxygen triple isotopic composition of water at photochemical equilibrium shifted towards ozone with Δ17O = 9‰ indicating reaction of ozone with water vapor via electronically excited oxygen atoms and transfer of the anomaly via hydroxyl radicals. HOx (HO, HO2) are extremely reactive and have very short life time (bearing minerals through surficial reactions. Series of experiments were performed to constrain the amount of H2O required to preserve the oxygen isotope anomaly observed in carbonate minerals in the Martian meteorites. These observation will help refine Mars photochemistry models and also to constrain the past hydrological cycle and its coupling with the regolith. The observed inverse correlation between ozone and water vapor also suggests a dynamic role of hydroxyl radical chemistry in the atmosphere of Mars.

  15. Oxygen isotopes in mammal bone phosphate: A new tool for paleohydrological and paleoclimatological research? (United States)

    Longinelli, Antonio


    Oxygen isotope analyses of water in blood of humans and domestic pigs indicate that the oxygen isotope fractionation effects between ingested water and body water are the same in all specimens of the same species. The δ18O of body water has been shown to vary linearly with the mean δ18O of local meteoric water. This conclusion also holds for the bone phosphate. Thus, δ18O( PO3-4) values of unaltered fossil bones from humans and domestic pigs can be used to reconstruct the δ18O values of local meteoric waters during the life-times of the mammals. Such data can be used for paleohydrological and paleoclimatological studies both on land and at sea.

  16. Mineralogy and Oxygen Isotope Compositions of Two C-Rich Hydrated Interplanetary Dust Particles (United States)

    Snead, C. J.; McKeegan, K. D.; Messenger, S.; Nakamura-Messenger, K.


    Oxygen isotopic compositions of chondrites reflect mixing between a O-16-rich reservoir and a O-17,O-18-rich reservoir produced via mass-independent fractionation. The composition of the O-16-rich reservoir is reasonably well constrained, but material representing the O-17,O-18-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in O-17 and O-18 18O by > 200%. Hydrated interplanetary dust particles (IDPs) rich in carbonaceous matter may be derived from comets; such particles likely contain the products of reaction between O-16-poor water and anhydrous silicates that formed in the inner solar system. Here we present mineralogy and oxygen isotope compositions of two C-rich hydrated IDPs, L2083E47 and L2071E35.

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

    International Nuclear Information System (INIS)

    Labeyrie, Laurent.


    This paper describes a new method allowing the measurement of the 18 O/ 16 O ratio of the biogenic silica oxygen, which takes into account the effects due to the organic matter and hydration water associated with this type of silica. By isotopic exchange with enriched water, we have been able to fix a treatment which eliminate all contamination and memory effects. This has permitted us to study the temperature dependance of the hydrated silica-water oxygen isotopic fractionation. As application, we present a study of the variations of the delta 18 O of fossil diatoms valves along an Equatorial Pacific sediment core covering the last 20.000 years. The results demonstrate the usefulness of the delta 18 O of the diatom silica for paleoclimatic investigations [fr

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

    DEFF Research Database (Denmark)

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


    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 Godthabsfjord (West Greenland), where glacier meltwater causes seasonal excursions with lower oxygen isotope water (delta O-18(w)) 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...

  19. Investigation of Nebular Processes Through Oxygen Isotopic Analysis of Primitive Meteorite Materials (United States)

    Leshin, Laurie


    As a direct result of support provided by this grant, precise and accurate determination of delta(18)O and delta(17)O in silicates (and other minerals) by ion microprobe (both IMS 6f and IMS 1270) are now being carried out in several laboratories, and these analyses, combined with application of laser fluorination techniques, have led to a proliferation of oxygen isotopic data in the past approx. 3 years. The applications of these techniques in cosmochemical research have been myriad, from understanding the most refractory objects in the nebula (CAIs) to the low temperature alteration processes on meteorite parent bodies. Here, we describe our progress in understanding the oxygen isotopic microdistributions in primitive meteorite materials, as directly supported by this Origins grant.

  20. Oxygen isotopic evidence for vigorous mixing during the Moon-forming giant impact. (United States)

    Young, Edward D; Kohl, Issaku E; Warren, Paul H; Rubie, David C; Jacobson, Seth A; Morbidelli, Alessandro


    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. Copyright © 2016, American Association for the Advancement of Science.

  1. The Carbon and Sulfur Cycles through the Cenozoic: Insight from Oxygen Isotopes in Marine Sulfate (United States)

    Turchyn, A. V.; Schrag, D. P.


    Marine sulfate plays an important role in the cycling of biochemicals in organic rich sediments, serving as the terminal electron acceptor in the remineralization of organic matter and responsible for nearly all anaerobic methane oxidation. Because sulfur isotopes are largely conserved during sulfur cycling in organic rich sediments, they reflect mostly changes in net sulfur burial, and have been used to study fluctuations in sulfur mineral burial over Earth history. Recently, we have shown that temporal variability in oxygen isotopes measured in marine sulfate (d18O-SO4) highlight changes the pathways of sulfur cycling on continental margins because the d18O-SO4 is reset during sulfate reduction and sulfide reoxidation. The fluxes associated with sulfur cycling, predominantly in shallow sediments, are nearly three times larger than riverine input. We present a continuous record of d18O-SO4 in marine barite over the Cenozoic. There is considerable variability in the d18OSO4, with major peaks 55, 15, and 3 million years ago. There is little correlation between sulfur isotopes in marine sulfate and d18O-SO4, illustrating the fact that different processes control the sulfur and oxygen isotopic composition of sulfate. The peaks in the d18O-SO4 at 55 and 15 Ma coincide with peaks in the d13C of benthic foraminifera, highlighting the connection between the carbon and sulfur cycles in organic rich sediments. In addition, the increase in the d18O of the ocean (measured in benthic foraminifera) between 34 and 28 Ma coincides with a slight increase in the d18O-SO4. We have modeled the sulfur cycle for both sulfur and oxygen isotopes and will show model results and interpretation over several key intervals over the Cenozoic, including the Mid-Miocene Climate Optimum, the Eocene-Oligocene boundary, and the Paleocene productivity high.

  2. Triple oxygen and hydrogen isotopes of gypsum hydration water for quantitative paleo-humidity reconstruction (United States)

    Gázquez, Fernando; Morellón, Mario; Bauska, Thomas; Herwartz, Daniel; Surma, Jakub; Moreno, Ana; Staubwasser, Michael; Valero-Garcés, Blas; Delgado-Huertas, Antonio; Hodell, David A.


    Atmospheric relative humidity is an important parameter affecting vegetation yet paleo-humidity proxies are scarce and difficult to calibrate. Here we use triple oxygen (δ17O and δ18O) and hydrogen (δD) isotopes of structurally-bound gypsum hydration water (GHW) extracted from lacustrine gypsum to quantify past changes in atmospheric relative humidity. An evaporation isotope-mass-balance model is used together with Monte Carlo simulations to determine the range of climatological conditions that simultaneously satisfy the stable isotope results of GHW, and with statistically robust estimates of uncertainty. We apply this method to reconstruct the isotopic composition of paleo-waters of Lake Estanya (NE Spain) and changes in normalized atmospheric relative humidity (RHn) over the last glacial termination and Holocene (from ∼15 to 0.6 cal. kyrs BP). The isotopic record indicates the driest conditions occurred during the Younger Dryas (YD; ∼12-13 cal. kyrs BP). We estimate a RHn of ∼40-45% during the YD, which is ∼30-35% lower than today. Because of the southward displacement of the Polar Front to ∼42°N, it was both windier and drier during the YD than the Bølling-Allerød period and Holocene. Mean atmospheric moisture gradually increased from the Preboreal to Early Holocene (∼11 to 8 cal. kyrs BP, 50-60%), reaching 70-75% RHn from ∼7.5 cal. kyrs BP until present-day. We demonstrate that combining hydrogen and triple oxygen isotopes in GHW provides a powerful tool for quantitative estimates of past changes in relative humidity.

  3. Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende (United States)

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


    Hibonite-rich Ca- and Al-rich inclusions (CAIs) are among the earliest formed solids that condensed in the early nebula. We discovered an unusual refractory inclusion from the Allende CV3 chondrite (SHAL) containing an approx 500 micron long single crystal of hibonite and co-existing coarse-grained perovskite. The mineralogy and petrography of SHAL show strong similarities to some FUN inclusions, especially HAL. Here we report on the mineralogy, petrography, mineral chemistry and oxygen isotopic compositions in SHAL.

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


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


    The oxygen isotopic composition (δ18O) of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy c...

  5. Phosphate oxygen isotopic evidence for a temperate and biologically active Archaean ocean. (United States)

    Blake, Ruth E; Chang, Sae Jung; Lepland, Aivo


    Oxygen and silicon isotope compositions of cherts and studies of protein evolution have been interpreted to reflect ocean temperatures of 55-85 degrees C during the early Palaeoarchaean era ( approximately 3.5 billion years ago). A recent study combining oxygen and hydrogen isotope compositions of cherts, however, makes a case for Archaean ocean temperatures being no greater than 40 degrees C (ref. 5). Ocean temperature can also be assessed using the oxygen isotope composition of phosphate. Recent studies show that (18)O:(16)O ratios of dissolved inorganic phosphate (delta(18)O(P)) reflect ambient seawater temperature as well as biological processing that dominates marine phosphorus cycling at low temperature. All forms of life require and concentrate phosphorus, and as a result of biological processing, modern marine phosphates have delta(18)O(P) values typically between 19-26 per thousand (VSMOW), highly evolved from presumed source values of approximately 6-8 per thousand that are characteristic of apatite in igneous rocks and meteorites. Here we report oxygen isotope compositions of phosphates in sediments from the 3.2-3.5-billion-year-old Barberton Greenstone Belt in South Africa. We find that delta(18)O(P) values range from 9.3 per thousand to 19.9 per thousand and include the highest values reported for Archaean rocks. The temperatures calculated from our highest delta(18)O(P) values and assuming equilibrium with sea water with delta(18)O = 0 per thousand (ref. 12) range from 26 degrees C to 35 degrees C. The higher delta(18)O(P) values are similar to those of modern marine phosphate and suggest a well-developed phosphorus cycle and evolved biologic activity on the Archaean Earth.

  6. The Largs high-latitude oxygen isotope anomaly (New Zealand) and climatic controls of oxygen isotopes in magma

    International Nuclear Information System (INIS)

    Blattner, P.; Williams, J.G.


    In northern Fiordland the Brook Street terrane of New Zealand consists of two units - the predominantly basaltic Plato and the predominantly andesitic Largs terrane. The Permian Plato terrane has normal to slightly enriched δ 18 O values, whereas the Largs terrane, which is of similar pre-early Triassic age, has not yielded a single normal δ 18 O SMOW result, with all of 17 total rocks showing less than 3.2per mille, seven less than -4per mille, and two less than -9per mille. These strongly anomalous data confirm an earlier suggested terrestrial character of Largs deposition, and demand the presence of Permo-Triassic geothermal systems running on subAntarctic to Antarctic meteoric water. The skewed data spectrum suggests a relatively immature flow system and likely values for the recharge water are -20per mille δ 18 O or less. For a climate distribution similar to the present one, inlcuding polar ice caps, this would indicate over 70deg of southern latitude. Rafts and xenoliths of Largs rocks have been entrained within Mackay Intrusives in the early Triassic. On field evidence the Mackay magmas have also intruded an early Darran Complex, but this complex has been substantially reactivated in the Cretaceous. It has δ 18 O values near 5.0per mille, which is distinctly low for island arc magmas. Since the complex is isotopically homogenous, its δ 18 O is unlikely to be a direct effect of the relatively shallow Largs terrane. More probable is a climate related slight depression of the δ 18 O of magma sources, in which other high-latitude, low-δ 18 O sediments and geothermal systems have been involved. (orig.)

  7. Climatic forcing of carbon-oxygen isotopic covariance in temperate-region marl lakes (United States)

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


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

  8. Searching for isovector signatures in the neutron-rich oxygen and calcium isotopes

    Directory of Open Access Journals (Sweden)

    Wei-Chia Chen


    Full Text Available We search for potential isovector signatures in the neutron-rich oxygen and calcium isotopes within the framework of a relativistic mean-field theory with an exact treatment of pairing correlations. To probe the isovector sector we calibrate a few relativistic density functionals using the same isoscalar constraints but with one differing isovector assumption. It is found that under certain conditions, the isotopic chain in oxygen can be made to terminate at the experimentally observed 24O isotope and in the case of the calcium isotopes at 60Ca. To produce such behavior, the resulting symmetry energy must be soft, with predicted values for the symmetry energy and its slope at saturation density being J=(30.92±0.47 MeV and L=(51.0±1.5 MeV, respectively. As a consequence, the neutron-skin thickness of 208Pb is rather small: Rskin208=(0.161±0.011 fm. This same model—labeled “FSUGarnet”—predicts R1.4=(13.0±0.1 km for the radius of a “canonical” 1.4M⊙ neutron star, yet is also able to support a two-solar-mass neutron star.

  9. Oxygen Isotopic Constraints on the Genesis of Carbonates from Martian Meteorite ALH84001 (United States)

    Leshin, Laurie A.; McKeegan, Kevin D.; Carpenter, Paul K.; Harvey, Ralph P.


    Ion microprobe oxygen isotopic measurements of a chemically diverse suite of carbonates from Martian meteorite ALH84001 are reported. The delta(sup 18)O values are highly variable, ranging from +5.4 to + 25.3%, and are correlated with major element compositions of the carbonate. The earliest forming (Ca-rich) carbonates have the lowest delta(sup 18)O values and the late-forming (Mg-rich) carbonates have the highest delta(sup 18)O values. Two models are presented which can explain the isotopic variations. The carbonates could have formed in a water rich environment at relatively low, but highly variable temperatures. In this open-system case the lower limit to the temperature variation is approx. 125 C, with fluctuations of over 250 C possible within the constraints of the model. Alternatively, the data can be explained by a closed-system model in which the carbonates precipitated from a limited amount of CO2-rich fluid. This scenario can reproduce the isotopic variations observed at a range of temperatures, including relatively high temperatures (less than 500 C). Thus the oxygen isotopic compositions do not provide unequivocal evidence for formation of the carbonates at low temperature. Although more information is needed in order to distinguish between the models, neither of the implied environments is consistent with biological activity. Thus, we suggest that features associated with the carbonates which have been interpreted to be the result of biological activity were most probably formed by inorganic processes.

  10. Oxygen isotopic heterogeneities, their petrological correlations, and implications for melt origins of chondrules in unequilibrated ordinary chondrites (United States)

    Gooding, J. L.; Mayeda, T. K.; Clayton, R. N.; Fukuoka, T.


    Clayton et al. (1976, 1982) established that equilibrated ordinary chondrites (EOC's) can be divided into the H- and L-groups on the basis of their oxygen isotopic composition. The present investigation is concerned with new oxygen isotopic analyses of petrologically well-characterized individual chondrules from the unequilibrated chondrites Dhajala (H3,4), Hallingeberg (L3), and Semarkona (LL3). A study is conducted regarding the implications of isotopic/petrologial correlations for the origin of chondrules in ordinary chondrites. It is found that the oxygen isotopic heterogeneities among chondrules are reminiscent of the bulk elemental and phase compositional heterogeneities among the same and other chondrules as reported by Gooding et al. (1979, 1980). It is concluded that chondrules formed possibly as a result of the melting of preexisting materials which were both chemically and isotopically heterogeneous.

  11. Intermineral oxygen three-isotope systematics of silicate minerals in equilibrated ordinary chondrites (United States)

    McDougal, David; Nakashima, Daisuke; Tenner, Travis J.; Kita, Noriko T.; Valley, John W.; Noguchi, Takaaki


    High-precision oxygen three-isotope ratios were measured for four mineral phases (olivine, low-Ca and high-Ca pyroxene, and plagioclase) in equilibrated ordinary chondrites (EOCs) using a secondary ion mass spectrometer. Eleven EOCs were studied that cover all groups (H, L, LL) and petrologic types (4, 5, 6), including S1-S4 shock stages, as well as unbrecciated and brecciated meteorites. SIMS analyses of multiple minerals were made in close proximity (mostly heterogeneous in both δ18O and Δ17O, showing similar systematics to those in type 3 chondrites. In type 5 and 6 chondrites, oxygen isotope ratios of the four mineral phases plot along mass-dependent fractionation lines that are consistent with the bulk average Δ17O of each chondrite group. The δ18O of three minerals, low-Ca and high-Ca pyroxene and plagioclase, are consistent with equilibrium fractionation at temperatures of 700-1000 °C. In most cases the δ18O values of olivine are higher than those expected from pyroxene and plagioclase, suggesting partial retention of premetamorphic values due to slower oxygen isotope diffusion in olivine than pyroxene during thermal metamorphism in ordinary chondrite parent bodies.

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

    International Nuclear Information System (INIS)

    Gerster, Richard


    The reaction of carbon dioxide with water has been studied by measuring the rate of oxygen exchange between C 18 O 2 and H 2 16 O. The mathematical treatment of the kinetics allows to determine with accuracy the diffusion flow between the gas and the liquid phase, in the same way as the CO 2 hydration rate. The velocity constant of this last process, whose value gives the in situ enzymatic activity of carbonic anhydrase, has been established in the case of chloroplast and Euglena suspensions and of aerial leaves. The study of the isotopic exchange between C 18 O 2 and a vegetable submitted to alternations of dark and light has allowed to calculate the isotopic abundance of the metabolized CO 2 whose value has been compared to that of the intracellular water and that of photosynthetic oxygen. In addition, a new method using 13 C 18 O 2 gives the means to measure with accuracy eventual isotopic effects. The labelling kinetics of the oxygen evolved by Euglena suspensions whose water has been enriched with 18 O have been established at different temperatures. (author) [fr

  13. Isotopic chains around oxygen from evolved chiral two- and three-nucleon interactions. (United States)

    Cipollone, A; Barbieri, C; Navrátil, P


    We extend the formalism of self-consistent Green's function theory to include three-body interactions and apply it to isotopic chains around oxygen for the first time. The third-order algebraic diagrammatic construction equations for two-body Hamiltonians can be exploited upon defining system-dependent one- and two-body interactions coming from the three-body force, and, correspondingly, dropping interaction-reducible diagrams. The Koltun sum rule for the total binding energy acquires a correction due to the added three-body interaction. This formalism is then applied to study chiral two- and three-nucleon forces evolved to low momentum cutoffs. The binding energies of nitrogen, oxygen, and fluorine isotopes are reproduced with good accuracy and demonstrate the predictive power of this approach. Leading order three-nucleon forces consistently bring results close to the experiment for all neutron rich isotopes considered and reproduce the correct driplines for oxygen and nitrogen. The formalism introduced also allows us to calculate form factors for nucleon transfer on doubly magic systems.

  14. In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite (United States)

    Zolensky, Michael E.; Engrand, Cecile; Gounelle, Matthieu; Zolensky, Mike E.


    We have measured the oxygen isotopic composition of several components of Tagish Lake by ion microprobe. This meteorite constitutes the best preserved sample of C2 matter presently available for study. It presents two different lithologies (carbonate-poor and -rich) which have fairly comparable oxygen isotopic composition, with regard to both the primary or secondary minerals. For the olivine and pyroxene grains, their delta O-18 values range from - 10.5% to + 7.4% in the carbonate-poor lithology, with a mean Delta O-17 value of - 3.7 2.4%. In the carbonate-rich lithology, delta O-18 varies from - 7.9% to + 3.3%, and the mean Delta O-17 value is - 4.7 +/- 1.4%. Olivine inclusions (Fo(sub >99)) with extreme O-16-enrichment were found in both lithologies: delta O-18 = - 46.1 %, delta O-187= - 48.3% and delta O-18 = - 40.6%, delta O-17 = - 41.2% in the carbonate-rich lithology; delta O-18 = - 41.5%, delta O-17 = -43.4%0 in the carbonate-poor lithology. Anhydrous minerals in the carbonate-poor lithology are slightly more O-16-rich than in the carbonate-rich one. Four low-iron manganese-rich (LIME) olivine grains do not have an oxygen isotopic composition distinct from the other "normal" olivines. The phyllosilicate matrix presents the same range of oxygen isotopic compositions in both lithologies: delta O-18 from approximately 11 % to approximately 6%, with an average Delta. O-17 approximately 0%. Because the bulk Tagish Lake oxygen isotopic composition given by Brown et al. is on the high end of our matrix analyses, we assume that this "bulk Tagish Lake" composition probably only represents that of the carbonate-rich lithology. Calcium carbonates have delta O-18 values up to 35%, with Delta O-17 approximately 0.5%0. Magnetite grains present very high Delta O-17 values approximately + 3.4%0 +/- 1.2%. Given our analytical uncertainties and our limited carbonate data, the matrix and the carbonate seem to have formed in isotopic equilibrium. In that case, their large

  15. LBA-ECO CD-02 Carbon and Oxygen Isotopes in Atmospheric CO2 in the Amazon: 1999-2004 (United States)

    National Aeronautics and Space Administration — This data set reports carbon and oxygen stable isotope ratios of atmospheric carbon dioxide (CO2) collected at several forest and pasture sites and in the free...

  16. LBA-ECO CD-02 Carbon and Oxygen Isotopes in Atmospheric CO2 in the Amazon: 1999-2004 (United States)

    National Aeronautics and Space Administration — ABSTRACT: This data set reports carbon and oxygen stable isotope ratios of atmospheric carbon dioxide (CO2) collected at several forest and pasture sites and in the...


    Elevated arsenic concentrations are coincident with enriched sulfur and oxygen isotopes of sulfate in bedrock ground water within Kelly's Cove watershed, Northport, Maine, USA. Interpretation of the data is complicated by the lack of correlations between sulfate concentrations an...

  18. Triple oxygen isotope evidence for elevated CO2 levels after a Neoproterozoic glaciation. (United States)

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


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

  19. Assessment of Renal Function by the Stable Oxygen and Hydrogen Isotopes in Human Blood Plasma (United States)

    Kuo, Tai-Chih; Wang, Chung-Ho; Lin, Hsiu-Chen; Lin, Yuan-Hau; Lin, Matthew; Lin, Chun-Mao; Kuo, Hsien-Shou


    Water (H2O) is the most abundant and important molecule of life. Natural water contains small amount of heavy isotopes. Previously, few animal model studies have shown that the isotopic composition of body water could play important roles in physiology and pathophysiology. Here we study the stable isotopic ratios of hydrogen (δ2H) and oxygen (δ18O) in human blood plasma. The stable isotopic ratio is defined and determined by δsample = [(Rsample/RSTD)−1] * 1000, where R is the molar ratio of rare to abundant, for example, 18O/16O. We observe that the δ2H and the δ18O in human blood plasma are associated with the human renal functions. The water isotope ratios of the δ2H and δ18O in human blood plasma of the control subjects are comparable to those of the diabetes subjects (with healthy kidney), but are statistically higher than those of the end stage renal disease subjects (pisotopes in all subjects, except the end stage renal disease subjects under the haemodialysis treatment. Furthermore, the unexpected water contents (δ2H and δ18O) in blood plasma of body water may shed light on a novel assessment of renal functions. PMID:22348150

  20. Analysis of Atmospheric Nitrate Deposition in Lake Tahoe Using Multiple Oxygen Isotopes (United States)

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


    Lake Tahoe in the Sierra Nevada Mountain Range is world renown for its depth and water clarity bringing 2.2 million visitors per year resulting in annual revenue of \\1.6 billion from tourism. In past decades the lake has suffered from decreased water clarity (from 32 m plate depth to less than 20), which is believed to be largely the result of algae growth initiated by increased nutrient loading. Lake nutrients have also seen a shift from a nitrogen limited to a phosphorous limited system indicating a large increase in the flux of fixed nitrogen. Several sources of fixed nitrogen of have been suggested including surface runoff, septic tank seepage from ground water and deposition from the atmosphere. Bio-available nitrogen in the form of nitrate (NO_{3}$-) is a main component of this system. Recent studies have estimated that approximately 50% of the nitrogen input into the lake is of atmospheric origin (Allison et al. 2000). However, the impact and magnitude of atmospheric deposition is still one of the least understood aspects of the relationship between air and water quality in the Basin (TRPA Threshold Assessment 2002). The utility of stable isotopes as tracers of nitrate reservoirs has been shown in several studies (Bohlke et al. 1997, Kendall and McDonnell 1998, Durka et al. 1994). Stable nitrogen (δ15N) and oxygen (δ18O) isotopes have been implemented in a dual isotope approach to characterize the various nitrate sources to an ecosystem. While δ18O distinguishes between atmospheric and soil sources of nitrate, processes such as denitrification can enrich the residual nitrate in δ18O leaving a misleading atmospheric signature. The benefit of δ15N as a tracer for NO3- sources is the ability to differentiate natural soil, fertilizer, and animal or septic waste, which contain equivalent δ18O values. The recent implementation of multiple oxygen isotopes to measure Δ17O in nitrate has proven to be a more sensitive tracer of atmospheric deposition. The

  1. Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt (United States)

    Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.


    Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

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

    Czech Academy of Sciences Publication Activity Database

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


    Roč. 51, SI, Supplement 1 (2016), A358-A358 ISSN 1086-9379. [Annual Meeting of the Meteoritical Society /79./. 07.08.2016-12.08.2016, Berlin] Institutional support: RVO:67985831 Keywords : impact glass * irghizites * geochemistry * meteoritic component * siderophile elements * osmium isotopes * triple-oxygen Isotopes * Zhamanshin Subject RIV: DD - Geochemistry

  3. In-Situ Oxygen Isotopic Composition of Individual Minerals in Tagish Lake, a Unique Type 2 Carbonaceous Meteorite (United States)

    Engrand, C.; Gounelle, M.; Duprat, J.; Zolensky, M. E.


    We measured the oxygen isotopic composition of individual minerals in Tagish Lake. The relationship with carbonaceous chondrites is confirmed. We found very O-16 enriched olivines. The carbonates will require a dedicated study of their C and O isotopes. Additional information is contained in the original extended abstract.

  4. Stable carbon, nitrogen, and oxygen isotope analysis as a potential tool for verifying geographical origin of beef

    International Nuclear Information System (INIS)

    Nakashita, Rumiko; Suzuki, Yaeko; Akamatsu, Fumikazu; Iizumi, Yoshiko; Korenaga, Takashi; Chikaraishi, Yoshito


    Stable isotope analysis of organic elements such as carbon and nitrogen has been employed as a powerful tool for provenance determination of food materials, because isotopic compositions of the materials reflect many factors in natural environment. In this study, we examined carbon, nitrogen, and oxygen isotope signatures of beef from Australia, Japan, and USA, in order to confirm the method as a potential tool for verifying geographical origin of beef commercially distributed in Japan. Defatted dry matter of beef from USA was characterized by higher carbon isotopic composition (-13.6 per mille to -11.1 per mille ) than that from Japan (-19.6 per mille to -17.0 per mille ) and Australia (-23.6 per mille to -18.7 per mille ). That from Australia was characterized by higher oxygen isotopic composition (+15.0 per mille to +19.4 per mille ) than that from Japan (+7.3 per mille to +13.6 per mille ) and USA (+9.5 per mille to +11.7 per mille ). The oxygen isotopic composition in Japanese beef showed a positive correlation with the isotopic composition of cattle drinking water, the difference in which is clearly latitude dependent. These results suggest that a comparison of carbon, nitrogen, and oxygen isotopic compositions is applicable as a potential tool to discriminate the provenance of beef not only between different countries (i.e. Australia, Japan, and USA) but also among different regions within Japan

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

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


    Water body' s nitrate pollution has become a common and severe environmental problem. In order to ensure human health and water environment benign evolution, it is of great importance to effectively identify the nitrate pollution sources of water body. Because of the discrepant composition of nitrogen and oxygen stable isotopes in different sources of nitrate in water body, nitrogen and oxygen stable isotopes can be used to identify the nitrate pollution sources of water environment. This paper introduced the fractionation factors of nitrogen and oxygen stable isotopes in the main processes of nitrogen cycling and the composition of these stable isotopes in main nitrate sources, compared the advantages and disadvantages of five pre-treatment methods for analyzing the nitrogen and oxygen isotopes in nitrate, and summarized the research advances in this aspect into three stages, i. e. , using nitrogen stable isotope alone, using nitrogen and oxygen stable isotopes simultaneously, and combining with mathematical models. The future research directions regarding the nitrate pollution sources identification of water environment were also discussed.

  6. Disentangling dissolved oxygen sources in shallow riparian groundwater by stable isotope analysis (United States)

    Mader, Michael; Porst, David; Schmidt, Christian; van Geldern, Robert; Barth, Johannes


    Dissolved oxygen (DO) is one of the strongest oxidation agents in aquatic environments. Besides gas-water-exchange, mixing and mineral oxidation, it is a key player in fundamental biogeochemical processes such as respiration and photosynthesis. These processes also systematically influence stable isotope ratios of DO and of dissolved inorganic carbon (DIC). Simultaneous measurements of DO and DIC concentrations in conjunction with their stable isotope ratios (δ18ODO and δ13CDIC) can thus provide useful tools to quantify oxygen and carbon sources and sinks in natural waters. This study focused on the Selke River in the Harz Mountains (Germany) with steep DO gradients between the stream water and the shallow, adjacent groundwater and associated stable isotope shifts. δ13CDIC values decreased from -13 ‰ to -18 ‰ versus the Vienna Pee Dee Belemnite standard (VPDB) from May to November 2016 and indicated the dominant influence of microbial respiration on the observed DO gradients. With such respiration dominance, we have expected a simultaneous enrichment of δ18ODOto values higher than the one of atmospheric O2 (+23.9 ‰ versus Vienna Standard Mean Ocean Water standard - VSMOW). However, our measurements revealed anomalously low δ18ODO values between +22 ‰ and +18 ‰ versus VSMOW for the same time period. These δ18ODO values were lower than those found in the river. Latter were close to equilibrium with the atmosphere (24.9 ‰ versus VSMOW). The observed δ18ODO ratios in the shallow groundwater can be explained with DO from the river that is subject to fractionation by microbial respiration with a typical fractionation factor (αr) of 0.995. In addition, mass balances revealed that this oxygen pool receives contributions of up to 25 % by diffused oxygen from the vadose zone. Consequently, isotope shifts by respiration and admixture with surface water are masked by diffusion effects that result in a decoupling of carbon and oxygen isotope systematics in

  7. AMS 14C and 230Th/U dating on stalagmites from North Altai Mountain, Siberia, Russia (United States)

    Li, H. C.; Yin, J. J.; Blyakharchuk, T.; Shen, C. C.


