Oxygen isotope corrections for online δ34S analysis

USGS Publications Warehouse

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

2002-01-01

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

A latitudinal study of oxygen isotopes within horsehair

NASA Astrophysics Data System (ADS)

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

2016-12-01

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.

Using Triple Oxygen Isotope Analyses of Biogenic Carbonate to Reconstruct Early Triassic Ocean Oxygen Isotopic Values and Temperatures

NASA Astrophysics Data System (ADS)

Gibbons, J. A.; Sharp, Z. D.; Atudorei, V.

2017-12-01

The calcite-water triple oxygen isotope fractionation is used to determine isotopic equilibrium and ancient ocean oxygen isotopic values and temperatures. Unlike conventional δ18O analysis where the formation water's isotopic value is assumed, paired δ17O-δ18O measurements allow for the water's isotopic composition to be calculated because there is only one unique solution for equilibrium fractionation using Δ17O-δ18O values (where Δ17O=δ17O-0.528δ18O). To a first approximation, the calcite-water equilibrium fractionation factor, θ (where θ=ln17α/ln18α), varies with temperature by 0.00001/°. The calcite-water equilibrium fractionation line was determined at two temperatures, 30° and 0°, by using modern carbonate samples that formed in ocean water with a δ18O value of 0‰. The θ values for the 30° and 0° samples are 0.52515 and 0.52486, respectively. Oxygen values were measured using complete fluorination in nickel tubes with BrF5 as the reaction reagent. We calibrated all oxygen values to the SMOW-SLAP scale by measuring SMOW, SLAP, San Carlos olivine, NBS-18, NBS-19, and PDB. The triple oxygen isotope calcite-water equilibrium fractionation line was applied to well preserved Early Triassic ammonite shells from the Western United States. Based on paired δ17O-δ18O measurements, the samples did not form in equilibrium with an ice-free ocean with an oxygen isotopic value of -1‰ or the modern ocean value of 0‰. Assuming the calcite is still primary and formed in equilibrium with the ocean water, our data indicate that the δ18O value of the ocean in the early Triassic was 3-5‰ lower than modern. Samples from the Smithian thermal maximum formed in water 10° warmer than samples from after the thermal maximum. Paired δ17O-δ18O measurements of pristine ancient carbonates may provide a better understanding of past ocean conditions during climate change events.

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

PubMed

Yurimoto, H; Ito, M; Nagasawa, H

1998-12-04

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

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

PubMed

Yurimoto; Ito; Nagasawa

1998-12-04

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

The oxygen isotopes

NASA Astrophysics Data System (ADS)

Brown, B. Alex

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

The oxygen isotopes

NASA Astrophysics Data System (ADS)

Alex Brown, B.

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

Disentangling the impacts of climate and human colonization on the flora and fauna of the Australian arid zone over the past 100 ka using stable isotopes in avian eggshell

NASA Astrophysics Data System (ADS)

Miller, Gifford H.; Fogel, Marilyn L.; Magee, John W.; Gagan, Michael K.

2016-11-01

Throughout the Quaternary, the flora and fauna of Australia evolved and adapted to the high-amplitude, low- and high-frequency climate changes that characterized the ice-age cycles. However, during the last glacial cycle, between ∼120 and 15 ka, unprecedented irreversible changes in flora and fauna occurred, and in that same interval modern humans established their first firm presence in the landscape. Disentangling the impacts of the first-order trend toward a colder, drier planet through the Late Quaternary from the impacts of human colonization has been challenging, from both the chronological and paleoenvironmental perspectives. We utilize the stable isotopes of carbon and oxygen preserved in near-continuous time series of Dromaius (emu) eggshell from five regions across Australia to provide independent reconstructions of ecosystem status and climate over the past 100 ka. Carbon isotopes are determined by the diet consumed by the female bird, whereas oxygen isotopes record the status of local moisture balance in the months prior to breeding. Together, δ13C and δ18O provide ecosystem status and climate from the same dated sample, reducing correlation uncertainties between proxies. Combined with recent improvements in the chronologies of Late Quaternary shorelines fringing inland lake basins and deflation during arid times, these data collectively reaffirm that Australia generally became increasingly, albeit irregularly, drier from the last interglaciation through to the last glacial maximum. Dromaius eggshell δ18O documents peak aridity between 30 and 15 ka, but shows no evidence of exceptional climate change between 60 and 40 ka. In contrast, Dromaius δ13Cdiet documents an irreversible loss of the majority of palatable summer-rainfall-related C4 grasses across the Australian arid zone between 50 and 45 ka, about the same time that the giant megafaunal bird, Genyornis, became extinct, and coincident with human dispersal across the continent. Our data

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

NASA Astrophysics Data System (ADS)

Channell, J. E.

2013-12-01

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

Post‐mortem oxygen isotope exchange within cultured diatom silica

PubMed Central

Sloane, Hilary J.; Rickaby, Rosalind E.M.; Cox, Eileen J.; Leng, Melanie J.

2017-01-01

Rationale Potential post‐mortem alteration to the oxygen isotope composition of biogenic silica is critical to the validity of palaeoclimate reconstructions based on oxygen isotope ratios (δ18O values) from sedimentary silica. We calculate the degree of oxygen isotope alteration within freshly cultured diatom biogenic silica in response to heating and storing in the laboratory. Methods The experiments used freshly cultured diatom silica. Silica samples were either stored in water or dried at temperatures between 20 °C and 80 °C. The mass of affected oxygen and the associated silica‐water isotope fractionation during alteration were calculated by conducting parallel experiments using endmember waters with δ18O values of −6.3 to −5.9 ‰ and −36.3 to −35.0 ‰. Dehydroxylation and subsequent oxygen liberation were achieved by stepwise fluorination with BrF5. The 18O/16O ratios were measured using a ThermoFinnigan MAT 253 isotope ratio mass spectrometer. Results Significant alterations in silica δ18O values were observed, most notably an increase in the δ18O values following drying at 40–80 °C. Storage in water for 7 days between 20 and 80 °C also led to significant alteration in δ18O values. Mass balance calculations suggest that the amount of affected oxygen is positively correlated with temperature. The estimated oxygen isotope fractionation during alteration is an inverse function of temperature, consistent with the extrapolation of models for high‐temperature silica‐water oxygen isotope fractionation. Conclusions Routinely used preparatory methods may impart significant alterations to the δ18O values of biogenic silica, particularly when dealing with modern cultured or field‐collected material. The significance of such processes within natural aquatic environments is uncertain; however, there is potential that similar processes also affect sedimentary diatoms, with implications for the interpretation of biogenic silica‐hosted δ18O

The oxygen isotope composition of Almahata Sitta

NASA Astrophysics Data System (ADS)

Rumble, Douglas; Zolensky, Michael E.; Friedrich, Jon M.; Jenniskens, Peter; Shaddad, Muawia H.

2010-10-01

Eleven fragments of the meteorite Almahata Sitta (AHS) have been analyzed for oxygen isotopes. The fragments were separately collected as individual stones from the meteorite's linear strewn field in the Nubian Desert. Each of the fragments represents a sample of a different and distinct portion of asteroid 2008 TC3. Ten of the fragments span the same range of values of δ18O, δ17O, and Δ17O, and follow the same trend along the carbonaceous chondrite anhydrous minerals (CCAM) line as monomict and polymict members of the ureilite family of meteorites. The oxygen isotope composition of fragment #25 is consistent with its resemblance petrographically to an H5 ordinary chondrite. Our results demonstrate that a single small asteroidal parent body, asteroid 2008 TC3, only 4 m in length, encompassed the entire range of variation in oxygen isotope compositions measured for monomict and polymict ureilites.

The Oxygen Isotopic Composition of the Sun

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Late Pleistocene paleoclimatic history documented by an oxygen isotope record from carbonate sediments in Qarhan Salt Lake, NE Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Fan, QiShun; Ma, HaiZhou; Wei, HaiCheng; Shan, FaShou; An, FuYuan; Xu, LiMing; Madsen, David B.

2014-05-01

Late Pleistocene paleoclimatic variability on the northeastern Qinghai-Tibetan Plateau (NE QTP) was reconstructed using a chronology based on AMS 14C and 230Th dating results and a stable oxygen isotopic record. These are derived from lake carbonates in a 102-m-long Qarhan sediment core (ISL1A) collected from the eastern Qaidam Basin. Previous research indicates that the δ18O values of lacustrine carbonates are mainly controlled by the isotopic composition of lake water, which in turn is a function of regional P/E balance and the proportion of precipitation that is monsoon-derived on the NE QTP. Modern isotopic observations indicate that the δ18O values of lake carbonates in hyper-arid Qaidam Basin are more positive during the warm and wet period. Due to strong evaporation and continental effect in this basin, the positive δ18O values in the arid region indicate drier climatic conditions. Based on this interpretation and the δ18O record of fine-grained lake carbonates and dating results in ISL1A, the results imply that drier climatic conditions in the Qarhan region occurred in three intervals, around 90-80 ka, 52-38 ka and 10-9 ka, which could correspond to late MIS 5, middle MIS 3 and early Holocene, respectively. These three phases were almost coincided with low lake level periods of Gahai, Toson and Qinghai Lakes (to the east of Qarhan Lake) influenced by ASM on the orbital timescales. Meanwhile, there was an episode of relatively high δ18O value during late MIS 3, suggesting that relatively dry climatic condition in this period, rather than “a uniform Qarhan mega-paleolake” spanning the ˜44 to 22 ka period. These results insight into the understanding of “the Greatest Lake Period” on the QTP.

Calcium and Oxygen Isotopic Composition of Calcium Carbonates

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Oxygen isotope fractionation between analcime and water - An experimental study

NASA Technical Reports Server (NTRS)

Karlsson, Haraldur R.; Clayton, Robert N.

1990-01-01

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

Isotopic Composition of Oxygen in Lunar Zircons

NASA Technical Reports Server (NTRS)

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

2005-01-01

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

Oxygen isotope geospeedometry by SIMS

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Isotopic evidence for oxygenated Mesoarchaean shallow oceans

NASA Astrophysics Data System (ADS)

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

2018-02-01

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.

Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature

NASA Astrophysics Data System (ADS)

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

2017-12-01

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnaughey, T.A.

1986-01-01

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

Latest Pleistocene crustal cannibalization at Baekdusan (Changbaishan) as traced by oxygen isotopes of zircon from the Millennium Eruption

NASA Astrophysics Data System (ADS)

Cheong, Albert Chang-sik; Sohn, Young Kwan; Jeong, Youn-Joong; Jo, Hui Je; Park, Kye-Hun; Lee, Youn Soo; Li, Xian-Hua

2017-07-01

The silicic volcanism of Baekdusan (Changbaishan), which is on the border between North Korea and China, was initiated in the Late Pleistocene and culminated in the 10th century with a powerful (volcanic explosivity index = 7) commendite-trachyte eruption commonly referred to as the "Millennium Eruption." This study presents oxygen isotope data of zircon in trachydacitic pumices ejected during the Millennium Eruption, together with whole-rock geochemical and Sr-Nd-Pb isotopic data that manifest once again the A-type and EM1 affinities of the Millennium Eruption magma. The zircon crystals, dated by previous studies at ca. 12-9 ka, show a moderate inter-grain variation in δ18O from 3.69‰ to 5.03‰. These values are consistently lower than the normal mantle range, and interpreted to have resulted from the digestion of meteoric-hydrothermally altered intracaldera rocks in the shallow magma chamber beneath Baekdusan just prior to the crystallization of the zircons, rather than from derivation from low-δ18O sources deep in the mantle. The whole-rock geochemical/isotopic considerations suggest that the magma mainly self-cannibalized the earlier erupted volcanic carapace around the magma chamber. This study highlights the usefulness of zircon oxygen isotopes for characterizing past volcanic activity that has now been commonly eroded away and implies that the generation of Yellowstone-type low-δ18O magma is not a rare phenomenon in large-volume silicic eruptions.

Normalization of oxygen and hydrogen isotope data

USGS Publications Warehouse

Coplen, T.B.

1988-01-01

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

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

NASA Technical Reports Server (NTRS)

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

2013-01-01

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

Oxygen and iron isotope studies of magnetite produced by magnetotactic bacteria

USGS Publications Warehouse

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

1999-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-08-01

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

Sediment Sulfur Isotopes Reflect Seawater Oxygen Rise in Neoarchean

NASA Astrophysics Data System (ADS)

Fakhraee, M.; Crowe, S.; Katsev, S.

2017-12-01

The oxygenation of the ocean-atmosphere system is recorded in S isotopes preserved in sedimentary pyrites. Disappearance of mass independent fractionation of S (S-MIF) around 2.45 Ga signals the first large-scale oxygenation of the atmosphere (the GOE), while a narrow range of pyritic δ34S during the Archean eon suggests limited oxidative cycling of S. Both δ34S and S-MIF ranges, however, undergo a clear and unexplained expansion in the Neoarchean between 2.7 and 2.45 Ga, indicating a change in global S-cycling. By analyzing the preservation patterns of isotopic signals with a 1D reaction-transport model, we show that the rock record points to the rise of oxygen in shallow marine environments around 2.7 billion years ago. The model tracks d34S and Δ33S isotopic transformations during early diagenesis in a reaction-transport framework. The results indicate that δ34S and MIF signatures in >2.7Ga sulfides require deposition from anoxic or minimally oxygenated seawater, whereas the 2.7-2.4 Ga expansion in both δ34S and D33S ranges points to at least localized accumulation oxygen to low μM levels, accompanied by a moderate rise in sulfate from low μM concentrations to up to 200 μM. In contrast to the role of oxygen in the atmosphere where it suppresses the production of MIF, oxygen in seawater at levels below 25 μM does not necessarily suppress the MIF preservation, which instead depends on the availability of reactive organic matter, sulfate, and electron acceptors for sulfide re-oxidation. The S-isotopes in Neoarchean sulfides thus paint a picture of gradual oxygenation of shallow marine environments under a nearly anoxic atmosphere where the atmospherically produced S isotopic signals are overprinted by increasingly oxidative diagenesis, rising sulfate levels, and increasing organic sedimentation.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Relative paleointensity (RPI) and oxygen isotope stratigraphy at IODP Site U1308: North Atlantic RPI stack for 1.2-2.2 Ma (NARPI-2200) and age of the Olduvai Subchron

NASA Astrophysics Data System (ADS)

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

2016-01-01

Integrated Ocean Drilling Program (IODP) Site U1308 (49°53‧N, 24°14‧W; water depth 3871 m) provides a record of relative paleointensity (RPI) and benthic stable isotope stratigraphy back to 3.2 Ma. The record since 1.5 Ma was published previously, and here we present the interval from 1.5 Ma to 3.2 Ma (Early Pleistocene-Late Pliocene). The benthic oxygen isotope record in this interval is correlated to Marine Isotope Stage (MIS) 51 to KM2, with an apparent hiatus that removed part of the interval spanning MIS 104-G2 (2.6-2.65 Ma), at the Gauss-Matuyama boundary. The mean sedimentation rate for the 1.5-3.2 Ma period is 8.5 cm/kyr. The age model was built by correlation of the benthic oxygen isotope record to a global stack (LR04). Apart from the expected polarity reversals, three magnetic excursions are recorded: Punaruu in MIS 31/32 at 1092 ka, Gilsa in MIS 54/55 at 1584 ka, and a newly recognized excursion labeled Porcupine (after the nearby Porcupine Abyssal Plain) in MIS G6/G7 at 2737 ka. The ages of polarity reversals at Site U1308, on the LR04 time scale, are consistent with the current geomagnetic polarity timescale (GPTS) with the exception of the base of the Olduvai Subchron that occurred in MIS 73, corresponding to 1925 ka on the LR04 time scale, 25 kyr younger than in the current GPTS. The RPI record at Site U1308 is calibrated using the oxygen isotope age model, and combined with four other North Atlantic records to obtain a North Atlantic RPI stack for 1.2-2.2 Ma (NARPI-2200) that is compared with published RPI stacks: Epapis, Sint-2000 and PADM2M. For 2.2-3.2 Ma, the Site U1308 RPI record is compared with a RPI record from North Atlantic IODP Site U1314, and with the Pacific Epapis stack. The mean sedimentation rates of the North Atlantic sites in NARPI-2200 are greater (by about an order of magnitude) than most of the records incorporated in other stacks. The comparison of Epapis and NARPI-2200 yields an apparent lag for NARPI-2200 relative to

Growth history of cultured pearl oysters based on stable oxygen isotope analysis

NASA Astrophysics Data System (ADS)

Nakashima, R.; Furuta, N.; Suzuki, A.; Kawahata, H.; Shikazono, N.