    Three stalagmites, two from Lunnaya Cave (LUN-1 and LUN-2, 52º40.729'N, 88º43.854' E, 481 m a.s.l.), one from Nadezhda Cave (HOP-1, 52º38.872'N, 88º39.194'E, 550 m a.s.l.) located along Mrassy River in the northern Altai Mountains, Siberia, Russia were collected in the summer of 2016 for paleoclimate reconstruction. HOP-1 is a 21-cm long stalagmite which contains very low U content (238U = 70 ppb) and relatively high Th content (232Th = 2 9.3 ppb), resulting in unsuccessful 230Th/U dating (-262 ± 284 yr BP in the top and -19,935 ± 22,246 yr BP). Thirty one AMS 14C dates from 27 horizons of the stalagmite provide a detailed chronology, showing that the stalagmite grew from 6,350 ± 45 yr BP to 490 ± 10 Calib. yr BP. Both LUN-1 and LUN-2 are about 20-cm long. The growth feature of LUN-2 is similar to that of HOP-1 with continuous growth, clear bands of depositional cycles in white non-transparent calcite, whereas LUN-1 has light yellow transparent calcite in the center part with multiple growth hiatuses. The 230Th/U dates show that LUN-1 from 2725 ± 775 yr BP at 193 mm depth to 823 ± 28 yr BP at 12 mm depth with very fast growth rate during 900 1500 yr BP. The AMS 14C dates of LUN-1 provide similar growth pattern with very fast growth between the first hiatus at 12 mm depth and the second hiatus at 155 cm depth. Six 14C dates from this fast growth period are all around 1500 Calib. yr BP without a correct age sequence. Two 14C dates from the top 12 mm exhibit "nuclear bomb signal" (percentage of modern carbon >100%). Similar ages of AMS 14C and 230Th/U dating results in the lower part indicate that dead carbon influence in radiocarbon ages are negligible. 230Th/U dating is not successful for LUN-2. The preliminary AMS 14C dating on LUN-2 shows that the stalagmite continuously deposited from 13335 ± 150 Calib. yr BP. All three stalagmites do not have growth deposition during the Little Ice Age due to cold and dry climates. Further work on stable isotope

  8. Exploring Holocene climate fluctuations registered in Bosnian stalagmites adopting a multiproxy approach (United States)

    Chiarini, Veronica; Couchoud, Isabelle; Drysdale, Russell; Bajo, Petra; Milanolo, Simone; Hellstrom, John; De Waele, Jo


    The central Mediterranean area, a crucial region for present day and future climate change, has been characterised by contrasting patterns between northern and southern climate influences over the Holocene (e.g. Magny et al., 2012; Peyron et al., 2013). Several records from the Italian Peninsula identify this phenomenon: relatively dry conditions experienced during the first half of the Holocene are followed by an increase in moisture in the northern regions, while in the southern portion of the Peninsula the opposite trend occurs. On the Balkan side of the Adriatic Sea, this contrasting pattern is less well documented. The available studies focused on lake sediments show a more gradual and less warm early Holocene and more stable conditions during the early-mid Holocene compared to Italy (Bordon et al., 2009; Vogel et al., 2010). Several speleothems have been collected from Banja Stijena and Govještica Caves (Bosnia and Herzegovina). Preliminary U-Th dating allowed to choose the five most promising samples for further study. Stable oxygen and carbon isotopes have been analysed along the stalagmite growth axes and trace elements of one sample have been investigated. Air-mass back-trajectory analyses of present day precipitation in the area have been performed in association with GNIP rainfall isotope data analyses, with the aim of understanding the parameters driving rainfall stable oxygen isotope composition variations. Considering the impossibility of having a detailed monitoring of cave conditions due to the practical difficulties of identifying the original location of the samples collected, petrographic observations have been coupled with δ13C and δ18O in order to improve the understanding of the environmental processes recorded by these samples, as suggested in Frisia (2015) and Borsato et al. (2015). Here we will present the results of these multiproxy analyses, exploring the potential of these samples in recording regional climate fluctuations and

  9. Stratigraphy on Oxygen and Carbon Isotope of Paciran Formation East Java

    International Nuclear Information System (INIS)

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


    Paleotemperature fluctuation in tropical zone (centennial and decad al scale) has been known. It's based on stable isotopic analysis from each of unconformity zones. Those boundaries have derived on reef units of shallows marine reef complex of Paciran Formation, Tuban area in Northeast Java Basin. From 25 samples have been choosen on undeformed calcite and analyzed by oxygen and carbon stable isotope. It used to validizing a sea level changes during the formation to Reef 1 to Reef 17 from Paciran formation with sea surface temperature (SST) since 4 Ma until now. On early forming of Reef 1 to Reef 3 (since 4 Ma - 2,88 Ma), sea level occurred marine flooding surface. Since the formation of reef 4 (2,59 Ma) to Reef 8 (1,4 Ma) occurred stagnant temperature and almost to warmer condition. Then, δ 18 O have arise up drastically to 5 0/00 and shows warmer condition to Reef 8 formation, in contrary, the sea level have been arised to Reef 10 formation (0,7 Ma). The temperature have been fluctuated between 0,5 o and 1 o C until the formation of Reef 17 (Early Holocene) and continued to Reef 17 formation at 2 o C based on the rapidity sampling of Po rites sp. Wholly, in centennial scale, since the formation of Reef 4 (2,59 Ma) to Reef 17 (1 Ma), the curve of oxygen stable isotope shows decrease or cooler condition. Those condition have conducted to sea level drop since the formation to Reef 7 and Reef 8. There are 4 periods of interglacial since the formation of Reef 4. The warmer condition indicated since the formation of Reef 9, Reef 11 and Reef 17. Recently, a curve of oxygen isotopes reveals warmer drastically or sea level have been arisen. (author)


    Directory of Open Access Journals (Sweden)

    E. Ristin Pujiindiyati


    Full Text Available There are at least 30 high temperature systems; eleven active volcanoes, five degassing volcanoes and one caldera volcano controlled by Sumatra Fault Zone over a length of 1700 km. To understand this geothermal field system, some information about geochemistry including isotope composition in its fluid is needed. Sulphur-34 and oxygen-18 isotopes in dissolved sulphate pair have been used to determine the origin of acidic fluid of sulphate and to evaluate the process involved. The fluids from eight hot springs, two fumaroles, four deep wells and crater have been collected in along Sumatra geothermal fields. Sulphur-34 (d 34S (SO4, 0/00 CDT and oxygen-18 (d 18O (SO4, 0/00 SMOW in sulphate is analyzed according to Robinson-Kusakabe and Rafter method, respectively. The d 34S (SO4 values from Sibayak wells are more enriched of 16.8 0/00 to 18.2 0/0 that may indicate the dissolution of anhydrite minerals or isotope partitioning in hydration of SO2. The d 34S (SO4 values from two fumaroles (Pusuk Bukit - North Sumatra and Rantau Dadap - South Sumatra are at depleted value of -0.150/00 and 1.80/00, those are close to d 34S from magmatic sulphur.  In general, the d 34S (SO4 of springs spread in a wide range of 5.250/00 to14.20/00 and show a mixing process between atmospheric sulphate and sulphate from deep wells. The d 18O (SO4 from wells exhibits depleted value around -3.60/00 suggesting that 87.5% of sulphate oxygen is derived from groundwater oxygen and 12.5% is derived from atmospheric molecular oxygen in sulphide oxidation reaction. In the other hand, hot springs (except Semurup, crater and fumaroles have enriched value of d 18O (SO4. These enriched values suggest that a higher percentage of atmospherically derived oxygen compared to those from the depth.   Keywords: isotope, geothermal, Sumatra


    Energy Technology Data Exchange (ETDEWEB)

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


    Based on the mineralogy and petrography, coarse-grained, igneous, anorthite-rich (Type C) calcium-aluminum-rich inclusions (CAIs) in the CV3 carbonaceous chondrite Allende have been recently divided into three groups: (i) CAIs with melilite and Al,Ti-diopside of massive and lacy textures (coarse grains with numerous rounded inclusions of anorthite) in a fine-grained anorthite groundmass (6-1-72, 100, 160), (ii) CAI CG5 with massive melilite, Al,Ti-diopside and anorthite, and (iii) CAIs associated with chondrule material: either containing chondrule fragments in their peripheries (ABC, TS26) or surrounded by chondrule-like, igneous rims (93) (Krot et al., 2007a,b). Here, we report in situ oxygen isotopic measurements of primary (melilite, spinel, Al,Ti-diopside, anorthite) and secondary (grossular, monticellite, forsterite) minerals in these CAIs. Spinel ({Delta}{sup 17}O = -25{per_thousand} to -20{per_thousand}), massive and lacy Al,Ti-diopside ({Delta}{sup 17}O = -20{per_thousand} to -5{per_thousand}) and fine-grained anorthite ({Delta}{sup 17}O = -15{per_thousand} to -2{per_thousand}) in 100, 160 and 6-1-72 are {sup 16}O-enriched relative spinel and coarse-grained Al,Ti-diopside and anorthite in ABC, 93 and TS26 ({Delta}{sup 17}O ranges from -20{per_thousand} to -15{per_thousand}, from -15{per_thousand} to -5{per_thousand}, and from -5{per_thousand} to 0{per_thousand}, respectively). In 6-1-72, massive and lacy Al,Ti-diopside grains are {sup 16}O-depleted ({Delta}{sup 17}O {approx} -13{per_thousand}) relative to spinel ({Delta}{sup 17}O = -23{per_thousand}). Melilite is the most {sup 16}O-depleted mineral in all Allende Type C CAIs. In CAI 100, melilite and secondary grossular, monticellite and forsterite (minerals replacing melilite) are similarly {sup 16}O-depleted, whereas grossular in CAI 160 is {sup 16}O-enriched ({Delta}{sup 17}O = -10{per_thousand} to -6{per_thousand}) relative to melilite ({Delta}{sup 17}O = -5{per_thousand} to -3{per_thousand}). We infer

  12. Using Oxygen and Carbon Isotopic Signatures in Order to Infer Climatic and Dietary Information in Roman Edessa, Greece (United States)

    Michael, Dimitra-Ermioni; Dotsika, Elissavet


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

  13. Laboratory investigations of stable carbon and oxygen isotope ratio data enhance monitoring of CO2 underground (United States)

    Barth, Johannes A. C.; Myrttinen, Anssi; Becker, Veith; Nowak, Martin; Mayer, Bernhard


    Stable carbon and oxygen isotope data play an important role in monitoring CO2 in the subsurface, for instance during carbon capture and storage (CCS). This includes monitoring of supercritical and gaseous CO2 movement and reactions under reservoir conditions and detection of potential CO2 leakage scenarios. However, in many cases isotope data from field campaigns are either limited due to complex sample retrieval or require verification under controlled boundary conditions. Moreover, experimentally verified isotope fractionation factors are also accurately known only for temperatures and pressures lower than commonly found in CO2 reservoirs (Myrttinen et al., 2012). For this reason, several experimental series were conducted in order to investigate effects of elevated pressures, temperatures and salinities on stable carbon and oxygen isotope changes of CO2 and water. These tests were conducted with a heateable pressure device and with glass or metal gas containers in which CO2 reacted with fluids for time periods of hours to several weeks. The obtained results revealed systematic differences in 13C/12C-distributions between CO2 and the most important dissolved inorganic carbon (DIC) species under reservoir conditions (CO2(aq), H2CO3 and HCO3-). Since direct measurements of the pH, even immediately after sampling, were unreliable due to rapid CO2 de-gassing, one of the key results of this work is that carbon isotope fractionation data between DIC and CO2 may serve to reconstruct in situ pH values. pH values reconstructed with this approach ranged between 5.5 and 7.4 for experiments with 60 bars and up to 120 °C and were on average 1.4 pH units lower than those measured with standard pH electrodes directly after sampling. In addition, pressure and temperature experiments with H2O and CO2 revealed that differences between the oxygen isotope ratios of both phases depended on temperature, water-gas ratios as well as salt contents of the solutions involved. Such

  14. Partitioning water and carbon fluxes in a Mediterranean oak woodland using stable oxygen isotopes (United States)

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


    Water is a key factor driving ecosystem productivity, especially in water-limited ecosystems. A separation of the component fluxes is needed to gain a functional understanding on the development of net ecosystem water fluxes and their coupling with biogeochemical cycles. Oxygen isotope signatures are valuable tracers for water movements within the ecosystem because of the distinct isotopic compositions of water in soil and vegetation. In the past, determination of isotopic signatures of evaporative or transpirational fluxes has been challenging since measurements of water vapor isotopes were difficult to obtain using cold-trap methods, delivering data with low time resolution. Recent developments in laser spectroscopy now enable direct high frequency measurements of the isotopic composition of atmospheric water vapor (δv), evapotranspiration (δET), and its components and allow validations of common modeling approaches for estimating δE and δT based on Craig and Gordon (1965). Here, a novel approach was used, combining a custom build flow-through gas-exchange branch chamber with a Cavity Ring-Down Spectrometer in a Mediteranean cork-oak woodland where two vegetation layers respond differently to drought: oak-trees (Quercus suber L.) avoid drought due to their access to ground water while herbaceous plants survive the summer as seeds. We aimed at 1) testing the Craig and Gordon equation for soil evaporation against directly measured δE and 2) quantifying the role of non-steady-state transpiration under natural conditions. Thirdly, we used this approach to quantify the impact of the understory herbaceous vegetation on ecosystem carbon and water fluxes throughout the year and disentangle how ET components of the ecosystem relate to carbon dioxide exchange. We present one year data comparing modeled and measured stable oxygen isotope signatures (δ18O) of soil evaporation, confirming that the Craig and Gordon equation leads to good agreement with measured δ18O of

  15. Stable carbon and oxygen isotopes of natural waters in the Netherlands

    International Nuclear Information System (INIS)

    Mook, W.G.


    The carbon and oxygen isotopes in the Dutch surface water and groundwater present an internally consistent picture of the hydrologic cycle. The 18 O content of the average annual precipitation (-7.9 per mille) fits in with the temperature relation of Dansgaard. The average seasonal variation can be explained comparatively. The groundwater generally reflects the isotopic composition of precipitation during the seasons of maximum infiltration (δ 18 = -7.5 to -8 per mille). River water appears to have a component derived from groundwater of a specific isotopic composition, as observed in winter. Certain processes during the rest of the year cause a marked seasonal variation in both isotopes. The δ 13 of the dissolved bicarbonate generally varies between -12 and -8 per mille, largely due to isotope exchange with the atmospheric CO 2 . The meltwater and rain-water rivers show opposite variations in 18 O content, the Rhine from -9 to -10.5 per mille and the Vecht from -7.5 to -6.5 per mille between winter and summer respectively. The δ 13 values of sea-water bicarbonate (+1.5 to +2.0 per mille) point to a condition of isotopic equilibrium between the dissolved bicarbonate and the atmospheric carbon dioxide at an average temperature between 14 and 20 degrees C. In an estuary the isotopic compositions of the bicarbonate and the water turn out to be solely determined by the mixing ratio of the fresh and sea-water. The δ 18 -chlorinity relation yields a straight line, whereas the similar relation for 13 C gives a smooth curve, the form depending on the relative quantities of dissolved carbon in the fresh and sea-water. In the lake IJsselmeer the 13 C content approaches an isotopic equilibrium with atmospheric CO 2 along the flow direction, due to the relatively long residence time of the water in the lake. The observed chemical and isotopic changes in the flow direction can be explained quantitatively. (author)

  16. Mass-Independent Fractionation of Oxygen Isotope in Earth Wind: First Principle Calculations for Photodissociation (United States)

    Yamada, A.; Nanbu, S.; Kasai, Y.; Ozima, M.


    Mass-independently fractionated oxygen isotope were reported on metal particles extracted from Apollo lunar soils [1, 2], but these origins are still unknown. Since the substantial fraction of Earth-escaping O+ flux (Earth Wind, EW hereafter), comparable to the amount of the anomalous oxygen implanted on the metal particles, could reach the lunar surface [3], Ozima et al. [4] suggested that EW may be responsible to the anomalous oxygen. The purpose is to test this EW hypothesiss, we study oxygen isotopic ratios of O+ at the upper atmosphere. From quantum chemical calculations of photo-dissociation of O2, we show the results in mass-independent isotopic fractionation of oxygen, thereby in conformity with the EW hypothesis. First principles reaction dynamics simulations were performed to compute the photolysis rate for the B3Σu- ← X3Σg- electronic transition, for Schumann-Runge band. With the assumption of the Born-Oppenheimer approximation, we performed the wave-packet dynamics for the nuclei-motion in the potential energy curves determined by the first step calculation. Quantum chemical program package [5] was used for the first step calculation, and the quantum dynamics was carried out by our own program package. Assuming the quantum yield of the corresponding photolysis is unity, the photo-absorption cross section can be correlated with the photolysis rate. Therefore, following the time dependent approach, the autocorrelation function (A(t) = ) was numerically computed by the second step calculation. Finally, the theoretical spectrum as a function of wavelength of excitation light was estimated by the Fourier transform of the autocorrelation function A(t) [6]. Calculated absorption cross sections for C16O showed similar wavelength dependence with experiment [7], although the absolute magnitude was yet to be calibrated for a quantitative comparison. Assuming Boltzmann distribution at 1200 K, we estimated enrichment factors defined as σι(λ)/σ16(λ) - 1 (i

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

    Directory of Open Access Journals (Sweden)

    Alberta Silvestri


    Full Text Available The present paper emphasizes the importance of measuring the oxygen isotopic and chemical compositions of ancient glass, in order to constrain some features such as age, raw materials, and production technologies and to identify the “fingerprint” of local productions. In this context, thirty-nine Roman and late Antique glass samples and eight chert samples from northern Greece were selected and analysed for their oxygen isotopic and chemical compositions. Results show that the majority of glass samples are produced using natron as flux and have δ18O values of about 15.5‰, plus or minus a few tenths of one per mil, suggesting that raw materials probably come from Levantine area. Four samples are heavily enriched in 18O, and their chemical composition clearly shows that they were made with soda plant ash as flux. Isotopic and chemical data of Greek chert samples support the hypothesis of local production of the above samples. About half of the glass samples have chemical compositions, which allow their age to be constrained to the late Antique period. For the remaining glass, similarities with literature compositional groups are reported and discussed.

  18. [Hydrogen and Oxygen Isotopic Compositions of Precipitation and Its Water Vapor Sources in Eastern Qaidam Basin]. (United States)

    Zhu, Jian-jia; Chen, Hui; Gong, Guo-li


    Stable hydrogen and oxygen isotopes can be used as a tracer to analyze water vapor sources of atmospheric precipitation. We choose Golmud and Delingha as our study areas, Golmud locates in the south of Qaidam basin, and Delingha locates in the northeast. Based on the analysis of monthly change of hydrogen and oxygen isotopic compositions of precipitation during June to September of 2010, and the relationship between deltaD and delta18O in precipitation, we investigated the water vapor sources of precipitation in eastern Qaidam basin. The results show that: (1) meteoric water line between June to September in Golmud is: deltaD = 7.840 delta18O - 4.566 (R2 = 0.918, P isotopes. However, the delta18O content of precipitation becomes lower from late July to early September, especially for the late September. The 8180 content of precipitation in Delingha is higher in June to August than that in late September. (3) the water vapor sources of precipitation in Golmud and Delingha are different, Golmud area is the northern border of Qinghai-Tibet Plateau where the southwest monsoon can reach, and the southwest monsoon brings water vapors of precipitation, but the water vapors of precipitation in Delingha are mainly from local evaporation.

  19. Isotopic probing of molecular oxygen activation at copper(I) sites. (United States)

    Lanci, Michael P; Smirnov, Valeriy V; Cramer, Christopher J; Gauchenova, Ekaterina V; Sundermeyer, Jörg; Roth, Justine P


    Copper-dioxygen (CuO2) adducts are frequently proposed as intermediates in enzymes, yet their electronic and vibrational structures have not always been understood. [Cu(eta1-O2)TMG3tren]+ (TMG3tren = 1,1,1-tris{2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl}amine) features end-on (eta1) O2 coordination in the solid state. Described here is an investigation of the compound's solution properties by nuclear magnetic resonance spectroscopy, density functional calculations, and oxygen isotope effects. The study yields two major findings. First, [Cu(eta1-O2)TMG3tren]+ is paramagnetic due to a triplet electronic structure; this is in contrast to other copper compounds where O2 is bound in a side-on manner. Second, the oxygen equilibrium isotope effect upon O2 binding to copper(I) (18O EIE [triple bond] K(16O16O)/K(16O18O) = 1.0148 +/- 0.0012) is significantly larger than those determined for iron and cobalt eta1-O2 adducts. This result is suggested to reflect greater ionic (CuII-O2-I) character within the valence bond description. A revised interpretation of the physical origins of the 18O EIEs upon O2 binding to redox metals is also advanced along with experimental data that should be used as benchmarks for interpreting 18O kinetic isotope effects upon enzyme reactions.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    Recent experiments have shown a reduction of spectroscopic strengths to about 60-70% for stable nuclei. When going to drip lines this tendency is changing, loosely bound nucleons have spectroscopic strengths close unity while deeply bound nucleons have a large reduction of the strength. We aim to make a systematic study of spectroscopic factors (SF) of the Oxygen isotopes using quasi-free (p,2p) and (p,pn) knockout reactions in inverse kinematics. Quasi-free knockout reactions are a direct tool to study the occupancy and the location of valance and deeply bound single particle states. The Oxygen isotopes offer a large variation of separation energies which will allow us to obtain a qualitative and quantitative understanding of SF in a large variation of isospin asymmetry. For this we performed an experiment at the R3B-LAND setup at the GSI with secondary beams containing {sup 14-24}O. The {sup 16-18}O and {sup 21-23}O isotopes have been analyzed and the preliminary results will be presented. The results include the partial cross sections, gamma ray spectra of the residual fragments in coincidence, and the SF obtained via comparison with theory.

  1. Three distinct Holocene intervals of stalagmite deposition and nondeposition revealed in NW Madagascar, and their paleoclimate implications (United States)

    Riavo Gilbertinie Voarintsoa, Ny; Railsback, Loren Bruce; Brook, George Albert; Wang, Lixin; Kathayat, Gayatri; Cheng, Hai; Li, Xianglei; Edwards, Richard Lawrence; Rakotondrazafy, Amos Fety Michel; Olga Madison Razanatseheno, Marie


    Petrographic features, mineralogy, and stable isotopes from two stalagmites, ANJB-2 and MAJ-5, respectively from Anjohibe and Anjokipoty caves, allow distinction of three intervals of the Holocene in NW Madagascar. The Malagasy early Holocene (between ca. 9.8 and 7.8 ka) and late Holocene (after ca. 1.6 ka) intervals (MEHI and MLHI, respectively) record evidence of stalagmite deposition. The Malagasy middle Holocene interval (MMHI, between ca. 7.8 and 1.6 ka) is marked by a depositional hiatus of ca. 6500 years. Deposition of these stalagmites indicates that the two caves were sufficiently supplied with water to allow stalagmite formation. This suggests that the MEHI and MLHI intervals may have been comparatively wet in NW Madagascar. In contrast, the long-term depositional hiatus during the MMHI implies it was relatively drier than the MEHI and the MLHI. The alternating wet-dry-wet conditions during the Holocene may have been linked to the long-term migrations of the Intertropical Convergence Zone (ITCZ). When the ITCZ's mean position is farther south, NW Madagascar experiences wetter conditions, such as during the MEHI and MLHI, and when it moves north, NW Madagascar climate becomes drier, such as during the MMHI. A similar wet-dry-wet succession during the Holocene has been reported in neighboring locations, such as southeastern Africa. Beyond these three subdivisions, the records also suggest wet conditions around the cold 8.2 ka event, suggesting a causal relationship. However, additional Southern Hemisphere high-resolution data will be needed to confirm this.

  2. Understanding the circulation of geothermal waters in the Tibetan Plateau using oxygen and hydrogen stable isotopes

    International Nuclear Information System (INIS)

    Tan, Hongbing; Zhang, Yanfei; Zhang, Wenjie; Kong, Na; Zhang, Qing; Huang, Jingzhong


    Highlights: • Unique geothermal resources in Tibetan Plateau were discussed. • Isotopes were used to trace circulation of geothermal water. • Magmatic water mixing dominates geothermal water evolution. - Abstract: With the uplift of the Tibetan Plateau, many of the world’s rarest and most unique geothermal fields have been developed. This study aims to systematically analyze the characteristics of the hydrogen and oxygen isotopic data of geothermal, river, and lake waters to understand the circulation of groundwater and to uncover the mechanism of geothermal formation in the Tibetan Plateau. Field observations and isotopic data show that geothermal water has higher temperatures and hydraulic pressures, as well as more depleted D and 18 O isotopic compositions than river and lake waters. Thus, neither lakes nor those larger river waters are the recharge source of geothermal water. Snow-melt water in high mountains can vertically infiltrate and deeply circulate along some stretching tensile active tectonic belts or sutures and recharge geothermal water. After deep circulation, cold surface water evolves into high-temperature thermal water and is then discharged as springs at the surface again in a low area, under high water-head difference and cold–hot water density difference. Therefore, the large-scale, high-temperature, high-hydraulic-pressure geothermal systems in the Tibetan Plateau are developed and maintained by rapid groundwater circulation and the heat source of upwelled residual magmatic water. Inevitably, the amount of geothermal water will increase if global warming accelerates the melting of glaciers in high mountains

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

    International Nuclear Information System (INIS)

    Sun Fengmei; Shi Guangyu; Wang Huiwen; Yang Shuming


    In order to research on stable hydrogen, oxygen, sulfur isotopes composition in different tissues of cattle, as well as the breed, δ 2 H and δ 34 S values of different defatted muscle, cattle tail hair, blood, liver, also δ 2h and δ 18 O values of water from muscle were determined by isotope ratio mass spectrometry. The stable sulfur isotope composition was not affected by cattle variety, meanwhile the hydrogen was uncertain; the δ 2 H and δ 34 S values between different defatted muscle, blood, liver, cattle hair were significantly different, at the same time the δ 34 S and δ 2 H values between each tissue were not significantly correlated; the δ 2 H values were strongly correlated with the δ 18 O values of muscle water. The above results indicated that stable sulfur and hydrogen isotopes fractionation in the various tissues were discrepant, thus the proper tissue should be selected according to the purpose and object in the beef traceability. (authors)

  4. Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars. (United States)

    Shaheen, R; Abramian, A; Horn, J; Dominguez, G; Sullivan, R; Thiemens, Mark H


    The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess (17)O (0.4-3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O(3) reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth.

  5. Isotope studies of hydrogen and oxygen in ground ice-experiences with the equilibration technique. (United States)

    Meyer, H; Schönicke, L; Wand, U; Hubberten, H W; Friedrichsen, H


    Equilibration technique suitable for a large amount of samples is described for hydrogen and oxygen isotope analyses of ground ice, especially ice wedges, including the sampling strategy and the analytical procedure as well as the calibration of the Finnigan MAT Delta-S mass spectrometer in June, 1999. Since for future analyses of ice wedges, a higher sampling resolution with limited sample volume is required, the limit of the equilibration technique for small water sample sizes of between 0.05 and 5 ml was checked. For water samples smaller than 1 ml, corresponding to a molar ratio [H2O]/[H2] of smaller than 0.994, a balance correction has to be applied. The experimental errors due to partial evaporation during evacuation, the balance calculation of the isotope equilibration process, the linearity as well as memory effects of the mass spectrometer for samples with large differences in delta18O and deltaD are tackled in this paper. In the polar regions of Northern Siberia without Late Pleistocene and Holocene glaciation, ground ice is used as an archive for paleoclimate studies. First results of stable isotope measurements on ice wedges clearly show a shift towards heavier isotopes and thus warmer winter temperatures as well as a change in the source of the precipitation between Late Pleistocene and Holocene. These results indicate the high potential of ground ice for paleoclimate studies.

  6. Oxygen and carbon isotope composition of Quaternary bivalve shells as a water mass indicator: Last interglacial and Holocene, East Greenland

    DEFF Research Database (Denmark)

    Israelson, C.; Buchardt, Bjørn; Funder, S.V.


    Oxygen and carhon isotope composition of arctic bivahe shells are used in an attempt to reCO'1struct -.urface water temperature and salinities in Scoresby Sund. East Greenland. The oxygen i:;otope compositions or .1,tw mllicuf£!. Hialclla arctica and Tridmlla hOl'm!is han~ been compared with pres...

  7. A novel pulse isotopic exchange technique for rapid determination of the oxygen surface exchange rate of oxide ion conductors

    NARCIS (Netherlands)

    Bouwmeester, Henricus J.M.; Song, Chunlin; Song, C.; Zhu, J.J.; van Sint Annaland, M.; Yi, Jianxin; Boukamp, Bernard A.


    We demonstrate the use of a novel pulse 18O–16O isotopic exchange technique for the rapid determination of the oxygen surface exchange rate of oxide ion conductors while simultaneously providing insight into the mechanism of the oxygen exchange reaction, which contributes to the efficient

  8. Oxygen isotopic relationships between the LEW85332 carbonaceous chondrite and CR chondrites (United States)

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


    LEW85332, originally described as a unique C3 chondrite, was shown to be a C2 chondrite with important linkages to the CR clan. An important petrologic aspect of LEW85332 is that it contains anhydrous chondrules and hydrated matrix, and new oxygen isotopic data on chondrules, matrix and whole rock are consistent with the petrology. Chondrules fall on the equilibrated chondrite line (ECL), with a slope near 1, which goes through ordinary chondrite chondrules. This contrasts with the CR chondrule line which has a lower slope due to hydrated components. LEW85332 chondrules define a new carbonaceous chondrite chondrule line, parallel to the anhydrous CV chondrule line (CCC), consistent with the well-established concept of two oxygen isotopic reservoirs. Matrix and whole rock fall on the CR line. The whole rock composition indicates that the chondrite is dominated by chondrules, and that most of them contain light oxygen similar to that of anhydrous olivine and pyroxene separates in the Renazzo and Al Rais CR chondrites.

  9. The isotopic exchange of oxygen as a tool for detection of the glycation sites in proteins. (United States)

    Kijewska, Monika; Stefanowicz, Piotr; Kluczyk, Alicja; Szewczuk, Zbigniew


    A nonenzymatic reaction of reducing sugars with the free amino group located at the N terminus of the polypeptide chain or in the lysine side chain results in glycation of proteins. The fragments of glycated proteins obtained by enzymatic hydrolysis could be considered as the biomarkers of both the aging process and diabetes mellitus. Here we propose a new method for the identification of peptide-derived Amadori products in the enzymatic digest of glycated proteins. The products of enzymatic hydrolysis of the model protein ubiquitin were incubated with H(2)(18)O under microwave activation. We observed that at these conditions the Amadori compounds selectively exchange one oxygen atom in the hexose moiety. The characteristic isotopic pattern of Amadori products treated with H(2)(18)O allows fast and convenient identification of this group of compounds, whereas nonglycated peptides are not susceptible to isotopic exchange. Copyright © 2011 Elsevier Inc. All rights reserved.

  10. Oxygen isotope exchange in rocks and minerals from the Cerro Prieto geothermal system: Indicators of temperature distribution and fluid flow (United States)

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


    Paleotemperatures different from the present thermal regime were studied by examining coexisting mineral systems which exchanged their oxygen with the geothermal brines at different rates. Oxygen isotopic compositions were measured in drill cuttings and core and core samples from more than 40 wells. Oxygen isotopic profiles of pore filling calcites in sandstones are a measure of the recent equilibrium temperature distribution. A three dimensional map was developed, showing the equilibrium temperatures in the geothermal field. A mass balance calculation was performed using measured 18O enrichment of the geothermal brine. This calculation implies an overall water; rock volume ratio of approximately 3:1 during the history of the Cerro Prieto system.

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

    International Nuclear Information System (INIS)

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


    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species—specific factors on leaf water enrichment of D and 18 O have not been studied for different plants growing together. Accordingly, to learn whether leaf water enrichment patterns and processes for D and 18 O are different for individual species growing under the same environmental conditions we tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show higher slopes (m in the leaf water equation °D = m ° 18 O + b) than in C 3 plants. We determined the relationships between the stable hydrogen (°D) and oxygen (° 18 O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. Slopes (m in the above leaf water equation) ranged from 1.50 to 3.21, compared to °8 for meteoric water, but differences in slope could not be attributed to carboxylation pathway (CAM vs. C 3 ) nor climate (coastal California vs. Sonoran Desert). Higher slopes were correlated with greater overall ranges of leaf water enrichment of D and 18 O. Water in plants with higher slopes also differed most from unaltered meteoric water. Leaf water isotope ratios in plants with lower slopes were better correlated with temperature and humidity. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes

  12. Episodic growth of the Gondwana supercontinent from hafnium and oxygen isotopes in zircon. (United States)

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


    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.


    Energy Technology Data Exchange (ETDEWEB)

    Lugaro, Maria [Monash Centre for Astrophysics (MoCA), Building 28, Monash University, Clayton, VIC 3800 (Australia); Liffman, Kurt [CSIRO/MSE, P.O. Box 56, Highett, VIC 3190 (Australia); Ireland, Trevor R. [Planetary Science Institute and Research School of Earth Sciences, Australian National University, Canberra, ACT 0200 (Australia); Maddison, Sarah T., E-mail: [Centre for Astrophysics and Supercomputing, Swinburne University, H39, P.O. Box 218, Hawthorn, VIC 3122 (Australia)


    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.

  14. Can Lightning Produce Significant Levels of Mass-Independent Oxygen Isotopic Fractionation in Nebular Dust? (United States)

    Nuth, Joseph A.; Paquette, John A.; Farquhar, Adam


    Based on recent evidence that oxide grains condensed from a plasma will contain oxygen that is mass independently fractionated compared to the initial composition of the vapor, we present a first attempt to evaluate the potential magnitude of this effect on dust in the primitive solar nebula. This assessment relies on previous studies of nebular lightning to provide reasonable ranges of physical parameters to form a very simple model to evaluate the plausibility that lightning could affect a significant fraction of nebular dust and that such effects could cause a significant change in the oxygen isotopic composition of solids in the solar nebula over time. If only a small fraction of the accretion energy is dissipated as lightning over the volume of the inner solar nebula, then a large fraction of nebular dust will be exposed to lightning. If the temperature of such bolts is a few percent of the temperatures measured in terrestrial discharges, then dust will vaporize and recondense in an ionized environment. Finally, if only a small average decrease is assumed in the O-16 content of freshly condensed dust, then over the last 5 million years of nebular accretion the average delta O-17 of the dust could increase by more than 30 per mil. We conclude that it is possible that the measured " slope 1" oxygen isotope line measured in meteorites and their components represents a time-evolution sequence of nebular dust over the last several million years of nebular evolution O-16-rich materials formed first, then escaped further processing as the average isotopic composition of the dust graduaUy became increasingly depleted in O-16 .

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

    Directory of Open Access Journals (Sweden)

    T. D. Als


    Full Text Available 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 (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.

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

    International Nuclear Information System (INIS)

    Sial, A.N.


    Four groups of granitoids are present within the Cachoeirinha belt and in the adjacent migmatitic basement, between 37 0 and 40 0 W long. and 7 0 and 8 0 15' S lat., States of Pernambuco and Paraiba: a) K 2 O - enriched, very porphyritic; b) a calc-alkalic slightly porphyritic group; c) group with trondjemitic affinities; and d) peralkalic group. Petrology and oxygen isotope geochemistry for over 100 samples from these groups were studied. Almost all plutons for which 5 or more samples were analyzed, exhibit a total range of gamma 18 O less than 2% o. A broad range of mean oxygen isotope composition is observed, varying from 6.93 to 12.79% o. There is a systematic regional trend in which the calc-alkalic granitoids (conceicao-type) found within the Cachoeirinha space are the most 18 O - enriched rocks (10.6 to 12.9% o) while the lowest mean gamma 18 O values (4.5 to 9.7% o) are found in the K 2 O - enriched granitoids (Itaporanga-type). Intermediate gamma 18 O values were recorded in the bodies with trondhjemitic affinities (8.9 to 9.8% o) which intruded metasediments of the Salgueiro Group and in the peralkalic granitoids of Catingueira (8.1 to 9.8% o) which intruded Cachoeirinha metamorphics. Among the potassic granitoids, mean gamma 18 O increases from Bodoco to Itaporanga (from west to east). As a whole, the W.R. gamma 18 O of these plutons correlate with the type of grade of metamorphism of the host rocks and, therefore, with the tectonic framework, increasing from those which intruded the gneiss-migmatites to those which intruded the low-grade metamorphics of the Cachoeirinha Group. The possible origin of each rock group is discussed in light of the oxygen isotope geochemistry. (Author) [pt

  17. The Oxygen Isotope Composition of Dark Inclusions in HEDs, Ordinary and Carbonaceous Chondrites (United States)

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


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

  18. Oxygen isotope systematics in an evolving geothermal system: Coso Hot Springs, California (United States)

    Etzel, Thomas M.; Bowman, John R.; Moore, Joseph N.; Valley, John W.; Spicuzza, Michael J.; McCulloch, Jesse M.


    Oxygen isotope and clay mineralogy studies have been made on whole rock samples and feldspar separates from three wells along the high temperature West Flank of the Coso geothermal system, California. The reservoir rocks have experienced variable 18O/16O depletion, with δ18O values ranging from primary values of + 7.5‰ down to - 4.6‰. Spatial patterns of clay mineral distributions in the three wells are not closely correlated with the distributions expected from measured, pre-production temperature profiles, but do correlate with spatial patterns of 18O/16O depletion, indicating that the stability of clay minerals in the three wells is a function of fluid-rock interaction in addition to temperature. Detailed δ18O measurements in the three wells identify a limited number of localized intervals of extensive 18O/16O depletion. These intervals document localized zones of higher permeability in the geothermal system that have experienced significant fluid infiltration, water-rock interaction and oxygen isotopic exchange with the geothermal fluids. The local zones of maximum 18O/16O depletion in each well correspond closely with current hot water production zones. Most feldspar separates have measured δ18O values too high to have completely attained oxygen isotope exchange equilibrium with the reservoir fluid at pre-production temperatures. In general, the lower the δ18O value of the feldspar, the closer the feldspar approaches exchange equilibrium with the geothermal fluid. This correlation suggests that fracture-induced increases in permeability increase both fluid infiltration and the surface area of the host rock exposed to geothermal fluid, promoting fluid-rock interaction and oxygen isotope exchange. The two most 18O/16O-depleted feldspar samples have δ18O values too low to be in exchange equilibrium with the pre-production reservoir fluid at pre-production temperatures. These discrepancies suggest that the reservoir fluid in the West Flank of the Coso

  19. Closed system oxygen isotope redistribution in igneous CAIs upon spinel dissolution (United States)

    Aléon, Jérôme


    In several Calcium-Aluminum-rich Inclusions (CAIs) from the CV3 chondrites Allende and Efremovka, representative of the most common igneous CAI types (type A, type B and Fractionated with Unknown Nuclear isotopic anomalies, FUN), the relationship between 16O-excesses and TiO2 content in pyroxene indicates that the latter commonly begins to crystallize with a near-terrestrial 16O-poor composition and becomes 16O-enriched during crystallization, reaching a near-solar composition. Mass balance calculations were performed to investigate the contribution of spinel to this 16O-enrichment. It is found that a back-reaction of early-crystallized 16O-rich spinel with a silicate partial melt having undergone a 16O-depletion is consistent with the O isotopic evolution of CAI minerals during magmatic crystallization. Dissolution of spinel explains the O isotopic composition (16O-excess and extent of mass fractionation) of pyroxene as well as that of primary anorthite/dmisteinbergite and possibly that of the last melilite crystallizing immediately before pyroxene. It requires that igneous CAIs behaved as closed-systems relative to oxygen from nebular gas during a significant fraction of their cooling history, contrary to the common assumption that CAI partial melts constantly equilibrated with gas. The mineralogical control on O isotopes in igneous CAIs is thus simply explained by a single 16O-depletion during magmatic crystallization. This 16O-depletion occurred in an early stage of the thermal history, after the crystallization of spinel, i.e. in the temperature range for melilite crystallization/partial melting and did not require multiple, complex or late isotope exchange. More experimental work is however required to deduce the protoplanetary disk conditions associated with this 16O-depletion.

  20. Oxygen stable isotopic disparities among sympatric small land snail species from northwest Minnesota, USA (United States)

    Yanes, Yurena; Nekola, Jeffery C.; Rech, Jason A.; Pigati, Jeffery S.


    The oxygen isotopic composition (δ18O) of land snail shells can be a valuable paleoenvironmental archive if the climatic parameters that influence the isotopic system are fully understood. Previous calibration studies have examined a limited number of species or individuals, and most have focused on larger (> 10 mm) taxa, which do not represent the dominant shell material in the Quaternary fossil record. In this study, we evaluate the δ18O values of small land snails (isotopic information in their shells, regardless of differences in their ecology, dietary habits, behavior, and/or body size. We collected and analyzed 265 individuals of 11 species from 12 sites in northwest Minnesota (USA), which exhibits extremely abundant and diverse terrestrial malacofauna in North America. We did not observe significant correlations between shell δ18O values and the type of ecosystem (forest/grassland) or hydrologic setting (upland/lowland). However, the majority of species differed significantly in shell δ18O values. Larger taxa (Catinella, Succinea, Discus) consistently yielded higher δ18O values than smaller taxa (Euconulus, Gastrocopta, Hawaiia, Vallonia), by up to ~ 3‰. These isotopic offsets among sympatric taxa could be attributed to a number of physical, behavioral, and/or evolutionary traits, including the ability of larger species to tolerate drier conditions better than their smaller counterparts, differences in their preferred microhabitats or phylogentic non-independence. Regardless of the reason, our results imply that researchers should not combine isotopic data from different types of land snails without first investigating modern specimens to determine if it is appropriate. Moreover, our data suggest that combining instrumental climate data, a snail flux-balance model, and shell δ18O values can help us to better understand the ecology of land snails.

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

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


    A long-standing geoscience controversy has been the interpretation of the observed several per mil increase in the oxygen isotope compositions of marine calcites over the Phanerozoic Eon. Explanations for this trend have included decreasing seawater paleotemperatures, increasing seawater oxygen isotope values, and post-depositional calcite alteration. Carbonate clumped isotope paleothermometry is a useful geochemical tool to test these hypotheses because of its lack of dependence on the bulk isotopic composition of the water from which carbonate precipitated. This technique is increasingly applied to ancient marine invertebrate shells, which can be screened for diagenesis using chemical and microstructural approaches. After several years of clumped isotope analysis of these marine carbonates in a handful of laboratories, a long-term temperature and isotopic trend is emerging, with the results pointing to relatively invariant seawater δ18O and generally decreasing seawater temperatures through the Phanerozoic. Uncertainties remain, however, including the effects of reordering of primary clumped isotope compositions via solid-state diffusion of C and O through the mineral lattice at elevated burial temperatures over hundred million year timescales. To develop a quantitative understanding of such reordering, we present data from laboratory heating experiments of late Paleozoic brachiopod calcite. When combined with kinetic models of the reordering reaction, the results of these experiments suggest that burial temperatures less than ~120 °C allow for preservation of primary brachiopod clumped isotope compositions over geological timescales. Analyses of well-preserved Carboniferous and Permian brachiopods reinforce these results by showing that shells with apparent clumped isotope temperatures of ~150 °C are associated with deep sedimentary burial (>5 km), whereas those with putatively primary paleotemperatures in the 10-30 °C range experienced no more than ~1.5 km

  2. Constraints on Long-Term Seismic Hazard From Vulnerable Stalagmites (United States)

    Gribovszki, Katalin; Bokelmann, Götz; Mónus, Péter; Tóth, László; Kovács, Károly; Konecny, Pavel; Lednicka, Marketa; Spötl, Christoph; Bednárik, Martin; Brimich, Ladislav; Hegymegi, Erika; Novák, Attila


    Earthquakes hit urban centers in Europe infrequently, but occasionally with disastrous effects. Obtaining an unbiased view of seismic hazard (and risk) is therefore very important. In principle, the best way to test Probabilistic Seismic Hazard Assessments (PSHA) is to compare them with observations that are entirely independent of the procedure used to produce PSHA models. Arguably, the most valuable information in this context should be information on long-term hazard, namely maximum intensities (or magnitudes) occurring over time intervals that are at least as long as a seismic cycle. Long-term information can in principle be gained from intact stalagmites in natural caves. These formations survived all earthquakes that have occurred, over thousands of years - depending on the age of the stalagmite. Their "survival" requires that the horizontal ground acceleration has never exceeded a certain critical value within that time period. Here we present such a stalagmite-based case study from the Little Carpathians of Slovakia. A specially shaped, intact and vulnerable stalagmite (IVSTM) in Plavecká priepast cave was examined in 2013. This IVSTM is suitable for estimating the upper limit of horizontal peak ground acceleration generated by pre-historic earthquakes. The approach, used in our study, yields significant new constraints on the seismic hazard, as tectonic structures close to Plavecká priepast cave did not generate strong paleoearthquakes in the last few thousand years. A particular importance of this study results from the seismic hazard of two close-by capitals: Vienna and Bratislava.

  3. Oxygen isotope fractionation in the siderite-water system between 8.5 and 62 °C (United States)

    van Dijk, Joep; Fernandez, Alvaro; Müller, Inigo A.; Lever, Mark; Bernasconi, Stefano M.


    The oxygen isotope composition of siderites can be used to deduce the temperature and/or oxygen isotope composition of the fluids from which they precipitated. Previous siderite-water oxygen isotope fractionation calibrations are not well constrained at temperatures below 33 °C where most of the siderite forms at the Earth's surface. Moreover, the few experimental low temperature calibration points available are possibly inaccurate as the corresponding siderites may not have formed in equilibrium with the solution. In this study, we synthesized siderite in the laboratory from 8.5 to 62 °C, using both active-degassing experiments and microbial cultures. We used the enzyme carbonic anhydrase, which significantly reduces the equilibration time of oxygen isotopes among all dissolved inorganic carbon (DIC) species and water to minimize siderite formation out of equilibrium. Our calibration is based on many more data points than previous calibrations and significantly reduces the uncertainty in siderite-water oxygen isotope fractionation in natural siderites formed at low temperatures. The best fit equation is 1000 * ln α = 19.67 ± 0.42(103/T) -36.27 ± 1.34 where α (1000+δ18Osiderite/1000+δ18Owater) is the fractionation factor and T is the temperature in Kelvin.

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

    International Nuclear Information System (INIS)

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


    Equilibrium isotope effect in the exchange reaction of deuterium between phenol(P), 2-isopropyl phenol (IPP), 2,6-diisopropyl phenol (DIPP), 2,6-diterbutyl phenol (DTBP) and tertbutylthiol (TBT) has been studied in 296 K. The fractionation factors (α) have been measured in cyclohexane and carbon tetrachloride solutions and in a few oxygen bases: acetone, 1,4-dioxane, ethyl formate, ethyl ether, tetrahydrofurane, N,N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide. Using chemical shifts of phenol OH protons, the thermodynamic parameters of complex formation with the oxygen bases have been determined. The experimental data show that lnα correlates with the formation enthalpy of the phenol-oxygen base complex in DIPP-TBT-base system but there is no simple correlation in IPP-TBT-base system. Furthermore, it was found that in DTBT-TBT-base system lnα depends linearly on the basicity of the solvent (DN parameters). On the other hand, lnα correlates with acidic parameters of the solvents (AN) in IPP-TBT-base and P-TBT-base systems. All above correlations are explained by taking into account two competition processes: self association of phenol molecules and their solvation by oxygen bases. (author)

  5. Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems (United States)

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


    The oxygen isotopic composition of dissolved inorganic phosphate (δ18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ18O p to be a useful tool for source tracking, the δ18Op of phosphate sources must be distinguishable from one another; however, the δ18Op of potential sources has not been well characterized. We measured the δ18O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ18Op values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and δ18Op can be used for identifying phosphate sources to aquatic systems.

  6. Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems. (United States)

    Young, Megan B; McLaughlin, Karen; Kendall, Carol; Stringfellow, William; Rollog, Mark; Elsbury, Katy; Donald, Elizabeth; Paytan, Adina


    The oxygen isotopic composition of dissolved inorganic phosphate (delta18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source delta18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for delta18Op to be a useful tool for source tracking, the delta18Op of phosphate sources must be distinguishable from one another; however, the delta18Op of potential sources has not been well characterized. We measured the delta18Op of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of delta18Op, values (from +8.4 to +24.9 per thousand) for the various sources, and statistically significant differences were found between several of the source types. delta18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in delta18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and delta18Op can be used for identifying phosphate sources to aquatic systems.

  7. Towards a new proxy of continental atmospheric humidity: the triple oxygen isotopic composition of plant biosilica (United States)

    Alexandre, A. E.; Pauchet, S.; Landais, A.; Piel, C.; Devidal, S.; Roy, J.; Vallet-Coulomb, C.; Sonzogni, C.; Pasturel, M.; Cornuault, P.; Xin, J.; Mazur, J. C.; Prie, F.; Bentaleb, I.


    There is a serious lack of proxy suitable for reconstructing, in a quantitative way, past changes of continental atmospheric humidity. This reduces the possibility to make model-data comparisons necessary for the implementation of climate models. Over the past 10 years, analytical developments have enabled a few laboratories to reach sufficient precision for measuring the triple oxygen isotopes, expressed by the 17O-excess, in water, water vapor, atmospheric oxygen, and minerals. The 17O-excess represents an alternative to d-excess for investigating relative humidity conditions that prevail during water evaporation. The 17O-excess of water results from the increase of kinetic isotopic fractionation at evaporative sites as a function of decreasing relative humidity. This mechanism occurs at large scales, i.e. during seawater evaporation or during plant canopies transpiration. Unlike deuterium-excess, 17O-excess is supposed to be insensitive to temperature and less sensitive than δD and δ18O to equilibrium fractionation during transport and precipitation. Additionally, the 17O-excess is recorded in biogenic minerals less prone to weathering than organic compounds. Here, we calibrate the 17O-excess of plant biosilica as a new air humidity proxy. First, we examined the behavior of the 17O-excess in soil water, leaf water and phytoliths in growth chambers in response to changes in relative humidity. Second, we measured the 17O-excess of soil phytolith assemblages from inter-tropical savannas and forests distributed along humidity transects. Both approaches show similar dependency of phytolith 17O-excess to relative humidity. The results allow to discuss future calibration directions aimed at estimating the precision of the obtained relationship and at quantifying the successive isotopic fractionations in play at the soil-plant-atmosphere interface, to provide a strong proxy of past atmospheric relative humidity.

  8. High-temperature pyrolysis/gas chromatography/isotope ratio mass spectrometry: simultaneous measurement of the stable isotopes of oxygen and carbon in cellulose. (United States)

    Woodley, Ewan J; Loader, Neil J; McCarroll, Danny; Young, Giles H F; Robertson, Iain; Heaton, Timothy H E; Gagen, Mary H; Warham, Joseph O


    Stable isotope analysis of cellulose is an increasingly important aspect of ecological and palaeoenvironmental research. Since these techniques are very costly, any methodological development which can provide simultaneous measurement of stable carbon and oxygen isotope ratios in cellulose deserves further exploration. A large number (3074) of tree-ring α-cellulose samples are used to compare the stable carbon isotope ratios (δ(13)C) produced by high-temperature (1400°C) pyrolysis/gas chromatography (GC)/isotope ratio mass spectrometry (IRMS) with those produced by combustion GC/IRMS. Although the two data sets are very strongly correlated, the pyrolysis results display reduced variance and are strongly biased towards the mean. The low carbon isotope ratios of tree-ring cellulose during the last century, reflecting anthropogenic disturbance of atmospheric carbon dioxide, are thus overestimated. The likely explanation is that a proportion of the oxygen atoms are bonding with residual carbon in the reaction chamber to form carbon monoxide. The 'pyrolysis adjustment', proposed here, is based on combusting a stratified sub-sample of the pyrolysis results, across the full range of carbon isotope ratios, and using the paired results to define a regression equation that can be used to adjust all the pyrolysis measurements. In this study, subsamples of 30 combustion measurements produced adjusted chronologies statistically indistinguishable from those produced by combusting every sample. This methodology allows simultaneous measurement of the stable isotopes of carbon and oxygen using high-temperature pyrolysis, reducing the amount of sample required and the analytical costs of measuring them separately. Copyright © 2011 John Wiley & Sons, Ltd.

  9. An experiment to assess the effects of diatom dissolution on oxygen isotope ratios. (United States)

    Smith, Andrew C; Leng, Melanie J; Swann, George E A; Barker, Philip A; Mackay, Anson W; Ryves, David B; Sloane, Hilary J; Chenery, Simon R N; Hems, Mike


    Current studies which use the oxygen isotope composition from diatom silica (δ(18) Odiatom ) as a palaeoclimate proxy assume that the δ(18) Odiatom value reflects the isotopic composition of the water in which the diatom formed. However, diatoms dissolve post mortem, preferentially losing less silicified structures in the water column and during/after burial into sediments. The impact of dissolution on δ(18) Odiatom values and potential misinterpretation of the palaeoclimate record are evaluated. Diatom frustules covering a range of ages (6 samples from the Miocene to the Holocene), environments and species were exposed to a weak alkaline solution for 48 days at two temperatures (20 °C and 4 °C), mimicking natural dissolution post mucilage removal. Following treatment, dissolution was assessed using scanning electron microscope images and a qualitative diatom dissolution index. The diatoms were subsequently analysed for their δ(18) O values using step-wise fluorination and isotope ratio mass spectrometry. Variable levels of diatom dissolution were observed between the six samples; in all cases higher temperatures resulted in more frustule degradation. Dissolution was most evident in younger samples, probably as a result of the more porous nature of the silica. The degree of diatom dissolution does not directly equate to changes in the isotope ratios; the δ(18) Odiatom value was, however, lower after dissolution, but in only half the samples was this reduction outside the analytical error (2σ analytical error = 0.46‰). We have shown that dissolution can have a small negative impact on δ(18) Odiatom values, causing reductions of up to 0.59‰ beyond analytical error (0.46‰) at natural environmental temperatures. These findings need to be considered in palaeoenvironmental reconstructions using δ(18) Odiatom values, especially when interpreting variations in these values of <1‰. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Oxygen isotopes in tree rings of Abies alba: The climatic significance of interdecadal variations (United States)

    Saurer, Matthias; Cherubini, Paolo; Siegwolf, Rolf


    We determined the δ18O variations in the latewood of tree rings from four silver firs (Abies alba Mill.) for the period 1840-1997 at a mountain site in Switzerland, establishing the longest available tree ring record for δ18O in central Europe. The isotope ratios were determined on whole wood with a rapid continuous flow pyrolysis technique, thus avoiding cellulose extraction. We found significant correlations with δ18O tree ring records from the same region, although these involved different materials (cellulose extracted from whole rings rather than latewood) and different species. This indicates that physical factors are more important than biological influences as a determinant of δ18O in tree rings. The isotope tree ring chronology was highly correlated with the oxygen isotope variations in the June/July precipitation for the period 1972-1992 (r=0.72), and δ18O in whole wood of tree rings is therefore well suited for the reconstruction of δ18O in precipitation. We found a slow, quasi-periodic variation of the δ18O series with a periodicity of ˜24 years, which is correlated to variations in the July temperature. This could be caused by fluctuations in the large-scale atmospheric circulation over Europe and the North Atlantic, which may result in a change in source and flow path of atmospheric moisture, affecting the isotope ratio of precipitation in Switzerland. Although a significant correlation with summer temperature was found (p<0.01), the low correlation coefficient (r = 0.31) indicates that the δ18O variations cannot be explained by temperature variations alone. However, even when considering that the factors influencing δ18O in precipitation are not yet fully understood, our study shows the potential of tree rings to provide long records of δ18O in precipitation for continental areas, which will improve our understanding of the causes of natural perturbations of the climate system.

  11. Oxygen isotope fractionations across individual leaf carbohydrates in grass and tree species. (United States)

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


    Almost no δ 18 O data are available for leaf carbohydrates, leaving a gap in the understanding of the δ 18 O relationship between leaf water and cellulose. We measured δ 18 O values of bulk leaf water (δ 18 O LW ) and individual leaf carbohydrates (e.g. fructose, glucose and sucrose) in grass and tree species and δ 18 O of leaf cellulose in grasses. The grasses were grown under two relative humidity (rH) conditions. Sucrose was generally 18 O-enriched compared with hexoses across all species with an apparent biosynthetic fractionation factor (ε bio ) of more than 27‰ relative to δ 18 O LW , which might be explained by isotopic leaf water and sucrose synthesis gradients. δ 18 O LW and δ 18 O values of carbohydrates and cellulose in grasses were strongly related, indicating that the leaf water signal in carbohydrates was transferred to cellulose (ε bio  = 25.1‰). Interestingly, damping factor p ex p x , which reflects oxygen isotope exchange with less enriched water during cellulose synthesis, responded to rH conditions if modelled from δ 18 O LW but not if modelled directly from δ 18 O of individual carbohydrates. We conclude that δ 18 O LW is not always a good substitute for δ 18 O of synthesis water due to isotopic leaf water gradients. Thus, compound-specific δ 18 O analyses of individual carbohydrates are helpful to better constrain (post-)photosynthetic isotope fractionation processes in plants. © 2017 John Wiley & Sons Ltd.

  12. ENSO variability reflected in precipitation oxygen isotopes across the Asian Summer Monsoon region (United States)

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


    Oxygen isotope signals (δ18O) from paleo-archives are important proxies for past Asian Summer Monsoon (ASM) climate reconstruction. However, causes of interannual variation in the δ18O values of modern precipitation across the ASM region remain in argument. We report interannual δ18O variation in southern Tibetan Plateau precipitation based on long-term observations at Lhasa. These data, together with precipitation δ18O records from five Global Network of Isotopes in Precipitation (GNIP) stations and two ice core δ18O records, were used to define a regional metric of ASM precipitation δ18O (ASMOI). Back-trajectory analyses for rainy season precipitation events indicate that moisture sources vary little between years with relatively high and low δ18O values, a result that is consistent for the south (Lhasa), southeast (Bangkok), and east ASM regions (Hong Kong). In contrast, δ18O values at these three locations are significantly correlated with convection in the estimated source regions and along transport paths. These results suggest that upstream convection, rather than moisture source change, causes interannual variation in ASM precipitation δ18O values. Contrasting values of the ASMOI in El Niño and La Niña years reveal a positive isotope-El Niño Southern Oscillation (ENSO) response (e.g., high values corresponding to warm phases), which we interpret as a response to changes in regional convection. We show that the isotope-ENSO response is amplified at high elevation sites and during La Niña years. These findings should improve interpretations of paleo-δ18O data as a proxy for past ASM variation and provide new opportunities to use data from this region to study paleo-ENSO activity.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

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

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; ShyamPrasad, M.; Jones, R.H.; Nagashima, K.

    et al., 2015a). The micrometeorites that have entered Earth’s atmosphere at high zenith angle and low velocity are interesting because their petrologic and isotopic characteristics are largely preserved thereby providing constraints on the parent... et al., 2012). Oxygen isotope studies complemented by mineralogical compositions are vital to unravel the complexity involved in distinguishing the known components of micrometeorites and their parent bodies. For carbonaceous chondrites...

  15. Turnover of oxygen and hydrogen isotopes in the body water, CO 2, hair, and enamel of a small mammal (United States)

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


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

  16. Impact of uranium mining activity on cave deposit (stalagmite) and pine trees (S-Hungary) (United States)

    Siklosy, Z.; Kern, Z.; Demeny, A.; Pilet, S.; Leel-Ossy, Sz.; Lin, K.; Shen, C.-C.; Szeles, E.


    Speleothems are well known paleoclimate archives but their potential for monitoring environmental pollution has not been fully explored. This study deals with an actively growing stalagmite whose trace-element concentration suggests anthropogenic contamination, rather then natural forcing. Paralell, as a potential independent chemo-enviromental archive, living pine (Pinus sylvestis) trees were also involved into investigation. U production in S-Hungary started in 1957 and was expanded closer to the cave site in 1965, covering a mining plot area of ca. 65 km2. The deep-level ore production ended in 1997 and remediation of the mine site has since been completed. Our objective was to determine the possible effect of the four-decade-long uranium (U) ore mining activity on the environment, as recorded by a cave deposit and the pine trees. The Trio Cave is located in the Mecsek Mts (S-Hungary), ca. 1.5-3 km east from the nearest air-shaft and entrance of the uranium mine. A stalagmite located about 150 m away from the cave entrance was drilled and the core investigated for stable isotope and trace element compositions. Pine trees were sampled by increment borer. Continuous flow mass spectrometry was applied on carbonate samples and laser ablation ICP-MS was applied for trace element analysis of both stalagmite (Siklosy et al., 2009) and pine samples. The youngest 1 cm of the drill core was selected for this study that may represent the last cca. 100 years (based on MC-ICP-MS age dating of older parts of the core) that covers the uranium mining period. The pre-mining period is characterized by systematic co-variations of trace elements (U, P, Si, Al, Ba, Mg, etc.) that can be related to soil activity and precipitation amount. The youngest 1.3 mm, however, records a sudden change in U content uncorrelated with any other variables. Starting from a background value of 0.2-0.3 ppm, the concentration gradually increases to about 2 ppm (within about 1 mm), remains constant for

  17. The oxygen isotope enrichment of leaf-exported assimilates – does it always reflect lamina leaf water enrichment? (United States)

    Gessler, Arthur; Brandes, Elke; Keitel, Claudia; Boda, Sonja; Kayler, Zachary E; Granier, André; Barbour, Margaret; Farquhar, Graham D; Treydte, Kerstin


    The oxygen stable isotope composition of plant organic matter (OM) (particularly of wood and cellulose in the tree ring archive) is valuable in studies of plant–climate interaction, but there is a lack of information on the transfer of the isotope signal from the leaf to heterotrophic tissues. We studied the oxygen isotopic composition and its enrichment above source water of leaf water over diel courses in five tree species covering a broad range of life forms. We tracked the transfer of the isotopic signal to leaf water-soluble OM and further to phloem-transported OM. Observed leaf water evaporative enrichment was consistent with values predicted from mechanistic models taking into account nonsteady-state conditions. While leaf water-soluble OM showed the expected 18O enrichment in all species, phloem sugars were less enriched than expected from leaf water enrichment in Scots pine (Pinus sylvestris), European larch (Larix decidua) and Alpine ash (Eucalyptus delegatensis). Oxygen atom exchange with nonenriched water during phloem loading and transport, as well as a significant contribution of assimilates from bark photosynthesis, can explain these phloem 18O enrichment patterns. Our results indicate species-specific uncoupling between the leaf water and the OM oxygen isotope signal, which is important for the interpretation of tree ring data. PMID:23763637

  18. The isotopic fractionation of carbon, nitrogen, hydrogen, and oxygen during illicit production of cocaine base in South America. (United States)

    Mallette, Jennifer R; Casale, John F; Jones, Laura M; Morello, David R


    Stable isotope measurements have become a key component in sourcing the origin of illicit cocaine seized within the United States. Therefore, it is imperative to understand the process by which isotopes may be fractionated during illicit cocaine processing. In a controlled observational study, there was apparent isotopic fractionation of carbon, nitrogen, hydrogen, and oxygen. To investigate the potential source of the fractionation, cocaine base was fractionally precipitated from a dilute sulfuric acid solution with dilute ammonium hydroxide. The values of δ 13 C, δ 15 N, δ 2 H, and δ 18 O for each fraction were measured by isotope ratio mass spectrometry (IRMS). There was an equilibrium fractionation observed in all measured stable isotopes. Early fractions were depleted, and later fractions were enriched, with 15 N and 2 H being the most affected. The described trend is opposite of the Rayleigh distillation observed for cocaine hydrochloride precipitation. Published by Elsevier B.V.

  19. Phosphorus cycling in forest ecosystems: insights from oxygen isotopes in phosphate (United States)

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


    The current view on the phosphorus (P) cycle in forest ecosystems relies mostly on measurements and correlations of pools, and to a lower extent on measurement of fluxes. We have no direct insight into the processes phosphate goes through at the ecosystem level, and into the relative importance of organic and mineral pools in sustaining P nutrition of trees. The analysis of oxygen isotopes associated to P (18Op) is expected to bring this type of information. The German Priority Program SPP 1685 aims to test the overall hypothesis that the P-depletion of soils drives forest ecosystems from P acquiring systems (efficient mobilization of P from the mineral phase) to P recycling systems (highly efficient cycling of P). Our contribution to this project will consist in studying the relative importance of biological and geochemical processes in controlling the P cycle in temperate beech forest ecosystems in Germany along a gradient of decreasing soil P availability. We will follow the fate of phosphate from litter fall to the uptake of P by plants via P release by decomposition of organic matter or after release from P-containing minerals, by using a multi-isotope approach (O in water and phosphate plus 33P). To address our research question we will rely on measurements in experimental forest sites and on laboratory incubations of the organic layer or the mineral soil. We present here the first results issued from the 2014 sampling on three study sites, where we characterized the P pools in surface soil horizons by a sequential extraction (modified after Tiessen and Moir, 2007) and we analysed the 18Op of the resin extractable- and microbial-P fractions. Contrary to what was previously found (e.g. Tamburini et al. 2012) the isotopic composition of these fractions in most of the samples does not reflect the equilibrium value (as the result of the dominance of the pyrophosphatase activity on the other enzymatic processes, Blake et al. 2005). Depending on the P availability

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

    Keedakkadan, Habeeb Rahman; Abe, Osamu


    The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic

  1. Validation of chlorine and oxygen isotope ratio analysis to differentiate perchlorate sources and to document perchlorate biodegradation (United States)

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


    Increased health concerns about perchlorate (ClO4-) during the past decade and subsequent regulatory considerations have generated appreciable interest in source identification. The key objective of the isotopic techniques described in this guidance manual is to provide evidence concerning the origin of ClO4- in soils and groundwater and, more specifically, whether that ClO4- is synthetic or natural. Chlorine and oxygen isotopic analyses of ClO4- provide the primary direct approach whereby different sources of ClO4- can be distinguished from each other. These techniques measure the relative abundances of the stable isotopes of chlorine (37Cl and 35Cl) and oxygen (18O, 17O, and 16O) in ClO4- using isotope-ratio mass spectrometry (IRMS). In addition, the relative abundance of the radioactive chlorine isotope 36Cl is measured using accelerator mass spectrometry (AMS). Taken together, these measurements provide four independent quantities that can be used to distinguish natural and synthetic ClO4- sources, to discriminate different types of natural ClO4-, and to detect ClO4- biodegradation in the environment. Other isotopic, chemical, and geochemical techniques that can be applied in conjunction with isotopic analyses of ClO4- to provide supporting data in forensic studies are also described.

  2. A Simple Mechanism for Fractionating Oxygen Isotopes in the Solar Nebula (United States)

    Nuth, Joseph A., III; Johnson, N. M.


    Lightning in the Solar Nebula is caused by the tribo-electric charging of dust grains carried by massive turbulent flows and driven by the accretion energy in the disk: it has long been one agent assumed responsible for the formation of chondrules. The degree to which charge separation can occur is dependent upon a number of factors, including the concentration of radioactive sources and the total level of ionization in the nebula, and these factors determine the maximum energy likely to be released by a single bolt. While chondrule formation requires a massive discharge, even a small lightning bolt can vaporize grains in the ionized discharge channel. Experimental studies have shown that silica, iron silicate and iron oxide grains formed from a high voltage discharge in hydrogen rich gas containing some oxygen produces solids that are enriched in O-17 and O-18 relative to the composition of the starting gas. Vaporization of silicates produces SiO, metal and free oxygen atoms in each discharge and these species will immediately begin to recondense from the hot plasma. Freshly condensed grains are incrementally enriched in heavy oxygen while the gas is enriched in O-16. Repeated evaporation and condensation of silicates in continuously occurring lightning discharges will monotonically increase the fractionation of oxygen isotopes between the O-17 and O-18 rich dust and the O-16 rich gas. The first mass independently fractionated refractory oxide particles were produced in the lab following the condensation of a flowing gas mixture containing variable amounts of hydrogen, silane, pentacarbonyl iron and oxygen that passed through a high voltage discharge powered by a Tesla coil. While the exact chemical pathway is still uncertain, the most probable reaction mechanisms involve oxidation of the growing refractory clusters by O3, OH or O atoms. This model has some interesting consequences for chemical processes in the early solar nebula. Chemical fractionation of

  3. Clumped-isotope geochemistry of carbonates: A new tool for the reconstruction of temperature and oxygen isotope composition of seawater

    Energy Technology Data Exchange (ETDEWEB)

    Bernasconi, Stefano M., E-mail: [Geological Institute, ETH Zuerich, Sonneggstrasse 5, 8092 Zuerich (Switzerland); Schmid, Thomas W.; Grauel, Anna-Lena [Geological Institute, ETH Zuerich, Sonneggstrasse 5, 8092 Zuerich (Switzerland); Mutterlose, Joerg [Institut fuer Geologie, Mineralogie und Geophysik, Ruhr Universitaet Bochum, Universitaetsstr. 150, 44801 Bochum (Germany)


    Highlights: > Clumped-isotope thermometry of carbonates is discussed. > Clumped isotopes of Belemnites show higher sea surface temperatures than commonly assumed for the lower Cretaceous. > The potential of clumped-isotope measurement on foraminifera is discussed. - Abstract: Clumped-isotope geochemistry deals with State of ordering of rare isotopes in molecules, in particular with their tendency to form bonds with other rare isotopes rather than with the most abundant ones. Among its possible applications, carbonate clumped-isotope thermometry is the one that has gained most attention because of the wide potential of applications in many disciplines of the earth sciences. In particular, it allows reconstructing the temperature of formation of carbonate minerals without knowledge of the isotopic composition of the water from which they were formed. In addition, the O isotope composition of the waters from which they were formed can be calculated using the {delta}{sup 18}O of the same carbonate sample. This feature offers new approaches in paleoclimatology for reconstructing past global geochemical cycles. In this contribution two applications of this method are presented. First the potential of a new analytical method of measurement of clumped isotopes on small samples of foraminifera, for high-resolution SST and seawater {delta}{sup 18}O reconstructions from marine sediments is shown. Furthermore the potential of clumped isotope analysis of belemnites, for reconstructing seawater {delta}{sup 18}O and temperatures in the Cretaceous is shown.

  4. The magnesium isotope record of cave carbonate archives

    Directory of Open Access Journals (Sweden)

    S. Riechelmann


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

  5. Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles (United States)

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


    Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass

  6. The use of the oxygen isotopes from diatom silica as a proxy for North Atlantic Oscillation reconstruction (United States)

    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


    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

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

    Kumar, Pravin; Mal, Kedar; Rodrigues, G


    We report the charge state distributions of the pure, 25% and 50% oxygen mixed krypton plasma to shed more light on the understanding of the gas mixing and the isotope anomaly [A. G. Drentje, Rev. Sci. Instrum. 63 (1992) 2875 and Y Kawai, D Meyer, A Nadzeyka, U Wolters and K Wiesemann, Plasma Sources Sci. Technol. 10 (2001) 451] in the electron cyclotron resonance (ECR) plasmas. The krypton plasma was produced using a 10 GHz all-permanent-magnet ECR ion source. The intensities of the highly abundant four isotopes, viz. 82 Kr (~11.58%), 83 Kr (~11.49%), 84 Kr (~57%) and 86 Kr (17.3%) up to ~ +14 charge state have been measured by extracting the ions from the plasma and analysing them in the mass and the energy using a large acceptance analyzer-cum-switching dipole magnet. The influence of the oxygen gas mixing on the isotopic krypton ion intensities is clearly evidenced beyond +9 charge state. With and without oxygen mixing, the charge state distribution of the krypton ECR plasma shows the isotope anomaly with unusual trends. The anomaly in the intensities of the isotopes having quite closer natural abundance, viz. 82 Kr, 86 Kr and 83 Kr, 86 Kr is prominent, whereas the intensity ratio of 86 Kr to 84 Kr shows a weak signature of it. The isotope anomaly tends to disappear with increasing oxygen mixing in the plasma. The observed trends in the intensities of the krypton isotopes do not follow the prediction of linear Landau wave damping in the plasma. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  8. Rare sulfur and triple oxygen isotope geochemistry of volcanogenic sulfate aerosols (United States)

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


    We present analyses of stable isotopic ratios 17O/ 16O, 18O/ 16O, 34S/ 32S, and 33S/ 32S, 36S/ 32S in sulfate leached from volcanic ash of a series of well known, large and small volcanic eruptions. We consider eruptions of Mt. St. Helens (Washington, 1980, ˜1 km 3), Mt. Spurr (Alaska, 1953, Phillipines, 1991, 10 km 3), Bishop tuff (Long Valley, California, 0.76 Ma, 750 km 3), Lower Bandelier tuff (Toledo Caldera, New Mexico, 1.61 Ma, 600 km 3), and Lava Creek and Huckleberry Ridge tuffs (Yellowstone, Wyoming, 0.64 Ma, 1000 km 3 and 2.04 Ma 2500 km 3, respectively). This list covers much of the diversity of sizes and the character of silicic volcanic eruptions. Particular emphasis is paid to the Lava Creek tuff for which we present wide geographic sample coverage. This global dataset spans a significant range in δ34S, δ18O, and Δ17O of sulfate (29‰, 30‰, and 3.3‰, respectively) with oxygen isotopes recording mass-independent ( Δ17O > 0.2‰) and sulfur isotopes exhibiting mass-dependent behavior. Products of large eruptions account for most of' these isotopic ranges. Sulfate with Δ17O > 0.2‰ is present as 1-10 μm gypsum crystals on distal ash particles and records the isotopic signature of stratospheric photochemical reactions. Sediments that embed ash layers do not contain sulfate or contain little sulfate with Δ17O near 0‰, suggesting that the observed sulfate in ash is of volcanic origin. Mass-dependent fractionation of sulfur isotopic ratios suggests that sulfate-forming reactions did not involve photolysis of SO 2, like that inferred for pre-2.3 Ga sulfates from Archean sediments or Antarctic ice-core sulfate associated with few dated eruptions. Even though the sulfate sulfur isotopic compositions reflect mass-dependent processes, the products of caldera-forming eruptions display a large δ34S range and exhibit fractionation relationships that do not follow the expected equilibrium slopes of 0.515 and 1.90 for 33S/ 32S vs. 34S/ 32S and 36S

  9. An oxygen isotope study on hydrothermal sources of granite-type uranium deposits in South China

    International Nuclear Information System (INIS)

    Yongfei, Z.


    The usefulness of oxygen isotope measurements in solving problems of hydrothermal sources has been demonstrated in a number of detailed studies of the granite type uranium deposits in this paper. Remarkly the granite-type uranium deposits in Southr China have been shown to have formed from magmatic water, meteoric water, of mixtures of both the above, and origin of waters in the ore-forming fluid may be different for differing uranium deposits ore differing stages of the mineralization. Consequences obtained in this study for typical uranium deposits of different age and geologic sitting agree well with that obtained by other geologic-geochemical investigation. Furthermore, not only meteoric water is of importance to origin and evolution of the ore-forming fluid, but also mixing of waters from different sources is considered to be one of the most characteristic features of many hydrothermal uranium deposits related to granitoids or volcanics. (C.D.G.) [pt

  10. Spatiotemporal variability of oxygen isotope compositions in three contrasting glacier river catchments in Greenland

    DEFF Research Database (Denmark)

    Knudsen, N. Tvis; Yde, J.C.; Steffensen, J.P.


    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 spatio-temporal δ18O variations in glacier rivers, we have examined three glacierized catchments in Greenland...... composition is controlled by the proportion between snowmelt and ice melt with episodic inputs of rainwater and occasional storage and release of a specific water component due to changes in the subglacial drainage system. At Kuannersuit Glacier River on the island Qeqertarsuaq, the δ18O characteristics were...... sampling indicates that during the early melt season most of the river water (64–73 %) derived from the Qinnguata Kuussua tributary, whereas the water flow on 23 July 2009 was dominated by bulk meltwater from the Akuliarusiarsuup Kuua tributary (where 7 and 67 % originated from the Russell Glacier...