2007-12-01

We investigated the oxygen isotopic ratio in shells of the pearl oyster Pinctada martensii cultivated in embayments in Mie Prefecture, central Japan, to evaluate the biomineralization of shell structures of the species and its pearls in response to environmental change. Microsamples for oxygen isotope analysis were collected from the surfaces of shells (outer, middle, and inner shell layers) and pearls. Water temperature variations were estimated from the oxygen isotope values of the carbonate. Oxygen isotope profiles of the prismatic calcite of the outer shell layer reflected seasonal variations of water temperature, whereas those of nacreous aragonites of the middle and inner shell layers and pearls recorded temperatures from April to November, June to September, and July to September, respectively. Lower temperatures in autumn and winter might slow the growth of nacreous aragonites. The oxygen isotope values are controlled by both variations of water temperature and shell structures; the prismatic calcite of this species is useful for reconstructing seasonal changes of calcification temperature.

Oxygen isotope analysis of bacterial and fungal manganese oxidation.

PubMed

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

2018-07-01

The ability of micro-organisms to oxidize manganese (Mn) from Mn(II) to Mn(III/IV) oxides transcends boundaries of biological clade or domain. Many bacteria and fungi oxidize Mn(II) to Mn(III/IV) oxides directly through enzymatic activity or indirectly through the production of reactive oxygen species. Here, we determine the oxygen isotope fractionation factors associated with Mn(II) oxidation via various biotic (bacteria and fungi) and abiotic Mn(II) reaction pathways. As oxygen in Mn(III/IV) oxides may be derived from precursor water and molecular oxygen, we use a twofold approach to determine the isotope fractionation with respect to each oxygen source. Using both 18 O-labeled water and closed-system Rayleigh distillation approaches, we constrain the kinetic isotope fractionation factors associated with O atom incorporation during Mn(II) oxidation to -17.3‰ to -25.9‰ for O 2 and -1.9‰ to +1.8‰ for water. Results demonstrate that stable oxygen isotopes of Mn(III/IV) oxides have potential to distinguish between two main classes of biotic Mn(II) oxidation: direct enzymatic oxidation in which O 2 is the oxidant and indirect enzymatic oxidation in which superoxide is the oxidant. The fraction of Mn(III/IV) oxide-associated oxygen derived from water varies significantly (38%-62%) among these bio-oxides with only weak relationship to Mn oxidation state, suggesting Mn(III) disproportionation may account for differences in the fraction of mineral-bound oxygen from water and O 2 . Additionally, direct incorporation of molecular O 2 suggests that Mn(III/IV) oxides contain a yet untapped proxy of δ18OO2 of environmental O 2 , a parameter reflecting the integrated influence of global respiration, photorespiration, and several other biogeochemical reactions of global significance. © 2018 John Wiley & Sons Ltd.

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

NASA Astrophysics Data System (ADS)

Hayles, Justin; Bao, Huiming

2015-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

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

NASA Astrophysics Data System (ADS)

Price, Gregory; Grimes, Stephen

2015-04-01

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

Planetary Accretion, Oxygen Isotopes and the Central Limit Theorem

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

Oxygen isotopes and the moon-forming giant impact.

PubMed

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

2001-10-12

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

The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

NASA Astrophysics Data System (ADS)

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

2014-01-01

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

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

NASA Astrophysics Data System (ADS)

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

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

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

NASA Astrophysics Data System (ADS)

Chen, Guo; Schnyder, Hans; Auerswald, Karl

2017-04-01

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 (p<0.05) to the isotope composition in meteoric water in a regression analysis. 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.

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

USGS Publications Warehouse

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

2009-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2009-01-01

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

Central American rainfall variations since 100 ka and moisture delivery to Greenland

NASA Astrophysics Data System (ADS)

Lachniet, M. S.; Asmerom, Y.; Johnson, L.; Burns, S.; Polyak, V.; Patterson, W.

2007-12-01

We present a rainfall history for Central America based on oxygen isotope values in Uranium-series dated stalagmites collected from the Pacific Coast of Costa Rica over parts of the Holocene and from 25 to 100 ka. The oxygen isotope values of modern rainfall in our study area within the heart of the Intertropical Convergence Zone (ITCZ) are dominated by the amount effect and moisture source, and we interpret our data as a paleorainfall proxy. Our data show substantial oxygen isotope variability on centennial to multi-millennial time scales. Further, our paleorainfall time series is strongly correlated with the deuterium excess parameter in Greenland Ice, which suggests that the strength of the tropical hydrological cycle has modulated the flow of low-latitude moisture to Greenland on millennial time scales. Our results indicate a strong coupling between tropical and high latitude paleoclimate, that was likely linked via variations in the strength of the Hadley cell and its associated export of atmospheric moisture to the high latitudes. We observe the wettest periods in Central America when the Caribbean was warmer than 26.5 degrees C and the Caribbean to Pacific (cold tongue) SST gradient was largest, suggesting a combined Atlantic and Pacific Ocean control on ITCZ rainfall.

Oxygen Isotopic Compositions of Solar Corundum Grains

NASA Astrophysics Data System (ADS)

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

2009-11-01

Oxygen is one of the major rock-forming elements in the solar system and the third most abundant element of the Sun. Oxygen isotopic composition of the Sun, however, is not known due to a poor resolution of astronomical spectroscopic measurements. Several Δ17O values have been proposed for the composition of the Sun based on (1) the oxygen isotopic measurements of the solar wind implanted into metallic particles in lunar soil (< -20‰ by Hashizume & Chaussidon and ~ +26‰ by Ireland et al.), (2) the solar wind returned by the Genesis spacecraft (-27‰ ± 6‰ by McKeegan et al.), and (3) the mineralogically pristine calcium-aluminum-rich inclusions (CAIs) (-23.3‰ ± 1.9‰ by Makide et al. and -35‰ by Gounelle et al.). CAIs are the oldest solar system solids, and are believed to have formed by evaporation, condensation, and melting processes in hot nebular region(s) when the Sun was infalling (Class 0) or evolved (Class 1) protostar. Corundum (Al2O3) is thermodynamically the first condensate from a cooling gas of solar composition. Corundum-bearing CAIs, however, are exceptionally rare, suggesting either continuous reaction of the corundum condensates with a cooling nebular gas and their replacement by hibonite (CaAl12O19) or their destruction by melting together with less refractory condensates during formation of igneous CAIs. In contrast to the corundum-bearing CAIs, isolated micrometer-sized corundum grains are common in the acid-resistant residues from unmetamorphosed chondrites. These grains could have avoided multistage reprocessing during CAI formation and, therefore, can potentially provide constraints on the initial oxygen isotopic composition of the solar nebula, and, hence, of the Sun. Here we report oxygen isotopic compositions of ~60 micrometer-sized corundum grains in the acid-resistant residues from unequilibrated ordinary chondrites (Semarkona (LL3.0), Bishunpur (LL3.1), Roosevelt County 075 (H3.2)) and unmetamorphosed carbonaceous

Spatial and temporal oxygen isotope trends at the northern tree-line in Eurasia

NASA Astrophysics Data System (ADS)

Saurer, Matthias; Schweingruber, Fritz; Vaganov, Eugene A.; Shiyatov, Stepan G.; Siegwolf, Rolf

2002-05-01

The oxygen isotope ratio of ice cores and sea-sediments is an extremely useful source of information on long-term climatic changes. A similar approach has been applied to the oxygen isotope ratio of tree rings to enable a pattern-based reconstruction of the isotope variations on the continents. We present an oxygen isotope map for northern Eurasia spanning from Norway to Siberia, that reflects the isotope distribution in the late 19th century, and compare it with an equivalent map for the present-day situation. The average isotope values of 130 trees show a large east-to-west gradient and are highly correlated with the isotope distribution of precipitation. Surprisingly, the 18O/16O ratio of the wood has been decreasing in the interior of the continent since the late 19th century, in contrast to the strong temperature increase recorded by meteorological data. From this isotope trend over time a change in the seasonality of precipitation can be inferred.

Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Photosynthetic Fractionation of the Stable Isotopes of Oxygen and Carbon.

PubMed Central

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

1993-01-01

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

Stratigraphic Expression of the Turbidity Maximum and Evidence for Short-Term Climate Change from Estimates of Paleosalinity in the Hudson Estuary Between 6 and 2 ka

NASA Astrophysics Data System (ADS)

Pekar, S. F.; McHugh, C. M.; Lynch-Stieglitz, J.; Christie-Blick, N.

2002-12-01

Benthic foraminiferal biofacies and oxygen isotopes from juvenile bivalves have been used to estimate paleosalinity changes in three cores from the lower Hudson estuary (5 km north of the George Washington Bridge to north of the Tappan Zee Bridge) for the mid-Holocene between 6 and 2 ka. Four foraminiferal biofacies were identified and compared with living assemblages previously calibrated to salinity in the estuary. Oxygen isotopes were obtained from monospecific bivalves (Gemma gemma) within a narrow size fraction (1.0-1.7 mm) to minimize temperature effects that would otherwise tend to dominate isotopic records. A comparison shows good agreement between paleosalinity estimates from foraminiferal biofacies and oxygen isotopes; thus, permitting oxygen isotopes to be used as paleosalinity proxies. These data were integrated with sedimentological interpretations of the cores and C-14 ages to evaluate the patterns that emerged. West of the main channel and 5 km north of the Tappan Zee Bridge (20 km upstream of the northernmost present-day location of the ETM, Core SD-30), sedimentation increased by a factor of four at 4.9 ka, within an interval for which the highest paleosalinity is estimated (20-27‰ ) for this area. Paleosalinity decreased to 10-16‰ at 3.5 ka, coinciding with an abrupt decrease in the rate of sediment accumulation. Directly west of SD-30 and nearer to the shore, comparable changes in sedimentation were not observed although similar trends in paleosalinity are observed in the record (25‰ decreasing to 14‰ ). Further seaward and in the eastern part of the estuary, paleosalinities and sedimentation remained relatively constant (20-27‰ salinity and 0.8-1.9 mm/yr). Observations in the modern estuary indicate that sediment accumulates preferentially on the western subaqueous flats in the vicinity of the turbidity maximum that corresponds with salinities ranging from the low twenties to mid teens. We hypothesize that Holocene sedimentation

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

NASA Astrophysics Data System (ADS)

Nielson, Kristine E.; Bowen, Gabriel J.

2010-03-01

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

The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

NASA Astrophysics Data System (ADS)

von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.

2013-12-01

Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported

Isotope-coded, iodoacetamide-based reagent to determine individual cysteine pKa values by MALDI-TOF mass spectrometry

PubMed Central

Nelson, Kimberly J.; Day, Amanda E.; Zeng, Bubing B.; King, S. Bruce; Poole, Leslie B.

2008-01-01

Cysteine reactivity in enzymes is imparted to a large extent by the stabilization of the deprotonated form of the reduced cysteine (i.e. the thiolate) within the active site. While this is likely to be an important chemical attribute of many thiol-based enzymes including cysteine-dependent peroxidases (peroxiredoxins) and proteases, only relatively few pKa values have been determined experimentally. Presented here is a new technique for determining the pKa value of cysteine residues through quantitative mass spectrometry following chemical modification with an iodoacetamide-based reagent over a range of pH buffers. This isotope-coded reagent, N-phenyl iodoacetamide (iodoacetanilide), is readily prepared in deuterated (d5) and protiated (d0) versions and is more reactive toward free cysteine than is iodoacetamide. Using this approach, the pKa values for the two cysteine residues in Escherichia coli thioredoxin were determined to be 6.5 and > 10, in good agreement with previous reports using chemical modification approaches. This technique allows the pKa of specific cysteine residues to be determined in a clear, fast, and simple manner and, because cysteine residues on separate tryptic peptides are measured separately, is not complicated by the presence of multiple cysteines within the protein of interest. PMID:18162165

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

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

NASA Astrophysics Data System (ADS)

Helliker, B.

2007-12-01

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

Uranium-series coral ages from the US Atlantic Coastal Plain-the "80 ka problem" revisited

USGS Publications Warehouse

Wehmiller, J. F.; Simmons, K.R.; Cheng, H.; Edwards, R. Lawrence; Martin-McNaughton, J.; York, L.L.; Krantz, D.E.; Shen, C.-C.

2004-01-01

Uranium series coral ages for emergent units from the passive continental margin US Atlantic Coastal Plain (ACP) suggest sea level above present levels at the end of marine oxygen isotope stage (MIS) 5, contradicting age-elevation relations based on marine isotopic or coral reef models of ice equivalent sea level. We have reexamined this problem by obtaining high precision 230Th/238U and 231Pa/235U thermal ionization mass spectrometric ages for recently collected and carefully cleaned ACP corals, many in situ. We recognize samples that show no evidence for diagenesis on the basis of uranium isotopic composition and age concordance. Combining new and earlier data, among those ages close to or within the age range of MIS 5, over 85% cluster between 65 and 85 ka BP. Of the corals that we have analyzed, those that show the least evidence for diagenesis on the basis of uranium isotopic composition and age concordance have ages between 80 and 85 ka BP, consistent with a MIS 5a correlation. The units from which these samples have been collected are all emergent and have elevations within ???3-5m of those few units where early stage 5 (???125,000 ka BP) coral ages have been obtained. The ACP appears to record an unusual history of relative sea level throughout MIS 5, a history that is also apparent in the dated coral record for Bermuda. We speculate that this history is related to the regional (near-to intermediate-field) effects of ancestral Laurentide Ice sheets on last interglacial shorelines of the western North Atlantic. ?? 2004 Elsevier Ltd and INQUA. All rights reserved.

Meteorites and their parent bodies: Evidence from oxygen isotopes

NASA Technical Reports Server (NTRS)

Clayton, R. N.

1978-01-01

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

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

USGS Publications Warehouse

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

2010-01-01

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (??18OH2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ??18OSO4-H2O, of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ??SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O2 into sulfate. ??34SSO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ??34SSO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

PubMed

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

2012-09-30

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.

Fossil black smoker yields oxygen isotopic composition of Neoproterozoic seawater.

PubMed

Hodel, F; Macouin, M; Trindade, R I F; Triantafyllou, A; Ganne, J; Chavagnac, V; Berger, J; Rospabé, M; Destrigneville, C; Carlut, J; Ennih, N; Agrinier, P

2018-04-13

The evolution of the seawater oxygen isotopic composition (δ 18 O) through geological time remains controversial. Yet, the past δ 18 O seawater is key to assess past seawater temperatures, providing insights into past climate change and life evolution. Here we provide a new and unprecedentedly precise δ 18 O value of -1.33 ± 0.98‰ for the Neoproterozoic bottom seawater supporting a constant oxygen isotope composition through time. We demonstrate that the Aït Ahmane ultramafic unit of the ca. 760 Ma Bou Azzer ophiolite (Morocco) host a fossil black smoker-type hydrothermal system. In this system we analyzed an untapped archive for the ocean oxygen isotopic composition consisting in pure magnetite veins directly precipitated from a Neoproterozoic seawater-derived fluid. Our results suggest that, while δ 18 O seawater and submarine hydrothermal processes were likely similar to present day, Neoproterozoic oceans were 15-30 °C warmer on the eve of the Sturtian glaciation and the major life diversification that followed.