  11. Investigation on silcrete formation: oxygen isotope data of a silcrete quartz cement, Lake Eyre Basin (Australia) (United States)

    Alexandre, A.; Meunier, J. D.; Hill, S. M.; Savin, S. M.


    The oxygen isotope composition of the cement of a silcrete sample from the "Cordillo silcrete" (interpreted time of formation: Late Eocene-Early Oligocene) of the arid to semi-arid Lake Eyre Basin (Australia) is investigated in this study. Methodological problems which are not taken into account when analyzing bulk silcrete samples are assessed, and paleoenvironmental reconstruction tracts for a better understanding of silcrete formation and associated paleoenvironments are put forward. The massive structure of the studied silcrete and the absence of pedogenic features suggest that this silcrete formed from groundwater precipitation. Petrographic, mineralogical and infra-red data show three phases of cement made of: i) overgrowth; ii) opal-CT; and iii) micro-quartz. Infra-red analyses of the hydrated opal-CT allow us to estimate the percentage of Si-OH-exchangeable oxygen in the silcrete cement. As it represents less than 0.1% of the oxygen constituting the silcrete cement, an equilibration procedure, required prior to conventional oxygen isotope analysis of hydrous silicate, is not necessary for obtaining reliable d18O values. The purity of the extracted cement is checked using X-ray diffraction and cathodoluminescence (CL) spectroscopy. Average d18O value of the cement ranges from 24.9 to 25.7‰, which is related to a calculated average temperature of formation ranging from 15 to 20°C, lower than the present-day atmospheric (21-24°C) and 100cm depth ground (26.8°C) median temperatures. According to these data and to bibliographic data on the Tertiary evolution of the Lake Eyre Basin, the studied silcrete formed from shallow groundwater, frequently recharged under colder and wetter climate than the modern one. Slow tectonic uplift is preferred to climate changes for explaining water table fluctuations. This pattern would weaken the widely held opinion that groundwater silcrete formation is favored by a combination of climatic long periods of warm climate with

  12. Triple oxygen isotope analysis of tropospheric CO2 on the two sides of the Pacific Ocean (United States)

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


    The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, stratospheric photochemistry, cross-tropopause exchange, and subsequent vertical mixing between the free troposphere and planetary boundary. Oxygen isotopes, in particular, are affected by both the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, D17O (= ln(1+d17O) - 0.516 ln(1+d18O)) provides a powerful constraint on the strengths of the associated cycles involving CO2. Here, we report and compare summer to winter seasons CO2 isotopic composition from Taiwan (Taipei) and USA (Palos Verdes, CA). On average, the D17O values from Taiwan are significantly higher than those in USA. Analysis shows that the impact of 2014-2016 El Nino event on the observed D17O values is not visible, in contrast to what was reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Attempts are made to understand the elevated D17O values in the eastern Pacific compared to those in the western Pacific. Implications for utilizing the new tracer D17O along with the conventional d18O for carbon cycling studies are also discussed.

  13. Assessing the Role of Land Use in Watershed Nitrate Export Using Triple Oxygen Isotopes (United States)

    Bostic, J.; Nelson, D. M.; Eshleman, K. N.


    Quantifying the influence of land-use patterns on the amount and source(s) of nitrate (NO3) exported from watersheds is critical for understanding and mitigating the effects of nutrient pollution on downstream waterbodies. The isotopic composition of NO3 is valuable for fingerprinting of NO3 sources, including manure and atmospheric nitrate. To assess loads, sources, and potential transformations of NO3 in the Chesapeake Bay (CB) watershed, stream samples from fourteen sub-watersheds of the CB were collected semi-monthly and during multiple storm events from October 2015-September 2016 (Water Year 2016). The watersheds range in size (500 - 127,900 ha) and in dominant land-use (forest, urban, agriculture). The samples were analyzed for nitrate concentrations and isotopes (δ15N, as well as the triple oxygen isotope composition, defined as Δ17O ≅ δ17O - 0.52 x δ18O). Stream loads of nitrate were estimated using WRTDS (Weighted Regressions on Time, Discharge, and Season). NO3 deposition (dry and wet) was fairly uniform across all watersheds (2.1 - 3.0 kg NO3-N ha-1), whereas stream NO3 varied greatly (0.6 - 11.8 kg NO3-N ha-1). Stream loads of NO3 were positively related to the percent of agricultural land (r2 = 0.67, p watersheds are manure or pools of partially denitrified fertilizer. A positive relationship between Δ17ONO3 and the percent of forested land (r2 = 0.19, p watersheds to elucidate the amount and sources of NO3 exported from a variety of land-uses.

  14. Precipitation regime influence on oxygen triple-isotope distributions in Antarctic precipitation and ice cores (United States)

    Miller, Martin F.


    The relative abundance of 17O in meteoric precipitation is usually reported in terms of the 17O-excess parameter. Variations of 17O-excess in Antarctic precipitation and ice cores have hitherto been attributed to normalised relative humidity changes at the moisture source region, or to the influence of a temperature-dependent supersaturation-controlled kinetic isotope effect during in-cloud ice formation below -20 °C. Neither mechanism, however, satisfactorily explains the large range of 17O-excess values reported from measurements. A different approach, based on the regression characteristics of 103 ln (1 +δ17 O) versus 103 ln (1 +δ18 O), is applied here to previously published isotopic data sets. The analysis indicates that clear-sky precipitation ('diamond dust'), which occurs widely in inland Antarctica, is characterised by an unusual relative abundance of 17O, distinct from that associated with cloud-derived, synoptic snowfall. Furthermore, this distinction appears to be largely preserved in the ice core record. The respective mass contributions to snowfall accumulation - on both temporal and spatial scales - provides the basis of a simple, first-order explanation for the observed oxygen triple-isotope ratio variations in Antarctic precipitation, surface snow and ice cores. Using this approach, it is shown that precipitation during the last major deglaciation, both in western Antarctica at the West Antarctic Ice Sheet (WAIS) Divide and at Vostok on the eastern Antarctic plateau, consisted essentially of diamond dust only, despite a large temperature differential (and thus different water vapour supersaturation conditions) at the two locations. In contrast, synoptic snowfall events dominate the accumulation record throughout the Holocene at both sites.

  15. Oxygen isotopes and hydroclimatic change in the Yukon Flats National Wildlife Refuge, northeast Alaska (Invited) (United States)

    Anderson, L.; Finney, B. P.; Guldager, N.; Rover, J. A.; Shapley, M.; van Sistine, D. R.


    The Yukon Flats is the region surrounding the confluence of the Porcupine, Sheenjek, Christian, Chandalar, and Yukon Rivers including approximately 20,000 lakes. It is a diverse boreal mosaic landscape (~23,000 km2) that provides spring and summer habitat for over 150 bird species. The climate of the area is continental with severe winter temperatures and warm summers. High effective moisture deficits relative to most boreal environments lead to the unique occurrence of evaporite mineral deposits as well as the highest incidence of naturally occurring wildfires in Alaska. Lake levels are dynamic, and frequently localized, because of subdued topography, varying lake ages and surficial geologic substrates, permafrost extent, and corresponding surface and groundwater flow paths. To better understand the relationships between climate and hydro-environmental change, we are sampling oxygen isotope ratios spatially and temporally. Here we present preliminary GIS-spatial analyses from 108 water bodies and a late Holocene sediment oxygen isotope record from Twelve Mile Lake. We find that the first-order wetland water chemistry relation is with geographic location and hydrologic linkages. A 1.45-m sediment core from 8.8-m water depth was retrieved from Twelve Mile Lake because lake-water δ18O values indicate that evaporation dominates the lake’s hydrologic balance and because it is sufficiently alkaline to generate bioinduced endogenic carbonate sedimentation. The sediment δ18O trends during the last millennia have decade-to-century scale temporal resolution and similarities with paleoclimatic trends documented by other lakes in interior regions of Alaska and the Yukon Territory. Results from these preliminary studies reinforce that 1) wetland and lake sensitivity to climate-induced changes in hydrology varies spatially in the Yukon Flats because of dynamic hydrogeographic factors, and 2) recent hydro-environmental changes are better evaluated within a long-term context

  16. Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Perched Water Samples

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Brady D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Moran, James J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Nims, Megan K. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Saunders, Danielle L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)


    Fine-grained sediments associated with the Cold Creek Unit at Hanford have caused the formation of a perched water aquifer in the deep vadose zone at the B Complex area, which includes waste sites in the 200-DV-1 Operable Unit and the single-shell tank farms in Waste Management Area B-BX-BY. High levels of contaminants, such as uranium, technetium-99, and nitrate, make this aquifer a continuing source of contamination for the groundwater located a few meters below the perched zone. Analysis of deuterium (2H) and 18-oxygen (18O) of nine perched water samples from three different wells was performed. Samples represent time points from hydraulic tests performed on the perched aquifer using the three wells. The isotope analyses showed that the perched water had δ2H and δ18O ratios consistent with the regional meteoric water line, indicating that local precipitation events at the Hanford site likely account for recharge of the perched water aquifer. Data from the isotope analysis can be used along with pumping and recovery data to help understand the perched water dynamics related to aquifer size and hydraulic control of the aquifer in the future.

  17. Study of the carbon and oxygen isotopic compositions in marine shells of Salvador-Bahia, Brazil

    International Nuclear Information System (INIS)

    Freitas, J.C.B. de.


    The carbon and oxygen isotopic composition of 68 samples of marine shells from the region of Salvador was determined. These samples are from points on the open coast and in the interior of the Todos os Santos Bay and they are composed in part by recent specimens and in part by old specimens taken from Quaternary sediments. The results for δ 18 O are in the range of -2,83per mille to + 1,21per mille (PDB) and for δ 13 C in the range of -3,10per mille to +2,63per mille (PDB). The reults for the recent shells from the interior of the Todos os Santos Bay show variations in the δ 13 C values associated to the dominance of organic matter in some regions. For the old samoles, gathered in te variations in the δ 13 C values was associated to the existence in points of that region of deposits of fluvio-lagunar sediments, originated during the last marine transgression. It was identified, for a few species with the same age and location, the effect of biological fractionations. Nevertheless, the observed dominant factor on the isotopic differentiation was the environmental fractionation. (Author) [pt

  18. Temperature dependence of oxygen isotope acid fractionation for modern and fossil tooth enamels. (United States)

    Passey, Benjamin H; Cerling, Thure E; Levin, Naomi E


    The oxygen isotope ratio of CO(2) liberated from structural carbonate in tooth enamel apatite was measured at phosphoric acid reaction temperatures of 25 degrees C, 60 degrees C and 90 degrees C, and it was found that apparent acid fractionation factors for pristine enamel, fossilized enamel, and calcite follow different temperature relationships. Using sealed vessel reactions normalized to alpha(25) = 1.01025 (the fractionation factor for calcite at 25 degrees C), the apparent fractionation factor at 90 degrees C (alpha*(90)) for pristine enamel ranged between 1.00771 and 1.00820, and between 1.00695 and 1.00772 for fossilized enamel. Apparent fractionation factors for common acid bath reactions are similar to those for sealed vessel reactions. A significant correlation exists between alpha*(90) and F(-) content, suggesting that change in the acid fractionation factor may be related to the replacement of OH(-) with F(-) during fossilization of bioapatite. These results have important implications for making accurate comparisons between modern and fossil tooth enamel delta(18)O values, and for the uniformity of isotope data produced in different laboratories using different acid reaction temperatures.

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

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


    "RATIONALE: Because of the paucity of isotopic reference waters for daily use, a new secondary isotopic reference material has been prepared from Lake Louise water from Alberta, Canada for international distribution. MOTHODS: This water was filtered, homogenized, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.

  20. Heterogenous Oxygen Isotopic Composition of a Complex Wark-Lovering Rim and the Margin of a Refractory Inclusion from Leoville (United States)

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


    Wark-Lovering (WL) rims [1] surrounding many refractory inclusions represent marker events in the early evolution of the Solar System in which many inclusions were exposed to changes in pressure [2], temperature [3], and isotopic reservoirs [4-7]. The effects of these events can be complex, not only producing mineralogical variability of WL rims [2], but also leading to mineralogical [8-10] and isotopic [7, 11, 12] changes within inclusion interiors. Extreme oxygen isotopic heterogeneity measured in CAIs has been explained by mixing between distinct oxygen gas reservoirs in the nebula [13]. Some WL rims contain relatively simple mineral layering and/or are isotopically homogeneous [14, 15]. As part of a larger effort to document and understand the modifications observed in some CAIs, an inclusion (L6) with a complex WL rim from Leoville, a member of the reduced CV3 subgroup was studied. Initial study of the textures and mineral chemistry was presented by [16]. Here we present NanoSIMS oxygen isotopic measurements to complement these petrologic observations.

  1. Origin of magnetite in oxidized CV chondrites: in situ measurement of oxygen isotope compositions of Allende magnetite and olivine (United States)

    Choi, B. G.; McKeegan, K. D.; Leshin, L. A.; Wasson, J. T.


    Magnetite in the oxidized CV chondrite Allende mainly occurs as spherical nodules in porphyritic-olivine (PO) chondrules, where it is associated with Ni-rich metal and/or sulfides. To help constrain the origin of the magnetite, we measured oxygen isotopic compositions of magnetite and coexisting olivine grains in PO chondrules of Allende by an in situ ion microprobe technique. Five magnetite nodules form a relatively tight cluster in oxygen isotopic composition with delta 18O values from -4.8 to -7.1% and delta 17O values from -2.9 to -6.3%. Seven coexisting olivine grains have oxygen isotopic compositions from -0.9 to -6.3% in delta 18O and from -4.6 to -7.9% in delta 17O. The delta 17O values of the magnetite and coexisting olivine do not overlap; they range from -0.4 to -2.6%, and from -4.0 to -5.7%, respectively. Thus, the magnetite is not in isotopic equilibrium with the olivine in PO chondrules, implying that it formed after the chondrule formation. The delta 17O of the magnetite is somewhat more negative than estimates for the ambient solar nebula gas. We infer that the magnetite formed on the parent asteroid by oxidation of metal by H2O which had previously experienced minor O isotope exchange with fine-grained silicates.

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

    NARCIS (Netherlands)

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


    High-resolution records of Mediterranean and North Atlantic deep-sea sediments indicate that rapid changes in hydrology and climate occurred during marine oxygen isotope stage 100 (MIS100) (at ~2.52 Ma), which exhibits characteristics similar to late Pleistocene Dansgaard-Oeschger, Bond cycles and

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

    DEFF Research Database (Denmark)

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


    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...... during the years 2007 to 2010. Results show that δ18Ow values were not recorded at very low salinities (

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

    NARCIS (Netherlands)

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


    We use the fully coupled atmosphere-ocean three-dimensional model of intermediate complexity iLOVECLIM to simulate the climate and oxygen stable isotopic signal during the Last Glacial Maximum (LGM, 21 000 years). By using a model that is able to explicitly simulate the sensor (Î18O), results can be

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

    NARCIS (Netherlands)

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


    A palaeotemperature reconstruction based on periglacial phenomena in Europe north of approximately 51 °N, is compared with high-resolution regional climate model simulations of the marine oxygen isotope Stage 3 (Stage 3) palaeoclimate. The experiments represent Stage 3 warm (interstadial), Stage 3

  6. Oxygen Isotopic Signature of 4.4-3.9 Ga Zircons as a Monitor of Differentiation Processes on the Moon (United States)

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


    We report oxygen isotopic compositions for 14 zircon grains from a sample of sawdust from lunar breccia 14321. The zircons range in age from approx.4.4 to 3.9 Ga and in U and Th content from a few to several hundred ppm. As such these grains represent a range of possible source rocks, from granophyric to mafic composition, and cover the total age range of the major initial lunar bombardment. Nevertheless, results show that the oxygen isotopic compositions of the zircons fall within a narrow range of (delta18)O of about 1 per mil and have (delta18)O values indistinguishable from those observed for terrestrial mid-ocean ridge basalts confirming the coincidence of lunar and Earth oxygen isotopic compositions. In the (delta17)O vs. (delta18)O, coordinates data form a tight group with a limited trend on the terrestrial fractionation line. The zircon oxygen isotopes show minimal evidence of the extreme and variable mineral differentiation and element fractionation that have contributed to the formation of their parent rocks.

  7. The role of support oxygen in the epoxidation of propene over gold–titania catalysts investigated by isotopic transient kinetics

    NARCIS (Netherlands)

    Nijhuis, T.A.; Sacaliuc-Parvulescu, E.; Govender, N.S.; Schouten, J.C.; Weckhuysen, B.M.


    Transient kinetic experiments were performed on gold–titania catalysts for the epoxidation of propene using hydrogen and oxygen to investigate the reaction mechanism. A ‘classical’ 1 wt% gold on titania catalyst was studied, as well as a 1 wt% gold on Ti-SBA-15 catalyst. Steady-State Isotopic

  8. Oxygen isotopes as tracers of tektite source rocks: An example from the Ivory Coast tektites and Lake Bosumtwi Crater (United States)

    Blum, Joel D.; Koeberl, Christian; Chamberlain, C. Page


    Oxygen isotope studies of tektites and impact glasses provide an important tool to help in identifying the target lithologies for terrestrial impacts, including the K-T boundary impact. However, such studies may be complicated by modification of the original oxygen isotope values of some source rocks during the tektite formation process either by vapor fractionation or incorporation of meteoric water. To further investigate the relationship between the oxygen isotopic composition of tektites and their source rocks, Ivory Coast tektites and samples of impact glasses and bedrock lithologies from the Bosumtwi Crater in Ghana--which is widely believed to be the source crater for the Ivory Coast tektites--were studied. Our preliminary results suggest that the phyllites and metagraywackes from the Bosumtwi Crater were the predominant source materials for the impact glasses and tektites and that no significant oxygen isotope modification (less than 1 percent delta(O-18)) took place during impact melting. This contrasts with previous studies of moldavites and Australasian tektites and their sedimentary source materials which suggests a 4 to 5 percent lowering of delta(O-18) due to meteoric water incorporation during impact melting.

  9. Using oxygen isotope and magnetism to reconstruct the paleotemperature framework of the ancient travertine deposits in Death Valley, CA

    Czech Academy of Sciences Publication Activity Database

    Adachi, T.; Kletetschka, Günther


    Roč. 71, 15 S1 (2007), A5-A5 ISSN 0046-564X. [Annual V. M. Goldschmidt Conference /17./. 19.08.2007-24.08.2007, Cologne] Institutional research plan: CEZ:AV0Z30130516 Keywords : oxygen isotope * travertine * magnetism * paleotemperature Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics

  10. Interpreting species-specific variation in tree-ring oxygen isotope ratios among three temperate forest trees (United States)

    Xin Song; Kenneth S. Clark; Brent R. Helliker


    Although considerable variation has been documented in tree-ring cellulose oxygen isotope ratios (δ18Ocell) among co-occurring species, the underlying causes are unknown. Here, we used a combination of field measurements and modelling to investigate the mechanisms behind variations in late-wood δ

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

    Digital Repository Service at National Institute of Oceanography (India)

    Chauhan, O.S.

    Late Quaternary climate history of the Himalayas is inferred from sea surface salinity (SSS) changes determined from the oxygen isotope in planktonic foraminifers, in a turbidity-free, 14C-dated core from the Bay of Bengal. The heaviest d18O...

  12. Measurements of C-14 concentration in recently growing stalagmite and stalactite forms

    International Nuclear Information System (INIS)

    Pazdur, M.F.; Moscicki, W.; Pazdur, A.; Zastawny, A.


    The results of C-14 concentration measurements in stalagmites and stalactites formed in years 1966-1974 are presented. Samples of stalactites and stalagmites were collected in a deep coal mine near great dispersed outflow of water showing very low C-14 activity. It was found that C-14 concentration in stalactites and stalagmites exceeds over 30 to 50 times the C-14 concentration in dissolved bicarbonates. The mechanism causing observed enrichment of C-14 concentration in stalactites and stalagmites are discussed. The consequences for radiocarbon dating method are briefly outlined. (Author)

  13. A new isotopic reference material for stable hydrogen and oxygen isotope-ratio measurements of water - USGS50 Lake Kyoga Water. (United States)

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


    As a result of the need for isotopic reference waters having high δ(2) HVSMOW-SLAP and δ(18) OVSMOW-SLAP values for daily use, especially for tropical and equatorial-zone freshwaters, a new secondary isotopic reference material for international distribution was prepared from water collected from Lake Kyoga, Uganda. This isotopic reference lakewater was filtered through a membrane with 0.2-µm pore size, homogenized, loaded into glass ampoules that were sealed with a torch and autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This reference material is available in a case of 144 glass ampoules each containing 5 mL of water. The δ(2) H and δ(18) O values of this reference material are +32.8 ± 0.4 and +4.95 ± 0.02 mUr (milliurey = 0.001 = 1 ‰), respectively, relative to VSMOW, on scales normalized such that the δ(2) H and δ(18) O values of SLAP reference water are, respectively, -428 and -55.5 mUr. Each uncertainty is an estimated expanded uncertainty (U = 2uc ) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. 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. Published in 2015. This article is a U.S. Government work and is in the public domain in the USA.

  14. Triple oxygen isotope determination of oxygen exchange between sulfite and water preceding the aqueous oxidation of sulfite (pH=1-10) (United States)

    Kohl, I. E.; Bao, H.


    The use of sulfate isotope compositions to interpret past surface conditions has highlighted the importance of understanding sulfur redox pathways. Both O2 and H2O are known to contribute oxygen to sulfate produced from the oxidation of reduced sulfur compounds. The results from a set of our recent experiments pointed to sulfite as a key intermediate in controlling the δ18OSO4. Sulfite is produced as a sulfoxyanion intermediate during both dissimilatory sulfate reduction (DSR) and sulfide oxidation. The importance of sulfite is directly linked to its ability to readily exchange oxygen with water, resulting in a partial or total resetting of the oxygen isotope ratio in sulfite. We propose that during the production of sulfate via sulfide oxidation under Earth surface conditions, sulfate oxygen isotope composition is determined by rate competition between Fe (III)-shuttling (resulting in H2O oxygen incorporation) and direct O2 oxidation during both sulfide-sulfite and sulfite-sulfate oxidation as well as the rate of sulfite-water exchange. These competing rates are in direct control of: 1) the degree of preservation of the oxygen sources preceding sulfite formation, 2) the final SO42—oxygen source ratio, and 3) the δ18OSO4. In order to construct a unified, quantitative model, many rate efficiencies and isotope fractionation factors have to be determined. In this study, we focus on the competition between the rate of sulfite-water oxygen exchange and the rate of sulfite to sulfate oxidation. We set up a series of 50 ml (short term) and 150 ml (long term) D.D. and Δ17O-labeled, H2O reactors in which we introduced NaHSO3 to a concentration of 0.25 M at variable pH (1-10). Sulfate formed in solution and was collected and precipitated as BaSO4 at time intervals from 10 sec to 24hours (short term) or 1 to 21weeks (long term). The rates of sulfite-water oxygen exchange and sulfite to sulfate oxidation were quantitatively evaluated over the time range 10 sec to 21 weeks

  15. On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals (United States)

    Bauska, T.; Hodell, D. A.; Walters, G.


    Oxygen (16O,17O,18O) and hydrogen (H,D) isotopes of hydration water in minerals provide a rich source of information about the conditions under which hydrated minerals form on Earth and other planetary bodies (e.g. Mars). We have developed a new method for measuring different types of bonded water (e.g., molecular, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves step heating a mineral sample, precisely measuring the weight loss and enthalpy as the sample undergoes dehydration and dehydroxylation, whilst simultaneously determining the oxygen and hydrogen isotopes of the water vapor evolved from the mineral sample by cavity ring-down laser spectroscopy (CRDS). Nitrogen carrier gas is used to transfer the sample from the TG to the CRDS via a heated line and interface box. The interface includes the capability of (i) cryogenic trapping discrete types of water for samples containing small amounts of water; (ii) injecting small quantities of water of known isotopic value for calibration; and (iii) converting volatile organic compounds to nascent amounts of water using a catalyst. The CRDS continually measures water vapor concentration in the optical cavity and hydrogen and oxygen isotope ratios. Isotopic values are calculated by integrating the product of the water amount and its isotopic value for the separated peaks after correcting for background. Precision of the method was estimated by comparing isotope results of total water for gypsum measured by DTIA with our conventional method of extraction and analysis (Gázquez et al., 2015. Rapid Communications in Mass Spectrometry, 29, 1997-2006). Errors for the isotopic values of total hydration water vary between ±0.08 and ±0.34 ‰ for δ18O and between ±0.16 and ±0.86 ‰ for δD. We demonstrate the application of the DTIA method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous

  16. Groundwater oxygen isotope anomaly before the M6.6 Tottori earthquake in Southwest Japan. (United States)

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


    Geochemical monitoring of groundwater in seismically-active regions has been carried out since 1970s. Precursors were well documented, but often criticized for anecdotal or fragmentary signals, and for lacking a clear physico-chemical explanation for these anomalies. Here we report - as potential seismic precursor - oxygen isotopic ratio anomalies of +0.24‰ relative to the local background measured in groundwater, a few months before the Tottori earthquake (M 6.6) in Southwest Japan. Samples were deep groundwater located 5 km west of the epicenter, packed in bottles and distributed as drinking water between September 2015 and July 2017, a time frame which covers the pre- and post-event. Small but substantial increase of 0.07‰ was observed soon after the earthquake. Laboratory crushing experiments of aquifer rock aimed to simulating rock deformation under strain and tensile stresses were carried out. Measured helium degassing from the rock and 18 O-shift suggest that the co-seismic oxygen anomalies are directly related to volumetric strain changes. The findings provide a plausible physico-chemical basis to explain geochemical anomalies in water and may be useful in future earthquake prediction research.

  17. Long-Term (4 mo) Oxygen Isotope Exchange Experiment between Zircon and Hydrothermal Fluid (United States)

    Bindeman, I. N.; Schmitt, A. K.; Lundstrom, C.; Golledge, S.


    Knowing oxygen diffusivity in zircon has several critical applications: 1) establishing zircon stability and solubility in hot silica-saturated hydrothermal solutions; 2) deriving metamorphic and magmatic heating timescales from intra-crystal oxygen isotopic gradients; 3) assessing the survivability of oxygen isotopic signatures in Hadean zircons. We report results of a microanalytical investigation of an isotope exchange experiment using a cold-seal pressure apparatus at 850°C and 500 MPa over 4 months duration. Natural zircon, quartz and rutile were sealed with a silica-rich solution doped with 18-O, D, 7-Li and 10-B in a gold capsule. The diffusion length-scales were examined by depth profiling using time-of-flight (TOF) and high-sensitivity dynamic secondary ionization mass spectrometry (SIMS). Starting materials had distinct and homogeneous δ18O: zircon from Mesa Falls tuff of Yellowstone (+3.6‰), rutile from Karelia (-29‰), Bishop Tuff Quartz (+8.4‰), and δ18O doped water (+400‰). Starting material zircon showed invariant 18O/16O during depth profiling. After the 4 month experiment, rutile crystal surfaces displayed etching (100's of nm), while zircon exteriors lacked visible change. Quartz was completely dissolved and reprecipitated in a minor residue. Rutile developed ~2 μm long Fickian diffusion profiles largely consistent with the wet diffusion coefficients for rutile previously reported [1]. Surface U-Pb dating of zircon detected no significant Pb loss from the outermost ~300 nm of the crystal face and returned identical core-face ages. We performed δ18O depth profiling of zircon in two directions. First, forward profiles (crystal rim inwards) by dynamic SIMS (no surface treatment besides Au-coating; Cs+ beam of 20 kV impact energy) showed initially high and decreasing 18O/16O over ~130 nm; TOF-SIMS forward profiles using a 2 kV Cs+ sputter beam and 25 kV Bi3+ primary ions on uncoated zircon surfaces (cleaned for 2 min with HF) yielded

  18. Using oxygen isotopes to establish freshwater sources in Bedford Basin, Nova Scotia, a Northwestern Atlantic fjord (United States)

    Kerrigan, Elizabeth A.; Kienast, Markus; Thomas, Helmuth; Wallace, Douglas W. R.


    A weekly time-series of oxygen isotope (δ18O) measurements was collected over a 16-month period from near-surface (1 m) and near-bottom (60 m) waters of Bedford Basin, a coastal fjord adjacent to the Scotian Shelf, off eastern Canada. The time-series was complemented with δ18O measurements of local precipitation (rain and snow), river, and wastewater runoff. The isotopic composition of precipitation displayed strong seasonality with an average (volume-weighted) δ18O value of -5.39‰ (±0.96) for summer and a depleted value of -10.37‰ (±2.96) over winter. Winter precipitation exhibited more depleted and variable δ18O of solid precipitation relative to rainfall. The annual, amount-weighted average δ18O of Sackville River discharge (-6.49‰ ± 0.82) was not statistically different from precipitation (-7.24‰ ± 0.92), but exhibited less seasonal variation. Freshwater end-members (zero-salinity intercepts) estimated from annual and seasonal regressions of δ18O versus salinity (S) for Bedford Basin near-surface samples were consistent with the δ18O of summer precipitation and the annual, amount-weighted average for the Sackville River. However, the isotopically depleted signature of winter precipitation was not observed clearly in near-surface waters of Bedford Basin, which might reflect isotope enrichment during sublimation from accumulated snowfall prior to melting and discharge, or retention and mixing within the drainage basin. In near bottom waters, most of the δ18O-S variation (average freshwater end-member: 7.47‰ ± 2.17) could be explained by vertical mixing with near-surface waters (average freshwater end-member: -6.23‰ ± 0.34) and hence with locally-derived freshwater. However the near-bottom δ18O-S variation suggested an additional contribution of a freshwater end-member with a δ18O of -15.55‰ ± 2.3, consistent with a remotely-derived freshwater end-member identified previously for the Scotian Shelf. Residuals from a long

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

    International Nuclear Information System (INIS)

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


    Cellulose-inferred lake water δ 18 O (δ 18 O lw ) records from Lago Potosi, a seasonally-closed lake in a watershed that is not currently glaciated, and Lago Taypi Chaka Kkota, an overflowing lake in a glaciated watershed, provide the basis for late Pleistocene and Holocene paleoclimatic reconstruction in the Bolivian Andes. Deconvolution of the histories of changing evaporative isotopic enrichment from source water δ 18 O in the lake sediment records is constrained by comparison to the Sajama ice core oxygen isotope profile. At Lago Potosi, the δ 18 O lw record appears to be dominantly controlled by evaporative 18 O-enrichment, reflecting shifts in local effective moisture. Using an isotope-mass balance model, a preliminary quantitative reconstruction of summer relative humidity spanning the past 11,500 cal yr is derived from the Lago Potosi Π 18 O lw record. Results indicate that the late Pleistocene was moist with summer relative humidity values estimated at 10-20% greater than present. Increasing aridity developed in the early Holocene with maximum prolonged dryness spanning 7500 to 6000 cal yr BP at Lago Potosi, an interval characterized by summer relative humidity values that may have been 20% lower than present. Highly variable but dominantly arid conditions persist in the mid- to late Holocene, with average summer relative humidity values estimated at 15% below present, which then increase to about 10-20% greater than present by 2000 cal yr BP. Slightly more arid conditions characterize the last millennium with summer relative humidity values ranging from 5-10% lower than present. Similar long-term variations are evident in the Lago Taypi Chaka Kkota δ 18 O lw profile, except during the early Holocene when lake water evaporative 18 Oenrichment in response to low relative humidity appears to have been offset by enhanced inflow from 18 O-depleted snowmelt or groundwater from the large catchment. Close correspondence occurs between the isotope

  20. Oxygen isotope evidence for past and present hydrothermal regimes of Long Valley caldera, California (United States)

    Smith, Brian M.; Suemnicht, Gene A.


    Whole-rock oxygen isotope compositions of cores and cuttings from Long Valley exploration wells show that the Bishop Tuff has been an important reservoir for both fossil and active geothermal systems within the caldera. The deep Clay Pit-1 and Mammoth-1 wells on the resurgent dome penetrate mildly to strongly altered Bishop Tuff with δ 18O WR values as low as -2.6% (vs V-SMOW). The IDFU 44-16 well intercepts a thinner Bishop Tuff section with δ 18O WR values of +0.4 to +2.3%. in the western caldera moat, where milder and more sporadic 18O depletions occur in Tertiary volcanic rocks of the western caldera floor ( δ 18O WR = +2.2 to +6.4‰ ). Bishop Tuff samples from deeper parts of the 715 m RDO-8 (Shady Rest) well in the SW moat are also strongly depleted in 18O ( δ 18O WR = -1.5 to +0.6‰ ). Four shallow thermal gradient wells (469-715 m TD drilled in the western moat did not penetrate Bishop Tuff, but Early Rhyolites from two of these holes are depleted in 18O ( δ 18O WR = -1.2 to +6.0‰ inplv-1 +4.6 to +5.3%. inmlgrap-1 ), compared to lithologic equivalents from the other two holes ( δ 18O WR = +6.3 to +8.0‰ inplv-2 andmlgrap-2 ). Whole-rock oxygen isotope profiles for the resurgent dome wells are unlike profiles calculated assuming alkali feldspar-H 2O fractionation behavior and total O-isotopic equilibration with -14.3‰ fluids at measured temperatures. The sense of this divergence implies an earlier hydrothermal episode within the central caldera driven by one or more shallow intrusions. Geochemical similarities between an intrusive granophyre at the bottom of the Clay Pit-1 well and a nearby Moat Rhyolite dome with a K/Ar cooling age of ˜0.5 Ma suggest that vigorous hydrothermal activity beneath the central resurgent dome may have occurred as much as ˜0.5 m.y. ago. Calculated and measured O-isotope profiles are similar for deep wells that penetrate the western moat of the caldera, where steep temperature gradients and low δ18OWR values in

  1. Sulfur Isotope Trends in Archean Microbialite Facies Record Early Oxygen Production and Consumption (United States)

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


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

  2. A novel dynamic kinetic model of oxygen isotopic exchange on a supported metal catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Galdikas, Arvaidas; Duprez, Daniel; Descorme, Claude


    A time-resolved kinetic analysis has been developed for modeling experimental results of {sup 18}O/{sup 16}O isotopic exchange over oxide-supported metal catalysts. Model is based on two very important points: (1) the parallel calculation of surface and bulk diffusion and (2) the implication of certain O species such as superoxides. The model includes adsorption-desorption processes on metal clusters and oxygen spillover from the metal to the surface of support and vice versa. Different mechanisms of exchange were also taken into account via mononuclear (O atoms, O{sup -}, OH) or binuclear (superoxides) oxygen species. A refined model taking into account surface diffusion, direct exchange on surface of support by binuclear oxygen species and bulk diffusion was also developed. Kinetic (reaction rates and diffusion coefficients) as well as thermodynamic parameters (activation energies) were derived by fitting theoretical and experimental curves of {sup 18}O{sub 2}, {sup 18}O{sup 16}O and {sup 16}O{sub 2} gas phase concentrations versus time. The experimental results of Pt/CeZrO{sub 2} catalyst samples obtained in the 200-450 deg. C range of temperatures are examined. The refined model provides a very good fitting of the kinetic curves recorded with ceria-zirconia-supported catalysts. Moreover, values of diffusion coefficients and activation energies are in good agreement with already published values found by other methods. For a better understanding of all the steps of exchange, the kinetics of {sup 18}O and {sup 16}O distribution on the surface of metal clusters and on the surface of support are calculated and analyzed. On the basis of this model, a computer code is developed for analysis and calculations of kinetic and thermodynamic parameters of automotive catalysts.

  3. A laser fluorination method for oxygen isotope analysis of biogenic silica and a new oxygen isotope calibration of modern diatoms in freshwater environments (United States)

    Dodd, Justin P.; Sharp, Zachary D.


    An empirical calibration for the oxygen isotope fractionation between biogenic silica and water was determined for diatom frustules sampled from living diatom communities in the Jemez Mountains of northern New Mexico, USA. Over a temperature range from 5.1 to 37.8 °C, the silica-water fractionation is defined by the equation 1000 ln α (silica-water) = 2.39(±0.13) × 10 6T-2 + 4.23(±1.49). This relationship is in close agreement with other published silica-water fractionation factors for laboratory cultured diatom samples; however, it is as much as 8‰ lower than equilibrium quartz-water fractionations and 3-4‰ lower than observed silica-water fractionations in diatomaceous silica collected from sediment traps and sediment cores. There are three possible explanations for the disparate silica-water fractionation factors observed in diatom silica: (1) silica does not precipitate in equilibrium with ambient water, (2) silica does precipitate in equilibrium with ambient water, but the silica-water fractionation factor for diatom silica is considerably less than the equilibrium fractionation factor for quartz-water, or (3) silica precipitation is influenced by a 'vital' effect, where the δ 18O value of the water inside the diatom cell walls is lower than the δ 18O values of ambient water. Post-mortem loss of organic material results in an alteration or 'maturation' of diatom silica in which silica reequilibrates with a silica-water fractionation closer to the equilibrium quartz-water fractionation. Alteration is likely to occur rapidly after the diatom frustule loses its organic coating, either as it settles through the water column or at the sediment-water interface; δ 18O values recorded by paleo-diatom silica therefore do not record growing conditions but more likely record conditions at the sediment-water interface. In the case of lacustrine environments, where the bottom water remains at a nearly constant 4 °C, the reequilibration of diatom silica with

  4. Estimation of an upper limit on prehistoric horizontal peak ground acceleration using the parameters of intact stalagmites and the mechanical properties of broken stalagmites in Domica cave, Slovakia (United States)

    Gribovszki, Katalin; Brimich, Ladislav; Varga, Péter; Kovács, Károly; Shen, Chuan-Chou; Kele, Sándor; Török, Ákos; Novák, Attila


    The examination of special shaped, vulnerable, intact stalagmites in Domica cave (Slovakia) is the continuation of our previous examination of speleothems in Baradla cave (north eastern Hungary). (The Domica and Baradla caves really are two different parts of the same cave system.) The aim of our investigation is to estimate the upper limit for horizontal peak ground acceleration generated by paleoearthquake. There are many vulnerable, special shaped (high, slim and more or less cylindriform) stalagmites in Domica cave. The most vulnerable of these stalagmites have 5 m height and 6 or less than 6 cm diameter at the profile of cylinder, which we have found in Devil's Hall of Domica cave.. The method of our investigation is the same as before: the density, the Young's modulus and the tensile failure stress of the samples originating from broken stalagmites (lying on the ground of Domica cave) have been measured in mechanical laboratory, whereas the natural frequency of intact stalagmite was determined by in situ observation. The value of horizontal ground acceleration resulting in failure and the natural frequency of stalagmite were assessed by theoretical calculations. Our results show, that the tensile failure stress of the samples originating from Devil's Hall of Domica cave higher, than the tensile failure stress of the samples originating from Olimposz Hall of Baradla cave, however the value of Young-modulus is lower. The age of the samples taken from a stalagmite standing in Domica cave have been determined by inductively coupled plasma mass spectrometry analysis (MC-ICPMS). Our measurements show that this stalagmite is still growing and the oldest and bottommost part of it is not older than 117 000 years. The age of the oldest part of stalagmite in Domica nearly the same (130 000 years) as the 5.1 m high stalagmite situated in Olimposz Hall of Baradla cave. The ag value (upper limit for horizontal peak ground acceleration) coming from theoretical calculation

  5. Independent support for leaf homeothermy during carbon uptake and the implications for the interpretation of tree-ring oxygen isotopes (United States)

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


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

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

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


    The accuracy and precision of isotopic analysis in Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) relies on the appropriate reduction of the dead-time and detector saturation effects, especially when analyzing species with high ion yields or present in high concentrations. Conventional approaches to avoid these problems are based on Poisson dead-time correction and/or an overall decrease of the total secondary ion intensity by reducing the target current. This ultimately leads to poor detection limits for the minor isotopes and high uncertainties of the measured isotopic ratios. An alternative strategy consists of the attenuation of those specific secondary ions that saturate the detector, providing an effective extension of the linear dynamic range. In this work, the selective attenuation of secondary ion signals (SASI) approach is applied to the study of oxygen transport properties in electroceramic materials by isotopic labeling with stable (18)O tracer and ToF-SIMS depth profiling. The better analytical performance in terms of accuracy and precision allowed a more reliable determination of the oxygen surface exchange and diffusion coefficients while maintaining good mass resolution and limits of detection for other minor secondary ion species. This improvement is especially relevant to understand the ionic transport mechanisms and properties of solid materials, such as the parallel diffusion pathways (e.g., oxygen diffusion through bulk, grain boundary, or dislocations) in electroceramic materials with relevant applications in energy storage and conversion devices.

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

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


    Stable isotope data provide insight into the reconstruction of ancient human diet. However, cooking may alter the original stable isotope compositions of food due to losses and modifications of biochemical and water components. To address this issue, carbon, nitrogen and oxygen isotope ratios were measured on meat aliquots sampled from various animals such as pork, beef, duck and chicken, and also from the flesh of fishes such as salmon, European seabass, European pilchard, sole, gilt-head bream, and tuna. For each specimen, three pieces were cooked according to the three most commonly-known cooking practices: boiling, frying and roasting on a barbecue. Our data show that cooking produced isotopic shifts up to 1.8‰, 3.5‰, and 5.2‰ for δ 13 C, δ 15 N, and δ 18 O values, respectively. Such variations between raw and cooked food are much greater than previously estimated in the literature; they are more sensitive to the type of food rather than to the cooking process itself, except in the case of boiling. Reconstructions of paleodietary may thus suffer slight bias in cases of populations with undiversified diets that are restrained toward a specific raw or cooked product, or using a specific cooking mode. In cases of oxygen isotope compositions from skeletal remains (bones, teeth), they not only constitute a valuable proxy for reconstructing past climatic conditions, but they could also be used to improve our knowledge of past human diet. © 2017 Wiley Periodicals, Inc.

  8. The confines of triple oxygen isotope exponents in elemental and complex mass-dependent processes (United States)

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


    Small differences in triple isotope relationships, or Δ17O in the case of oxygen, have been increasingly used to study a range of problems including hydrological cycles, stratosphere-troposphere exchange, biogeochemical pathways and fluxes, and the Moon's origin in the geochemical and cosmochemical communities. A Δ17O value depends on the triple isotope exponent θ of involved reaction steps. However, the probabilistic distribution of the intrinsic and apparent θ values has not been examined for elemental processes and for processes that are out of equilibrium or bearing reservoir-transport complexities. A lack of knowledge on the confines of θ may hamper our understanding of the subtle differences among mass-dependent processes and may result in mischaracterization of a set of mass-dependent processes as being in violation of mass-dependent rules. Here we advocate a reductionist approach and explore θ confines starting from kinetic isotope effects (KIEs) within the framework of transition state theory (TST). The advantage of our KIE approach is that any elemental or composite, equilibrium or non-equilibrium process can be reduced to a set of KIEs with corresponding θKIE. We establish that the KIE between a reactant and a transition state (TS) is intrinsic. Given a range of KIEs known for Earth processes involving oxygen, we use a Monte Carlo calculation method and a range of oxygen-bonded molecular masses to obtain a distribution of θKIE values and subsequently that of θeq. Next, complexities are examined by looking into expected effects due to reaction progress, unbalanced fluxes, and reference frame. Finally, compounded reservoir-transport effects are examined using two simple processes - Rayleigh Distillation (RD) and Fractional Distillation (FD). Our results show that the apparent θ values between two species or two states of the same evolving species have much broader confines than the commonly used ;canonical; confines of 0.51-0.53, particularly

  9. On the use of stable oxygen isotope (δ (18)O) measurements for tracking avian movements in North America. (United States)

    Hobson, Keith A; Koehler, Geoff


    Tracking migratory animals has benefitted using measurements of naturally occurring stable isotopes of hydrogen (δ (2)H) in keratinous tissues such as hair and feathers to link animal origins to continental patterns or isoscapes of δ (2)H in precipitation. However, for most taxa, much less information exists on the use of stable oxygen isotope ratios (δ (18)O) despite the fact that δ (2)H and δ (18)O are strongly linked in environmental waters through the meteoric relationship and the possibility of using both isotopes to infer greater information on origins and climatic conditions where tissues are grown. A fundamental requirement of using stable isotopes to assign individuals and populations to origins is the development of a rescaling function linking environmental food web signals to the tissue of interest and for birds, this has not been carried out. Here, we derived the relationship between H and O isotopes in known source feathers of 104 individuals representing 11 species of insectivorous passerines sampled across the strong precipitation isoscape of North America. We determined again a strong expected relationship between feather δ (2)H (δ (2)Hf) and long-term amount-weighted precipitation δ (2)H (δ (2)Hp; r (2) = 0.77), but the corresponding relationship between δ (18)Of and δ (18)Op was poor (r (2) = 0.32) for the same samples. This suggests that δ (2)H measurements are currently more useful for assignment of insectivorous songbirds to precipitation isoscapes but does not preclude other uses of the δ (18)Of data. Currently, mechanisms responsible for the decoupling of H and O isotopes in food webs is poorly known, and we advocate a much broader sampling of both isotopes in the same keratinous tissues across precipitation isotope gradients and across taxa to resolve this issue and to increase the power of using water isotopes to track migratory animals.

  10. Oxygen Isotope Compositions of Meteoric Water Across an Elevation Gradient in Southern Peru (United States)

    Xu, D. R.; White, E.; Cassel, E. J.; Lynch, B.; Yanites, B.; Breecker, D.


    The Central Andes is a prime example of elevated topography generated by oceanic plate subduction. Whereas previous stable isotope studies have investigated the paleoelevation of the Andean Eastern Cordillera, little is known about the paleoelevation of the Western Cordillera, where arc volcanism now occurs. As a first step towards studying the paleoelevation of this region, we investigated the change in δ18O values of modern soil waters across an elevation gradient from sea level to about 4725 meters in southern Peru. We sampled soil profiles from 5 to 80 cm in 15-20cm increments, and we sampled water from flowing natural streams at various elevations. We used cryogenic vacuum extraction to quantitatively remove non-structural water from soil samples. The δ18O values of water extracted from soil samples varies with the depth in the soil due to the diminishing effect of seasonality and evaporation. Every high elevation (>3500m) soil profile we measured had nearly constant δ18O values below 5cm and a total range of δ18O values between -12.8‰ and -17.1‰, apart from the Cusco profile. In the Cusco profile, the δ18O values ranged from -7.2 ‰ at 5 cm to -21.8 ‰ at 60 cm, defining a strong monotonic decrease not seen in other soil profiles. The δ18O trend in the Cusco profile may be different due to the impact of evaporation, soil hydrology, and/or seasonality in the δ18O values of precipitation. Further spatial analysis must be conducted to pinpoint a specific cause. Considering only the samples collected below 40cm, which are likely the best estimate of mean annual precipitation, the δ18O values decrease with increasing elevation at a rate higher than the global mean, suggesting that oxygen isotope paleoaltimetry can work in this study region.

  11. Evaluation of diffuse and preferential flow pathways of infiltratedprecipitation and irrigation using oxygen and hydrogen isotopes (United States)

    Ma, Bin; Liang, Xing; Liu, Shaohua; Jin, Menggui; Nimmo, John R.; Li, Jingxin


    Subsurface-water flow pathways in three different land-use areas (non-irrigated grassland, poplar forest, and irrigated arable land) in the central North China Plain were investigated using oxygen (18O) and hydrogen (2H) isotopes in samples of precipitation, soils, and groundwater. Soil water in the top 10 cm was significantly affected by both evaporation and infiltration. Water at 10–40 cm depth in the grassland and arable land, and 10–60 cm in poplar forest, showed a relatively short residence time, as a substantial proportion of antecedent soil water was mixed with a 92-mm storm infiltration event, whereas below those depths (down to 150 cm), depleted δ18O spikes suggested that some storm water bypassed the shallow soil layers. Significant differences, in soil-water content and δ18O values, within a small area, suggested that the proportion of immobile soil water and water flowing in subsurface pathways varies depending on local vegetation cover, soil characteristics and irrigation applications. Soil-water δ18O values revealed that preferential flow and diffuse flow coexist. Preferential flow was active within the root zone, independent of antecedent soil-water content, in both poplar forest and arable land, whereas diffuse flow was observed in grassland. The depleted δ18O spikes at 20–50 cm depth in the arable land suggested the infiltration of irrigation water during the dry season. Temporal isotopic variations in precipitation were subdued in the shallow groundwater, suggesting more complete mixing of different input waters in the unsaturated zone before reaching the shallow groundwater.

  12. Oxygen and Magnesium Isotopic Compositions of Asteroidal Materials Returned from Itokawa by the Hayabusa Mission (United States)

    Yurimoto, H; Abe, M.; Ebihara, M.; Fujimura, A.; Hashizume, K.; Ireland, T. R.; Itoh, S.; Kawaguchi, K.; Kitajima, F.; Mukai, T.; hide


    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

  13. Stable oxygen isotope reconstruction of ambient temperature during the collapse of a cod (Gadus morhua) fishery. (United States)

    Jones, J Brin; Campana, Steven E


    Changing environmental conditions set against a backdrop of high exploitation can result in severe consequences for commercially harvested stocks. The collapse of the Eastern Scotian Shelf cod (Gadus morhua L.) off eastern Canada was primarily due to overexploitation but may have been exacerbated by a widespread temperature decline. Recent studies have called for accurate determination of ambient temperature (the actual temperature exposure history of the fish) before discarding environmental conditions as a factor in the collapse. We used the stable oxygen isotope composition of otoliths (delta18O(oto)) to reconstruct the ambient temperature history of Eastern Scotian Shelf cod from 1970 to 2000 in order to determine whether the stock experienced the temperature decline or shifted their distribution to avoid it. To correct delta18O(oto) for seawater isotope content (deltaO(w)), we generated a new meta-equation for the relationship between delta18O(w) (per mil) and salinity (S, in psu) on the Eastern Scotian Shelf: delta18O(w) = 0.539 x S - 18.790. The ambient temperature series revealed that the large-scale geographic distribution of mature cod remained constant through the cooling period, although their ambient temperature was cooler than expected in warmer periods and warmer than expected in cooler periods, indicating small-scale thermoregulatory movement. Although the mean hydrographic temperature was 4 degrees C, mature cod usually inhabited the coldest available waters (mean ambient temperature = 3 degrees C), while the juveniles usually inhabited warmer waters (mean ambient temperature = 5.5 degrees C). Length-at-age was significantly related to ambient temperature, especially in the early years of growth, and therefore declining ambient temperatures were at least partially responsible for declines in asymptotic length (up to age 8 yr). The most active thermoregulatory movement occurred during a moderate warming period; therefore extreme warming events (such

  14. Analysis of High Frequency Site-Specific Nitrogen and Oxygen Isotopic Composition of Atmospheric Nitrous Oxide at Mace Head, Ireland (United States)

    McClellan, M. J.; Harris, E. J.; Olszewski, W.; Ono, S.; Prinn, R. G.


    Atmospheric nitrous oxide (N2O) significantly impacts Earth's climate due to its dual role as an inert potent greenhouse gas in the troposphere and as a reactive source of ozone-destroying nitrogen oxides in the stratosphere. However, there remain significant uncertainties in the global budget of this gas. The marked spatial divide in its reactivity means that all stages in the N2O life cycle—emission, transport, and destruction—must be examined to understand the overall effect of N2O on climate. Source and sink processes of N2O lead to varying concentrations of N2O isotopologues (14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O being measured) due to preferential isotopic production and elimination in different environments. Estimation of source and sink fluxes can be improved by combining isotopically resolved N2O observations with simulations using a chemical transport model with reanalysis meteorology and treatments of isotopic signatures of specific surface sources and stratospheric intrusions. We present the first few months of site-specific nitrogen and oxygen isotopic composition data from the Stheno-TILDAS instrument (Harris et al, 2013) at Mace Head, Ireland and compare these to results from MOZART-4 (Model for Ozone and Related Chemical Tracers, version 4) chemical transport model runs including N2O isotopic fractionation processes and reanalysis meterological fields (NCEP/NCAR, MERRA, and GEOS-5). This study forms the basis for future inverse modeling experiments that will improve the accuracy of isotopically differentiated N2O emission and loss estimates. Ref: Harris, E., D. Nelson, W. Olszewski, M. Zahniser, K. Potter, B. McManus, A. Whitehill, R. Prinn, and S. Ono, Development of a spectroscopic technique for continuous online monitoring of oxygen and site-specific nitrogen isotopic composition of atmospheric nitrous oxide, Analytical Chemistry, 2013; DOI: 10.1021/ac403606u.

  15. Chemical and oxygen isotope zonings in garnet from subducted continental crust record mineral replacement and metasomatism (United States)

    Vho, Alice; Rubatto, Daniela; Regis, Daniele; Baumgartner, Lukas; Bouvier, Anne-Sophie


    Garnet is a key mineral in metamorphic petrology for constraining pressure, temperature and time paths. Garnet can preserve multiple growth stages due to its wide P-T stability field and the relatively slow diffusivity for major and trace elements at sub-solidus temperatures. Pressure-temperature-time-fluid paths of the host rock may be reconstructed by combining metamorphic petrology with microscale trace element and oxygen isotope measurements in garnet. Subduction zones represent relevant geological settings for geochemical investigation of element exchanges during aqueous fluid-rock interactions. The Sesia Zone consists of a complex continental sequence containing a variety of mono-metamorphic and poly-metamorphic lithologies such as metagranitoids, sediments and mafic boudins. The precursor Varisican-Permian amphibolite-facies basement (6-9 kbar 650-850°C; Lardeaux and Spalla, 1991; Robyr et al., 2013) experienced high pressure metamorphism (15-22 kbar 500-550°C; Regis, et al. 2014; Robyr et al., 2013) during Alpine subduction. In different lithologies of the Internal Complex (Eclogitic Micaschist Complex), including metabasites from the Ivozio Complex, Ti-rich metasediments from Val Malone and pre-Alpine Mn-quartzites associated to metagabbros from Cima Bonze, garnet is abundant and shows a variety of complex textures that cannot be reconciled with typical growth zoning, but indicate resorption and replacement processes and possible metasomatism. In-situ, microscale oxygen isotopes analysis of garnet zones was performed by ion microprobe with the SwissSIMS Cameca IMS 1280-HR at University of Lausanne and SHRIMP-SI at the Australian National University. Each sample has a distinct δ18O composition, and the δ18O values show different degrees of variation between domains. Homogeneously low values of Geology, 9, 35-59. Regis, D., Rubatto, D., Darling, J., Cenki-Tok, B., Zucali, M., & Engi, M. (2014). Multiple metamorphic stages within an eclogite

  16. Oxygen isotope geochemistry of Laurentide ice-sheet meltwater across Termination I (United States)

    Vetter, Lael; Spero, Howard J.; Eggins, Stephen M.; Williams, Carlie; Flower, Benjamin P.


    We present a new method that quantifies the oxygen isotope geochemistry of Laurentide ice-sheet (LIS) meltwater across the last deglaciation, and reconstruct decadal-scale variations in the δ18O of LIS meltwater entering the Gulf of Mexico between ∼18 and 11 ka. We employ a technique that combines laser ablation ICP-MS (LA-ICP-MS) and oxygen isotope analyses on individual shells of the planktic foraminifer Orbulina universa to quantify the instantaneous δ18Owater value of Mississippi River outflow, which was dominated by meltwater from the LIS. For each individual O. universa shell, we measure Mg/Ca (a proxy for temperature) and Ba/Ca (a proxy for salinity) with LA-ICP-MS, and then analyze the same O. universa for δ18O using the remaining material from the shell. From these proxies, we obtain δ18Owater and salinity estimates for each individual foraminifer. Regressions through data obtained from discrete core intervals yield δ18Ow vs. salinity relationships with a y-intercept that corresponds to the δ18Owater composition of the freshwater end-member. Our data suggest that from 15.5 through 14.6 ka, estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from -11‰ to -21‰ VSMOW, which is consistent with δ18O values from both regional precipitation and the low-elevation, southern margin of the LIS. During the Bølling and Allerød (14.0 through 13.3 ka), estimated δ18Ow values of Mississippi River discharge from discrete core intervals range from -22‰ to -38‰ VSMOW. These values suggest a dynamic melting history of different parts of the LIS, with potential contributions to Mississippi River outflow from both the low-elevation, southern margin of the LIS and high-elevation, high-latitude domes in the LIS interior that were transported to the ablation zone. Prior to ∼15.5 ka, the δ18Owater value of the Mississippi River was similar to that of regional precipitation or low-latitude LIS meltwater, but the Ba

  17. Digesting the data - Effects of predator ingestion on the oxygen isotopic signature of micro-mammal teeth (United States)

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


    Biogenic minerals such as dental apatite have become commonly analysed archives preserving geochemical indicators of past environmental conditions and palaeoecologies. However, post-mortem, biogenic minerals are modified due to the alteration/replacement of labile components, and recent moves to utilise micro-mammal tooth δ18O signatures for refined Cenozoic terrestrial palaeoclimate reconstructions has lacked consideration of the chemical effects of predator digestion. Here, the physical and chemical condition of laboratory-raised mouse (Mus musculus) teeth have been investigated in conjunction with their bulk phosphate and tissue-specific δ18O values prior, and subsequent, to ingestion and excretion by various predator species (owls, mammals and a reptile). Substantial variability (up to 2‰) in the δ18O values of both undigested teeth and those ingested by specific predators suggests significant natural heterogeneity of individual prey δ18O. Statistically distinct, lower δ18O values (∼0.7‰) are apparent in teeth ingested by barn owls compared to undigested controls as a result of the chemically and enzymatically active digestive and waste-pellet environments. Overall, dentine tissues preserve lower δ18O values than enamel, while the greatest modification of oxygen isotope signals is exhibited in the basal enamel of ingested teeth as a result of its incompletely mineralised state. However, recognition of 18O-depletion in chemically purified phosphate analyses demonstrates that modification of original δ18O values is not restricted to labile oxygen-bearing carbonate and organic phases. The style and magnitude of digestive-alteration varies with predator species and no correlation was identified between specific physical or minor/trace-element (patterns or concentrations) modification of ingested teeth and disruption of their primary oxygen isotope values. Therefore, there is a current lack of any screening tool for oxygen isotope disruption as a result

  18. The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase (United States)

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


    Phosphorus (P) is an essential nutrient for living organisms. Under P-limiting conditions plants and microorganisms can exude extracellular phosphatases that release inorganic phosphate (Pi) from organic phosphorus compounds (Porg). Phytic acid (myo-inositol hexakisphosphate, IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields available Pi and less phosphorylated inositol derivates as products. The hydrolysis of organic P compounds by phosphatases leaves an isotopic imprint on the oxygen isotope composition (δ18O) of released Pi, which might be used to trace P in the environment. This study aims at determining the effect of phytase on the oxygen isotope composition of released Pi. For this purpose, enzymatic assays with histidine acid phytases from wheat and Aspergillus niger were prepared using IP6, adenosine 5'-monophosphate (AMP) and glycerophosphate (GPO4) as substrates. For a comparison to the δ18O of Pi released by other extracellular enzymes, enzymatic assays with acid phosphatases from potato and wheat germ with IP6 as a substrate were prepared. During the hydrolysis of IP6 by phytase, four of the six Pi were released, and one oxygen atom from water was incorporated into each Pi. This incorporation of oxygen from water into Pi was subject to an apparent inverse isotopic fractionation (ϵ ~ 6 to 10 ‰), which was similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ~ 7 ‰), where less than three Pi were released. The incorporation of oxygen from water into Pi during the hydrolysis of AMP and GPO4 by phytase yielded a normal isotopic fractionation (ϵ ~ -12 ‰), similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ϵ to the same amino acid sequence motif (RHGXRXP) at the active site of these enzymes, which leads to similar reaction mechanisms. We suggest that the striking

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

    International Nuclear Information System (INIS)

    Spiegler, P.; Updegraff, D.


    Pathways which might alter the isotopic compositions of deuterium and oxygen-18 meteoric water, seawaters, and in hydration waters in gypsum to the isotopic compositions of brines encountered at ERDA-6 and WIPP-12 are discussed. Present geologic conditions do not favor the alteration of the isotopic compositions of waters that exist near the WIPP site to those of the brines by these pathways. It is concluded that the brines encountered at ERDA-6 and WIPP-12 are probably derived from ancient ocean waters that have been isotopically enriched in oxygen-18 by exchange interaction with rock. The dehydration of gypsum as a process of origin of these brines cannot be ruled out

  20. Evidence of past climate change in the Little Ice Age and of the Pacific Decadal Oscillation periodicity in Africa: comparison between two neighbor stalagmites from Namibia and Botswana (preliminary results) (United States)

    Voarintsoa, N. G.; Railsback, L. B.; Liang, F.; Brook, G. A.; Cheng, H.; Edwards, R.


    Stalagmites are potential sources of paleoenvironmental records because their characteristics respond to climate change. In this preliminary study we compare isotopic values resolvable at annual to bi-annual scale from two stalagmites from caves in Proterozoic dolomitic marbles, as a proxy for the past climate variability in Southern Africa. Stalagmite DP1 is from Dante Cave in the Otjozondjupa region of Namibia, and Stalagmite BC97-14 is from Bone Cave, in the Koanaka Hills of Northwest Botswana, ~125km west of the Okavango Delta. Dante and Bone Cave receive respectively ~532 and ~475mm annual rainfall with an annual average temperature of 21.0°C and 22.6°C. Both caves are in semi-arid areas with highly seasonal rainfall. Vegetation is distinctive for each location: deciduous woodland savanna with a relatively high diversity of scattered tall trees on the hill in which Dante is located and a sparser tree cover on the hillsite of Bone Cave area. The data from the two stalagmites are very different, reflecting the distinctive hydrological and vegetation settings of the caves where they formed. δ18O in BC97-14 is highly variable, ranging from -11.6 to -5.8 ‰, while δ13C is nearly constant (-10.5 to -8.5 ‰). In contrast, δ13C and δ18O are covariant in DP1, with much higher δ13C values (-10.8 to -5.1‰) and much lower δ18O (-11.7 to -6.5 ‰) compared to that of Bone Cave. The distance from the water vapor source (Indian Ocean) might explain the generally lower δ18O values from the Namibian stalagmite compared to that of Botswana; while the difference in vegetation cover reflects the difference between δ13C for the two areas. Regardless of this isotopic difference, the stalagmite data for Bone Cave show a marked 15- to 22-year periodicity that is much more subdued in the Namibia speleothem. This cycle matches with the 17- or 18-year periodicity in the Botswana historical rainfall record. The periodicity is very well pronounced between AD 1825 to 1925

  1. Phosphorus dynamics in soils irrigated with reclaimed waste water or fresh water - A study using oxygen isotopic composition of phosphate (United States)

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


    Transformations of phosphate (Pi) in different soil fractions were tracked using the stable isotopic composition of oxygen in phosphate (??18Op) and Pi concentrations. Clay soil from Israel was treated with either reclaimed waste water (secondary, low grade) or with fresh water amended with a chemical fertilizer of a known isotopic signature. Changes of ??18Op and Pi within different soil fractions, during a month of incubation, elucidate biogeochemical processes in the soil, revealing the biological and the chemical transformation impacting the various P pools. P in the soil solution is affected primarily by enzymatic activity that yields isotopic equilibrium with the water molecules in the soil solution. The dissolved P interacts rapidly with the loosely bound P (extracted by bicarbonate). The oxides and mineral P fractions (extracted by NaOH and HCl, respectively), which are considered as relatively stable pools of P, also exhibited isotopic alterations in the first two weeks after P application, likely related to the activity of microbial populations associated with soil surfaces. Specifically, isotopic depletion which could result from organic P mineralization was followed by isotopic enrichment which could result from preferential biological uptake of depleted P from the mineralized pool. Similar transformations were observed in both soils although transformations related to biological activity were more pronounced in the soil treated with reclaimed waste water compared to the fertilizer treated soil. ?? 2010 Elsevier B.V.

  2. Oxygen isotopic ratios in fine quartz silt from sediments and soils of southern Africa

    International Nuclear Information System (INIS)

    Le Roux, J.; Jackson, M.L.; Clayton, R.N.


    Fine quartz silt (1 to 10 μm dia, important in aerosol dust) isolated from a large number of soils, as well as Phanerozoic shales, sandstones and recent sands of the southern African stratigraphic column (Carboniferous, Permian and Triassic) exhibits a mean delta 18 O of 12.2 +- 2.1 parts per thousand. These values are similar to those reported for South Pacific pelagic sediments and adjacent land areas of similar latitude but are lower than those reported for this size fraction of 30 Mesozoic and Paleozoic shales (20.7 +- 1.8 parts per thousand) and soils from mid-continental U.S.A., for aerosol quartz in the North Pacific pelagic sediments, and for eolian caps in high-elevation soils of Hawaii. The lower oxygen isotopic ratios in fine quartz silt of southern Africa reinforces the earlier indication that Southern Hemisphere detrital sedimentary reservoirs contain a higher proportion of igneous and metamorphic quartz (lower delta 18 O) and less low-temperature authigenic quartz (higher delta 18 O) than Northern Hemisphere detrital sediments. The difference reflects climates, as continents drifted in latitude. (author)

  3. Using oxygen isotopes of phosphate to trace phosphorus sources and cycling in lake Erie (United States)

    Elsbury, K.E.; Paytan, A.; Ostrom, N.E.; Kendall, C.; Young, M.B.; McLaughlin, K.; Rollog, M.E.; Watson, S.


    Water samples collected during three sampling trips to Lake Erie displayed oxygen isotopic values of dissolved phosphate (??18O p) that were largely out of equilibrium with ambient conditions, indicating that source signatures may be discerned. ??18O p values in the Lake ranged from +10??? to +17???, whereas the equilibrium value was expected to be around +14???. The riverine weighted average ??18Op value was +11??? and may represent one source of phosphate to the Lake. The lake ?? 18Op values indicated that there must be one or more as yet uncharacterized source(s) of phosphate with a high ?? 18Op value. Potential sources other than rivers are not yet well-characterized with respect to ??18O of phosphate, but we speculate that a likely source may be the release of phosphate from sediments under reducing conditions created during anoxic events in the hypolimnion of the central basin of Lake Erie. Identifying potential phosphorus sources to the Lake is vital for designing effective management plans for reducing nutrient inputs and associated eutrophication. ?? 2009 American Chemical Society.

  4. Ultra-sensitive probe of spectral line structure and detection of isotopic oxygen (United States)

    Garner, Richard M.; Dharamsi, A. N.; Khan, M. Amir


    We discuss a new method of investigating and obtaining quantitative behavior of higher harmonic (> 2f) wavelength modulation spectroscopy (WMS) based on the signal structure. It is shown that the spectral structure of higher harmonic WMS signals, quantified by the number of zero crossings and turnings points, can have increased sensitivity to ambient conditions or line-broadening effects from changes in temperature, pressure, or optical depth. The structure of WMS signals, characterized by combinations of signal magnitude and spectral locations of turning points and zero crossings, provides a unique scale that quantifies lineshape parameters and, thus, useful in optimization of measurements obtained from multi-harmonic WMS signals. We demonstrate this by detecting weaker rotational-vibrational transitions of isotopic atmospheric oxygen (16O18O) in the near-infrared region where higher harmonic WMS signals are more sensitive contrary to their signal-to-noise ratio considerations. The proposed approach based on spectral structure provides the ability to investigate and quantify signals not only at linecenter but also in the wing region of the absorption profile. This formulation is particularly useful in tunable diode laser spectroscopy and ultra-precision laser-based sensors where absorption signal profile carries information of quantities of interest, e.g., concentration, velocity, or gas collision dynamics, etc.

  5. Meridional distribution and seasonal variation of stable oxygen isotope ratio of precipitation in the Southern Ocean

    Directory of Open Access Journals (Sweden)

    Kayo Nakamura


    Full Text Available The stable oxygen isotope ratio(δ^O in precipitation is known to have important meridional and seasonal variations, but there are almost no measurements of δ^O in precipitation over polar oceans. The present research took advantage of 4 opportunities for in situ observations in summer and winter at high latitudes in the Southern Ocean. In addition, we analyzed samples of precipitation at Syowa Station in 2008 to obtain year-round data. Based on these data, we consider the meridional and seasonal variations of δ^O in precipitation over the Southern Ocean. In general, δ^O decreases with increasing latitude, and is lower in winter than in summer. The latitude gradient is stronger in winter. At 60°S, δ^O is -5.4‰ and -11.3‰ in summer and winter, respectively, while the corresponding figures at 66°S are -10.5‰ and -20.8‰. These results will help us understand the mechanisms of the salinity distribution and its variation in the Antarctic Ocean.

  6. Method for the analysis of oxygen isotopic composition of soil phosphate fractions. (United States)

    Zohar, Iris; Shaviv, Avi; Klass, Tatania; Roberts, Kathryn; Paytan, Adina


    The isotopic signature of oxygen in phosphate (δ(18)O(P)) of various soil fractions may shed light on P transformations, including phosphorus (P) recycling by soil microorganisms, uptake by plants and P adsorption, precipitation and release by oxides and minerals, thus increasing our understanding on P cycling and lability in soils. We developed and tested a protocol to extract and purify inorganic phosphate (Pi) from different soil fractions distinguished by binding strength and precipitate it as silver phosphate (Ag(3)PO(4)) for δ(18)O(P) analysis. Soil P is extracted sequentially using water, NaHCO(3), NaOH and HCl and Pi in each solution is purified and precipitated as Ag(3)PO(4). The unique characteristics and possible interferences of the soil solution extracts are addressed. Two agricultural soil samples receiving reclaimed wastewater or fresh water were analyzed, and results indicate that all soil fractions analyzed have been impacted to some degree by biologically enzyme mediated cycling of P in the soil.

  7. Oxygen isotopic composition of individual olivine grains from the Allende meteorite (United States)

    Weinbruch, S.; Zinner, E. K.; El Goresy, A.; Steele, I. M.; Palme, H.


    The oxygen isotopic composition of a variety of individual olivine grains (including refractory forsterite grains, cores of isolated olivine grains, FeO-rich rims, and individual matrix olivine grains) from the Allende CV3 meteorite was investigated by ion microprobe mass spectrometry, in order to obtain information on the formation mechanism of these samples. It was found that the most primitive (i.e., refractory) olivine in Allende is far less enriched in O-16 than are spinel and pyroxene in Ca,Al-rich inclusions, suggesting that Allende olivine must have formed in an environment that is less enriched in O-16 compared to the gas from which Ca,Al-inclusions are formed. FeO-rich (26-30 wt pct) rims of isolated olivine grains are significantly higher in delta-O-17 and delta-O-18 than forsteritic cores, suggesting that these rims formed by condensation from an oxidized gas with higher delta-O-17 than delta-O-18. Matrix olivine was found to be highest in FeO and to have the lowest enrichment in O-16.