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

NASA Astrophysics Data System (ADS)

Kohn, Matthew J.; Valley, John W.

1998-06-01

The occurrence of coexisting amphiboles in rocks and the likelihood of concurrent isotope closure allows equilibrium oxygen isotope fractionations among the amphiboles to be recovered from natural samples. Oxygen isotope analyses of mineral separates using laser fluorination show that coexisting amphiboles increasingly partition 18O in the order: hornblende ≪ gedrite < cummingtonite ≤ anthophyllite. The observed fractionations at ˜575°C are: Δ(Ged-Hbl) = 0.8‰, Δ(Cum-Hbl) = 0.9, Δ(Cum-Ged) = 0.2, Δ(Ath-Ged) = 0.3, and Δ(Ath-Hbl) > 0.9. Previously published data for hornblende, actinolite, glaucophane, and garnet show that Δ(Act-Hbl) ˜ 0.2, Δ(Gln-Grt) ≫ 1, and Δ(Hbl-Grt) ˜ 0. Thus, glaucophane strongly partitions 18O relative to the calcic amphiboles. The fractionation between two amphiboles of arbitrary composition can be predicted from the known fractionations for mica endmembers, pyroxene endmembers, and exchange components such as CaAl(NaSi) -1, NaAl(CaMg) -1, CaMg -1, MgFe -1, FeMn -1, KNa -1, KAl( Si) -1, and Fe 3+Al -1. Applications of the exchange component method reproduce measured amphibole fractionations to within ±0.1 to ±0.2‰, whereas other predictive methods cause misfit for typical metamorphic hornblende of ≥0.5‰ at 575°C. Although the isotope effects of cation exchanges may be small at high-T, they magnify dramatically for minerals formed in surficial, diagenetic, and low-T metamorphic environments. Different composition clays are predicted to have equilibrium δ 18O differences of 2-9‰. If the isotope fractionation can be determined for one mineral endmember, then calibrated exchanges allow accurate prediction of the isotope fractionations for intermediate compositions of most ortho-, ring-, chain-, and sheet-silicates.

Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Relative paleointensity (RPI) in the latest Pleistocene (10-45 ka) and implications for the "mystery interval" in atmospheric radiocarbon production at 17 ka.

NASA Astrophysics Data System (ADS)

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

2017-12-01

Relative paleointensity (RPI) proxies have been used to improve the resolution of Quaternary stratigraphies, and have been matched to oxygen isotope stratigraphies over the last 2 Myrs. The archeomagnetic archive has been important for the Holocene RPI record, and the older Quaternary record has come largely from ODP/IODP and MD (Marion Dufresne - Calypso) marine cores. Beyond the range of archeomagnetic data, published RPI stacks have poor consistency in the 10-30 ka (latest Pleistocene) interval, possibly due to poor quality of ODP/IODP and MD cores in the upper few meters of the sedimentary sections. We report RPI data from a suite of conventional piston cores and Kasten cores from the SW Iberian margin collected during cruise JC089 of the RSS James Cook in August 2013. The age models were acquired by correlation of Ca/Ti XRF core-scanning data to L* reflectance from the Cariaco Basin that is tied to the Greenland ice-core chronology. Mean sedimentation rates are in the 10-20 cm/kyr range. The Holocene RPI record from these marine cores can be broadly correlated to the archeomagnetic RPI compilations. The preceding RPI data are characterized by a short-lived minimum at 13-15 ka, a high in RPI at 17-20 ka, preceded by a discontinuous RPI decrease to 40 ka at the time of the well-documented Laschamp geomagnetic excursion. A stack of 12 RPI records from the SW Iberian margin for the 0-45 ka interval are compared with 11 records from elsewhere, including marine and lake records from the Pacific and South Atlantic realms, chosen on the basis of mean sedimentation rates (>20 cm/kyr) and superior age models. The resulting stacks are very different to previously published RPI stacks, particularly for the 10-30 ka interval, and imply a global (dipole-field) high at 17-20 ka that has implications for the 190 ‰ drop in atmospheric 14C during the so-called "mystery interval" (17.5-14.5 ka).

Did the Laurentide ice sheet survive through Marine Isotope Stage 9?

NASA Astrophysics Data System (ADS)

Carlson, A. E.; Tarasov, L.; Ullman, D. J.

2016-12-01

Looking at the global benthic oxygen isotope stack, only marine oxygen isotope stage (MIS) 7 stands out as an anomalous interglaciation with a higher oxygen isotope value than other interglaciations of the last half million years. However, benthic oxygen isotopes are an integrator of global ice volume plus temperature, and records of local ice-sheet change are needed to partition the sources of the global signal. Here we use the Laurentide ice-sheet (LIS) proximal record of IODP Site U1302/1303 off of Orphan Knoll to test LIS presence/absence on the eastern Canadian shield. Ice-sheet model calibrated Si relative to Sr is low in most interglaciations of the last 500 ka reflecting the removal of the LIS and its erosive power from the Canadian Shield. However, like MIS 7, MIS 9 has continued elevated inputs of Si. Furthermore, planktic oxygen isotopes do not decrease to full interglacial levels like in MIS 1, 5e and 11. MIS 9 had a similar orbital forcing as MIS 5e, but a much shorter period of elevated interglacial carbon dioxide concentration. Based on climate model simulations of LIS stability, we suggest that the reduced period of elevated atmospheric carbon dioxide allowed the LIS to survive through MIS 9 (like MIS 7), providing important constraints for the climatic thresholds necessary for a full interglaciation.

Determining Oxygen Isotopic Fractionation between the ferrous sulfate, melanterite, and aqueous sulfate

NASA Astrophysics Data System (ADS)

Shulaker, D. Z.; Kohl, I.; Coleman, M. L.

2011-12-01

Studying regions on Earth that are analogous to Mars serve as case studies for studying astrobiology and planetary surface rock formation processes. Rio Tinto, Spain is very rich in iron sulfates, and has an environment that is possibly very similar to the former environment on Mars. Certain bacteria play significant roles in accelerating pyrite oxidation rates, the products of which contribute to the formation of ferrous sulfates, such as melanterite. During mineral crystallization in an aqueous solution, there are systematic isotopic differences between dissolved species and solid phases. Quantifying this fractionation enables isotopic analysis to be used to trace the original isotopic signature of the dissolved species. Isotope fractionation has been determined for minerals such as gypsum and epsomite, and from these results and theoretical predictions, it is expected that melanterite, a mineral potentially found on Mars, would be more enriched in oxygen-18 relative to the aqueous solution from which it crystallized.Thus, determining the oxygen-18 isotopic fractionation between melanterite and dissolved sulfate has many potential benefits for understanding surface processes on Mars and its past environment. To investigate the oxygen isotope fractionation for melanterite, acidic aqueous solutions saturated with dissolved hydrated ferrous sulfate were evaporated at 25 deg C and 40 deg C and under different conditions to induce different evaporation rates. During evaporation, the aqueous solution and crystallized melanterite were sampled at different stages. Oxygen-18 isotopic compositions were then measured. However, the fractionations observed in the experiments were opposite from predictions. At 25 deg C without enhanced evaporation, the dissolved sulfate was +5.5 per mil relative to the solid, while at 40 deg C it was +4.3 per mil. With enhanced evaporation, fractionation was +2.1 per mil, while at 40 deg C it was +3.6 per mil. In addition, at 40 deg C

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

NASA Astrophysics Data System (ADS)

Chen, Y. C.; Mii, H. S.; Li, K. T.

2015-12-01

To exam whether oxygen isotope records of Crassostrea gigasoysters can be used as proxies of environment, 133 cultivated oysters and 21 water samples were collected from Chi Ku area, Tainan City, southern Taiwan in December of 2012, and from March, 2013 to July, 2014. Instrumental air and water temperatures and precipitation records were obtained from a nearest Central Weather Bureau (CWB) station roughly 16 km north of Chi Ku. The oxygen and carbon isotope values of the ligamental area of the modern oyster shells are from -6.92‰ to -0.08‰ (-3.05 ± 1.17‰, N = 2280; 1σ; VPDB) and from -5.57‰ to 0.63‰ (-1.88 ± 0.81‰), respectively. Oxygen isotope values of the water samples are mainly between -0.28‰ and 0.74‰ (0.18 ± 0.29‰, N = 20; 1σ; VSMOW). However, water oxygen isotope value of -2.75‰ was observed for the water sample collected immediately after a typhoon heavy rainfall. Seasonal temperature fluctuation pattern of estimated oxygen isotope temperatures from modern shells is similar to that of CWB instrumental records. However, the oxygen isotope temperatures are respectively about 3 °C and 10°C higher than those of instrumental records for winter and summer. Higher estimated oxygen isotope temperatures are most likely caused by underestimated fraction of freshwater. We analyzed 5 archaeological oyster shells of Siraya culture (500~250B.P.) collected from Wu Chien Tuso North (WCTN) archaeological site of Tainan branch of Southern Taiwan Science Park to infer the harvest season of mollusks. Oxygen isotope values of the ligamental area of the archaeological oyster shells are between -5.98‰ and -1.26‰ (-3.34 ± 1.37‰, N = 60; 1σ), and carbon isotope values are between -3.21‰ and 0.60‰ (-2.04‰ ± 0.55‰). The oxygen isotope records of archaeological oyster shells also showed clear seasonality. Most of the oysters were collected in autumn and winter. Oxygen isotope values of archaeological oyster shells was 1‰ greater than that

Seasonal oxygen isotopic variations in living planktonic foraminifera off Bermuda

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, D.F.; Be, A.W.H.; Fairbanks, R.G.

1979-10-26

Seasonal variations in the oxygen-18/oxygen-16 ratio of calcite shells of living planktonic foraminifera in the Sargasso Sea off Bermuda are a direct function of surface water temperature. Seasonal occurrence as well as depth habitat are determining factors in the oxygen isotopic composition of planktonic foraminifera. These relationships may be used to determine the seasonal temperature contrast of oceans in the past.

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

PubMed

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

2013-04-01

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.

Oxygen and U-Th isotopes and the timescales of hydrothermal exchange and melting in granitoid wall rocks at Mount Mazama, Crater Lake, Oregon

USGS Publications Warehouse

Ankney, Meagan E.; Bacon, Charles R.; Valley, John W.; Beard, Brian L.; Johnson, Clark M.

2017-01-01

We report new whole rock U-Th and in-situ oxygen isotope compositions for partially melted (0–50 vol% melt), low-δ18O Pleistocene granitoid blocks ejected during the ∼7.7 ka caldera-forming eruption of Mt. Mazama (Crater Lake, Oregon). The blocks are interpreted to represent wall rocks of the climactic magma chamber that, prior to eruption, experienced variable amounts of exchange with meteoric hydrothermal fluids and subsequent partial melting. U-Th and oxygen isotope results allow us to examine the timescales of hydrothermal circulation and partial melting, and provide an “outside in” perspective on the buildup to the climactic eruption of Mt. Mazama. Oxygen isotope compositions measured in the cores and rims of individual quartz (n = 126) and plagioclase (n = 91) crystals, and for transects across ten quartz crystals, document zonation in quartz (Δ18OCore-Rim ≤ 0.1–5.5‰), but show homogeneity in plagioclase (Δ18OCore-Rim ≤ ±0.8‰). We propose that oxygen isotope zonation in quartz records hydrothermal exchange followed by high-temperature exchange in response to partial melting caused by injection of basaltic to andesitic recharge magma into the deeper portions of the chamber. Results of modeling of oxygen diffusion in quartz indicates that hydrothermal exchange in quartz occurred over a period of ∼1000–63,000 years. Models also suggest that the onset of melting of the granitoids occurred a minimum of ∼10–200 years prior to the Mazama climactic eruption, an inference which is broadly consistent with results for magnetite homogenization and for Zr diffusion in melt previously reported by others.Uranium-thorium isotope compositions of most granitoid blocks are in 238U excess, and are in agreement with a 238U enriched array previously measured for volcanic rocks at Mt. Mazama. Uranium excess in the granitoids is likely due to enrichment via hydrothermal circulation, given their low δ18O values. The sample with the

Climatic implications of the Quaternary fluvial tufa record in the NE Iberian Peninsula over the last 500 ka

NASA Astrophysics Data System (ADS)

Sancho, Carlos; Arenas, Concha; Vázquez-Urbez, Marta; Pardo, Gonzalo; Lozano, María Victoria; Peña-Monné, José Luis; Hellstrom, John; Ortiz, José Eugenio; Osácar, María Cinta; Auqué, Luis; Torres, Trinidad

2015-11-01

The drainage area of the Iberian Ranges (NE Spain) houses one of the most extensive Quaternary fluvial tufaceous records in Europe. In this study, tufa deposits in the Añamaza, Mesa, Piedra and Ebrón river valleys were mapped, stratigraphically described and chronologically referenced from U/Th disequilibrium series, amino acid racemization and radiocarbon methods. Tufa deposits accumulated in cascades, barrage-cascades and related damming areas developed in stepped fluvial systems. The maximum frequency of tufa deposition was identified at 120 ka (Marine Oxygen Isotope Stage [MIS] 5e), 102 ka (MIS 5c), 85 ka ( MIS 5a) and 7 ka (MIS 1), probably under warmer and wetter conditions than today. Additional phases of tufa deposition appear at 353 ka ( end of MIS 11), 258-180 ka (MIS 7) and 171-154 ka (MIS 6). Although most tufa deposition episodes are clearly correlated with interstadial periods, the occurrence of tufa deposits during the penultimate glaciation (MIS 6) is remarkable, indicating that the onset of this stage was climatically favourable in the Iberian Peninsula. Biostatic conditions and the dynamics of karstic systems regulating tufa deposition seem to be sensitive to the precipitation regime, controlled by shifts in the position of North Atlantic atmospheric belts, and summer insolation, regulated by orbital forcing.

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

USGS Publications Warehouse

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

2015-01-01

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

Detection of phosphohydrolytic enzyme activity through the oxygen isotope composition of dissolved phosphate

NASA Astrophysics Data System (ADS)

Colman, A. S.

2016-02-01

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.

Oxygen isotope variation in stony-iron meteorites.

PubMed

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

2006-09-22

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

Stable isotope analysis of molecular oxygen from silicates and oxides using CO2 laser extraction

NASA Technical Reports Server (NTRS)

Perry, Eugene

1996-01-01

A laser-excited system for determination of the oxygen isotope composition of small quantities of silicate and oxide minerals was constructed and tested at JSC. This device is the first reported to use a commercially available helium cryostat to transfer and purify oxygen gas quantitatively within the system. The system uses oxygen gas instead of the conventional CO2 for mass spectrometer analyses. This modification of technique permits determination of all three stable oxygen isotopes, an essential requirement for oxygen isotope analysis of meteoritic material. Tests of the system included analysis of standard silicate materials NBS 28 and UWMG2 garnet, six SNC meteorites, and inclusions and chondrules from the Allende meteorite. Calibration with terrestrial standards was excellent. Meteorite values are close to published values and show no evidence of terrestrial oxygen contamination. The one limitation observed is that, in some runs on fine-grained SNC matrix material, sample results were affected by other samples in the sample holder within the reaction chamber. This reemphasizes the need for special precautions in dealing with fine-grained, reactive samples. Performance of the JSC instrument compares favorably with that of any other instrument currently producing published oxygen isotope data.