  8. Comparison of prediction methods for oxygen-18 isotope composition in shallow groundwater. (United States)

    Cerar, Sonja; Mezga, Kim; Žibret, Gorazd; Urbanc, Janko; Komac, Marko


    Groundwater is the most important source of drinking water in the world. Therefore, information on the quality and quantity is important, as is new information related to the characteristics of the aquifer and the recharge area. In the present study we focused on the isotope composition of oxygen (δ 18 O) in groundwater, which is a natural tracer and provides a better understanding of the water cycle, in terms of origin, dynamics and interaction. The groundwater δ 18 O at 83 locations over the entire Slovenian territory was studied. Each location was sampled twice during the period 2009-2011. Geostatistical tools (such us ordinary kriging, simple and multiple linear regressions, and artificial neural networks were used and compared to select the best tool. Measured values of δ 18 O in the groundwater were used as the dependent variable, while the spatial characteristics of the territory (elevation, distance from the sea and average annual precipitation) were used as independent variables. Based on validation data sets, the artificial neural network model proved to be the most suitable method for predicting δ 18 O in the groundwater, since it produced the smallest deviations from the real/measured values in groundwater. Copyright © 2018 Elsevier B.V. All rights reserved.

  9. Raman spectral, elemental, crystallinity, and oxygen-isotope variations in conodont apatite during diagenesis (United States)

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


    crystallinity and Raman spectral or elemental parameters. Oxygen isotopes show substantial variation within the conodont study specimens. Albid crown is on average 0.28-0.32‰ more depleted in 18O (equivalent to 1.2-1.4 °C higher temperatures) than hyaline crown and basal body, and the interiors of conodont elements are 1.08 ± 0.37‰ more depleted in 18O (equivalent to 3.0-6.4 °C higher temperatures) relative to their outer layers. Although albid crown is widely regarded as better preserved than other conodont tissue types, its 18O-depleted composition and greater development of secondary crystallinity suggest that, in fact, it may be the most strongly altered tissue type. We conclude that Raman spectral, LA elemental, and HXRD microstructural data can provide useful information about the extent of diagenetic alteration of conodont elements, and that such information should be taken into consideration in using conodont elemental and oxygen-isotope data in paleoenvironmental studies.

  10. Stable oxygen isotopic fractionation during photolytic O(2) consumption in stream waters. (United States)

    Chomicki, K M; Schiff, S L


    Oxygen (O(2)) is required for life in higher organisms, however, processes such as respiration, the oxidation of reduced inorganic species, and the photolytic breakdown of dissolved organic matter (DOM) decrease the O(2) concentrations in aquatic systems. Filtered, inoculated, and sterile samples of stream waters from Ontario, Canada, were incubated in natural sunlight to examine the effects of photolysis of DOM, respiration, and abiotic reactions on O(2) consumption and delta(18)O of dissolved oxygen (delta(18)O-O(2)). Oxygen consumption rates in the light were up to an order of magnitude greater than in the dark, suggesting light-mediated processes controlled O(2) consumption. Rates of O(2) loss were the same for each treatment (i.e. filtered, inoculated, and sterile) indicating that photolysis was the dominant O(2) consuming process over respiration in these incubations. O(2) consumption rates were different between streams, even when normalized to the change in dissolved organic carbon (DOC), signifying that DOM photolability varied among streams. During DOM breakdown to CO(2), the lighter (16)O isotopomer was preferentially consumed. Fractionation factors observed for photolysis, respiration, and abiotic reactions ranged between 0.988 and 0.995, and were similar in both the light and in the dark incubations in all streams. These fractionation factors are not a function of O(2) consumption rates, and are outside the range published for respiration (0.975-0.982). In current models of O(2) and delta(18)O-O(2), photolysis and respiration are not considered separately and the isotopic fractionation during respiration that is measured in the dark is used in the light. In these incubations, DOM degradation and abiotic reactions are important O(2) consuming and delta(18)O-O(2) fractionating processes. Current models of O(2) and delta(18)O-O(2) incorporate photolysis of DOM and other abiotic processes into the respiratory component of O(2) consumption, thereby

  11. Quantum and thermal ionic motion, oxygen isotope effect, and superexchange distribution in La2CuO4

    DEFF Research Database (Denmark)

    Haefliger, P. S.; Gerber, S.; Pramod, R.


    We study the zero-point and thermal ionic motion in La2CuO4 by means of high-resolution neutron-diffraction experiments. Our results demonstrate anisotropic motion of O and, to a lesser extent, Cu ions, both consistent with the structure of coupled CuO6 octahedra, and quantify the relative effects...... of zero-point and thermal contributions to ionic motion. By substitution of O-18, we find that the oxygen isotope effect on the lattice dimensions is small and negative (-0.01%), while the isotope effect on the ionic displacement parameters is significant (-6 to 50%). We use our results as input...... for theoretical estimates of the distribution of magnetic interaction parameters, J, in an effective one-band model for the cuprate plane. We find that ionic motion causes only small (1%) effects on the average value , which vary with temperature and O isotope, but results in dramatic (10-20%) fluctuations...

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

    DEFF Research Database (Denmark)

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


    Melting of the Greenland Ice Sheet (GrIS) is accelerating and will contribute significantly to global sea level rise during the 21st century. Instrumental data on GrIS melting only cover the last few decades, and proxy data extending our knowledge into the past are vital for validating models...... predicting the influence of ongoing climate change. We investigated a potential meltwater proxy in Godthåbsfjord (West Greenland), where glacier meltwater causes seasonal excursions with lower oxygen isotope water (δ18Ow) values and salinity. The blue mussel (Mytilus edulis) potentially records...... its potential as a palaeo-meltwater proxy. First, we confirmed that M. edulis shell calcite oxygen isotope (δ18Oc) values are in equilibrium with ambient water and generally reflect meltwater conditions. Subsequently we investigated if this species recorded the full range of δ18Ow values occurring...

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

    Atar, L.; Paschalis, S.; Barbieri, C.; Bertulani, C. A.; Díaz Fernández, P.; Holl, M.; Najafi, M. A.; Panin, V.; Alvarez-Pol, H.; Aumann, T.; Avdeichikov, V.; Beceiro-Novo, S.; Bemmerer, D.; Benlliure, J.; Boillos, J. M.; Boretzky, K.; Borge, M. J. G.; Caamaño, M.; Caesar, C.; Casarejos, E.; Catford, W.; Cederkall, J.; Chartier, M.; Chulkov, L.; Cortina-Gil, D.; Cravo, E.; Crespo, R.; Dillmann, I.; Elekes, Z.; Enders, J.; Ershova, O.; Estrade, A.; Farinon, F.; Fraile, L. M.; Freer, M.; Galaviz Redondo, D.; Geissel, H.; Gernhäuser, R.; Golubev, P.; Göbel, K.; Hagdahl, J.; Heftrich, T.; Heil, M.; Heine, M.; Heinz, A.; Henriques, A.; Hufnagel, A.; Ignatov, A.; Johansson, H. T.; Jonson, B.; Kahlbow, J.; Kalantar-Nayestanaki, N.; Kanungo, R.; Kelic-Heil, A.; Knyazev, A.; Kröll, T.; Kurz, N.; Labiche, M.; Langer, C.; Le Bleis, T.; Lemmon, R.; Lindberg, S.; Machado, J.; Marganiec-Gałązka, J.; Movsesyan, A.; Nacher, E.; Nikolskii, E. Y.; Nilsson, T.; Nociforo, C.; Perea, A.; Petri, M.; Pietri, S.; Plag, R.; Reifarth, R.; Ribeiro, G.; Rigollet, C.; Rossi, D. M.; Röder, M.; Savran, D.; Scheit, H.; Simon, H.; Sorlin, O.; Syndikus, I.; Taylor, J. T.; Tengblad, O.; Thies, R.; Togano, Y.; Vandebrouck, M.; Velho, P.; Volkov, V.; Wagner, A.; Wamers, F.; Weick, H.; Wheldon, C.; Wilson, G. L.; Winfield, J. S.; Woods, P.; Yakorev, D.; Zhukov, M.; Zilges, A.; Zuber, K.; R3B Collaboration


    Quasifree one-proton knockout reactions have been employed in inverse kinematics for a systematic study of the structure of stable and exotic oxygen isotopes at the R3B /LAND setup with incident beam energies in the range of 300 - 450 MeV /u . The oxygen isotopic chain offers a large variation of separation energies that allows for a quantitative understanding of single-particle strength with changing isospin asymmetry. Quasifree knockout reactions provide a complementary approach to intermediate-energy one-nucleon removal reactions. Inclusive cross sections for quasifree knockout reactions of the type O A (p ,2 p )N-1A have been determined and compared to calculations based on the eikonal reaction theory. The reduction factors for the single-particle strength with respect to the independent-particle model were obtained and compared to state-of-the-art ab initio predictions. The results do not show any significant dependence on proton-neutron asymmetry.

  14. Modeling of Diffusion Process in the Isotopic Oxygen Exchange Experiments of CexZr(1-xO2 Catalysts

    Directory of Open Access Journals (Sweden)

    Arvaidas GALDIKAS


    Full Text Available The oxygen mobility processes during the temperature programmed oxygen isotopic exchange is considered by proposed kinetic model. Model includes simple and complex heteroexchange reactions and bulk diffusion processes. The model is applied to fit experimental curves of CexZr(1-xO2 catalysts with different composition in order to calculate reaction rates and diffusion coefficients, and activation energies of those processes.DOI:

  15. A study of oxygen transport in mixed conducting oxides using isotopic exchange and conductivity relaxation

    NARCIS (Netherlands)

    den Otter, M.W.


    Mixed conducting oxygen ion conductors can be applied as membranes for the separation of oxygen from air, as electrodes for both oxygen pumps and solid oxide fuel cells. In these applications, oxygen molecules dissociate on the surface of the material. The atomic oxygen species pick up two electrons

  16. The Bauru group: a continental Cretaceous unit in Brazil - Concepts based on micropaleontological, oxygen isotope and stratigraphical data


    Dias-Brito, D. [UNESP; Musacchio, E. A. [UNESP; de Castro, J. C. [UNESP; Maranhiao, M. S A S [UNESP; Suárez, J. M. [UNESP; Rodrigues, R. [UNESP


    The integration of outcrop and subsurface information, including micropaleontological data, facies and sequence stratigraphic studies, and oxygen isotope analysis, allow us to present a new stratigraphic model for the Cretaceous continental deposits of the Bauru Group, Brazil. Thirty-eight fossil taxa were recovered from these deposits, including 29 species of ostracodes and 9 species of charophytes. Seven of these ostracode species and three subspecies are new and formally described here. Th...

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


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


    High-resolution records of Mediterranean and North Atlantic deep-sea sediments indicate that rapid changes in hydrology and climate occurred during marine oxygen isotope stage 100 (MIS100) (at ∼2.52 Ma), which exhibits characteristics similar to late Pleistocene Dansgaard-Oeschger, Bond cycles and Heinrich events. As in the late Pleistocene, North Atlantic oceanographic and atmospheric changes were probably transmitted into the Mediterranean by some combination of surface water inflow and Atl...

  18. Using Oxygen Isotopic Values in Order to Infer Palaeoclimatic Differences between Northern and Central-Southern Greece (United States)

    Michael, Dimitra-Ermioni; Dotsika, Elissavet


    Even though isotopic analyses have been extensively implemented on human skeletal remains for the purpose of dietary reconstruction, less attention has been given to the ingested water and thus to the investigation of palaeoclimatic conditions. In particular, oxygen isotopic fingerprinting has never been applied on human skeletal remains from Greece for the abovementioned purpose before. The basic aim of the present study is to compare climatic conditions from two ancient populations, deriving from two different ecological locations; Edessa (Greek Macedonia; 2nd-4th c. AD) and Thebes (Sterea Hellas, 13th-14th c. AD). Oxygen values in Edessa are at -7.69 ±1.13 ‰ and -9.18 ±1.88 ‰ for tooth enamel and bone apatite respectively. On the other hand, oxygen signals in Thebes are at -5.8 ±2.16 ‰ and -9.23 ±1.3 % for the enamel and bone apatite respectively. The utility of oxygen isotopic signatures for the purpose of palaeoclimatic investigation lies on the fact that the ratio of 18 to 16O of meteoric precipitation, expressed as δ18O per mill (‰), relative to the international standard (vSMOW) varies geographically by temperature, humidity, evaporation, distance to the sea, altitude and latitude. Therefore, results as expected, point out that Edessa do presents more negative enamel isotopic values in relation to Thebes, however the noted difference is not observed for the bone apatite samples. The lack of bone apatite differentiation between sites could be attributed to cultural diversity (particularly in Thebes), shift in dietary habits due to migration or social status, climatic fluctuations within each site or to possible diagenetic alteration of bone apatite samples.

  19. Validation of Chlorine and Oxygen Isotope Ratio Analysis to Differentiate Perchlorate Sources and to Document Perchlorate Biodegradation (United States)


    natural . Chlorine and oxygen isotopic analyses of perchlorate provide the primaty direct approach whereby different sources of perchlorate can be...REPORT NUMBER U.S. Geological Survey NA University of Illinois at Chicago 9 . SPONSORII\\IGI MONITORING AGENCY NAME(S) A ND ADDRESS( ESl 10 . SPONSOR...Unlimited 13. SUPPLEMENTARY NOTES None 14.ABSTRACT Perchlorate in the environment is derived from both synthetic and natural sources. Synthetic

  20. Oxygen isotopic evidence for accretion of Earth's water before a high-energy Moon-forming giant impact. (United States)

    Greenwood, Richard C; Barrat, Jean-Alix; Miller, Martin F; Anand, Mahesh; Dauphas, Nicolas; Franchi, Ian A; Sillard, Patrick; Starkey, Natalie A


    The Earth-Moon system likely formed as a result of a collision between two large planetary objects. Debate about their relative masses, the impact energy involved, and the extent of isotopic homogenization continues. We present the results of a high-precision oxygen isotope study of an extensive suite of lunar and terrestrial samples. We demonstrate that lunar rocks and terrestrial basalts show a 3 to 4 ppm (parts per million), statistically resolvable, difference in Δ 17 O. Taking aubrite meteorites as a candidate impactor material, we show that the giant impact scenario involved nearly complete mixing between the target and impactor. Alternatively, the degree of similarity between the Δ 17 O values of the impactor and the proto-Earth must have been significantly closer than that between Earth and aubrites. If the Earth-Moon system evolved from an initially highly vaporized and isotopically homogenized state, as indicated by recent dynamical models, then the terrestrial basalt-lunar oxygen isotope difference detected by our study may be a reflection of post-giant impact additions to Earth. On the basis of this assumption, our data indicate that post-giant impact additions to Earth could have contributed between 5 and 30% of Earth's water, depending on global water estimates. Consequently, our data indicate that the bulk of Earth's water was accreted before the giant impact and not later, as often proposed.

  1. Oxygen isotopic evidence for accretion of Earth’s water before a high-energy Moon-forming giant impact (United States)

    Barrat, Jean-Alix; Sillard, Patrick; Starkey, Natalie A.


    The Earth-Moon system likely formed as a result of a collision between two large planetary objects. Debate about their relative masses, the impact energy involved, and the extent of isotopic homogenization continues. We present the results of a high-precision oxygen isotope study of an extensive suite of lunar and terrestrial samples. We demonstrate that lunar rocks and terrestrial basalts show a 3 to 4 ppm (parts per million), statistically resolvable, difference in Δ17O. Taking aubrite meteorites as a candidate impactor material, we show that the giant impact scenario involved nearly complete mixing between the target and impactor. Alternatively, the degree of similarity between the Δ17O values of the impactor and the proto-Earth must have been significantly closer than that between Earth and aubrites. If the Earth-Moon system evolved from an initially highly vaporized and isotopically homogenized state, as indicated by recent dynamical models, then the terrestrial basalt-lunar oxygen isotope difference detected by our study may be a reflection of post–giant impact additions to Earth. On the basis of this assumption, our data indicate that post–giant impact additions to Earth could have contributed between 5 and 30% of Earth’s water, depending on global water estimates. Consequently, our data indicate that the bulk of Earth’s water was accreted before the giant impact and not later, as often proposed. PMID:29600271

  2. Temperature and atmospheric CO2 concentration estimates through the PETM using triple oxygen isotope analysis of mammalian bioapatite (United States)

    Gehler, Alexander; Gingerich, Philip D.; Pack, Andreas


    The Paleocene-Eocene Thermal Maximum (PETM) is a remarkable climatic and environmental event that occurred 56 Ma ago and has importance for understanding possible future climate change. The Paleocene-Eocene transition is marked by a rapid temperature rise contemporaneous with a large negative carbon isotope excursion (CIE). Both the temperature and the isotopic excursion are well-documented by terrestrial and marine proxies. The CIE was the result of a massive release of carbon into the atmosphere. However, the carbon source and quantities of CO2 and CH4 greenhouse gases that contributed to global warming are poorly constrained and highly debated. Here we combine an established oxygen isotope paleothermometer with a newly developed triple oxygen isotope paleo-CO2 barometer. We attempt to quantify the source of greenhouse gases released during the Paleocene-Eocene transition by analyzing bioapatite of terrestrial mammals. Our results are consistent with previous estimates of PETM temperature change and suggest that not only CO2 but also massive release of seabed methane was the driver for CIE and PETM.

  3. Oxygen and strontium isotope tracing of human migration at the Bell Beaker site Le Tumulus des Sables, France. (United States)

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


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

  4. Isotopic and hydrologic responses of small, closed lakes to climate variability: Hydroclimate reconstructions from lake sediment oxygen isotope records and mass balance models (United States)

    Steinman, Byron A.; Abbott, Mark B.


    Hydroclimate sensitivity simulations were conducted with a lake-catchment hydrologic and isotope mass balance model adapted to two small, closed lakes (Castor and Scanlon) located in the Pacific Northwest. Model simulations were designed to investigate the combined influences of persistent disequilibrium, reddening, and equifinality on lake water and sediment (i.e., biogenic and endogenic carbonate mineral) oxygen isotope (δ18O) values and to provide a basis for quantitative, probabilistic climate reconstructions using lake sediment δ18O records. Simulation results indicate that within closed-basin lakes changes in long-term (i.e., multi-decadal) precipitation amounts produce inconsistent responses in lake water and sediment δ18O values that are strongly influenced by lake basin outseepage and morphometry. Simulations of variable initial conditions in which randomly generated monthly climate data (i.e., precipitation, temperature, and relative humidity) were used to force the model during the equilibration period (which precedes the application of instrumental climate data) demonstrate that Castor Lake and Scanlon Lake have a somewhat limited isotopic 'memory' of ˜10 years. Additional tests conducted using a Monte Carlo ensemble (in which random climate data were used to force the model) combined with δ18O analyses of water samples collected from 2003 to 2011 AD, indicate that within small, closed lakes in the Pacific Northwest November-February precipitation is the strongest seasonal, climatic control on sediment oxygen-isotope values. Further, a Monte Carlo based reconstruction of 20 year average November-February precipitation amounts strongly correlates (R2 = 0.66) to instrumental values from the 20th century (with all observed values falling within modeled 95% prediction limits), indicating that probabilistic, quantitative paleoclimate interpretations of lake sediment δ18O records are attainable.

  5. Oxygen-isotope trends and seawater temperature changes across the Late Cambrian Steptoean positive carbon-isotope excursion (SPICE event) (United States)

    Elrick, M.; Rieboldt, S.; Saltzman, M.; McKay, R.M.


    The globally recognized Late Cambrian Steptoean positive C-isotope excursion (SPICE) is characterized by a 3???-5??? positive ??13C shift spanning thermohaline circulation rates contributed to decreased dissolved O2 concentrations, which enhanced the preservation/burial of Corg causing the positive ??13C shift. ?? 2011 Geological Society of America.

  6. The isotopic composition of valves and organic tissue of diatoms grown in steady state cultures under varying conditions of temperature, light and nutrients. Implications for the interpretation of oxygen isotopes from sedimentary biogenic opal as proxies of environmental variations

    International Nuclear Information System (INIS)

    Kowalczyk, K.


    The oxygen isotopes of diatomaceous silica from marine and freshwater sediments are frequently used as indicators of the palaeotemperature development, particularly in cases where calcareous microfossils are rare or absent. With regard to terrestrial waters it is unknown whether or not palaeotemperature scale can be used in a limnic ecosystem. Due to the fact that the seasonal variations in lakes are larger than in oceans, specific problems arise when working with freshwater sediments. Thus, an understanding of the contribution of the various factors (e.g. temperature, light nutrients, competition) influencing the formation of isotope signals in biogenic opal is a prerequisite for the accurate interpretation of environmental processes. Since it is impossible to examine the influence of a single parameter under natural ecosystem conditions due to permanent changes of the environment, laboratory experiments with single diatom species are needed. Therefore, the aim of this study was to investigate the correlation between the oxygen isotope variations in biogenic opal and different environmental parameters using steady state cultures with diatoms. It should be examined whether or not the different diatom species grown under identical conditions show equal oxygen isotope ratios (species relationship), if variations of the water temperature induce variations of the oxygen isotope ratio (relationship with temperature), variable parameters such as light intensity and nitrate concentration influence the isotope ratio, and if vital effects (e.g. growth rate) lead to variations of the oxygen isotope ratio. (orig.)

  7. The isotopic composition of valves and organic tissue of diatoms grown in steady state cultures under varying conditions of temperature, light and nutrients. Implications for the interpretation of oxygen isotopes from sedimentary biogenic opal as proxies of environmental variations

    Energy Technology Data Exchange (ETDEWEB)

    Kowalczyk, K.


    The oxygen isotopes of diatomaceous silica from marine and freshwater sediments are frequently used as indicators of the palaeotemperature development, particularly in cases where calcareous microfossils are rare or absent. With regard to terrestrial waters it is unknown whether or not palaeotemperature scale can be used in a limnic ecosystem. Due to the fact that the seasonal variations in lakes are larger than in oceans, specific problems arise when working with freshwater sediments. Thus, an understanding of the contribution of the various factors (e.g. temperature, light nutrients, competition) influencing the formation of isotope signals in biogenic opal is a prerequisite for the accurate interpretation of environmental processes. Since it is impossible to examine the influence of a single parameter under natural ecosystem conditions due to permanent changes of the environment, laboratory experiments with single diatom species are needed. Therefore, the aim of this study was to investigate the correlation between the oxygen isotope variations in biogenic opal and different environmental parameters using steady state cultures with diatoms. It should be examined whether or not the different diatom species grown under identical conditions show equal oxygen isotope ratios (species relationship), if variations of the water temperature induce variations of the oxygen isotope ratio (relationship with temperature), variable parameters such as light intensity and nitrate concentration influence the isotope ratio, and if vital effects (e.g. growth rate) lead to variations of the oxygen isotope ratio. (orig.)

  8. Does compression wood affect the climatic signal in carbon and oxygen isotopes of Norway spruce? (United States)

    Janecka, Karolina; Kaczka, Ryszard; Gärtner, Holger; Treydte, Kerstin


    Compression wood is a special tissue present in the trunk of mechanically stressed coniferous trees, more frequently occurring in branches and roots. The main role of the compression wood is to increase the mechanical strength and regain the vertical orientation of a leaning stem. The anatomical structure of compression wood is characterized by (i) rounded tracheids causing intercellular spaces, (ii) a thickened secondary wall (S2 layer) showing helical cavities and (iii) lack of a tertiary cell wall (S3 layer). The aim of our study was to test if and how the presence of compression wood of different intensity influences the climatic signal in stable carbon and oxygen isotopes (δ13C and δ18O) from tree-ring cellulose of Norway spruce trees (Picea abies (L.) Karst.). Four trees growing in the montane zone of the Western Tatra Mountains were selected, and two radii per tree were taken, one with compression wood (CW) and one from the opposite side of a trunk (OW). Four reference trees (REF) without compression wood were sampled from the same valley, however, from a slightly different location. All analyses were performed for the period 1935-1954 with CW present in all trees. It was possible to establish the δ13C and δ18O CW, OW and REF chronologies, however, the EPS values for δ13C chronologies did not reach the established threshold (0.85). In general the comparison between δ13C and δ18O CW, OW and REF chronologies showed statistically significant (p<0.05) correlation values between CW and OW chronologies for both isotopes. The response patterns of δ13C in CW, OW and REF chronologies respectively to climate were quite similar with strongest correlations to temperature, cloud cover and precipitation during summer (Jul-Aug) and to SPEI during late summer - early autumn (Aug-Sep). The correlations between the same climate variables and δ18O of CW, and OW chronologies respectively revealed quite similar response patterns with strongest correlations to

  9. Reconstruction of drip-water δ18O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany

    Directory of Open Access Journals (Sweden)

    T. Kluge


    Full Text Available The geochemical signature of many speleothems used for reconstruction of past continental climates is affected by kinetic isotope fractionation. This limits quantitative paleoclimate reconstruction and, in cases where the kinetic fractionation varies with time, also affects relative paleoclimate interpretations. In carbonate archive research, clumped isotope thermometry is typically used as proxy for absolute temperatures. In the case of speleothems, however, clumped isotopes provide a sensitive indicator for disequilibrium effects. The extent of kinetic fractionation co-varies in Δ47 and δ18O so that it can be used to account for disequilibrium in δ18O and to extract the past drip-water composition. Here we apply this approach to stalagmites from Bunker Cave (Germany and calculate drip-water δ18Ow values for the Eemian, MIS3, and the Holocene, relying on independent temperature estimates and accounting for disequilibrium. Applying the co-variation method to modern calcite precipitates yields drip-water δ18Ow values in agreement with modern cave drip-water δ18Ow of −7.9 ± 0.3‰, despite large and variable disequilibrium effects in both calcite δ18Oc and Δ47. Reconstructed paleo-drip-water δ18Ow values are lower during colder periods (e.g., MIS3: −8.6 ± 0.4‰ and the early Holocene at 11 ka: −9.7 ± 0.2‰ and show higher values during warmer climatic periods (e.g., the Eemian: −7.6 ± 0.2‰ and the Holocene Climatic Optimum: −7.2 ± 0.3‰. This new approach offers a unique possibility for quantitative climate reconstruction including the assessment of past hydrological conditions while accounting for disequilibrium effects.

  10. Forward Modeling of Carbonate Proxy Data from Planktonic Foraminifera using Oxygen Isotope Tracers in a Global Ocean Model (United States)

    Schmidt, Gavin A.


    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.

  11. Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths. (United States)

    Coplen, T. B.; Hanshaw, B. B.


    Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 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 0.01N. 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. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

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

    Energy Technology Data Exchange (ETDEWEB)

    Laukert, Georgi


    Disentangling the sources, distribution and mixing of water masses involved in the transport and transfer of heat and freshwater in the Arctic Mediterranean (i.e. the Arctic Ocean and the Nordic Seas, AM) is critical for the understanding of present and future hydrological changes in the high-latitude regions. This study refines the knowledge of water mass circulation in the AM and provides new insights into the processes occurring on the Arctic shelves and in high-latitude estuaries. A multi-proxy approach is used combining dissolved radiogenic Nd isotopes (ε{sub Nd}), rare earth elements (REEs) and stable oxygen isotopes (δ{sup 18}O) together with standard hydrographic tracers. The sources, distribution and mixing of water masses that circulate in the AM and pass the Fram Strait are assessed through evaluation of dissolved ε{sub Nd} and REE, and δ{sup 18}O data obtained from samples recovered in 2012, 2014 and 2015, and through a compilation and reassessment of literature Nd isotope and concentration data previously reported for other sites within the AM. The Nd isotope and REE distribution in the central Fram Strait and the open AM is shown to primarily reflect the lateral advection of water masses and their mixing, whereas seawater-particle interactions exert important control only above the shelf regions. New insights into the processes occurring in high latitude estuaries are provided by dissolved Nd isotope and REE compositions together with δ{sup 18}O data for the Laptev Sea based on filtered samples recovered in 2012, 2013 and 2014. A combination of REE removal through coagulation of nanoparticles and colloids and REE redistribution within the water column through formation and melting of sea ice and river ice is suggested to account for the distribution of all REEs, while no REE release from particles is observed. The ice-related processes contribute to the redistribution of other elements and ultimately may also affect primary productivity in high

  13. Non-destructive estimates of soil carbonic anhydrase activity and associated soil water oxygen isotope composition (United States)

    Jones, Sam P.; Ogée, Jérôme; Sauze, Joana; Wohl, Steven; Saavedra, Noelia; Fernández-Prado, Noelia; Maire, Juliette; Launois, Thomas; Bosc, Alexandre; Wingate, Lisa


    The contribution of photosynthesis and soil respiration to net land-atmosphere carbon dioxide (CO2) exchange can be estimated based on the differential influence of leaves and soils on budgets of the oxygen isotope composition (δ18O) of atmospheric CO2. To do so, the activity of carbonic anhydrases (CAs), a group of enzymes that catalyse the hydration of CO2 in soils and plants, needs to be understood. Measurements of soil CA activity typically involve the inversion of models describing the δ18O of CO2 fluxes to solve for the apparent, potentially catalysed, rate of CO2 hydration. This requires information about the δ18O of CO2 in isotopic equilibrium with soil water, typically obtained from destructive, depth-resolved sampling and extraction of soil water. In doing so, an assumption is made about the soil water pool that CO2 interacts with, which may bias estimates of CA activity if incorrect. Furthermore, this can represent a significant challenge in data collection given the potential for spatial and temporal variability in the δ18O 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 inferring the rate of CO2 hydration and the δ18O of soil water from the relationship between the δ18O of CO2 fluxes and the δ18O of CO2 at the soil surface measured at different ambient CO2 conditions. This approach was tested through laboratory incubations of air-dried soils that were re-wetted with three waters of different δ18O. Gas exchange measurements were made on these soils to estimate the rate of hydration and the δ18O of soil water, followed by soil water extraction to allow for comparison. Estimated rates of CO2 hydration were 6.8-14.6 times greater than the theoretical uncatalysed rate of hydration, indicating that CA were active in these soils. Importantly, these estimates were not significantly different among water treatments, suggesting

  14. Silicon in Mars' Core: A Prediction Based on Mars Model Using Nitrogen and Oxygen Isotopes in SNC Meteorites (United States)

    Mohapatra, R. K.; Murty, S. V. S.


    Chemical and (oxygen) isotopic compositions of SNC meteorites have been used by a number of workers to infer the nature of precursor materials for the accretion of Mars. The idea that chondritic materials played a key role in the formation of Mars has been the central assumption in these works. Wanke and Dreibus have proposed a mixture of two types of chondritic materials, differing in oxygen fugacity but having CI type bulk chemical composition for the nonvolatile elements, for Mars' precursor. But a number of studies based on high pressure and temperature melting experiments do not favor a CI type bulk planet composition for Mars, as it predicts a bulk planet Fe/Si ratio much higher than that reported from the recent Pathfinder data. Oxygen forms the bulk of Mars (approximately 40% by wt.) and might provide clues to the type of materials that formed Mars. But models based on the oxygen isotopic compositions of SNC meteorites predict three different mixtures of precursor materials for Mars: 90% H + 10% CM, 85% H + 11% CV + 4% CI and 45% EH + 55% H. As each of these models has been shown to be consistent with the bulk geophysical properties (such as mean density, and moment of inertia factor) of Mars, the nature of the material that accreted to form Mars remains ambiguous.

  15. Oxygen isotopic ratios in quartz as an indicator of provenance of dust

    International Nuclear Information System (INIS)

    Jackson, M.L.


    Quartz was isolated in the long range aerosol size range (fine silt, 1-10 μm in diameter) from atmospheric aerosols, wind-erosive soils, soil silts, shales, and Pacific pelagic sediments of the Northern and Southern Hemispheres, to trace their provenance or origin, as part of a study of dust mineral sequestering of 137 Cs and other products of nuclear fission. The oxygen isotopic ratio ( 18 O/ 16 O) was determined by mass spectrometry. The provenance has been established for this fine silt fraction which reflects the relative proportion of two classes of quartz source: (a) weathering of igneous and metamorphic rocks (high temperature origin and low 18 O/ 16 O ratio) and (b) of quartz crystallized in cherts and overgrowths (low temperature origin and high 18 O/ 16 O ratio). This quartz mixing ratio is a basic model or paradigm. Analyses of present day atmospheric aerosols and eolian-derived soils, Pacific pelagic sediments, and now-raised Phanerozoic marine sediments show that the Northern and Southern Hemispheres have separate large-scale reservoirs of the fine grain sizes that contribute to aerosol dusts. These can be identified by distinctive values of 18 O/ 16 O ratios of the quartz therein. The difference in quartz delta 18 O value in parts per thousand per ml ( 0 / 00 of about 12 +- 2 0 / 00 in Southern Hemisphere mixed detrital sediments and about 19 +- 2 0 / 00 in those of the Northern Hemisphere (for constant size, the 1-10 μm size fraction) results from the presence of a considerably larger proportion of quartz having low-temperature origin and higher delta 18 O values (chert, silica overgrowths, etc.) in the Northern Hemisphere reservoirs. The early paleoclimatic and paleogeochemical differences remain the control of the North-South Hemisphere difference in delta 18 O values in long-range aerosol sized quartz

  16. Nontrivial origin for the large nuclear radii of dripline oxygen isotopes (United States)

    Itagaki, N.; Tohsaki, A.


    The anomalous large radii are exotic phenomena observed around the neutron dripline. Around the neutron dripline, the weak binding of the last bound neutron(s) causes the drastic increase of the radius, which is called the neutron halo structure. Although the nucleus 24O is located at the dripline of oxygen isotopes, the separation energies of one and two neutron(s) are 4.19 MeV and 6.92 MeV, respectively. In spite of this sufficient binding, the enhancement of the matter radius is observed. In this study, we microscopically describe the structure change of the 22O core in 24O and explain the observed large radius based on the cluster model. Two degrees of freedom for the large radius, the relative distances among four α clusters and the size of each α cluster, are examined, where the Tohsaki interaction, which has finite range three-body terms, is employed. The nucleus 22O has smaller α -α distance compared with 16O owing to the gluelike effect of six valence neutrons around four α clusters. When two neutrons are added at the center of 22O, the expansion of each α cluster is energetically more favored than increasing the α -α distances for reducing the kinetic energy of the neutrons. The calculated rms matter radii of 22O and 24O are 2.75 fm and 2.92 fm, respectively. Although these are slightly smaller than the experimental values, the jump at 24O from 22O is reproduced.