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

NASA Astrophysics Data System (ADS)

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

2003-12-01

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

Nitrogen and Oxygen Isotopic Studies of the Marine Nitrogen Cycle

NASA Astrophysics Data System (ADS)

Casciotti, Karen L.

2016-01-01

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

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

USGS Publications Warehouse

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

2002-01-01

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

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

USGS Publications Warehouse

O'Neil, J.R.; Kharaka, Y.K.

1976-01-01

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

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

PubMed Central

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

2012-01-01

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

Sulfur and oxygen isotope fractionation during benzene, toluene, ethyl benzene, and xylene degradation by sulfate-reducing bacteria.

PubMed

Knöller, Kay; Vogt, Carsten; Richnow, Hans-Herrmann; Weise, Stephan M

2006-06-15

We examined the oxygen and sulfur isotope fractionation of sulfate during anaerobic degradation of toluene by sulfate-reducing bacteria in culture experiments with Desulfobacula toluolica as a type strain and with an enrichment culture Zz5-7 obtained from a benzene, toluene, ethylbenzene, and xylene (BTEX)-contaminated aquifer. Sulfur isotope fractionation can show considerable variation upon sulfate reduction and may react extremely sensitively to changes in environmental conditions. In contrast, oxygen isotope fractionation seems to be less sensitive to environmental changes. Our results clearly indicate that oxygen isotope fractionation is dominated by isotope exchange with ambient water. To verify our experimental results and to test the applicability of oxygen and sulfur isotope investigations under realistic field conditions, we evaluated isotope data from two BTEX-contaminated aquifers presented in the recent literature. On a field scale, bacterial sulfate reduction may be superimposed by processes such as dispersion, adsorption, reoxidation, or mixing. The dual isotope approach enables the identification of such sulfur transformation processes. This identification is vital for a general qualitative evaluation of the natural attenuation potential of the contaminated aquifer.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Growth of the European abalone ( Haliotis tuberculata L.) in situ: Seasonality and ageing using stable oxygen isotopes

NASA Astrophysics Data System (ADS)

Roussel, Sabine; Huchette, Sylvain; Clavier, Jacques; Chauvaud, Laurent

2011-02-01

The ormer, Haliotis tuberculata is the only European abalone species commercially exploited. The determination of growth and age in the wild is an important tool for fisheries and aquaculture management. However, the ageing technique used in the past in the field is unreliable. The stable oxygen isotope composition ( 18O/ 16O) of the shell depends on the temperature and oxygen isotope composition of the ambient sea water. The stable oxygen isotope technique, developed to study paleoclimatological changes in shellfish, was applied to three H. tuberculata specimens collected in north-west Brittany. For the specimens collected, the oxygen isotope ratios of the shell reflected the seasonal cycle in the temperature. From winter-to-winter cycles, estimates of the age and the annual growth increment, ranging from 13 to 55 mm per year were obtained. This study shows that stable oxygen isotopes can be a reliable tool for ageing and growth studies of this abalone species in the wild, and for validating other estimates.

Oxygen isotope fractionation in the siderite-water system between 8.5 and 62 °C

NASA Astrophysics Data System (ADS)

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

2018-01-01

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.

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

PubMed

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

2012-07-01

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

Defining Uncertainty and Error in Planktic Foraminiferal Oxygen Isotope Measurements

NASA Astrophysics Data System (ADS)

Fraass, A. J.; Lowery, C.

2016-12-01

Foraminifera are the backbone of paleoceanography, and planktic foraminifera are one of the leading tools for reconstructing water column structure. Currently, there are unconstrained variables when dealing with 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 the precision and accuracy of oxygen isotope measurements. FIRM produces synthetic isotope data using parameters including location, depth habitat, season, number of individuals included in measurement, diagenesis, misidentification, size variation, and vital effects. Reproducibility is then tested using Monte Carlo simulations. The results from a series of experiments show that reproducibility is 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. Currently FIRM is a tool to estimate isotopic error values best employed in the Holocene. It is also a tool to explore the impact of myriad factors on the fidelity of paleoceanographic records. FIRM was constructed in the open-source computing environment R and is freely available via GitHub. We invite modification and expansion, and have planned inclusions for benthic foram reproducibility and stratigraphic uncertainty.

99 Tc NMR determination of the oxygen isotope content in 18 O-enriched water.

PubMed

Tarasov, Valerii P; Kirakosyan, Gayana А; German, Konstantin E

2018-03-01

99 Tc NMR has been suggested as an original method of evaluating the content of oxygen isotopes in oxygen-18-enriched water, a precursor for the production of radioisotope fluorine-18 used in positron emission tomography. To this end, solutions of NH 4 TcO 4 or NaTcO 4 (up to 0.28 mol/L) with natural abundance of oxygen isotopes in virgin or recycled 18 O-enriched water have been studied by 99 Tc NMR. The method is based on 16 O/ 17 O/ 18 O intrinsic isotope effects in the 99 Tc NMR chemical shifts, and the statistical distribution of oxygen isotopes in the coordination sphere of TcO 4 - and makes it possible to quantify the composition of enriched water by measuring the relative intensities of the 99 Tc NMR signals of the Tc 16 O 4-n 18 O n - isotopologues. Because the oxygen exchange between TcO 4 - and enriched water in neutral and alkaline solutions is characterized by slow kinetics, gaseous HCl was bubbled through a solution for a few seconds to achieve the equilibrium distribution of oxygen isotopes in the Tc coordination sphere without distortion of the oxygen composition of the water. Pertechnetate ion was selected as a probe due to its high stability in solutions and the significant 99 Tc NMR shift induced by a single 16 O→ 18 O substitution (-0.43 ± 0.01 ppm) in TcO 4 - and spin coupling constant 1 J( 99 Tc- 17 O) (131.46 Hz) favourable for the observation of individual signals of Tc 16 O 4-n 18 O n - isotopologues. Copyright © 2017 John Wiley & Sons, Ltd.

The NO+O3 reaction: a triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly.

PubMed

Savarino, J; Bhattacharya, S K; Morin, S; Baroni, M; Doussin, J-F

2008-05-21

Atmospheric nitrate shows a large oxygen isotope anomaly (Delta 17 O), characterized by an excess enrichment of 17 O over 18 O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO(x), greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8+/-5)%(+/-2 sigma) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship Delta 17 O(NO2)=A x Delta 17 O(O3)+B, with A=1.18+/-0.07(+/-1 sigma) and B=(6.6+/-1.5)[per thousand](+/-1 sigma). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

Oxygen Isotopic Fractionation During Evaporation of SiO2 in Vacuum and in H Gas

NASA Astrophysics Data System (ADS)

Nagahara, H.; Young, E. D.; Hoering, T. C.; Mysen, B. O.

1993-07-01

Chondritic components, chondrules, CAIs, and some parts of the matrix are believed to have formed and/or thermally processed in the solar nebula. If this scenario is the case, they should be fractionated for major and minor elements and isotopes according to the formation temperature. This is true for major and trace elements, but is not the case for isotopes. Differences in oxygen isotopic composition among meteorite groups are interpreted to be the results of mixing of gas and dust from different oxygen reservoirs, and the effect of isotopic fractionation is negligible for most meteorites except for rare CAIs. Davis et al. [1] studied the isotopic fractionation of SiO2, MgO, and forsterite and showed that oxygen isotopic fractionation from solid materials is very small, but that from liquid is significant. Evaporation in the solar nebula should, however, be in hydrogen gas, which is reactive with silicates. Therefore, the effect of hydrogen gas on the evaporation behaviors of silicates, including mode of evaporation, evaporation rate, and compositional and isotopic fractionation, should be studied. Nagahara [2] studied the evaporation rate of SiO2 in equilibrium, in constant evacuation (free evaporation), and in hydrogen, and showed that the rate in hydrogen gas is orders of magnitude larger than that in vacuum; the mode of evaporation also differs from that in vacuum. Oxygen isotopic fractionation during evaporation of SiO2 in constant evacuation and in hydrogen gas at two different total pressures are studied in the present study. The starting material is a single crystal of natural quartz, which should transform into high cristobalite at experimental conditions. The powdered starting material was kept in a graphite capsule without a cap and set in a vacuum chamber with and without hydrogen gas flow. Experimental temperature was 1600 degrees C. Oxygen isotopic compositions (^18O/^16O) were measured with the CO2laser heating fluorination technique. Oxygen

From Mars Meteorites to Laboratory Investigations: Understanding Heterogeneous Photochemical Transformations Using Oxygen Triple Isotope Anomalies of Carbonates

NASA Astrophysics Data System (ADS)

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

2016-12-01

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 (< μs), however, our data indicate that its signature is preserved through surficial interactions with adsorbed CO2 on mineral surfaces. Hydroxyl radicals may have played a significant role in heterogeneous photochemical transformations on mineral dust in the atmosphere of Mars and transfer of ozone anomaly to water and other oxygen 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

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

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

Triple oxygen isotope composition of leaf waters in Mpala, central Kenya

NASA Astrophysics Data System (ADS)

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

2017-06-01

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.

Investigating the Direct Meltwater Effect in Terrestrial Oxygen-Isotope Paleoclimate Records Using an Isotope-Enabled Earth System Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jiang; Liu, Zhengyu; Brady, Esther C.

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. In this work, 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 δ 18O signals in precipitation over Greenland and eastern Brazilmore » for large freshwater forcings (0.25–0.50 sverdrup (10 6 m 3/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 δ 18O.« less

Investigating the Direct Meltwater Effect in Terrestrial Oxygen-Isotope Paleoclimate Records Using an Isotope-Enabled Earth System Model

DOE PAGES

Zhu, Jiang; Liu, Zhengyu; Brady, Esther C.; ...

2017-12-28

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. In this work, 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 δ 18O signals in precipitation over Greenland and eastern Brazilmore » for large freshwater forcings (0.25–0.50 sverdrup (10 6 m 3/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 δ 18O.« less

Climate, Environment and Early Human Innovation: Stable Isotope and Faunal Proxy Evidence from Archaeological Sites (98-59ka) in the Southern Cape, South Africa

PubMed Central

Keene, Petro; Gledhill, Andrew; Reynard, Jerome; Badenhorst, Shaw

2016-01-01

The Middle Stone Age (MSA) of southern Africa, and in particular its Still Bay and Howiesons Poort lithic traditions, represents a period of dramatic subsistence, cultural, and technological innovation by our species, Homo sapiens. Climate change has frequently been postulated as a primary driver of the appearance of these innovative behaviours, with researchers invoking either climate instability as a reason for the development of buffering mechanisms, or environmentally stable refugia as providing a stable setting for experimentation. Testing these alternative models has proved intractable, however, as existing regional palaeoclimatic and palaeoenvironmental records remain spatially, stratigraphically, and chronologically disconnected from the archaeological record. Here we report high-resolution records of environmental shifts based on stable carbon and oxygen isotopes in ostrich eggshell (OES) fragments, faunal remains, and shellfish assemblages excavated from two key MSA archaeological sequences, Blombos Cave and Klipdrift Shelter. We compare these records with archaeological material remains in the same strata. The results from both sites, spanning the periods 98–73 ka and 72–59 ka, respectively, show significant changes in vegetation, aridity, rainfall seasonality, and sea temperature in the vicinity of the sites during periods of human occupation. While these changes clearly influenced human subsistence strategies, we find that the remarkable cultural and technological innovations seen in the sites cannot be linked directly to climate shifts. Our results demonstrate the need for scale-appropriate, on-site testing of behavioural-environmental links, rather than broader, regional comparisons. PMID:27383620

Climate, Environment and Early Human Innovation: Stable Isotope and Faunal Proxy Evidence from Archaeological Sites (98-59ka) in the Southern Cape, South Africa.

PubMed

Roberts, Patrick; Henshilwood, Christopher S; van Niekerk, Karen L; Keene, Petro; Gledhill, Andrew; Reynard, Jerome; Badenhorst, Shaw; Lee-Thorp, Julia

2016-01-01

The Middle Stone Age (MSA) of southern Africa, and in particular its Still Bay and Howiesons Poort lithic traditions, represents a period of dramatic subsistence, cultural, and technological innovation by our species, Homo sapiens. Climate change has frequently been postulated as a primary driver of the appearance of these innovative behaviours, with researchers invoking either climate instability as a reason for the development of buffering mechanisms, or environmentally stable refugia as providing a stable setting for experimentation. Testing these alternative models has proved intractable, however, as existing regional palaeoclimatic and palaeoenvironmental records remain spatially, stratigraphically, and chronologically disconnected from the archaeological record. Here we report high-resolution records of environmental shifts based on stable carbon and oxygen isotopes in ostrich eggshell (OES) fragments, faunal remains, and shellfish assemblages excavated from two key MSA archaeological sequences, Blombos Cave and Klipdrift Shelter. We compare these records with archaeological material remains in the same strata. The results from both sites, spanning the periods 98-73 ka and 72-59 ka, respectively, show significant changes in vegetation, aridity, rainfall seasonality, and sea temperature in the vicinity of the sites during periods of human occupation. While these changes clearly influenced human subsistence strategies, we find that the remarkable cultural and technological innovations seen in the sites cannot be linked directly to climate shifts. Our results demonstrate the need for scale-appropriate, on-site testing of behavioural-environmental links, rather than broader, regional comparisons.

Quasi-free Proton Knockout Reactions on the Oxygen Isotopic Chain

NASA Astrophysics Data System (ADS)

Atar, Leyla; Aumann, Thomas; Bertulani, Carlos; Paschalis, Stefanos; R3B Collaboration

2017-09-01

It is well known from electron-induced knockout data that the single-particle (SP) strength is reduced to about 60-70% for stable nuclei in comparison to the independent particle model due to the presence of short- and long-range correlations. This finding has been confirmed by nuclear knockout reactions using stable and exotic beams, however, with a strong dependency on the proton-neutron asymmetry. The observed strong reduction of SP cross sections for the deeply bound valence nucleons in asymmetric nuclei is theoretically not understood. To understand this dependency quantitatively a complementary approach, quasi-free (QF) knockout reactions in inverse kinematics, is introduced. We have performed a systematic study of spectroscopic strength of oxygen isotopes using QF (p,2p) knockout reactions in complete kinematics at the R3B/LAND setup at GSI with secondary beams containing 13-24O. The oxygen isotopic chain covers a large variation of separ ation energies, which allow a systematic study of SF with respect to isospin asymmetry. We will present results on the (p,2p) cross sections for the entire oxygen isotopic chain obtained from a single experiment. By comparison with the Eikonal reaction theory the SF and reduction factors will be presented. The work is supported by GSI-TU Darmstadt cooperation and BMBF project 05P15RDFN1.

Evidence for higher-than-average air temperatures after the 8.2 ka event provided by a Central European δ18O record

NASA Astrophysics Data System (ADS)

Andersen, Nils; Lauterbach, Stefan; Erlenkeuser, Helmut; Danielopol, Dan L.; Namiotko, Tadeusz; Hüls, Matthias; Belmecheri, Soumaya; Dulski, Peter; Nantke, Carla; Meyer, Hanno; Chapligin, Bernhard; von Grafenstein, Ulrich; Brauer, Achim

2017-09-01

The so-called 8.2 ka event represents one of the most prominent cold climate anomalies during the Holocene warm period. Accordingly, several studies have addressed its trigger mechanisms, absolute dating and regional characteristics so far. However, knowledge about subsequent climate recovery is still limited although this might be essential for the understanding of rapid climatic changes. Here we present a new sub-decadally resolved and precisely dated oxygen isotope (δ18O) record for the interval between 7.7 and 8.7 ka BP (103 calendar years before AD 1950), derived from the calcareous valves of benthic ostracods preserved in the varved lake sediments of pre-Alpine Mondsee (Austria). Besides a clear reflection of the 8.2 ka event, showing a good agreement in timing, duration and magnitude with other regional stable isotope records, the high-resolution Mondsee lake sediment record provides evidence for a 75-year-long interval of higher-than-average δ18O values directly after the 8.2 ka event, possibly reflecting increased air temperatures in Central Europe. This observation is consistent with evidence from other proxy records in the North Atlantic realm, thus most probably reflecting a hemispheric-scale climate signal rather than a local phenomenon. As a possible trigger we suggest an enhanced resumption of the Atlantic meridional overturning circulation (AMOC), supporting assumptions from climate model simulations.

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

NASA Astrophysics Data System (ADS)

Severmann, S.

2015-12-01

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

Oxygen isotopes as a tool to quantify reservoir-scale CO2 pore-space saturation

NASA Astrophysics Data System (ADS)

Serno, Sascha; Flude, Stephanie; Johnson, Gareth; Mayer, Bernard; Boyce, Adrian; Karolyte, Ruta; Haszeldine, Stuart; Gilfillan, Stuart

2017-04-01

Structural and residual trapping of carbon dioxide (CO2) are two key mechanisms of secure CO2 storage, an essential component of Carbon Capture and Storage technology [1]. Estimating the amount of CO2 that is trapped by these two mechanisms is a vital requirement for accurately assessing the secure CO2 storage capacity of a formation, but remains a key challenge. Recent field [2,3] and laboratory experiment studies [4] have shown that simple and relatively inexpensive measurements of oxygen isotope ratios in both the injected CO2 and produced water can provide an assessment of the amount of CO2 that is stored by these processes. These oxygen isotope assessments on samples obtained from observation wells provide results which are comparable to other geophysical techniques. In this presentation, based on the first comprehensive review of oxygen isotope ratios measured in reservoir waters and CO2 from global CO2 injection projects, we will outline the advantages and potential limitations of using oxygen isotopes to quantify CO2 pore-space saturation. We will further summarise the currently available information on the oxygen isotope composition of captured CO2. Finally, we identify the potential issues in the use of the oxygen isotope shifts in the reservoir water from baseline conditions to estimate accurate saturations of the pore space with CO2, and suggest how these issues can be reduced or avoided to provide reliable CO2 pore-space saturations on a reservoir scale in future field experiments. References [1] Scott et al., (2013) Nature Climate Change, Vol. 3, 105-111 doi:10.1038/nclimate1695 [2] Johnson et al., (2011) Chemical Geology, Vol. 283, 185-193 http://dx.doi.org/10.1016/j.ijggc.2016.06.019 [3] Serno et al., (2016) IJGGC, Vol. 52, 73-83 http://dx.doi.org/10.1016/j.ijggc.2016.06.019 [4] Johnson et al., (2011) Applied Geochemistry, Vol. 26 (7) 1184-1191 http://dx.doi.org/10.1016/j.apgeochem.2011.04.007

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

PubMed Central

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

1984-01-01

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

Oxygen isotope variations in phosphate of deer bones

NASA Astrophysics Data System (ADS)

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

1990-06-01

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

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Stable isotope compositions of speleothems from the last interglacial - Spatial patterns of climate fluctuations in Europe

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Oxygen and hydrogen isotope geochemistry of zeolites

NASA Technical Reports Server (NTRS)

Karlsson, Haraldur R.; Clayton, Robert N.

1990-01-01

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

Estimation of oxygen isotope in source water of tree-ring cellulose in Indonesia using tree-ring oxygen isotope model

NASA Astrophysics Data System (ADS)

Hisamochi, R.; Watanabe, Y.; Kurita, N.; Sano, M.; Nakatsuka, T.; Matsuo, M.; Yamamoto, H.; Sugiyama, J.; Tsuda, T.; Tagami, T.

2016-12-01

Oxygen isotope composition (δ18O) of tree-ring cellulose has been used as paleoclimate proxy because its origin is atmospheric precipitation. However, interpretation of tree-ring cellulose δ18O is not simple because source water of tree-ring cellulose (the water took up by tree) is not atmospheric precipitation but soil water or ground water in growing season, precisely. In this study, we investigate the relationship between source water of tree-ring cellulose and precipitation in order to improve interpretation of tree-ring cellulose δ18O as paleoclimate proxy. We collected ten teak (Tectona grandis) plantation samples in Java Island, Indonesia. Teak is deciduous tree and grows in rainy season. Samples were cut into annual rings after cellulose extraction. δ18O of individual rings were measured by TCEA-IRMS at the Research Institute of Humanity and Nature. We calculatedδ18O of source water by means of tree-ring oxygen isotope model and then comparedδ18O of source water and that of monthly atmospheric precipitation at Jakarta (GNIP; Global Network of isotopes in Precipitation). Source waterδ18O shows two types of significant correlation withδ18O in atmospheric precipitation. One is positive correlation withδ18O of atmospheric precipitation in previous rainy season. Another is negative correlation with δ18O of atmospheric precipitation in beginning of the growing season. The former indicates that soil water in growing season contains rainfall in previous rainy season and teak mainly takes it up. The latter is difficult to interpret. It may be related to soil moisutre in beginning of growing season.

Millennial-scale variability to 735 ka: High-resolution climate records from Santa Barbara Basin, CA

NASA Astrophysics Data System (ADS)

White, Sarah M.; Hill, Tessa M.; Kennett, James P.; Behl, Richard J.; Nicholson, Craig

2013-06-01

Determining the ultimate cause and effect of millennial-scale climate variability remains an outstanding problem in paleoceanography, partly due to the lack of high-resolution records predating the last glaciation. Recent cores from Santa Barbara Basin provide 2500-5700 year "windows" of climate with 10-50 year resolution. Ages for three cores, determined by seismic stratigraphic correlation, oxygen isotope stratigraphy, and biostratigraphy, date to 293 ka (MIS 8), 450 ka (MIS 12), and 735 ka (MIS 18). These records sample the Late Pleistocene, during which the 100 kyr cycle strengthened and the magnitude of glacial-interglacial cyclicity increased. Thus, these records provide a test of the dependence of millennial-scale behavior on variations in glacial-interglacial cyclicity. The stable isotopic (δ18O) composition of planktonic foraminifera shows millennial-scale variability in all three intervals, with similar characteristics (duration, cyclicity) to those previously documented during MIS 3 at this site. Stadial G. bulloides δ18O values are 2.75-1.75‰ (average 2.25‰) and interstadial values are 1.75-0.5‰ (average 1‰), with rapid (decadal-scale) interstadial and stadial initiations of 1-2‰, as in MIS 3. Interstadials lasted 250-1600 years and occurred every 650-1900 years. Stadial paleotemperatures were 3.5-9.5°C and interstadial paleotemperatures were 7.5-13°C. Upwelling, evidenced by planktonic foraminiferal assemblages and δ13C, increased during interstadials, similar to MIS 3; high productivity during some stadials was reminiscent of the Last Glacial Maximum. This study builds upon previous records in showing that millennial-scale shifts were an inherent feature of Northern Hemisphere glacial climates since 735 ka, and they remained remarkably constant in the details of their amplitude, cyclicity, and temperature variability.

Oxygen isotope analysis of fossil organic matter by secondary ion mass spectrometry

NASA Astrophysics Data System (ADS)

Tartèse, Romain; Chaussidon, Marc; Gurenko, Andrey; Delarue, Frédéric; Robert, François

2016-06-01

We have developed an analytical procedure for the measurement of oxygen isotope composition of fossil organic matter by secondary ion mass spectrometry (SIMS) at the sub-per mill level, with a spatial resolution of 20-30 μm. The oxygen isotope composition of coal and kerogen samples determined by SIMS are on average consistent with the bulk oxygen isotope compositions determined by temperature conversion elemental analysis - isotope ratio mass spectrometry (TC/EA-IRMS), but display large spreads of δ18O of ∼5-10‰, attributed to mixing of remnants of organic compounds with distinct δ18O signatures. Most of the δ18O values obtained on two kerogen residues extracted from the Eocene Clarno and Early Devonian Rhynie continental chert samples and on two immature coal samples range between ∼10‰ and ∼25‰. Based on the average δ18O values of these samples, and on the O isotope composition of water processed by plants that now constitute the Eocene Clarno kerogen, we estimated δ18Owater values ranging between around -11‰ and -1‰, which overall correspond well within the range of O isotope compositions for present-day continental waters. SIMS analyses of cyanobacteria-derived organic matter from the Silurian Zdanow chert sample yielded δ18O values in the range 12-20‰. Based on the O isotope composition measured on recent cyanobacteria from the hypersaline Lake Natron (Tanzania), and on the O isotope composition of the lake waters in which they lived, we propose that δ18O values of cyanobacteria remnants are enriched by about ∼18 ± 2‰ to 22 ± 2‰ relative to coeval waters. This relationship suggests that deep ocean waters in which the Zdanow cyanobacteria lived during Early Silurian times were characterised by δ18O values of around -5 ± 4‰. This study, establishing the feasibility of micro-analysis of Phanerozoic fossil organic matter samples by SIMS, opens the way for future investigations of kerogens preserved in Archean cherts and of the

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

NASA Astrophysics Data System (ADS)

Brookman, Tom H.; Ambrose, Stanley H.

2012-09-01

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

Oxygen isotopes of phosphatic compounds - Application for marine particulate matter, sediments and soils

USGS Publications Warehouse

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

2006-01-01

The phosphate oxygen isotopic composition in naturally occurring particulate phosphatic compounds (??18Op) can be used as a tracer for phosphate sources and to evaluate the cycling of phosphorus (P) in the environment. However, phosphatic compounds must be converted to silver phosphate prior to isotopic analysis, a process that involves digestion of particulate matter in acid. This digestion will hydrolyze some of the phosphatic compounds such that oxygen from the acid solution will be incorporated into the sample as these phosphatic compounds are converted to orthophosphate (PO 43-). To determine the extent of incorporation of reagent oxygen into the sample, we digested various phosphatic compounds in both acid amended with H218O (spiked) and unspiked acid and then converted the samples to silver phosphate for ??18Op analysis. Our results indicate that there is no isotopic fractionation associated with acid digestion at 50??C. Furthermore, we found that reagent oxygen incorporation is a function of the oxygen to phosphorus ratio (O:P) of the digested compound whereby the percentage of reagent oxygen incorporated into the sample is the same as that which is required to convert all of the P-compounds into orthophosphate. Based on these results, we developed a correction for reagent oxygen incorporation using simple mass balance, a procedure that allows for the determination of the ??18O p of samples containing a mixture of phosphatic compounds. We analyzed a variety of environmental samples for ??18O p to demonstrate the utility of this approach for understanding sources and cycling of P. ?? 2005 Elsevier B.V. All rights reserved.

Ground Based Observation of Isotopic Oxygen in the Martian Atmosphere Using Infrared Heterodyne Spectroscopy

NASA Technical Reports Server (NTRS)

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

2010-01-01

Infrared heterodyne spectra of isotopic CO2 in the Martian atmosphere were obtained using the Goddard Heterodyne Instrument for Planetary Wind and Composition, HIPWAC, which was interfaced with the 3-meter telescope at the NASA Infrared Telescope Facility- Spectra were colle cted at a resolution of lambda/delta lambda=10(exp 7). Absorption fea tures of the CO2 isotopologues have been identified from which isotop ic ratios of oxygen have been determined. The isotopic ratios O-17/O -16 and O-18/O-16 in the Martian atmosphere can be related to Martian atmospheric evolution and can be compared to isotopic ratios of oxyg en in the Earth's atmosphere. Isotopic carbon and oxygen are importa nt constraints on any theory for the erosion of the Martian primordia l atmosphere and the interaction between the atmosphere and surface o r subsurface chemical reservoirs. This investigation explored the pr esent abundance of the stable isotopes of oxygen in Mars' atmospheric carbon dioxide by measuring rovibrational line absorption in isotop ic species of CO2 using groundbased infrared heterodyne spectroscopy in the vicinity of the 9.6 micron and 10.6 micron CO2 lasing bands. T he target transitions during this observation were O-18 C-12 O-16 as well as O-178 C-12 O-16 and O-16 C-113 O-16 at higher resolving power of lambda/delta lambda=10(exp 7) and with high signal-to-noise ratio (longer integration time) in order to fully characterize the absorpt ion line profiles. The fully-resolved lineshape of both the strong n ormal-isotope and the weak isotopic CO2 lines were measured simultane ously in a single spectrum.

Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

USGS Publications Warehouse

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

2012-01-01

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

In-Situ Oxygen Isotopic Composition of Tagish Lake: An Ungrouped Type 2 Carbonaceous Chondrite

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-09-01

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

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

USGS Publications Warehouse

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

1978-01-01

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

Triple oxygen isotope composition of tropospheric carbon dioxide and terrestrial carbonates

NASA Astrophysics Data System (ADS)

Hofmann, M. E.; Horváth, B.; Pack, A.

2011-12-01

The triple oxygen isotope composition of tropospheric CO2 is a potential new tracer in urban air studies and for biosphere-atmosphere interactions [1]. In this study, we are analyzing CO2 from different provenances in order to trace the influx of anthropogenic CO2 to urban air and to test predictions on the stratosphere-troposphere exchange flux. Since July 2010, we are monitoring the triple oxygen isotope composition of CO2 in urban air in a two-week interval. For this purpose, carbon dioxide was extracted from ~450L of ambient air on the campus of the University of Göttingen using a Russian Doll type cryogenic trap [2]. The CO2 was analyzed by CO2-CeO2 equilibration at 685°C and subsequent IR laser fluorination of CeO2 and CF-irmMS [3]. All triple oxygen isotope data are reported as Δ17OTFL values relative to the terrestrial fractionation line (TFL) with a slope βTFL=0.5251 and an intercept γTFL=-0.014%. On average, the Δ17OTFL value of ambient CO2 was -0.11±0.05% (SD) with a seasonal cycle of 0.04±0.01%. Lower Δ17O values were observed during wintertime. In order to test the potential of Δ17O as a tracer for anthropogenic CO2, we analyzed CO2 from different combustion processes. Our results showed that the Δ17O anomaly of tropospheric O2 [4] is passed on fully, or partially to the combustion CO2 [5]. We estimate that elevated anthropogenic emission during wintertime could be responsible for a decrease in Δ17O of urban air CO2 of -0.02±0.01%. In order to predict the triple oxygen isotope composition of tropospheric CO2 on a global scale, we revised the box model calculation from Hoag et al. [1]. For the exponent β for CO2-water equilibrium, we assume that βCO2-water=0.522±0.001 [6]. Furthermore, we took into account that the Δ17OTFL value of CO2 released from soils is affected by kinetic fractionation. Thus, we obtained a Δ17OTFL value for global tropospheric CO2 of -0.13%. The model calculation agrees well with the Δ17OTFL value determined for

Oxygen Isotopes and Origin of Opal in an Antarctic Ureilite

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Oxygen isotopes reveal crustal contamination and a large, still partially molten magma chamber in Chaîne des Puys (French Massif Central)

NASA Astrophysics Data System (ADS)

France, Lydéric; Demacon, Mickael; Gurenko, Andrey A.; Briot, Danielle

2016-09-01

The two main magmatic properties associated with explosive eruptions are high viscosity of silica-rich magmas and/or high volatile contents. Magmatic processes responsible for the genesis of such magmas are differentiation through crystallization, and crustal contamination (or assimilation) as this process has the potential to enhance crystallization and add volatiles to the initial budget. In the Chaîne des Puy series (French Massif Central), silica- and H2O-rich magmas were only emitted during the most recent eruptions (ca. 6-15 ka). Here, we use in situ measurements of oxygen isotopes in zircons from two of the main trachytic eruptions from the Chaîne des Puys to track the crustal contamination component in a sequence that was previously presented as an archetypal fractional crystallization series. Zircons from Sarcoui volcano and Puy de Dôme display homogeneous oxygen isotope compositions with δ18O = 5.6 ± 0.25‰ and 5.6 ± 0.3‰, respectively, and have therefore crystallized from homogeneous melts with δ18Omelt = 7.1 ± 0.3‰. Compared to mantle derived melts resulting from pure fractional crystallization (δ18Odif.mant. = 6.4 ± 0.4‰), those δ18Omelt values are enriched in 18O and support a significant role of crustal contamination in the genesis of silica-rich melts in the Chaîne des Puys. Assimilation-fractional-crystallization models highlight that the degree of contamination was probably restricted to 5.5-9.5% with Rcrystallization/Rassimilation varying between 8 and 14. The very strong intra-site homogeneity of the isotopic data highlights that magmas were well homogenized before eruption, and consequently that crustal contamination was not the trigger of silica-rich eruptions in the Chaîne des Puys. The exceptionally strong inter-site homogeneity of the isotopic data brings to light that Sarcoui volcano and Puy de Dôme were fed by a single large magma chamber. Our results, together with recent thermo-kinetic models and an experimental

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

NASA Astrophysics Data System (ADS)

Juillet-Leclerc, A.; Reynaud, S.