  17. Preservation of NOM-metal complexes in a modern hyperalkaline stalagmite: Implications for speleothem trace element geochemistry (United States)

    Hartland, Adam; Fairchild, Ian J.; Müller, Wolfgang; Dominguez-Villar, David


    We report the first quantitative study of the capture of colloidal natural organic matter (NOM) and NOM-complexed trace metals (V, Co, Cu, Ni) in speleothems. This study combines published NOM-metal dripwater speciation measurements with high-resolution laser ablation ICPMS (LA-ICPMS) and sub-annual stable isotope ratio (δ18O and δ13C), fluorescence and total organic carbon (TOC) analyses of a fast-growing hyperalkaline stalagmite (pH ˜11) from Poole’s Cavern, Derbyshire UK, which formed between 1997 and 2008 AD. We suggest that the findings reported here elucidate trace element variations arising from colloidal transport and calcite precipitation rate changes observed in multiple, natural speleothems deposited at ca. pH 7-8. We find that NOM-metal(aq) complexes on the boundary between colloidal and dissolved (˜1 nm diameter) show an annual cyclicity which is inversely correlated with the alkaline earth metals and is explained by calcite precipitation rate changes (as recorded by kinetically-fractionated stable isotopes). This relates to the strength of the NOM-metal complexation reaction, resulting in very strongly bound metals (Co in this system) essentially recording NOM co-precipitation (ternary complexation). More specifically, empirical partition coefficient (Kd) values between surface-reactive metals (V, Co, Cu, Ni) [expressed as ratio of trace element to Ca ratios in calcite and in solution] arise from variations in the ‘free’ fraction of total metal in aqueous solution (fm). Hence, differences in the preservation of each metal in calcite can be explained quantitatively by their complexation behaviour with aqueous NOM. Differences between inorganic Kd values and field measurements for metal partitioning into calcite occur where [free metal] ≪ [total metal] due to complexation reactions between metals and organic ligands (and potentially inorganic colloids). It follows that where fm ≈ 0, apparent inorganic Kd app values are also ≈0, but the

  18. Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

    International Nuclear Information System (INIS)

    Tichomirowa, Marion; Junghans, Manuela


    Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO 4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O 2 ) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O 2 ) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO 4 and water was observed over a pH range of 0-2 only at 50 deg. C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 deg. C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T ≤ 25 deg. C, pH ≥ 3) for decades. Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O 2 to pyrite surface sites. The sorption of molecular O 2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO 4 . The calculated bulk contribution of atmospheric O 2 in the dissolved SO 4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O 2 in the early-formed sulfates, chemisorption and electron transfer of molecular O 2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction

  19. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO2 surface: The case of terminal oxygen atom exchange (United States)

    Kevorkyants, Ruslan; Sboev, Mikhail. N.; Chizhov, Yuri V.


    Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between 16O18O and terminal oxygen atom of a defect TiO2 surface, which is modeled by amorphous Ti8O16 nanocluster in excited S1 electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O3- chemisorption species match well EPR data on O2 adsorption on UV-irradiated nanocrystalline TiO2. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction's mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VOx/TiO2 reported earlier.

  20. Late Quaternary environmental changes inferred from stable carbon, nitrogen and oxygen isotope values at Teshekpuk Lake, North Slope, Alaska (United States)

    Randall, J. J.; Booth, A. L.; Wooller, M. J.; Jones, B. M.; Gaglioti, B.


    Global surface air temperatures increased by ~0.74°C between 1906-2005, with average temperatures in the Arctic increasing at almost twice the rate as the rest of the planet. The Arctic Coastal Plain of Alaska is particularly susceptible and responsive to these fluctuations in climate. Better understanding both short- and long-term climate variability is important as this ecosystem provides food and habitat for hundreds of thousands of migratory birds and caribou. Despite the ecological importance of the Arctic Coastal Plain, relatively few studies exist that provide multi-proxy paleoclimatic data for the region and thus the rate at which climate and ecosystems have changed during the past century lack a longer term context. Here we present stable carbon and nitrogen isotope values from the analysis of bulk organic matter in samples from a ~6 m sediment core from Teshekpuk Lake, 80 miles southeast of Barrow, Alaska. AMS 14C dates on a nearby core indicate a basal age of ~15 kyr. The relatively low C/N values (mean base of the core to peaks of ~-23‰ between ~10 and 8 kyr, inferring highs in lake production during this time. We also present stable oxygen isotope values from analyses of chironomid and aquatic invertebrate chitin preserved in the core. Non-biting midges in the family Chironomidae begin their lifecycles in freshwater. During their larval stages chironomids synthesize and molt chitinous head capsules. These head capsules record the oxygen isotopic composition of the lake water present at the time of synthesis, and are well preserved in lake sediments. These isotopic results are interpreted in terms of other recent isotope data from the north slope of Alaska in addition to a pollen reconstruction from the same core and their implications in terms of past environmental changes.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail:; Sboev, Mikhail N.; Chizhov, Yuri V.


    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  2. Sino-orbital spelunking: stalagmite formation in fibrous dysplasia with dystrophic calcification. (United States)

    Katz, Steven E; Das, Subinoy; Wakely, Paul E; Kirsch, Claudia


    Fibrous dysplasia (FD) involving the mid-face may be associated with cystic and other secondary changes that make diagnosis more difficult. We present a case of FD associated with a remote history of blunt facial trauma and extensive cystic changes involving the medial orbit and sinuses. An endoscopic exploration revealed "stalagmites" along the floor of the cystic cavity that were consistent with dystrophic calcification. This case was unusual given the degree of dystrophic calcification and the presence of sino-orbital stalagmites within the cystic cavity. Radiologic and pathologic features of the stalagmites are characterized.

  3. Oxygen-isotope, X-ray-diffraction and scanning-electron-microscope examinations of authigenic-layer-silicate minerals from Mississippian and Pennsylvanian sandstones in the Michigan Basin (United States)

    Zacharias, K.F.; Sibley, D.F.; Westjohn, D.B.; Weaver, T. L.


    Oxygen-isotope compositions of authigenic-layer silicates (scanning-electron-microscope examinations, and X-ray diffractograms show that chlorite and kaolinite are the most common authigenic-layer silicates in Mississippian sandstones. The range of oxygen-isotope compositions of chlorite and kaolinite are +10.3 to +11.9 and +12.9 to +19.3 pars per thousand (per mil) (relative to Standard Mean Ocean Water), respectively. Kaolinite is the only authigenic-isotopic compositions of kaolinite range from +16.8 to +19.0 per mil.

  4. Ion Microprobe Measurements of Comet Dust and Implications for Models of Oxygen Isotope Heterogeneity in the Solar System (United States)

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


    The oxygen isotopic compositions of anhydrous minerals in carbonaceous chondrites reflect mixing between a O-16-rich and O-17, O18-rich reservoir. The UV photodissociation of CO (i.e. selfshielding) has been proposed as a mass-independent mechanism for producing these isotopically distinct reservoirs. Self-shielding models predict the composition for the CO gas reservoir to be O-16-rich, and that the accreting primordial dust was in isotopic equilibrium with the gaseous reservoir [1, 2]. Self-shielding also predicts that cometary water, presumed to represent the O-17, O-18-rich reservoir, should be enriched in O-17 and O-18, with compositions of 200 -1000per mille, and that the interaction with this O-17, O-18-rich H2O reservoir altered the compositions of the primordial dust toward planetary values. The bulk composition of the solar nebula, which may be an approximation to the 16O-rich gaseous reservoir, has been constrained by the Genesis results [3]. However, material representing the O-17, O-18-rich end-member is rare [4], and dust representing the original accreting primordial dust has been challenging to conclusively identify in current collections. Anhydrous dust from comets, which accreted in the distal cold regions of the nebula at temperatures below approximately 30K, may provide the best opportunity to measure the oxygen isotope composition of primordial dust. Chondritic porous interplanetary dust particles (CP-IDPs) have been suggested as having cometary origins [5]; however, until direct comparisons with dust from a known comet parent body were made, link between CP-IDPs and comets remained circumstantial. Oxygen isotope analyses of particles from comet 81P/Wild 2 collected by NASA's Stardust mission have revealed surprising similarities to minerals in carbonaceous chondrites which have been interpreted as evidence for large scale radial migration of dust components from the inner solar nebula to the accretion regions of Jupiter- family comets [6

  5. Impact of Leaf Traits on Temporal Dynamics of Transpired Oxygen Isotope Signatures and Its Impact on Atmospheric Vapor (United States)

    Dubbert, Maren; Kübert, Angelika; Werner, Christiane


    Oxygen isotope signatures of transpiration (δE) are powerful tracers of water movement from plant to global scale. However, a mechanistic understanding of how leaf morphological/physiological traits effect δE is missing. A laser spectrometer was coupled to a leaf-level gas-exchange system to measure fluxes and isotopic signatures of plant transpiration under controlled conditions in seven distinct species (Fagus sylvatica, Pinus sylvestris, Acacia longifolia, Quercus suber, Coffea arabica, Plantago lanceolata, Oxalis triangularis). We analyzed the role of stomatal conductance (gs) and leaf water content (W) on the temporal dynamics of δE following changes in relative humidity (rH). Changes in rH were applied from 60 to 30% and from 30 to 60%, which is probably more than covering the maximum step changes occurring under natural conditions. Further, the impact of gs and W on isotopic non-steady state isofluxes was analyzed. Following changes in rH, temporal development of δE was well described by a one-pool modeling approach for most species. Isofluxes of δE were dominantly driven by stomatal control on E, particularly for the initial period of 30 min following a step change. Hence, the deviation of isofluxes from isotopic steady state can be large, even though plants transpire near to isotopic steady state. Notably, not only transpiration rate and stomatal conductance, but also the leaf traits stomatal density (as a measure of gmax) and leaf water content are significantly related to the time constant (τ) and non-steady-state isofluxes. This might provide an easy-to-access means of a priori assumptions for the impact of isotopic non-steady-state transpiration in various ecosystems. We discuss the implications of our results from leaf to ecosystem scale. PMID:28149303

  6. Chondrule heritage and thermal histories from trace element and oxygen isotope analyses of chondrules and amoeboid olivine aggregates (United States)

    Jacquet, Emmanuel; Marrocchi, Yves


    We report combined oxygen isotope and mineral-scale trace element analyses of amoeboid olivine aggregates (AOA) and chondrules in ungrouped carbonaceous chondrite, Northwest Africa 5958. The trace element geochemistry of olivine in AOA, for the first time measured by LA-ICP-MS, is consistent with a condensation origin, although the shallow slope of its rare earth element (REE) pattern is yet to be physically explained. Ferromagnesian silicates in type I chondrules resemble those in other carbonaceous chondrites both geochemically and isotopically, and we find a correlation between 16O enrichment and many incompatible elements in olivine. The variation in incompatible element concentrations may relate to varying amounts of olivine crystallization during a subisothermal stage of chondrule-forming events, the duration of which may be anticorrelated with the local solid/gas ratio if this was the determinant of oxygen isotopic ratios as proposed recently. While aqueous alteration has depleted many chondrule mesostases in REE, some chondrules show recognizable subdued group II-like patterns supporting the idea that the immediate precursors of chondrules were nebular condensates.

  7. The source of phosphate in the oxidation zone of ore deposits: Evidence from oxygen isotope compositions of pyromorphite (United States)

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


    Pyromorphite (Pb5[PO4]3Cl) is an abundant mineral in oxidized zones of lead-bearing ore deposits and due to its very low solubility product effectively binds Pb during supergene alteration of galena (PbS). The capacity of a soil or near-surface fluid to immobilize dissolved Pb depends critically on the availability of phosphate in this soil or fluid. Potential phosphorus sources in soil include (i) release during biological processes, i.e. leaching from litter/lysis of microbial cells (after intracellular enzyme activity) in soil and hydrolysis from soil organic matter by extracellular enzymes and (ii) inorganic phosphate from the dissolution of apatite in the adjacent basement rocks. Intracellular enzyme activity in plants/microorganisms associated with kinetic fractionation produces an oxygen isotope composition distinctly different from inorganic processes in soil. This study presents the first oxygen isotope data for phosphate (δ18OP) in pyromorphite and a comprehensive data set for apatite from crystalline rocks. We investigated 38 pyromorphites from 26 localities in the Schwarzwald (Southwest Germany) and five samples from localities outside the Schwarzwald in addition to 12 apatite separates from gneissic and granitic host rocks. Pyromorphites had δ18OP values between +10‰ and +19‰, comparable to literature data on δ18OP in the readily available P fraction in soil (resin-extractable P) from which minerals potentially precipitate in soils. δ18OP values below the range of equilibrium isotope fractionation can be attributed either to apatites that formed geochemically (δ18OP of apatites:+6‰ to +9‰) or less likely to biological processes (extracellular enzyme activity). However, for most of our samples isotopic equilibrium with ambient water was indicated, which suggests biological activity. Therefore, we conclude that the majority of pyromorphites in oxidized zones of ore bodies formed from biologically cycled phosphate. This study highlights that

  8. Water vapour source impacts on oxygen isotope variability in tropical precipitation during Heinrich events

    Directory of Open Access Journals (Sweden)

    S. C. Lewis


    Full Text Available Water isotope records such as speleothems provide extensive evidence of past tropical hydrological changes. During Heinrich events, isotopic changes in monsoon regions have been interpreted as implying a widespread drying through the Northern Hemisphere tropics and an anti-phased precipitation response in the south. Here, we examine the sources of this variability using a water isotope-enabled general circulation model, Goddard Institute for Space Studies ModelE. We incorporate a new suite of vapour source distribution tracers to help constrain the impact of precipitation source region changes on the isotopic composition of precipitation and to identify nonlocal amount effects. We simulate a collapse of the North Atlantic meridional overturning circulation with a large freshwater input to the region as an idealised analogue to iceberg discharge during Heinrich events. An increase in monsoon intensity, defined by vertical wind shear, is modelled over the South American domain, with small decreases simulated over Asia. Simulated isotopic anomalies agree well with proxy climate records, with lighter isotopic values simulated over South America and enriched values across East Asia. For this particular abrupt climate event, we identify which climatic change is most likely linked to water isotope change – changes in local precipitation amount, monsoon intensity, water vapour source distributions or precipitation seasonality. We categorise individual sites according to the climate variability that water isotope changes are most closely associated with, and find that the dominant isotopic controls are not consistent across the tropics – simple local explanations, in particular, fall short of explaining water isotope variability at all sites. Instead, the best interpretations appear to be site specific and often regional in scale.

  9. Teleconnection among Asian Summer Monsoon, ENSO and PDO revealed by instrumental and historic records as well as an annual resolution stalagmite record from Lianhua Cave, northwestern Hunan, China (United States)

    Li, H.; Yin, J.; Yuan, D.; Li, T.


    A 33-cm long aragonite stalagmite, LHN-1, from Lianhua Cave (29°09'N, 109°33'E , 459m a.s.l.) in NW Hunan Province of China has been dated by ICP-MS 230Th/U method. The 14 230Th/U dates with less than ×37 years uncertainties yield excellent chronology, showing that the stalagmite grew continuously over the past 3400 years. The 0.1-mm sampling interval for stable isotope analyses provides annual resolution δ18O and δ13C records of the LHN-1 stalagmite. Up-to-dated, a total of 887 measurements for δ18O and δ13C have been made, which reveal detailed monsoonal climatic changes during the past 1000 years. The average values of δ18O and δ13C are -5.83 (‰, PDB) and -3.29 (‰, PDB), respectively. For the youngest part of the δ18O record, we have compared with the instrumentally meteorological records and historical dryness/wetness indexes from the studying area, indicating that stalagmite δ18O on annual-to-decadal scales reflects mainly rainfall change in the monsoonal area, with lighter δ18O reflecting wetter condition. The comparison of the δ18O with the East Asian Summer Monsoon (EASM) index since AD 1850 adopted by IPCC (2007) illustrates that lighter stalagmite δ18O corresponds to stronger EASM. Taking the average δ18O value of the 1000-yr record as an average climatic condition, we have found that the δ18O values during AD 1050~1100, 1125~1225, 1300~1350, 1430~1630 and 1900~1960 are lighter than the average, reflecting stronger EASM and wetter condition. The δ18O values during AD 1100~1125, 1225~1300, 1350~1430, 1630~1900 and 1960 to the present are heavier than the average, indicating weak EASM and drier condition. On decadal-to-centennial scales, the δ13C variations generally follow that of δ18O which probably demonstrates that vegetation above the cave controls the δ13C variations. Further comparisons of the δ18O, EASM, ENSO and PDO show that a negative SOI (El Nino phase) correlates warm PDO phase and higher N. Pacific pressure, resulting

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

    International Nuclear Information System (INIS)

    Taylor, B.E


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

  11. Oxygen-isotopic Compositions of Relict and Host Grains in Chondrules in the Yamato 81020 CO3.0 Chondrite (United States)

    Kunihiro, Takuya; Rubin, Alan E.; McKeegan, Kevin D.; Wasson, John T.


    We report the oxygen-isotope compositions of relict and host olivine grains in six high-FeO porphyritic olivine chondrules in one of the most primitive carbonaceous chondrites, CO3.0 Yamato 81020. Because the relict grains predate the host phenocrysts, microscale in situ analyses of O-isotope compositions can help assess the degree of heterogeneity among chondrule precursors and constrain the nebular processes that caused these isotopic differences. In five of six chondrules studied, the DELTA O-17 (=delta O-17 - 0.52 (raised dot) delta O-18) compositions of host phenocrysts are higher than those in low-FeO relict grains; the one exception is for a chondrule with a moderately high-FeO relict. Both the fayalite compositions as well as the O-isotope data support the view that the low-FeO relict grains formed in a previous generation of low-FeO porphyritic chondrules that were subsequently fragmented. It appears that most low-FeO porphyritic chondrules formed earlier than most high-FeO porphyritic chondrules, although there were probably some low-FeO chondrules that formed during the period when most high-FeO chondrules were forming.

  12. FeO-rich silicates in the Sahara 97159 (EH3) enstatite chondrite: Mineralogy, oxygen isotopic compositions, and origin (United States)

    Kimura, M.; Hiyagon, H.; Lin, Y.; Weisberg, M. K.


    We report the mineralogy and oxygen isotopic compositions of FeO-rich silicates in the Sahara 97159 EH3 chondrite. This component is referred to as FeO-rich because it contains substantially more FeO than the characteristic FeO-poor silicates in the highly reduced enstatite meteorites. These FeO-rich silicates are mostly low-Ca pyroxene (Fs5­35) and their compositions suggest an origin under more oxidizing conditions, like those for the ordinary chondrites. However, the mafic silicates in ordinary and carbonaceous chondrites are dominantly olivine, and the FeO-rich silicates in the E chondrites are less commonly olivine. The oxygen isotopic compositions of the FeO- rich silicates are indistinguishable from those of FeO-poor silicates in Sahara 97159. These observations suggest that both the FeO-rich silicates and the FeO-poor silicates in EH chondrites formed from the same oxygen reservoir where redox conditions varied widely.

  13. High-precision measurement of (186)Os/(188)Os and (187)Os/(188)Os: isobaric oxide corrections with in-run measured oxygen isotope ratios. (United States)

    Chu, Zhu-Yin; Li, Chao-Feng; Chen, Zhi; Xu, Jun-Jie; Di, Yan-Kun; Guo, Jing-Hui


    We present a novel method for high precision measurement of (186)Os/(188)Os and (187)Os/(188)Os ratios, applying isobaric oxide interference correction based on in-run measurements of oxygen isotopic ratios. For this purpose, we set up a static data collection routine to measure the main Os(16)O3(-) ion beams with Faraday cups connected to conventional 10(11) amplifiers, and (192)Os(16)O2(17)O(-) and (192)Os(16)O2(18)O(-) ion beams with Faraday cups connected to 10(12) amplifiers. Because of the limited number of Faraday cups, we did not measure (184)Os(16)O3(-) and (189)Os(16)O3(-) simultaneously in-run, but the analytical setup had no significant influence on final (186)Os/(188)Os and (187)Os/(188)Os data. By analyzing UMd, DROsS, an in-house Os solution standard, and several rock reference materials, including WPR-1, WMS-1a, and Gpt-5, the in-run measured oxygen isotopic ratios were proven to present accurate Os isotopic data. However, (186)Os/(188)Os and (187)Os/(188)Os data obtained with in-run O isotopic compositions for the solution standards and rock reference materials show minimal improvement in internal and external precision, compared to the conventional oxygen correction method. We concluded that, the small variations of oxygen isotopes during OsO3(-) analytical sessions are probably not the main source of error for high precision Os isotopic analysis. Nevertheless, use of run-specific O isotopic compositions is still a better choice for Os isotopic data reduction and eliminates the requirement of extra measurements of the oxygen isotopic ratios.

  14. Unraveling the photocatalytic mechanisms on TiO2 surfaces using the oxygen-18 isotopic label technique. (United States)

    Pang, Xibin; Chen, Chuncheng; Ji, Hongwei; Che, Yanke; Ma, Wanhong; Zhao, Jincai


    During the last several decades TiO2 photocatalytic oxidation using the molecular oxygen in air has emerged as a promising method for the degradation of recalcitrant organic pollutants and selective transformations of valuable organic chemicals. Despite extensive studies, the mechanisms of these photocatalytic reactions are still poorly understood due to their complexity. In this review, we will highlight how the oxygen-18 isotope labeling technique can be a powerful tool to elucidate complicated photocatalytic mechanisms taking place on the TiO2 surface. To this end, the application of the oxygen-18 isotopic-labeling method to three representative photocatalytic reactions is discussed: (1) the photocatalytic hydroxylation of aromatics; (2) oxidative cleavage of aryl rings on the TiO2 surface; and (3) photocatalytic decarboxylation of saturated carboxylic acids. The results show that the oxygen atoms of molecular oxygen can incorporate into the corresponding products in aqueous solution in all three of these reactions, but the detailed incorporation pathways are completely different in each case. For the hydroxylation process, the O atom in O2 is shown to be incorporated through activation of O2 by conduction band electrons. In the cleavage of aryl rings, O atoms are inserted into the aryl ring through the site-dependent coordination of reactants on the TiO2 surface. A new pathway for the decarboxylation of saturated carboxylic acids with pyruvic acid as an intermediate is identified, and the O2 is incorporated into the products through the further oxidation of pyruvic acid by active species from the activation of O2 by conduction band electrons.

  15. Meteoric water in normal fault systems: Oxygen and hydrogen isotopic measurements on authigenic phases in brittle fault rocks (United States)

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


    The nature of fluid circulation systems in normal fault systems is fundamental to understanding the nature of fluid movement within the upper crust, and has important implications for the on-going controversy about the strength of faults. Authigenic phases in clay gouges and fault breccias record the isotopic signature of the fluids they formed in equilibrium with, and can be used to understand the ‘plumbing system’ of brittle fault environments. We obtained paired oxygen and hydrogen isotopic measurements on authigenic illite and/or smectite in clay gouge from normal faults in two geologic environments, 1.) low-angle normal faults (Ruby Mountains detachment, NV; Badwater Turtleback, CA; Panamint range-front detachment; CA; Amargosa detachment; CA; Waterman Hills detachment, CA), and 2.) An intracratonic high-angle normal fault (Moab Fault, UT). All authigenic phases in these clay gouges are moderately light isotopically with respect to oxygen (illite δ18O -2.0 - + 11.5 ‰ SMOW, smectite δ18O +3.6 and 17.9 ‰) and very light isotopically with respect to hydrogen (illite δD -148 to -98 ‰ SMOW, smectite δD -147 to -92 ‰). Fluid compositions calculated from the authigenic clays at temperatures of 50 - 130 ○C (as indicated by clay mineralogy) indicate that both illite and smectite in normal fault clay gouge formed in the presence of near-pristine to moderately-evolved meteoric fluids and that igneous or metamorphic fluids are not involved in clay gouge formation in these normal fault settings. We also obtained paired oxygen and hydrogen isotopic measurements on chlorites derived from footwall chlorite breccias in 4 low-angle normal fault detachment systems (Badwater and Mormon Point Turtlebacks, CA, the Chemehuevi detachment, CA, and the Buckskin-Rawhide detachment, AZ). All chlorites are isotopically light to moderately light with respect to oxygen (δ18O +0.29 to +8.1 ‰ SMOW) and very light with respect to hydrogen (δD -97 to -113 ‰) and indicate

  16. Stable carbon and oxygen isotope signatures in molluscan shells under ocean acidification (United States)

    Nishida, K.; Hayashi, M.; Suzuki, A.; Sato, M.; Nojiri, Y.


    Stable carbon and oxygen isotope compositions (δ13C, δ18O) of biogenic carbonate have been widely used for many paleoclimate, paleoecological, and biomineralization studies. δ13C of molluscan shells reflects the mixing of δ13C of dissolved inorganic carbon (DIC) of seawater and respiratory carbon. Previous studies reported physiological effects on molluscs by ocean acidification, and thus the metabolic changes could potentially appear in shell δ13C as changes in a fraction of two carbon sources. In addition, shell δ18O, a commonly used proxy of seawater temperature and seawater δ18O, is also affected by seawater carbonate chemistry. As changes in the marine carbonate system, such as pH and pCO2, have occurred in the past 300 million years, to estimate pH effect on paleotemperature reconstruction is important. Here, we experimentally examined acidification effects on shell δ13C and δ18O of two species of clams for understanding of environmental and physiological proxies. Juvenile specimens of bloody clam Scapharca broughtonii and Japanese surf clam Pseudocardium sachalinense were cultured at five (400, 600, 800, 1000, and 1200 µatm, P. sachalinense) or six (280, 400, 600, 800, 1000, and 1200 µatm, S. broughtonii) different pCO2 levels using CO2 control system of the Demonstration Laboratory, MERI, Japan. Significant negative correlations between shell δ13C and pH appeared in S. broughtonii, which showed non-significant pH effects on calcification, and the slope of the relationship of shell carbonate was lower than that of seawater DIC. On the other hand, in P. sachalinense which showed a decrease in calcification at low-pH treatment, the slopes of the relationship between shell δ13C and pH was roughly the same as that of seawater DIC. Thus, the extrapallial fluid of P. sachalinense might more strongly affected by acidified seawater than S. broughtonii. The results of two species might be attributable to differences in physiological responses to

  17. The oxygen isotope composition of baddeleyite and a test of crystal orientation effects during SIMS analysis (United States)

    Ibanez-Mejia, M.; DesOrmeau, J. W.; Eddy, M. P.; Kitajima, K.; Valley, J. W.


    Baddeleyite, the monoclinic polymorph of ZrO2, is a relatively common accessory phase in undersaturated and alkaline igneous rocks that is rapidly developing into a widely-used tool for studying the age and initial 176Hf/177Hf composition of many terrestrial and planetary rocks that typically lack zircon. The prospect of combining U-Pb-Hf data from baddeleyite with δ18O information, as regularly done with zircon, could prove a very powerful addition to the `analytical toolbox' of the igneous petrologist and for studies of crust and mantle evolution. However, the oxygen isotope systematics of this mineral remain poorly explored, as are the potential analytical hurdles involved in obtaining accurate spatially-resolved δ18O data by SIMS. Here, we report laser fluorination δ18O measurements from two baddeleyite megacrysts from Kovdor (δ18O = 0.24 ± 0.11 ‰) and Phalaborwa (4.58 ± 0.11 ‰), which were subsequently analyzed by SIMS to explore their compositional homogeneity and potential as reference materials for correcting instrumental mass fractionation (IMF). Randomly oriented grain fragments analyzed by SIMS were subsequently mapped using high-resolution EBSD, such that the incidence angle of the Cs+ primary ion beam relative to the baddeleyite crystallographic axes could be determined for each spot. We found that: a) δ18O values for both crystals reproduce fairly well, but several apparent outliers (ca. 10% of all data) were measured with no evident correlation to orientation, cracks or inclusions, suggesting these might not be ideal standards; b) there is a systematic difference in mean measured IMFs of ca. 0.6 ‰ between the two baddeleyite crystals; c) mean 16OH/16O values for Phalaborwa (2.5x10-4) are significantly higher than those of Kovdor (2.9x10-6), suggesting that different degrees of radiation damage affect IMF; and d) there is no statistically significant correlation in our dataset (n= 96 spot analyses) between IMF and crystallographic

  18. Bunker Cave stalagmites: an archive for central European Holocene climate variability

    Directory of Open Access Journals (Sweden)

    J. Fohlmeister


    Full Text Available Holocene climate was characterised by variability on multi-centennial to multi-decadal time scales. In central Europe, these fluctuations were most pronounced during winter. Here we present a record of past winter climate variability for the last 10.8 ka based on four speleothems from Bunker Cave, western Germany. Due to its central European location, the cave site is particularly well suited to record changes in precipitation and temperature in response to changes in the North Atlantic realm. We present high-resolution records of δ18O, δ13C values and Mg/Ca ratios. Changes in the Mg/Ca ratio are attributed to past meteoric precipitation variability. The stable C isotope composition of the speleothems most likely reflects changes in vegetation and precipitation, and variations in the δ18O signal are interpreted as variations in meteoric precipitation and temperature. We found cold and dry periods between 8 and 7 ka, 6.5 and 5.5 ka, 4 and 3 ka as well as between 0.7 and 0.2 ka. The proxy signals in the Bunker Cave stalagmites compare well with other isotope records and, thus, seem representative for central European Holocene climate variability. The prominent 8.2 ka event and the Little Ice Age cold events are both recorded in the Bunker Cave record. However, these events show a contrasting relationship between climate and δ18O, which is explained by different causes underlying the two climate anomalies. Whereas the Little Ice Age is attributed to a pronounced negative phase of the North Atlantic Oscillation, the 8.2 ka event was triggered by cooler conditions in the North Atlantic due to a slowdown of the thermohaline circulation.

  19. Evaluation of perchlorate sources in the Rialto-Colton and Chino California subbasins using chlorine and oxygen isotope ratio analysis (United States)

    Hatzinger, Paul B.; Böhlke, John Karl; Izbicki, John; Teague, Nicholas F.; Sturchio, Neil C.


    Perchlorate (ClO4-) in groundwater can be from synthetic or natural sources, the latter of which include both historical application of imported nitrate fertilizers from the Atacama Desert of Chile and naturally deposited ClO4- that forms atmospherically and accumulates in arid regions such as the southwestern US. The objective of this study was to evaluate the use of isotopic data to distinguish sources of ClO4- in groundwater in a specific region of the Rialto-Colton and Chino, CA groundwater subbasins (Study Area). This region includes two groundwater ClO4- plumes emanating from known military/industrial source areas, and a larger area outside of these plumes having measurable ClO4-. Perchlorate extracted from wells in this region was analyzed for chlorine and oxygen stable isotope ratios (δ37Cl, δ18O, δ17O) and radioactive chlorine-36 (36Cl) isotopic abundance, along with other geochemical, isotopic, and hydrogeologic data. Isotope data indicate synthetic, Atacama, and indigenous natural ClO4- were present in the Study Area. Stable isotope data from nearly all sampled wells within the contours of the two characterized plumes, including those located in a perched zone and within the regional groundwater aquifer, were consistent with a dominant synthetic ClO4- source. In wells downgradient from the synthetic plumes and in the Chino subbasin to the southwest, isotopic data indicate the dominant source of ClO4- largely was Atacama, presumably from historical application of nitrate fertilizer in this region. Past agricultural land use and historical records are consistent with this source being present in groundwater. The 36Cl and δ18O data indicate that wells having predominantly synthetic or Atacama ClO4- also commonly contained small fractions of indigenous natural ClO4-. The indigenous ClO4- was most evident isotopically in wells having the lowest overall ClO4- concentrations (contamination in the Rialto-Colton and Chino subbasins. Where indigenous natural

  20. Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric CO2 by the Phoenix Lander (United States)

    Niles, Paul B.; Boynton, W. V.; Hoffman, J. H.; Ming, D. W.; Hamara, D.


    Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars [1]. The isotopic composition of the martian atmosphere has been measured using a number of different methods (Table 1), however a precise value (isotopic composition of martian atmospheric CO2 to within 0.5%. The mass spectrometer is a miniature instrument intended to measure both the martian atmosphere as well as gases evolved from heating martian soils.

  1. The parent body controls on cosmic spherule texture: Evidence from the oxygen isotopic compositions of large micrometeorites (United States)

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


    High-precision oxygen isotopic compositions of eighteen large cosmic spherules (>500 μm diameter) from the Atacama Desert, Chile, were determined using IR-laser fluorination - Isotope Ratio Mass spectrometry. The four discrete isotopic groups defined in a previous study on cosmic spherules from the Transantarctic Mountains (Suavet et al., 2010) were identified, confirming their global distribution. Approximately 50% of the studied cosmic spherules are related to carbonaceous chondrites, 38% to ordinary chondrites and 12% to unknown parent bodies. Approximately 90% of barred olivine (BO) cosmic spherules show oxygen isotopic compositions suggesting they are related to carbonaceous chondrites. Similarly, ∼90% porphyritic olivine (Po) cosmic spherules are related to ordinary chondrites and none can be unambiguously related to carbonaceous chondrites. Other textures are related to all potential parent bodies. The data suggests that the textures of cosmic spherules are mainly controlled by the nature of the precursor rather than by the atmospheric entry parameters. We propose that the Po texture may essentially be formed from a coarse-grained precursor having an ordinary chondritic mineralogy and chemistry. Coarse-grained precursors related to carbonaceous chondrites (i.e. chondrules) are likely to either survive atmospheric entry heating or form V-type cosmic spherules. Due to the limited number of submicron nucleation sites after total melting, ordinary chondrite-related coarse-grained precursors that suffer higher peak temperatures will preferentially form cryptocrystalline (Cc) textures instead of BO textures. Conversely, the BO textures would be mostly related to the fine-grained matrices of carbonaceous chondrites due to the wide range of melting temperatures of their constituent mineral phases, allowing the preservation of submicron nucleation sites. Independently of the nature of the precursors, increasing peak temperatures form glassy textures.

  2. Oxygen and sulfur isotopes in sulfate in modern euxinic systems with implications for evaluating the extent of euxinia in ancient oceans (United States)

    Gomes, Maya L.; Johnston, David T.


    Euxinic conditions, which are defined by the presence of sulfide in the water column, were common in ancient oceans. However, it is not clear how the presence of sulfide in the water column affects the balance between rates of sulfide oxidation and sulfate reduction, which plays a major role in regulating the net redox state of the ocean-atmosphere system. Euxinia could lead to higher rates of sulfide oxidation because sulfide may diffuse more rapidly into the oxic zone in solution than in sediment. Alternatively, sulfide oxidation could be inhibited by low overall availability of suitable oxidants in euxinic settings. Here, we constrain rates of sulfide oxidation versus sulfate reduction in four euxinic water columns in coastal ponds by modeling the evolution of the concentration and sulfur and oxygen isotope compositions of sulfate from post-hurricane, well-oxygenated conditions to modern, euxinic conditions. The results of the one-dimensional, depth-dependent models of water column sulfate geochemistry indicate that the fraction of sulfate reduced that is subsequently reoxidized is low (0.11-0.42) in euxinic systems relative to the modern well-oxygenated ocean (0.75-0.90). This implies that sulfide reoxidation rates are low in euxinic systems because of oxidant limitation and physical transport. Low fractional sulfide reoxidation in euxinic systems has important implications for exploring how oxygen levels in the ocean and atmosphere have changed through Earth history. We use a marine sulfate isotope box model to explore how low reoxidation rates in euxinic systems affect marine sulfate sulfur and oxygen isotope records. Model results indicate that marine sulfate sulfur and oxygen isotope compositions increase during the expansion of euxinia with patterns that are distinct from other isotopic changes to the marine sulfate reservoir. Thus, marine sulfate sulfur and oxygen isotope box models can be applied to ancient isotope records in order to evaluate the

  3. Oxygen isotopes and trace elements in the Tiva Canyon Tuff, Yucca Mountain and vicinity, Nye County, Nevada

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, B.D.; Kyser, T.K.; Peterman, Z.E.