2009-04-01

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

Abrupt hydroclimate disruption across the Australian arid zone 50 ka coincident with human colonization

NASA Astrophysics Data System (ADS)

Miller, G. H.; Fogel, M. L.; Magee, J. W.; Gagan, M. K.

2016-12-01

Although many studies focus on how climate change impacted ancient societies, in Australia a growing body of evidence indicates that activities of the earliest human colonizers in turn altered the Australian climate. We utilize the stable isotopes of carbon and oxygen preserved in near-continuous 100 ka time series of avian eggshell from five regions across the Australian arid zone to reconstruct ecosystem status (d13C) and effective moisture (d18O). Training sets of sub-modern samples provide the basis for the reconstructions. Together, d13C and d18O provide independent estimates of ecosystem status and climate over the past 100 ka from the same dated sample, reducing correlation uncertainties between proxies. Changes in eggshell d13C document a dramatic reduction of palatable summer-wet C4 grasses in all regions between 50 and 45 ka, that has persisted through to modern times. Continuous 100 ka records of effective moisture derived from eggshell d18O show moist conditions from 100 to 60 ka, with variable drying after 60 ka, but the strong shift toward greatest aridity is coincident with the onset of the last glacial maximum 30 ka ago, 15 ka after the observed ecosystem restructuring. Combining the d13C and d18O time-series shows that an abrupt and permanent restructuring of the moisture/ecosystem balance occurred between 50 and 45 ka. Additional studies show that most large monsoon-fed inland arid-zone lakes carried permanent water at least intermittently between 120 and 50 ka, but never experienced permanent deep-water status after 45 ka, despite a wide range of global climate states, including the early Holocene when most other monsoon systems were reinvigorated. The lack of exceptional climate shifts either locally or globally between 60 and 40 ka eliminates climate as the cause of the ecosystem restructuring and persistent lake desiccation. Collectively these data suggest the wave of human colonization across Australia in altered land surface characteristics

Using Oxygen and Carbon Isotopic Signatures in Order to Infer Climatic and Dietary Information in Roman Edessa, Greece

NASA Astrophysics Data System (ADS)

Michael, Dimitra-Ermioni; Dotsika, Elissavet

2017-12-01

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

Oxygen isotope fractionation in the vacuum ultraviolet photodissociation of carbon monoxide: Wavelength, pressure and temperature dependency.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid

Several absorption bands exist in the VUV region of Carbon monoxide (CO). Emission spectra indicate that these bands are all predissociative. An experimental investigation of CO photodissociation by vacuum ultraviolet photons (90 to 108 nm; ~13 to 11 eV) from the Advanced Light Source Synchrotron and direct measurement of the associated oxygen isotopic composition of the products are presented here. A wavelength dependency of the oxygen isotopic composition in the photodissociation product was observed. Slope values (δ'{sup 18}O/ δ'{sup 17}O) ranging from 0.76 to 1.32 were observed in oxygen three-isotope space (δ'{sup 18}O vs. δ'{sup 17}O) which correlated with increasingmore » synchrotron photon energy, and indicate a dependency of the upper electronic state specific dissociation dynamics (e.g., perturbation and coupling associated with a particular state). An unprecedented magnitude in isotope separation was observed for photodissociation at the 105 and 107 nm synchrotron bands and are found to be associated with accidental predissociation of the vibrational states ({nu} = 0 and 1) of the upper electronic state E{sup 1}Π. For each synchrotron band, a large (few hundred per mil) extent of isotopic fractionation was observed and the range of fractionation is a combination of column density and exposure time. A significant temperature dependency in oxygen isotopic fractionation was observed, indicating a rotational level dependency in the predissociation process.« less

High Precision Oxygen Three Isotope Analysis of Wild-2 Particles and Anhydrous Chondritic Interplanetary Dust Particles

NASA Technical Reports Server (NTRS)

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

2011-01-01

One of the most important discoveries from comet Wild-2 samples was observation of crystalline silicate particles that resemble chondrules and CAIs in carbonaceous chondrites. Previous oxygen isotope analyses of crystalline silicate terminal particles showed heterogeneous oxygen isotope ratios with delta(sup 18)O to approx. delta(sup 17)O down to -50% in the CAI-like particle Inti, a relict olivine grain in Gozen-sama, and an olivine particle. However, many Wild-2 particles as well as ferromagnesian silicates in anhydrous interplanetary dust particles (IDPs) showed Delta(sup 17)O values that cluster around -2%. In carbonaceous chondrites, chondrules seem to show two major isotope reservoirs with Delta(sup 17)O values at -5% and -2%. It was suggested that the Delta(sup 17)O = -2% is the common oxygen isotope reservoir for carbonaceous chondrite chondrules and cometary dust, from the outer asteroid belt to the Kuiper belt region. However, a larger dataset with high precision isotope analyses (+/-1-2%) is still needed to resolve the similarities or distinctions among Wild-2 particles, IDPs and chondrules in meteorites. We have made signifi-cant efforts to establish routine analyses of small particles (< or =10micronsm) at 1-2% precision using IMS-1280 at WiscSIMS laboratory. Here we report new results of high precision oxygen isotope analyses of Wild-2 particles and anhydrous chondritic IDPs, and discuss the relationship between the cometary dust and carbonaceous chondrite chondrules.

Humans permanently occupied the Andean highlands by at least 7 ka

PubMed Central

Stefanescu, Ioana C.; Garcia-Putnam, Alexander; Aldenderfer, Mark S.; Clementz, Mark T.; Murphy, Melissa S.; Llave, Carlos Viviano; Watson, James T.

2017-01-01

High-elevation environments above 2500 metres above sea level (m.a.s.l.) were among the planet's last frontiers of human colonization. Research on the speed and tempo of this colonization process is active and holds implications for understanding rates of genetic, physiological and cultural adaptation in our species. Permanent occupation of high-elevation environments in the Andes Mountains of South America tentatively began with hunter–gatherers around 9 ka according to current archaeological estimates, though the timing is currently debated. Recent observations on the archaeological site of Soro Mik'aya Patjxa (8.0–6.5 ka), located at 3800 m.a.s.l. in the Andean Altiplano, offer an opportunity to independently test hypotheses for early permanent use of the region. This study observes low oxygen (δ18O) and high carbon (δ13C) isotope values in human bone, long travel distances to low-elevation zones, variable age and sex structure in the human population and an absence of non-local lithic materials. These independent lines of evidence converge to support a model of permanent occupation of high elevations and refute logistical and seasonal use models. The results constitute the strongest empirical support to date for permanent human occupation of the Andean highlands by hunter–gatherers before 7 ka. PMID:28680685

Determining the oxygen isotope composition of evapotranspiration with eddy covariance

USDA-ARS?s Scientific Manuscript database

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

Oxygen isotopes in crystalline silicates of comet Wild 2: A comparison of oxygen isotope systematics between Wild 2 particles and chondritic materials

NASA Astrophysics Data System (ADS)

Nakashima, Daisuke; Ushikubo, Takayuki; Joswiak, David J.; Brownlee, Donald E.; Matrajt, Graciela; Weisberg, Michael K.; Zolensky, Michael E.; Kita, Noriko T.

2012-12-01

Oxygen three-isotope ratios of nine crystalline silicate particles from comet Wild 2 were measured to investigate oxygen isotope systematics of cometary materials. We are able to analyze particles as small as 4 μm using an ion microprobe with a˜1×2 μm beam by locating the analysis spots with an accuracy of ±0.4 μm. Three particles of Mn-rich forsterite, known as low-iron, manganese-enriched (LIME) olivine, showed extremely 16O-rich signatures (δ18O, δ17O˜-50‰), similar to refractory inclusions in chondrites. The three Mn-rich forsterite particles may have formed by condensation from an 16O-rich solar nebula gas. Other particles consist of olivine and/or pyroxene with a wide range of Mg# [=molar MgO/(FeO+MgO) %] from 60 to 96. Their oxygen isotope ratios plot nearly along the carbonaceous chondrite anhydrous mineral (CCAM) and Young and Russell lines with Δ17O(=δ17O-0.52×δ18O) values of -3.0‰ to +2.5‰. These data are similar to the range observed from previous analyses of Wild 2 crystalline silicates and those of chondrules in carbonaceous chondrites. Six particles extracted from Stardust track 77 show diverse chemical compositions and isotope ratios; two Mn-rich forsterites, FeO-poor pigeonite, and three FeO-rich olivines with a wide range of Δ17O values from -24‰ to +1.6‰. These results confirmed that the original projectile that formed track 77 was an aggregate (>6 μm) of silicate particles that formed in various environments. The Δ17O values of ferromagnesian Wild 2 particles (including data from previous studies) increase from ˜-23‰ to+2.5‰ with decreasing Mg#: Δ17O values of Mn-rich forsterite particles (Mg#=98-99.8) cluster at -23‰, those of FeO-poor particles (Mg#=95-97) cluster at -2‰, and those of FeO-rich particles (Mg#≤90) scatter mainly from -1.5‰ to+2.5‰. Compared to chondrules in primitive chondrites, the systematic trend between Mg# and Δ17O among the Wild 2 particles is most similar to that reported for CR

Multiple taxon multiple locality approach to providing oxygen isotope evidence for warm-blooded theropod dinosaurs

NASA Astrophysics Data System (ADS)

Fricke, Henry C.; Rogers, Raymond R.

2000-09-01

Oxygen isotope ratios of fossil remains of coexisting taxa from several different localities can be used to help investigate dinosaur thermoregulation. Focusing on the Late Cretaceous, oxygen isotope ratios of crocodile tooth enamel from four separate localities exhibit less of a decrease with latitude than do ratios of tooth enamel from coexisting theropod dinosaurs. A shallower latitudinal gradient for crocodiles is consistent with how oxygen isotope ratios should vary for heterothermic animals having body temperatures coupled with their environments (“cold blooded”), while a steeper gradient for theropods is consistent with how these ratios should vary for homeothermic animals having constant body temperatures independent of their environments (“warm blooded”). This inferred homoethermy in theropods is likely due to higher rates of metabolic heat production relative to crocodiles and is not an artifact of body size.

Negative Oxygen Isotope Effect in Manganites with an Ordered Cation Arrangement in a High Magnetic Field

NASA Astrophysics Data System (ADS)

Taldenkov, A. N.; Snegirev, V. V.; Babushkina, N. A.; Kalitka, V. S.; Kaul', A. R.

2018-03-01

The oxygen isotope effect in PrBaMn2 16-18 O5.97 manganite with an ordered cation arrangement is studied. The field dependences of magnetic susceptibility and magnetization are measured in the temperature range 100-270 K and magnetic fields up to 32 T. A significant increase in the temperature of the spin-reorientation antiferromagnet-ferromagnet phase transition is detected in samples enriched in heavy oxygen 18O (negative isotope effect). The transition temperature and the isotope effect depend strongly on the magnetic field. An H-T phase diagram is plotted for samples with various isotope compositions. An analysis of the experimental results demonstrates that the detected negative isotope effect and the giant positive isotope effect revealed earlier in doped manganites have the same nature. The mechanisms of appearance of isotope effects are discussed in terms of the double exchange model under a polaron narrowing of the free carrier band.

Assessment of oceanic productivity with the triple-isotope composition of dissolved oxygen.

PubMed

Luz, B; Barkan, E

2000-06-16

Plant production in the sea is a primary mechanism of global oxygen formation and carbon fixation. For this reason, and also because the ocean is a major sink for fossil fuel carbon dioxide, much attention has been given to estimating marine primary production. Here, we describe an approach for estimating production of photosynthetic oxygen, based on the isotopic composition of dissolved oxygen of seawater. This method allows the estimation of integrated oceanic productivity on a time scale of weeks.

The oxygen isotope enrichment of leaf-exported assimilates--does it always reflect lamina leaf water enrichment?

PubMed

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

2013-10-01

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 (18)O 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 (18)O 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. © 2013 The Authors. New Phytologist © 2013 New Phytologist Trust.

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

USGS Publications Warehouse

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

2013-01-01

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

On-line Differential Thermal Isotope Analysis: A New Method for Measuring Oxygen and Hydrogen Isotopes of Hydration Water in Minerals

NASA Astrophysics Data System (ADS)

Bauska, T.; Hodell, D. A.; Walters, G.

2016-12-01

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

Oxygen isotopic relationships between the LEW85332 carbonaceous chondrite and CR chondrites

NASA Technical Reports Server (NTRS)

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

1993-01-01

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.

Evaluation of the performance of high temperature conversion reactors for compound-specific oxygen stable isotope analysis.

PubMed

Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans-Hermann

2017-05-01

In this study conversion conditions for oxygen gas chromatography high temperature conversion (HTC) isotope ratio mass spectrometry (IRMS) are characterised using qualitative mass spectrometry (IonTrap). It is shown that physical and chemical properties of a given reactor design impact HTC and thus the ability to accurately measure oxygen isotope ratios. Commercially available and custom-built tube-in-tube reactors were used to elucidate (i) by-product formation (carbon dioxide, water, small organic molecules), (ii) 2nd sources of oxygen (leakage, metal oxides, ceramic material), and (iii) required reactor conditions (conditioning, reduction, stability). The suitability of the available HTC approach for compound-specific isotope analysis of oxygen in volatile organic molecules like methyl tert-butyl ether is assessed. Main problems impeding accurate analysis are non-quantitative HTC and significant carbon dioxide by-product formation. An evaluation strategy combining mass spectrometric analysis of HTC products and IRMS 18 O/ 16 O monitoring for future method development is proposed.

A 75 ka Stalagmite Paleoclimate Record from Northern Venezuela

NASA Astrophysics Data System (ADS)

Retrum, J. B.; Gonzalez, L. A.; Edwards, R.; Tincher, S. M.; Cheng, H.; Urbani, F.