    Yucca Mountain is being studied as a potential site for an underground repository for high-level radioactive waste. Because Yucca Mountain is located in a resource-rich geologic setting, one aspect of the site characterization studies is an evaluation of the resource potential at Yucca Mountain. The Tiva Canyon Tuff (TCT) is a widespread felsic ash-flow sheet that is well exposed in the Yucca Mountain area. Samples of the upper part of the TCT were selected to evaluate the potential for economic mineral deposits within the Miocene volcanic section. These samples of the upper cliff and caprock subunits have been analyzed for oxygen isotopes and a large suite of elements. Oxygen isotope compositions ({delta}{sup 18}O) of the TCT are typical of felsic igneous rocks but range from 6.9 to 11.8 permil, indicating some post-depositional alteration. There is no evidence of the low {delta}{sup 18}O values (less than 6 permil) that are typical of epithermal precious-metal deposits in the region. The variation in oxygen isotope ratios is probably the result of deuteric alteration during late-stage crystallization of silica and low-temperature hydration of glassy horizons; these processes are also recorded by the chemical compositions of the rocks. However, most elemental contents in the TCT reflect igneous processes, and the effects of alteration are observed only in some of the more mobile elements. These studies indicate that the TCT at Yucca Mountain has not been affected by large-scale meteoric-water hydrothermal circulation. The chemical compositions of the TCT, especially the low concentrations of most trace elements including typical pathfinder elements, show no evidence for epithermal metal deposits. Together, these data indicate that the potential for economic mineralization in this part of the volcanic section at Yucca Mountain is small.

  4. Oxygen Isotope Evidence for the Relationship between CM and CO Chondrites: Could they Both Coexist on a Single Asteroid (United States)

    Greenwood, R. C.; Howard, K. T.; Franchi, I. A.; Zolensky, M. E.; Buchanan, P. C.; Gibson, J. M.


    Water played a critical role in the early evolution of asteroids and planets, as well as being an essential ingredient for life on Earth. However, despite its importance, the source of water in the inner solar system remains controversial. Delivery of water to Earth via comets is inconsistent with their relatively elevated D/H ratios, whereas carbonaceous chondrites (CCs) have more terrestrial-like D/H ratios [1]. Of the eight groups into which the CCs are divided, only three (CI, CM, CR) show evidence of extensive aqueous alteration. Of these, the CMs form the single most important group, representing 34% of all CC falls and a similar percentage of finds (Met. Bull. Database). CM material also dominates the population of CC clasts in extraterrestrial samples [2, 3]. The Antarctic micrometeorites population is also dominated by CM and CI-like material and similar particles may have transported water and volatiles to the early Earth [4]. CCs, and CMs in particular, offer the best opportunity for investigating the evolution of water reservoirs in the early solar system. An important aspect of this problem involves identifying the anhydrous silicate component which co-accreted with ice in the CM parent body. A genetic relationship between the essentially anhydrous CO group and the CMs was proposed on the basis of oxygen isotope evidence [5]. However, previous CM whole-rock oxygen isotope data scattered about a line of approximately 0.5 that did not intersect the field of CO chondrites [5]. Here we discuss new oxygen isotope data which provides additional constraints on the relationship between CO and CM chondrites.

  5. Analogue modelling of the rupture process of vulnerable stalagmites in an earthquake simulator (United States)

    Gribovszki, Katalin; Bokelmann, Götz; Kovács, Károly; Hegymegi, Erika; Esterhazy, Sofi; Mónus, Péter


    Earthquakes hit urban centers in Europe infrequently, but occasionally with disastrous effects. Obtaining an unbiased view of seismic hazard is therefore very important. In principle, the best way to test Probabilistic Seismic Hazard Assessments (PSHA) is to compare them with observations that are entirely independent of the procedure used to produce PSHA models. Arguably, the most valuable information in this context should be information on long-term hazard, namely maximum intensities (or magnitudes) occurring over time intervals that are at least as long as a seismic cycle. Long-term information can in principle be gained from intact and vulnerable stalagmites in natural caves. These formations survived all earthquakes that have occurred, over thousands of years - depending on the age of the stalagmite. Their "survival" requires that the horizontal ground acceleration has never exceeded a certain critical value within that time period. To determine this critical value for the horizontal ground acceleration more precisely we need to understand the failure process of these intact and vulnerable stalagmites. More detailed information of the vulnerable stalagmites' rupture is required, and we have to know how much it depends on the shape and the substance of the investigated stalagmite. Predicting stalagmite failure limits using numerical modelling is faced with a number of approximations, e.g. from generating a manageable digital model. Thus it seemed reasonable to investigate the problem by analogue modelling as well. The advantage of analogue modelling among other things is that nearly real circumstances can be produced by simple and quick laboratory methods. The model sample bodies were made from different types of concrete and were cut out from real broken stalagmites originated from the investigated caves. These bodies were reduced-scaled with similar shape as the original, investigated stalagmites. During the measurements we could change both the shape and

  6. The potential of deuterium and oxygen isotopes in evaluating different water sources

    International Nuclear Information System (INIS)

    Costinel, Diana; Ionete, Roxana; Vremera, Raluca; Jong Soo, C.


    Full text: The meteoric waters (precipitations) are depleted in heavy isotopic species of H and O relative to the ocean waters, whereas waters in evaporative systems such as lakes, plants, and soil waters are relatively enriched. Noting the differences between the values of stable isotopic concentration ratios we can get information regarding the origin of water sources or hydrological processes that took place. The present paper describes various methods of stable isotopic analysis (D/H, 18 O/ 16 O) of different water sources (ex. natural water, precipitation, grape vine sap, water extract from wine) using a new generation Isotope Ratio Mass Spectrometer with Continuous Flow (CF-IRMS) Delta V Plus coupled to the equilibration system GasBench II. (authors)

  7. Carbon and oxygen isotopes in carbonatites from Puna, Jujuy and Salta, Argentina

    International Nuclear Information System (INIS)

    Zappettini, Eduardo O.; Rubiolo, Daniel


    δ 13 and δ 18 O data from carbonatites indicate that bodies formed by crystallization of carbonate magma with subsequent formation of metasomatic and hydrothermal carbonatitic veins. The isotopic data are consistent with the available geochemical and petrologic information. (author)

  8. Nitrogen and Oxygen Gas Isotopes in the Siple Dome and Byrd Ice Cores, Antarctica, Version 1 (United States)

    National Aeronautics and Space Administration — This data set consists of Gas-isotopic data from the Siple Dome and and Greenland Ice Sheet Project 2 (GISP2) ice cores covering roughly the last 100,000 years (100...

  9. Spontaneous Oxygen Isotope Exchange between Carbon Dioxide and Oxygen-Containing Minerals: Do the Minerals "breathe" CO2?

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Bouša, Milan; Zukal, Arnošt; Knížek, Antonín; Kubelík, Petr; Rojík, P.; Nováková, Jana; Ferus, Martin


    Roč. 120, č. 1 (2016), s. 508-516 ISSN 1932-7447 R&D Projects: GA MŠk LD14115; GA MŠk(CZ) LD13060; GA ČR(CZ) GA14-12010S Grant - others:COST(XE) CM1104 Institutional support: RVO:61388955 Keywords : Absorption spectroscopy * Infrared spectrometers * Oxygen Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.536, year: 2016

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

    International Nuclear Information System (INIS)

    Sugimoto, Satoru


    The tensor force plays important roles in nuclear structure. Recently, we have developed a mean-field-type model which can treat the two-particle-two-hole correlation induced by the tensor force. We applied the model to sub-closed-shell oxygen isotopes and found that an sizable attractive energy comes from the tensor force. We also studied the tensor correlation in 16O using a shell model including two-particle-two-hole configurations. In this case, quite a large attractive energy is obtained for the correlation energy from the tensor force

  11. Chromatographic determination of the relative retention of isotopic species of oxygen in methanol and methan-d3-ol

    International Nuclear Information System (INIS)

    Pauls, R.E.; Mahle, N.H.; Shepard, A.T.; Gaw, J.C.; Rogers, L.B.


    A high-precision gas chromatograph was used in conjunction with a quadrupole mass filter and an on-line computer to study the fractionation of oxygen isotopes by Porapak T and glycerol in CH 3 OH and CD 3 OH as a function of temperature. Values of relative retention on the order of 1.002 compared favorably with results for the vapor pressure ratio obtained by classical means. Differences from unity were much smaller for the activity-coefficient ratio than for the vapor-pressure ratio. Differential thermodynamic data were also reported

  12. Oxygen isotope fluctuations in a modern North Sea oyster (Crassostrea gigas) compared with annual variations in seawater temperature

    DEFF Research Database (Denmark)

    Ullmann, Clemens Vinzenz; Wiechert, Uwe; Korte, Christoph


    A total of 181 oxygen isotope values from sequential samples of the left shell of a modern Pacific Oyster (Crassostrea gigas) that lived on a sub-tidal oyster bank in the List Basin (North Sea, Germany) shows periodically varying values between + 1.3‰ and -2.5‰. In order to test whether these d18O...... equilibrium with the ambient seawater. A cessation of the oyster shell calcification starts at water temperatures below 6 °C, at lower temperatures than previously thought for Crassostrea. For palaeoclimate investigations the termination of shell production is important because the lowest temperatures might...

  13. Comparison of cellulose extraction methods for analysis of stable-isotope ratios of carbon and oxygen in plant material. (United States)

    Cullen, Louise E; Macfarlane, Craig


    The Jayme-Wise and diglyme-HCl methods for extracting cellulose from plant material for stable-isotope analysis differ considerably in ease of use, with the latter requiring significantly less time and specialized equipment. However, the diglyme-HCl method leaves a small lignin residue in the crude cellulose that may affect stable-isotope values, whereas alpha-cellulose produced by the Jayme-Wise method is relatively pure. We examined whether adding a bleaching step to the diglyme-HCl method could produce cellulose of comparable purity to alpha-cellulose by comparing the yield, percent carbon, and carbon (delta13C) and oxygen (delta18O) stable isotope ratios of the two celluloses. We tested each method on the wood of five species that differ in ease of delignification, Eucalyptus maculata Hook., E. botryoides Sm., E. resinifera Sm., Pinus pinaster Ait. and Callitris glaucophylla J. Thompson & L.A.S. Johnson, as well as the foliage of C. glaucophylla. For hardwoods such as the eucalypts, the diglyme-HCl method without bleaching produced cellulose with delta13C and delta18O ratios similar to alpha-cellulose. For the softwood, C. glaucophylla, 3 h of bleaching with acidified chlorite following treatment with diglyme-HCl produced cellulose with delta13C and delta18O ratios similar to alpha-cellulose. Bleached and unbleached crude celluloses and alpha-cellulose of P. pinaster were similar in delta18O, but not delta13C. Both types of crude cellulose produced from the foliage of C. glaucophylla had significantly different isotope ratios from alpha-cellulose. Overall, the diglyme-HCl method, with or without bleaching, appears to be a simple, fast method for extracting alpha-cellulose from hardwoods for stable-isotope analyses, but its suitability for softwoods and foliage needs to be evaluated depending on the species.

  14. Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region (United States)

    Johnson, Craig A.; Day, Warren C.; Rye, Robert O.


    Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition

  15. Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study (United States)

    Warwick, Peter D.; Ruppert, Leslie F.


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

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

    Lightfoot, Emma; O’Connell, Tamsin C.


    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

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

    Directory of Open Access Journals (Sweden)

    Emma Lightfoot

    Full Text Available Oxygen isotope analysis of archaeological skeletal remains is an increasingly popular tool to study past human migrations. It is based on the assumption that human body chemistry preserves the δ18O of precipitation in such a way as to be a useful technique for identifying migrants and, potentially, their homelands. In this study, the first such global survey, we draw on published human tooth enamel and bone bioapatite data to explore the validity of using oxygen isotope analyses to identify migrants in the archaeological record. We use human δ18O results to show that there are large variations in human oxygen isotope values within a population sample. This may relate to physiological factors influencing the preservation of the primary isotope signal, or due to human activities (such as brewing, boiling, stewing, differential access to water sources and so on causing variation in ingested water and food isotope values. We compare the number of outliers identified using various statistical methods. We determine that the most appropriate method for identifying migrants is dependent on the data but is likely to be the IQR or median absolute deviation from the median under most archaeological circumstances. Finally, through a spatial assessment of the dataset, we show that the degree of overlap in human isotope values from different locations across Europe is such that identifying individuals' homelands on the basis of oxygen isotope analysis alone is not possible for the regions analysed to date. Oxygen isotope analysis is a valid method for identifying first-generation migrants from an archaeological site when used appropriately, however it is difficult to identify migrants using statistical methods for a sample size of less than c. 25 individuals. In the absence of local previous analyses, each sample should be treated as an individual dataset and statistical techniques can be used to identify migrants, but in most cases pinpointing a specific

  18. Coordinated Oxygen Isotopic and Petrologic Studies of CAIS Record Varying Composition of Protosolar (United States)

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


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

  19. New estimates of oxygen isotope fractionation by plants and soils - Implications for the isotopic composition of the atmosphere

    International Nuclear Information System (INIS)

    Angert, A.; Luz, B.


    Oxygen concentration and δ 18 O of O 2 have been monitored in light and heavy soils. Steep oxygen gradients were present at the heavy soil site (minimal O 2 concentration was 1% at 150cm depth) and δ 18 O values typically ranged from 0 per mille to -1.6 per mille relative to air O 2 . In the light-soil site, the O 2 concentration was 20.38% to 20.53% and δ 18 O values ranged from -0.06±0.015 per mille to 0.06±0.015 per mille relative to atmospheric O 2 . The fractionation in soil respiration was estimated from the observed [O 2 ] and δ 18 O profiles and their change with time by a five-box numerical model. Diffusion due to concentration and temperature gradients was taken into account. Good agreement was found between the model results and the measured values. The average discrimination against 18 O in the two study sites was 12±1 per mille. The current understanding of the composition of air O 2 attributes the magnitude of the fractionation in soil respiration to biochemical mechanisms alone. Thus the discrimination against 18 O is assumed to be 18 per mille in cyanide-sensitive dark respiration and 25 per mille to 30 per mille in cyanide-resistant respiration. The discrimination we report is significantly less than in dark respiration. This overall low discrimination is explained by slow diffusion in soil aggregates, and in root tissues that results in low O 2 concentration in the consumption site. Since about half of the terrestrial respiration occurs in soils, our new discrimination estimate lowers significantly the discrimination value for terrestrial uptake. Higher then currently assumed discrimination was found in experiments with illuminated plants. This high discrimination might compensate for the low discrimination found in soils. (author)

  20. Does Oxygen Isotopic Heterogeneity in Refractory Inclusions and Their Wark-Lovering Rims Record Nebular Repressing? (United States)

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


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

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

    International Nuclear Information System (INIS)

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


    The exchange rate of the oxygen in La 0,7 Sr 0,3 CoO 3-δ has been measured by an isotopic exchange method at temperatures 620-1250 K and pressures 1.6-10 torr. The activation energy and the dependence of the exchange rate on pressures in gas have been defined. It is suggested that the knees on the temperature dependences of the exchange rate are attributed to the appearance of Co 2+ ions on the surface of the sample at elevated temperature as new centres of the exchange reaction. The activation energies of the adsorption and desorption processes on the La 0,7 Sr 0,3 CoO 3-δ surface have been estimated

  2. Absolute rate constant, kinetic isotope effect, and mechanism of the reaction of ethylene oxide with oxygen(3P) atoms

    International Nuclear Information System (INIS)

    Bogan, D.J.; Hand, C.W.


    The kinetics of the reaction of ethylene oxide with O( 3 P) atoms has been investigated in detail using a discharge flow system with mass spectrometric and photometric detection. Absolute measurements of the rate constant, kinetic isotope effect, and stoichiometry have been made. The overall stoichiometry is 3 +- 1 oxygen atoms consumed per ethylene oxide molecule. Arrhenius parameters for the reaction of C 2 H 4 O with O are A = 10/sup (9.28+-0.08)/ L mol -1 s -1 and E = 5250 +- 150 cal mol -1 over the temperature range 298 to 691 0 K, and Arrhenius parameters for the kinetic isotope effect are A/sub H//A/sub D/ = 0.9 +- 0.20 and E/sub D/--E/sub H/ = 1460 +- 230 cal mol -1 , over the temperature range 482 to 691 0 K. The magnitude of the preexponential factor and the temperature dependence of the isotope effect establish that hydrogen abstraction, rather than insertion to form a dioxetane intermediate, is the sole reactive channel for ethylene oxide plus O( 3 P). The Arrhenius parameters are discussed and compared to other hydrogen abstraction reactions of O( 3 P). Comparison is also made to the reactions of O( 3 P) with other strained three-membered ring compounds. The final products H 2 , H 2 O, HCHO, CO, and CO 2 were identified, and a mechanism is proposed to account for their formation from the radical products of the initial step

  3. Carbon and oxygen isotope composition of carbonates from an L6 chondrite: Evidence for terrestrial weathering from the Holbrook meteorite (United States)

    Socki, R. A.; Gibson, E. K.; Jull, A. J. T.; Karlsson, H. R.


    Terrestrial weathering in meteorites is an important process which alters pristine elemental and isotopic abundances. The Holbrook L6 chondrite fell in 1912. Material was recovered at the time of the fall, in 1931, and 1968. The weathering processes operating on the freshly fallen meteorite in a semi-arid region of northeastern Arizona have been studied after a ground residence of 19 and 56 years. It has been shown that a large portion of the carbonate material in 7 Antarctic ordinary chondrites either underwent extensive isotopic exchange with atmospheric CO2, or formed recently in the Antarctic environment. In fact it has been demonstrated that hydrated Mg-carbonates, nesquehonite and hydromagnesite, formed in less than 40 years on LEW 85320. In order to help further constrain the effects of terrestrial weathering in meteorites, the carbon and oxygen isotopes extracted from carbonates of three different samples of Holbrook L6: a fresh sample at the time of the fall in 1912, a specimen collected in 1931, and a third specimen collected at the same site in 1968.

  4. A model composition for Mars derived from the oxygen isotopic ratios of martian/SNC meteorites. [Abstract only (United States)

    Delaney, J. S.


    Oxygen is the most abundant element in most meteorites, yet the ratios of its isotopes are seldom used to constrain the compositional history of achondrites. The two major achondrite groups have O isotope signatures that differ from any plausible chondritic precursors and lie between the ordinary and carbonaceous chondrite domains. If the assumption is made that the present global sampling of chondritic meteorites reflects the variability of O reservoirs at the time of planetessimal/planet aggregation in the early nebula, then the O in these groups must reflect mixing between known chondritic reservoirs. This approach, in combination with constraints based on Fe-Mn-Mg systematics, has been used previously to model the composition of the basaltic achondrite parent body (BAP) and provides a model precursor composition that is generally consistent with previous eucrite parent body (EPB) estimates. The same approach is applied to Mars exploiting the assumption that the SNC and related meteorites sample the martian lithosphere. Model planet and planetesimal compositions can be derived by mixing of known chondritic components using O isotope ratios as the fundamental compositional constraint. The major- and minor-element composition for Mars derived here and that derived previously for the basaltic achondrite parent body are, in many respects, compatible with model compositions generated using completely independent constraints. The role of volatile elements and alkalis in particular remains a major difficulty in applying such models.

  5. Ice-free conditions in Fennoscandia during Marine Oxygen Isotope Stage 3?

    Energy Technology Data Exchange (ETDEWEB)

    Wohlfarth, Barbara (Dept. of Geology and Geochemistry, Stockholm Univ., Stockholm (Sweden))


    One of the central aims of the climate research conducted by the Swedish Nuclear Fuel and Waste Management Company (SKB) is to investigate the extremes within which climate conditions may vary within a 100,000 year perspective. The 100,000 year time perspective corresponds to one glacial cycle during which warm interstadial and cold stadial conditions alternated, leading to ice sheet advance and retreat over Fennoscandia. To address the issue of how extreme climate conditions may impact the deep nuclear waste repository, a climate modelling study was initiated with the aim to investigate the response to different climate scenarios: glacial conditions, permafrost conditions and temperate conditions. A model set-up for the permafrost and glacial scenario required information on, for example past ice cover, vegetation, and land-sea configuration. The permafrost climate scenario focussed on a stadial event (Greenland stadial 12) during Marine Oxygen Isotope Stage (MIS) 3, because it was assumed that southern Sweden and the areas of Forsmark and Oskarshamn were not ice covered, but possibly experienced permafrost conditions. This assumption however needed to be validated by paleoenvironmental and paleoclimatic records for MIS 3. Available paleoenvironmental records for this time interval are comparably scarce and due to chronological uncertainties also partly conflicting. Most records are derived from marginal areas of the former Fennoscandian ice sheet and only little and inconsistent information exists for the central part. Geological investigations along the Norwegian coast, in Denmark, southern Sweden, northern and eastern Finland have for example shown that the Fennoscandian ice sheet margin responded distinctly to some of the warmest middle Weichselian interstadials (MIS 3). Interstadial organic sediments from the central part of the former ice sheet have been described from several localities in Sweden, but radiocarbon (14C) dates for these deposits provided ages

  6. Ice-free conditions in Fennoscandia during Marine Oxygen Isotope Stage 3?

    International Nuclear Information System (INIS)

    Wohlfarth, Barbara


    One of the central aims of the climate research conducted by the Swedish Nuclear Fuel and Waste Management Company (SKB) is to investigate the extremes within which climate conditions may vary within a 100,000 year perspective. The 100,000 year time perspective corresponds to one glacial cycle during which warm interstadial and cold stadial conditions alternated, leading to ice sheet advance and retreat over Fennoscandia. To address the issue of how extreme climate conditions may impact the deep nuclear waste repository, a climate modelling study was initiated with the aim to investigate the response to different climate scenarios: glacial conditions, permafrost conditions and temperate conditions. A model set-up for the permafrost and glacial scenario required information on, for example past ice cover, vegetation, and land-sea configuration. The permafrost climate scenario focussed on a stadial event (Greenland stadial 12) during Marine Oxygen Isotope Stage (MIS) 3, because it was assumed that southern Sweden and the areas of Forsmark and Oskarshamn were not ice covered, but possibly experienced permafrost conditions. This assumption however needed to be validated by paleoenvironmental and paleoclimatic records for MIS 3. Available paleoenvironmental records for this time interval are comparably scarce and due to chronological uncertainties also partly conflicting. Most records are derived from marginal areas of the former Fennoscandian ice sheet and only little and inconsistent information exists for the central part. Geological investigations along the Norwegian coast, in Denmark, southern Sweden, northern and eastern Finland have for example shown that the Fennoscandian ice sheet margin responded distinctly to some of the warmest middle Weichselian interstadials (MIS 3). Interstadial organic sediments from the central part of the former ice sheet have been described from several localities in Sweden, but radiocarbon ( 14 C) dates for these deposits provided

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

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


    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.

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

    DEFF Research Database (Denmark)

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


    The very neutron-rich oxygen isotopes 25O and 26O are investigated experimentally and theoretically. The unbound states are populated in an experiment performed at the R3B-LAND setup at GSI via proton-knockout reactions from 26F and 27F at relativistic energies around 442 and 414 MeV/nucleon, res......The very neutron-rich oxygen isotopes 25O and 26O are investigated experimentally and theoretically. The unbound states are populated in an experiment performed at the R3B-LAND setup at GSI via proton-knockout reactions from 26F and 27F at relativistic energies around 442 and 414 MeV...... at around 4 MeV. The experimental findings are compared to theoretical shell-model calculations based on chiral two- and three-nucleon (3N) forces, including for the first time residual 3N forces, which are shown to be amplified as valence neutrons are added....

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

    International Nuclear Information System (INIS)

    Costa Pinto, N.M.A.C.


    Determination of the carbon and oxygen isotopic compositions were made on approximately 100 samples of Late Precambrian metasedimentary rocks of the Rio Pardo Group from Southern Bahia. The results obtained show that carbon varies from δ 13 =C=5,73 per mille to δ 13 C=+9,00 per mille, and oxygen from δ 18 O=-1,87 per mille to δ 18 O=-19,67 per mille relative to PBD. The interpretations lead to some conclusions which confirm the validity the isotopic technique as auxiliary instrument in the study of geological problems. These include: 1) the evidence of a marine transgression during the Camaca sedimentation; 2) the probability that the dolomitic metalimestones of the Agua Preta formation belong to the Serra do Paraiso formation; 3) the assignment of the dolomitic metalismestones, which occur in Itiroro and which had been previously grouped with the crystalline basement rocks, to the Serra do Paraiso formation; 4) the removal of the marble from Serra do Paraiso formation and re-signment to the basement rocks, and finally; 5) the sedimentary evolution of the Rio Pardo Group from a typical fresh-water to a marine environment. (Author) [pt

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

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


    For accurate interpretation of oxygen isotopes in tree rings (δ(18) O), it is necessary to disentangle the mechanisms underlying the variations in the tree's internal water cycle and to understand the transfer of source versus leaf water δ(18) O to phloem sugars and stem wood. We studied the seasonal transfer of oxygen isotopes from precipitation and soil water through the xylem, needles and phloem to the tree rings of Larix decidua at two alpine sites in the Lötschental (Switzerland). Weekly resolved δ(18) O records of precipitation, soil water, xylem and needle water, phloem organic matter and tree rings were developed. Week-to-week variations in needle-water (18) O enrichment were strongly controlled by weather conditions during the growing season. These short-term variations were, however, not significantly fingerprinted in tree-ring δ(18) O. Instead, seasonal trends in tree-ring δ(18) O predominantly mirrored trends in the source water, including recent precipitation and soil water pools. Modelling results support these findings: seasonal tree-ring δ(18) O variations are captured best when the week-to-week variations of the leaf water signal are suppressed. Our results suggest that climate signals in tree-ring δ(18) O variations should be strongest at temperate sites with humid conditions and precipitation maxima during the growing season. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

  11. Stable isotope hydrology. Deuterium and oxygen-18 in the water cycle

    International Nuclear Information System (INIS)

    Gat, J.R.; Gonfiantini, R.


    This monograph is mainly intended for hydrologists, hydrogeologists and geochemists who want to become acquainted, rapidly but in some detail, with the theoretical background of stable isotope fractionation in natural physico-chemical processes involving fresh water, with the isotopic differences actually encountered in natural waters and with their use for practical hydrological purposes. Throughout the monograph, and in particular in the last chapter, a series of examples are discussed, giving the results obtained with stable isotope techniques in current hydrological and hydrogeological investigations or, more generally, in water resources exploration and assessment. One chapter is also dedicated to the techniques for measuring D/H and 18 O/ 16 O ratios in water

  12. Stable isotope compositions of speleothems from the last interglacial - Spatial patterns of climate fluctuations in Europe (United States)

    Demény, Attila; Kern, Zoltán; Czuppon, György; Németh, Alexandra; Leél-Őssy, Szabolcs; Siklósy, Zoltán; Lin, Ke; Hu, Hsun-Ming; Shen, Chuan-Chou; Vennemann, Torsten W.; Haszpra, László


    Studies on the last interglacial (LIG) can provide information on how our environment behaved in a period of slightly higher global temperatures at about 125 ± 4 ka, even if it is not the best analogue for the Holocene. The available LIG climate proxy records are usually better preserved and can be studied at a higher resolution than those of the preceding interglacials, allowing detailed comparisons. This paper presents complex stable hydrogen, carbon and oxygen isotope records obtained for carbonate (δ13C and δ18Ocarb) and fluid inclusion hosted water (δD and δ18Ow) of a stalagmite from the Baradla Cave system in Central Europe that covers most of the LIG, as proven by U-Th dates. Comparing its C and O isotope data with records reported for other speleothem (cave-hosted carbonate) deposits from Europe revealed the complex behavior of these climate proxies, with a concerted relative increase in 18O of carbonates from 128 to 120 ka and synchronized shifts in the opposite direction after 119 ka. The hydrogen isotope analyses of inclusion-hosted water extracted from the BAR-II stalagmite also correspond to the regional climate proxy records, with meaningful deviations from global temperature trends. Beside following the general paleotemperature pattern from the climate optimum (high δD values up to -64‰ around 120 ka) to the subsequent cooling starting at about 119 ka (low δD values down to -90‰ at about 109 ka), a period between 126.5 and 123 ka with low δD values (down to -81‰) is detected in the BAR-II stalagmite. Although the isotope shifts are muted in the C-O isotope data of carbonate due to competitive fractionation processes, the δ13C data show a positive relationship with the δD pattern, indicating humidity - and possibly temperature - variations. The periods with low δD values fit well to temperature and humidity changes inferred from proxy records from western Europe to the eastern Mediterranean. Spatial distributions of these variables

  13. Petrologic and Oxygen-Isotopic Investigations of Eucritic and Anomalous Mafic Achondrites (United States)

    Mittlefehldt, D. W.; Greenwood, R. C.; Peng, Z. X.; Ross, D. K.; Berger, E. L.; Barrett, T. J.


    The most common asteroidal igneous meteorites are eucrite-type basalts and gabbros rocks composed of ferroan pigeonite and augite, calcic plagioclase, silica, ilmenite, troilite, Ca-phosphate, chromite and Fe-metal. These rocks are thought to have formed on a single asteroid along with howardites and diogenites (HEDs). However, Northwest Africa (NWA) 011 is mineralogically identical to eucrites, but has an O-isotopic composition distinct from them and was derived from a different asteroid. Modern analyses with higher precision have shown that some eucrites have smaller O-isotopic differences that are nevertheless well-resolved from the group mean.

  14. Ocean circulation and freshwater pathways in the Arctic Mediterranean based on a combined Nd isotope, REE and oxygen isotope section across Fram Strait (United States)

    Laukert, Georgi; Frank, Martin; Bauch, Dorothea; Hathorne, Ed C.; Rabe, Benjamin; von Appen, Wilken-Jon; Wegner, Carolyn; Zieringer, Moritz; Kassens, Heidemarie


    The water masses passing the Fram Strait are mainly responsible for the exchange of heat and freshwater between the Nordic Seas and the Arctic Ocean (the Arctic Mediterranean, AM). Disentangling their exact sources, distribution and mixing, however, is complex. This work provides new insights based on a detailed geochemical tracer inventory including dissolved Nd isotope (εNd), rare earth element (REE) and stable oxygen isotope (δ18O) data along a full water depth section across Fram Strait. We find that Nd isotope and REE distributions in the open AM primarily reflect lateral advection of water masses and their mixing. Seawater-particle interactions exert important control only above the shelf regions, as observed above the NE Greenland Shelf. Advection of northward flowing warm Atlantic Water (AW) is clearly reflected by an εNd signature of -11.7 and a Nd concentration ([Nd]) of 16 pmol/kg in the upper ∼500 m of the eastern and central Fram Strait. Freshening and cooling of the AW on its way trough the AM are accompanied by a continuous change towards more radiogenic εNd signatures (e.g. -10.4 of dense Arctic Atlantic Water). This mainly reflects mixing with intermediate waters but also admixture of dense Kara Sea waters and Pacific-derived waters. The more radiogenic εNd signatures of the intermediate and deep waters (reaching -9.5) are mainly acquired in the SW Nordic Seas through exchange with basaltic formations of Iceland and CE Greenland. Inputs of Nd from Svalbard are not observed and surface waters and Nd on the Svalbard shelf originate from the Barents Sea. Shallow southward flowing Arctic-derived waters (form the core of the East Greenland Current above the Greenland slope and can be traced by their relatively radiogenic εNd (reaching -8.8) and elevated [Nd] (21-29 pmol/kg). These properties are used together with δ18O and standard hydrographic tracers to define the proportions of Pacific-derived (<∼30% based on Nd isotopes) and Atlantic

  15. Stable carbon, oxygen, and nitrogen, isotope analysis of plants from a South Asian tropical forest: Implications for primatology. (United States)

    Roberts, Patrick; Blumenthal, Scott A; Dittus, Wolfgang; Wedage, Oshan; Lee-Thorp, Julia A


    Stable isotope analysis of primate tissues in tropical forest contexts is an increasingly popular means of obtaining information about niche distinctions among sympatric species, including preferences in feeding height, forest canopy density, plant parts, and trophism. However, issues of equifinality mean that feeding height, canopy density, as well as the plant parts and plant species consumed, may produce similar or confounding effects. With a few exceptions, researchers have so far relied largely on general principles and/or limited plant data from the study area as references for deducing the predominant drivers of primate isotope variation. Here, we explore variation in the stable carbon (δ 13 C), nitrogen (δ 15 N), and oxygen (δ 18 O) isotope ratios of 288 plant samples identified as important to the three primate species from the Polonnaruwa Nature Sanctuary, Sri Lanka, relative to plant part, season, and canopy height. Our results show that plant part and height have the greatest effect on the δ 13 C and δ 18 O measurements of plants of immediate relevance to the primates, Macaca sinica, Semnopithecus priam thersites, and Trachypithecus vetulus, living in this monsoonal tropical forest. We find no influence of plant part, height or season on the δ 15 N of measured plants. While the plant part effect is particularly pronounced in δ 13 C between fruits and leaves, differential feeding height, and plant taxonomy influence plant δ 13 C and δ 18 O differences in addition to plant organ. Given that species composition in different regions and forest types will differ, the results urge caution in extrapolating general isotopic trends without substantial local baselines studies. © 2017 Wiley Periodicals, Inc.

  16. Review of data of oxygen and hydrogen isotope composition in thermal waters in China

    International Nuclear Information System (INIS)

    Fan Zhicheng; Wang Jiyang


    Based on the data of δD and δ 18 O content from more than 600 water samples, this paper reviews the stable isotope composition of thermal waters in China. Data to be used in this paper were mostly collected from published literatures with a few by authors. 9 figs, 2 tabs

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

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; Ushikubo, T.; Nakashima, D.; Kita, N.T.

    in local dust-rich protoplanetary disk, from which the CV3 parent asteroid formed. A compilation of 225 olivine and low-Ca pyroxene isotopic data from 36 chondrules analyzed in the present study lie between carbonaceous chondrite anhydrous mineral (CCAM...

  18. elemental and isotopic compositions of organic carbon and nitrogen ...

    African Journals Online (AJOL)

    Muzuka – Elements and isotopic composition of organic carbon and nitrogen … 88. (2000), the East African region experienced drought during Medieval warm period and humid conditions during little ice age. Further south in South Africa, Holmgren et al. (2001) using record of stalagmite from. Cold air cave in the ...

  19. Seasonality of bottom water temperature in the northern North Sea reconstructed from the oxygen isotope composition of the bivalve Arctica islandica (United States)

    Trofimova, Tamara; Andersson, Carin; Bonitz, Fabian


    The seasonality of temperature changes is an important characteristic of climate. However, observational data for the ocean are only available for the last 150 year from a limited number of locations. Prior to 18th century information is only available from proxy reconstructions. The vast majority of such reconstructions depend on land-based archives, primarily from dendrochronology. Established marine proxy records for the ocean, especially at high latitudes, are both sparsely distributed and poorly resolved in time. Therefore, the identification and development of proxies for studying key ocean processes at sub-annual resolution that can extend the marine instrumental record is a clear priority in marine climate science. In this study, we have developed a record of early Holocene seasonal variability of bottom water temperature from the Viking Bank in the northern most North Sea. This area is of a particular interest since the hydrography is controlled by the inflow of Atlantic water. The reconstruction is based on the oxygen isotope composition of the growth increments in two sub-fossil shells of Arctica islandica (Bivalvia), dated to 9600-9335 cal. yr BP. By combining radiocarbon dating and sclerochronological techniques a floating chronology spanning over 200 years was constructed. Using the chronology as an age model, oxygen isotope measurements from 2 shells were combined into a 22-years long record. The results from this oxygen isotope record are compared with stable oxygen isotope profiles from modern shells to estimate changes in the mean state and seasonality between present and early Holocene. Shell-derived oxygen isotope values together with ice-volume corrected oxygen isotope values for the seawater were used to calculate bottom-water temperatures on a sub-annual time-scale. Preliminary results of the reconstructed early Holocene bottom water temperature indicate higher seasonality and lower minimum temperature compared to the present.

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

    DEFF Research Database (Denmark)

    Hesselbo, Stephen P.; Korte, Christoph


    , to the extent that meaningful comparisons between these events can begin to be made. Here we present new carbon and oxygen isotope da