2011-12-01

A stalagmite collected from Cueva Zarraga in the northern Venezuelan Andes was analyzed to determine local paleoclimatic history and help examine climate change in the Caribbean. Ages were determined by U/Th disequilibrium and the stalagmite shows a nearly complete record for ~ 75 ka. Two significant periods of non-deposition have been identified. The first period ranges between the Last Glacial Maximum at 19,820 ± 149 cal yr BP and a brief resumption of stalagmite growth at 15,409 ± 747 cal yr BP, likely representing the Bølling-Allerød interstadial. After the brief period of deposition, growth does not resume unil the Holocene at 10,408 ± 78 cal yr BP. Carbon and oxygen isotopes show a major depletion shift from the last glacial period to the Holocene, suggesting warmer and wetter conditions during the Holocene. The oxygen isotope depletion shift is also seen in the Cariaco Basin foraminifera record off the northern coast of Venezuela. While tempting to attribute δ13C depletion to decrease of the C4 plant contribution, there is no evidence that the area experience major vegetation changes. We attribute the δ13C depletion to enhanced recycling of soil CO2 resulting from canopy effects. Today, Cueva Zarraga is at the northern extent of the Inter-Tropical Convergence Zone (ITCZ). The cooler and drier conditions of the last glacial period suggest a southern displacement of the ITCZ. The close proximity of Cueva Zarraga to Cariaco Basin may allow for a high resolution tropical terrestrial and oceanic climatic response comparison.

Oxygen isotopic fractionation of O₂ during adsorption and desorption processes using molecular sieve at low temperatures.

PubMed

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

2014-06-15

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

The formation and alteration of the Renazzo-like carbonaceous chondrites I: Implications of bulk-oxygen isotopic composition

NASA Astrophysics Data System (ADS)

Schrader, Devin L.; Franchi, Ian A.; Connolly, Harold C., Jr.; Greenwood, Richard C.; Lauretta, Dante S.; Gibson, Jenny M.

2011-01-01

To better understand the role of aqueous alteration on the CR chondrite parent asteroid, a whole-rock oxygen isotopic study of 20 meteorites classified as Renazzo-like carbonaceous chondrites (CR) was conducted. The CR chondrites analyzed for their oxygen isotopes were Dhofar 1432, Elephant Moraine (EET) 87770, EET 92042, EET 96259, Gao-Guenie (b), Graves Nunataks (GRA) 95229, GRA 06100, Grosvenor Mountains (GRO) 95577, GRO 03116, LaPaz Ice Field (LAP) 02342, LAP 04720, Meteorite Hills (MET) 00426, North West Africa (NWA) 801, Pecora Escarpment (PCA) 91082, Queen Alexandra Range (QUE) 94603, QUE 99177, and Yamato-793495 (Y-793495). Three of the meteorites, Asuka-881595 (A-881595), GRA 98025, and MET 01017, were found not to be CR chondrites. The remaining samples concur petrographically and with the well-established oxygen-isotope mixing line for the CR chondrites. Their position along this mixing line is controlled both by the primary oxygen-isotopic composition of their individual components and their relative degree of aqueous alteration. Combined with literature data and that of this study, we recommend the slope for the CR-mixing line to be 0.70 ± 0.04 (2σ), with a δ 17O-intercept of -2.23 ± 0.14 (2σ). Thin sections of Al Rais, Shişr 033, Renazzo, and all but 3 samples analyzed for oxygen isotopes were studied petrographically. The abundance of individual components is heterogeneous among the CR chondrites, but FeO-poor chondrules and matrix are the most abundant constituents and therefore, dominate the whole-rock isotopic composition. The potential accreted ice abundance, physico-chemical conditions of aqueous alteration (e.g. temperature and composition of the fluid) and its duration control the degree of alteration of individual CR chondrites. Combined with literature data, we suggest that LAP 02342 was exposed to lower temperature fluid during alteration than GRA 95229. With only two falls, terrestrial alteration of the CR chondrites complicates the

Comparison of the oxygen and hydrogen isotopes in the juices of fast-growing vegetables and slow-growing fruits.

PubMed

Bong, Yeon-Sik; Lee, Kwang-Sik; Shin, Woo-Jin; Ryu, Jong-Sik

2008-09-01

We have analyzed the oxygen and hydrogen isotopic composition of juices from fruits and vegetables collected from a small orchard in order to investigate the differences in isotopic enrichment and evaporation intensity between fast-growing vegetables and slow-growing fruits grown under the same climatic conditions. The oxygen and hydrogen isotope levels were much higher in the juices of the fruits and vegetables than in the source waters in which they grew because of evaporation effects. According to our data, fast-growing vegetables are subject to greater evaporation than slow-growing fruits. An evaporation experiment using the source water showed that the oxygen and hydrogen isotopic composition of the 60-80% residual fraction was similar to that of the isotopically enriched grape juice, whereas those of the plume and tomato juices were very close to that of the 80-90% residual fraction, thus proving the effect of evaporation. Copyright (c) 2008 John Wiley & Sons, Ltd.

Oxygen isotope composition of mafic magmas at Vesuvius

NASA Astrophysics Data System (ADS)

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

2009-12-01

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

A Critical Look at the Combined Use of Sulfur and Oxygen Isotopes to Study Microbial Metabolisms in Methane-Rich Environments

PubMed Central

Antler, Gilad; Pellerin, André

2018-01-01

Separating the contributions of anaerobic oxidation of methane and organoclastic sulfate reduction in the overall sedimentary sulfur cycle of marine sediments has benefited from advances in isotope biogeochemistry. Particularly, the coupling of sulfur and oxygen isotopes measured in the residual sulfate pool (δ18OSO4 vs. δ34SSO4). Yet, some important questions remain. Recent works have observed patterns that are inconsistent with previous interpretations. We differentiate the contributions of oxygen and sulfur isotopes to separating the anaerobic oxidation of methane and organoclastic sulfate reduction into three phases; first evidence from conventional high methane vs. low methane sites suggests a clear relationship between oxygen and sulfur isotopes in porewater and the metabolic process taking place. Second, evidence from pure cultures and organic matter rich sites with low levels of methane suggest the signatures of both processes overlap and cannot be differentiated. Third, we take a critical look at the use of oxygen and sulfur isotopes to differentiate metabolic processes (anaerobic oxidation of methane vs. organoclastic sulfate reduction). We identify that it is essential to develop a better understanding of the oxygen kinetic isotope effect, the degree of isotope exchange with sulfur intermediates as well as establishing their relationships with the cell-specific metabolic rates if we are to develop this proxy into a reliable tool to study the sulfur cycle in marine sediments and the geological record. PMID:29681890

Oxygen isotope values in bone carbonate and collagen are consistently offset for New World monkeys

PubMed Central

Crowley, Brooke Erin

2014-01-01

Stable oxygen isotopes are increasingly used in ecological research. Here, I present oxygen isotope (δ18O) values for bone carbonate and collagen from howler monkeys (Alouatta palliata), spider monkeys (Ateles geoffroyi) and capuchins (Cebus capucinus) from three localities in Costa Rica. There are apparent differences in δ18Ocarbonate and δ18Ocollagen among species. Monkeys from moist forest have significantly lower isotope values than those from drier localities. Because patterns are similar for both substrates, discrimination (Δ) between δ18Ocarbonate and δ18Ocollagen is relatively consistent among species and localities (17.6 ± 0.9‰). Although this value is larger than that previously obtained for laboratory rats, consistency among species and localities suggests it can be used to compare δ18Ocarbonate and δ18Ocollagen for monkeys, and potentially other medium-bodied mammals. Establishing discrimination for oxygen between these substrates for wild monkeys provides a foundation for future environmental and ecological research on modern and ancient organisms. PMID:25392315

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

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

Seasonal temperature and precipitation recorded in the intra-annual oxygen isotope pattern of meteoric water and tree-ring cellulose

NASA Astrophysics Data System (ADS)

Schubert, Brian A.; Jahren, A. Hope

2015-10-01

Modern and ancient wood is a valuable terrestrial record of carbon ultimately derived from the atmosphere and oxygen inherited from local meteoric water. Many modern and fossil wood specimens display rings sufficiently thick for intra-annual sampling, and analytical techniques are rapidly improving to allow for precise carbon and oxygen isotope measurements on very small samples, yielding unprecedented resolution of seasonal isotope records. However, the interpretation of these records across diverse environments has been problematic because a unifying model for the quantitative interpretation of seasonal climate parameters from oxygen isotopes in wood is lacking. Towards such a model, we compiled a dataset of intra-ring oxygen isotope measurements on modern wood cellulose (δ18Ocell) from 33 globally distributed sites. Five of these sites represent original data produced for this study, while the data for the other 28 sites were taken from the literature. We defined the intra-annual change in oxygen isotope value of wood cellulose [Δ(δ18Ocell)] as the difference between the maximum and minimum δ18Ocell values determined within the ring. Then, using the monthly-resolved dataset of the oxygen isotope composition of meteoric water (δ18OMW) provided by the Global Network of Isotopes in Precipitation database, we quantified the empirical relationship between the intra-annual change in meteoric water [Δ(δ18OMW)] and Δ(δ18Ocell). We then used monthly-resolved datasets of temperature and precipitation to develop a global relationship between Δ(δ18OMW) and maximum/minimum monthly temperatures and winter/summer precipitation amounts. By combining these relationships we produced a single equation that explains much of the variability in the intra-ring δ18Ocell signal through only changes in seasonal temperature and precipitation amount (R2 = 0.82). We show how our recent model that quantifies seasonal precipitation from intra-ring carbon isotope profiles can be

Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

NASA Astrophysics Data System (ADS)

Boshers, D.; Granger, J.; Bohlke, J. K.

2016-12-01

Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

Measurement of infiltration rates in urban sewer systems by use of oxygen isotopes.

PubMed

De Bénédittis, J; Bertrand-Krajewski, J L

2005-01-01

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.

Triple oxygen isotope systematics of structurally bonded water in gypsum

NASA Astrophysics Data System (ADS)

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

2017-07-01

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.

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

PubMed

Langlois, C; Simon, L; Lécuyer, Ch

2003-12-01

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

Analysis of Atmospheric Nitrate Deposition in Lake Tahoe Using Multiple Oxygen Isotopes

NASA Astrophysics Data System (ADS)

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

2002-12-01

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

Stalagmite-inferred centennial variability of the Asian summer monsoon in southwest China between 58 and 79 ka BP

NASA Astrophysics Data System (ADS)

Zhang, Tao-Tao; Li, Ting-Yong; Cheng, Hai; Edwards, R. Lawrence; Shen, Chuan-Chou; Spötl, Christoph; Li, Hong-Chun; Han, Li-Yin; Li, Jun-Yun; Huang, Chun-Xia; Zhao, Xin

2017-03-01

We use a new spliced stalagmite oxygen isotope record from Yangkou Cave and Xinya Cave, Chongqing, southwest China, to reconstruct the centennial-millennial-scale changes in Asian Summer Monsoon (ASM) intensity between 58.0 and 79.3 thousand years before present (ka BP, before AD 1950). This multidecadally resolved record shows four strong ASM periods, corresponding to Greenland Interstadials (GIS) 17-20, and three weak ASM episodes, among which, the one starting at 61.5 ± 0.2 ka BP and ending at 59.4 ± 0.2 ka BP that may correlate with Heinrich Event 6. The close agreement of climate events between China and Greenland supports the notion that the ASM is dominantly governed by high-latitude forcings in the Northern Hemisphere. The short-lived interstadial GIS 18, however, lasted for over 3 kyr in the records derived from ASM region, reflecting a gradual decline of ASM intensity, which coincides with a millennial-scale warming trend in Antarctica. This suggests an additional forcing of the ASM by the Southern Hemisphere, which also affected GIS 8-12, H4 and H5, as shown by previous speleothem studies from the ASM region.

Climatic and environmental controls on speleothem oxygen-isotope values

NASA Astrophysics Data System (ADS)

Lachniet, Matthew S.

2009-03-01

Variations in speleothem oxygen-isotope values ( δ18O) result from a complicated interplay of environmental controls and processes in the ocean, atmosphere, soil zone, epikarst, and cave system. As such, the controls on speleothem δ18O values are extremely complex. An understanding of the processes that control equilibrium and kinetic fractionation of oxygen isotopes in water and carbonate species is essential for the proper interpretation of speleothem δ18O as paleoclimate and paleoenvironmental proxies, and is best complemented by study of site-specific cave processes such as infiltration, flow routing, drip seasonality and saturation state, and cave microclimate, among others. This review is a process-based summary of the multiple controls on δ18O in the atmosphere, soil, epikarst, and speleothem calcite, illustrated with case studies. Primary controls of δ18O in the atmosphere include temperature and relative humidity through their role in the multiple isotope "effects". Variability and modifications of water δ18O values in the soil and epikarst zones are dominated by evaporation, mixing, and infiltration of source waters. The isotopically effective recharge into a cave system consists of those waters that participate in precipitation of CaCO 3, resulting in calcite deposition rates which may be biased to time periods with optimal dripwater saturation state. Recent modeling, experimental, and observational data yield insight into the significance of kinetic fractionation between dissolved carbonate phases and solid CaCO 3, and have implications for the 'Hendy' test. To assist interpretation of speleothem δ18O time series, quantitative and semi-quantitative δ18O-climate calibrations are discussed with an emphasis on some of the difficulties inherent in using modern spatial and temporal isotope gradients to interpret speleothems as paleoclimate proxy records. Finally, several case studies of globally significant speleothem paleoclimate records are

Triple oxygen isotopes in biogenic and sedimentary carbonates

NASA Astrophysics Data System (ADS)

Passey, Benjamin H.; Hu, Huanting; Ji, Haoyuan; Montanari, Shaena; Li, Shuning; Henkes, Gregory A.; Levin, Naomi E.

2014-09-01

The 17O anomaly (Δ17O) of natural waters has been shown to be sensitive to evaporation in a way analogous to deuterium excess, with evaporated bodies of water (e.g., leaf waters, lake waters, animal body waters) tending to have lower Δ17O than primary meteoric waters. In animal body water, Δ17O relates to the intake of evaporated waters, evaporative effluxes of water, and the Δ17O value of atmospheric O2, which itself carries signatures of global carbon cycling and photochemical reactions in the stratosphere. Carbonates have the potential to record the triple oxygen isotope compositions of parent waters, allowing reconstruction of past water compositions, but such investigations have awaited development of methods for high-precision measurement of Δ17O of carbonate. We describe optimized methods based on a sequential acid digestion/reduction/fluorination approach that yield Δ17O data with the high precision (∼0.010‰, 1σ) needed to resolve subtle environmental signals. We report the first high-precision Δ17O dataset for terrestrial carbonates, focusing on vertebrate biogenic carbonates and soil carbonates, but also including marine invertebrates and high-temperature carbonates. We determine apparent three-isotope fractionation factors between the O2 analyte derived from carbonate and the parent waters of the carbonate. These in combination with appropriate temperature estimates (from clumped isotope thermometry, or known or estimated body temperatures) are used to calculate the δ18O and Δ17O of parent waters. The clearest pattern to emerge is the strong 17O-depletion in avian, dinosaurian, and mammalian body water (from analyses of eggshell and tooth enamel) relative to meteoric waters, following expected influences of evaporated water (e.g., leaf water) and atmospheric O2 on vertebrate body water. Parent waters of the soil carbonates studied here have Δ17O values that are similar to or slightly lower than global precipitation. Our results suggest

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

USGS Publications Warehouse

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

2014-01-01

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

The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

NASA Technical Reports Server (NTRS)

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

2012-01-01

MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

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

PubMed Central

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

2013-01-01

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

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

PubMed

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

2016-12-01

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ 18 O P ) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L -1 NaHCO 3 (pH = 8.5), 0.1 mol L -1 NaOH and 1 mol L -1 HCl) of agricultural soils from the Beijing area. The δ 18 O P results of the water extracts and NaHCO 3 extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ 18 O P value of the water extracts and NaHCO 3 extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ 18 O P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ 18 O P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ 18 O p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.

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

EPA Science Inventory

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

Forensic applications of nitrogen and oxygen isotopes in tracing nitrate sources in urban environments

USGS Publications Warehouse

Silva, S.R.; Ging, P.B.; Lee, R.W.; Ebbert, J.C.; Tesoriero, A.J.; Inkpen, E.L.

2002-01-01

Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing ??15N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

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

NASA Astrophysics Data System (ADS)

Chan, Sharleen

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

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

PubMed

Keedakkadan, Habeeb Rahman; Abe, Osamu

2015-04-30

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

Holocene Climate Reconstructions from Lake Water Oxygen Isotopes in NW and SW Greenland

NASA Astrophysics Data System (ADS)

Lasher, G. E.; Axford, Y.; McFarlin, J. M.; Kelly, M. A.; Osterberg, E. C.; Berkelhammer, M. B.; Berman, K.; Kotecki, P.; Gawin, B.

2016-12-01

Reconstructions of stable isotopes of precipitation (SIP) from currently unglaciated parts of Greenland can help elucidate spatial patterns of past climate shifts in this climatically important and complex region. We have developed a 7700-year record of lake water δ18O from a small non-glacial lake in NW Greenland (near Thule Air Base), inferred from the δ18O of subfossil chironomid (insect) head capsules and aquatic mosses. Lake water δ18O remains constant from 8 ka until 4 ka and then declines by 2.5 ‰ to the present, representing a +2.5 to 5.5 °C Holocene Thermal Maximum temperature anomaly for this region. For comparison, two new sediment records from hydrologically connected lakes south of Nuuk in SW Greenland record 8500 years of lake water δ18O, also inferred from δ18O of chironomids. At the time cores were collected during the summer in 2014 and 2015, all lakes reflected SIP and exhibited minimal evaporation influence. Historical monitoring of stable isotopes of precipitation from Thule Air Base and Grønnedal in south Greenland suggest the controls on SIP differ greatly between our two study sites, as would be predicted based upon the strongly Arctic (in the NW) versus North Atlantic (in the SW) atmospheric and marine influences at the two sites. Interpretation of Holocene climate from these two contrasting sites will be discussed. These climate records from the same proxy allow us to compare millennial scale Holocene climate responses to northern hemisphere solar insolation trends in two different climate regimes of Greenland.

Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Groundwater Samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Brady D.; Moran, James J.; Nims, Megan K.

Report summarizing stable oxygen and hydrogen isotope analysis of two groundwater samples from the B-Complex. Results from analyses were compared to perched water and pore water analyses performed previously.

Oxygen isotope values in bone carbonate and collagen are consistently offset for New World monkeys.

PubMed

Crowley, Brooke Erin

2014-11-01

Stable oxygen isotopes are increasingly used in ecological research. Here, I present oxygen isotope (δ(18)O) values for bone carbonate and collagen from howler monkeys (Alouatta palliata), spider monkeys (Ateles geoffroyi) and capuchins (Cebus capucinus) from three localities in Costa Rica. There are apparent differences in δ(18)Ocarbonate and δ(18)Ocollagen among species. Monkeys from moist forest have significantly lower isotope values than those from drier localities. Because patterns are similar for both substrates, discrimination (Δ) between δ(18)Ocarbonate and δ(18)Ocollagen is relatively consistent among species and localities (17.6 ± 0.9‰). Although this value is larger than that previously obtained for laboratory rats, consistency among species and localities suggests it can be used to compare δ(18)Ocarbonate and δ(18)Ocollagen for monkeys, and potentially other medium-bodied mammals. Establishing discrimination for oxygen between these substrates for wild monkeys provides a foundation for future environmental and ecological research on modern and ancient organisms. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

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

PubMed

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

2014-08-01

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

Ultrafiltration by a compacted clay membrane-I. Oxygen and hydrogen isotopic fractionation

USGS Publications Warehouse

Coplen, T.B.; Hanshaw, B.B.

1973-01-01

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01 N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disc compacted to a porosity of 35 per cent by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5%. and in O18 by 0.8%. relative to the residual solution. No additional isotopic fractionation due to a salt filtering mechanism was observed at NaCl concentrations up to 0.01 N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. ?? 1973.

Crystal growth and disequilibrium distribution of oxygen isotopes in an igneous Ca-Al-rich inclusion from the Allende carbonaceous chondrite

NASA Astrophysics Data System (ADS)

Kawasaki, Noriyuki; Simon, Steven B.; Grossman, Lawrence; Sakamoto, Naoya; Yurimoto, Hisayoshi

2018-01-01

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of

Three-Body Forces and the Limit of Oxygen Isotopes

NASA Astrophysics Data System (ADS)

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

2010-07-01

The limit of neutron-rich nuclei, the neutron drip line, evolves regularly from light to medium-mass nuclei except for a striking anomaly in the oxygen isotopes. This anomaly is not reproduced in shell-model calculations derived from microscopic two-nucleon forces. Here, we present the first microscopic explanation of the oxygen anomaly based on three-nucleon forces that have been established in few-body systems. This leads to repulsive contributions to the interactions among excess neutrons that change the location of the neutron drip line from O28 to the experimentally observed O24. Since the mechanism is robust and general, our findings impact the prediction of the most neutron-rich nuclei and the synthesis of heavy elements in neutron-rich environments.

Dolomite clumped isotope constraints on the oxygen isotope composition of the Phanerozoic Sea

NASA Astrophysics Data System (ADS)

Ryb, U.; Eiler, J. M.

2017-12-01

The δ18O value of the Phanerozoic Sea has been debated several decades, largely motivated by an 8‰ increase in δ18O of sedimentary carbonates between the Cambrian and the present. Some previous studies have interpreted this increase to be a primary depositional signal, resulting from an increase in the 18O content of ocean water over time, or from a decrease in ocean temperature increasing the oxygen isotope fractionation between seawater and carbonates. In contrast, other studies have interpreted lower δ18O compositions as the products of diagenetic alteration at elevated burial temperatures. Here, we show that the Phanerozoic dolomite δ18O record overlaps with that of well-preserved calcite fossils, and use carbonate clumped isotope measurements of Cambrian to Pleistocene dolomites to calculate their formation temperatures and the isotopic compositions of their parent-waters. The observed variation in dolomite δ18O is largely explained by dolomite formation at burial temperatures of up to 158°C. The δ18O values of dolomite parent-waters range -2 to +12‰ and are correlated with formation temperatures. Such correlation is consistent with the modification of seawater (0±2‰, VSMOW) toward isotopically heavier compositions through water-rock reactions at elevated burial temperatures. The similarity between the dolomite and calcite δ18O records, and published clumped isotope-based calculations of water compositions, suggests that like dolomite, temporal variations of the calcite δ18O record may also be largely driven by diagenetic alteration. Finally, the relationship we observe between temperature of dolomitization and d18O of dolomite suggests platform carbonates generally undergo dolomitization through reaction with modified marine waters, and that there is no evidence those waters were ever significantly lower in d18O than the modern ocean.

Age and isotopic constraints on pleistocene pluvial episodes in the Western Desert, Egypt.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crombie, M. K.; Arvidson, R. E.; Sturchio, N. C.

1997-01-01

North Africa has undergone drastic climatic changes over the past several hundred thousand years. The timing of humid intervals called pluvials was investigated by uranium-series disequilibrium dating of travertines from the Kurkur Oasis, Western Desert, Egypt. The youngest and best dated travertines (70-160 ka) are found in Wadi Kurkur and include spring and lacustrine units exposed as 2 to 3 m high terraces. Travertines having an age of approximately 191-220 ka are exposed by differential erosion as linear mounds produced by spring systems over fracture zones in ancient wadis. The oldest travertines, having ages >260 ka, are extensive, cap limestonemore » units above the oasis, and were deposited in paludal and lacustrine environments. Oxygen isotope ratios were measured for the wadi travertines ({delta}{sup 18}O values ranging from 16.7 to 19.1{per_thousand} SMOW) and for spring mound travertines (18.5-20.5{per_thousand}). Equilibrium oxygen isotope fractionation calculations indicate that the Kurkur travertines were deposited from waters having {delta}{sup 18}O values similar to ancient Western Desert groundwaters ({approx} -11{per_thousand}). The ages of the travertines correspond to times of monsoonal maxima, eustatic sea level high stands and interglacial maxima. Rainfall producing these groundwaters (and travertines) was significantly fractionated during atmospheric transport, in contrast to modern meteoric waters (-2.09{per_thousand}), implying a distant source for the pluvial waters. Increased precipitation, recharge of Western Desert groundwaters, and resultant travertine deposition are interpreted to be consequences of Milankovitch insolation cycle forcing, through enhanced Atlantic and Indian Ocean monsoons during interglacial time periods.« less

Holocene Climate in Northwest Greenland Inferred from Oxygen Isotopes of Preserved Aquatic Organic Material

NASA Astrophysics Data System (ADS)

Lasher, G. E.; Axford, Y.; McFarlin, J. M.; Kelly, M. A.; Osterberg, E. C.; Farnsworth, L. B.; Kotecki, P.

2015-12-01

Oxygen isotopes of paleo lake-water archived in subfossil aquatic organic material offer new insights into Arctic Holocene climate history. Here we present new constraints on the timing and magnitude of Holocene climate change in NW Greenland inferred from δ18O of chironomid head capsules, Cladocera ephippia, and aquatic macrophytes. δ18O of chironomids from surface sediments of multiple lakes in the region show consistent enrichment relative to lake-water (-18 to -22 ‰), on the order of 23 ‰. Lake-water δ18O collected during the summer of 2014 is comparable to modern and historical seasonal local meteoric water, and landscape position suggests dominantly precipitation inputs. Sediment cores recovered from two small, non-glacial lakes in 2014 near Thule Air Base capture continuous 7.7 kyr and 10.4 kyr records. δ18O of chironomids and macrophytes from Secret Lake decreases after 6 ka by 3 ‰ into the Neoglacial. Early Holocene values from Wax Lips Lake (informal name) are 3 to 4 ‰ higher than modern and decrease to the present, except for a large negative excursion ~5 ka. This is contemporaneous with a major change in stratigraphy and the hypothesized transient incursion of a regional, ice-dammed glacial lake system. At both lakes, declining δ18O from the early/middle to late Holocene is clearly recorded in multiple aquatic materials and is greater in magnitude than the mid to late Holocene changes in δ18O of the nearest ice core records (Agassiz and Camp Century, ~2 ‰). The temperature change of 4 to 6 °C inferred from this new δ18O approach is also larger than, but within the error of, chironomid assemblage based temperatures from Wax Lips Lake by McFarlin et al. (this meeting). This may indicate larger temperature changes at the ice sheet's margin than inferred from high-elevation ice core sites and/or some overprinting by enhanced evaporation of lake-water in the warmer climate of the early Holocene.

Isotopic evolution of Mauna Loa volcano

NASA Astrophysics Data System (ADS)

Kurz, Mark D.; Kammer, David P.

1991-04-01

In an effort to understand the temporal helium isotopic variations in Mauna Loa volcano, we have measured helium, strontium and lead isotopes in a suite of Mauna Loa lavas that span most of the subaerial eruptive history of the volcano. The lavas range in age from historical flows to Ninole basalt which are thought to be several hundred thousand years old. Most of the samples younger than 30 ka in age (Kau Basalt) are radiocarbon-dated flows, while the samples older than 30 ka are stratigraphically controlled (Kahuku and Ninole Basalt). The data reveal a striking change in the geochemistry of the lavas approximately 10 ka before present. The lavas older than 10 ka are characterized by high 3He/ 4He ( ˜ 16-20 times atmospheric), higher 206Pb/ 204Pb ( ˜ 18.2), and lower 87Sr/ 86Sr ( ˜ 0.70365) ratios than the younger Kau samples (having He, Pb and Sr ratios of approximately 8.5 × atmospheric, 18.1 and 0.70390, respectively). The historical lavas are distinct in having intermediate Sr and Pb isotopic compositions with 3He/ 4He ratios similar to the other young Kau basalt ( ˜ 8.5 × atmospheric). The isotopic variations are on a shorter time scale (100 to 10,000 years) than has previously been observed for Hawaiian volcanoes, and demonstrate the importance of geochronology and stratigraphy to geochemical studies. The data show consistency between all three isotope systems, which suggests that the variations are not related to magma chamber degassing processes, and that helium is not decoupled from the other isotopes. However, the complex temporal evolution suggests that three distinct mantle sources are required to explain the isotopic data. Most of the Mauna Loa isotopic variations could be explained by mixing between a plume type source, similar to Loihi, and an asthenospheric source with helium isotopic composition close to MORB and elevated Sr isotopic values. An asthenospheric source, or variation within the plume source, is considered more likely than

Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

NASA Astrophysics Data System (ADS)

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

2017-08-01

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.

Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

NASA Astrophysics Data System (ADS)

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

2018-05-01

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.

Oxygen isotopes in garnet and accessory minerals to constrain fluids in subducted crust

NASA Astrophysics Data System (ADS)

Rubatto, Daniela; Gauthiez-Putallaz, Laure; Regis, Daniele; Rosa Scicchitano, Maria; Vho, Alice; Williams, Morgan

2017-04-01

Fluids are considered a fundamental agent for chemical exchanges between different rock types in the subduction system. Constraints on the sources and pathways of subduction fluids thus provide crucial information to reconstruct subduction processes. Garnet and U-Pb accessory minerals constitute some of the most robust and ubiquitous minerals in subducted crust and can preserve multiple growth zones that track the metamorphic evolution of the sample they are hosted in. Microbeam investigation of the chemical (major and trace elements) and isotopic composition (oxygen and U-Pb) of garnet and accessory minerals is used to track significant fluid-rock interaction at different stages of the subduction system. This approach requires consideration of the diffusivity of oxygen isotopes particularly in garnet, which has been investigated experimentally. The nature of the protolith and ocean floor alteration is preserved in relict accessory phases within eclogites that have been fully modified at HP conditions (e.g. Monviso and Dora Maira units in the Western Alps). Minerals in the lawsonite-blueschists of the Tavsanli zone in Turkey record pervasive fluid exchange between mafic and sedimentary blocks at the early stage of subduction. High pressure shear zones and lithological boundaries show evidence of intense fluid metasomatism at depth along discontinuities in Monviso and Corsica. In the UHP oceanic crust of the Zermatt-Saas Zone, garnet oxygen isotopes and tourmaline boron isotopes indicate multistage fluid infiltration during prograde metamorphism. Localized exchanges of aqueous fluids are also observed in the subducted continental crust of the Sesia-Lanzo Zone. In most cases analyses of distinct mineral zones enable identification of multiple pulses of fluids during the rock evolution.

The mechanism of oxygen isotopic fractionation during fungal denitrification - A pure culture study

NASA Astrophysics Data System (ADS)

Wrage-Moennig, Nicole; Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Annette; Lewicka-Szczebak, Dominika; Well, Reinhard

2014-05-01

Nitrous oxide (N2O) from soil denitrification originates from bacteria and - to an unknown extent - also from fungi. During fungal denitrification, oxygen (O) exchange takes place between H2O and intermediates of the denitrification process as in bacterial exchange[1,2]. However, information about enzymes involved in fungal O exchanges and the associated fractionation effects is lacking. The objectives of this study were to estimate the O fractionation and O exchange during the fungal denitrifying steps using a conceptual model[2] adapted from concepts for bacterial denitrification[3], implementing controls of O exchange proposed by Aerssens, et al.[4] and using fractionation models by Snider et al.[5] Six different pure fungal cultures (five Hypocreales, one Sordariales) known to be capable of denitrification were incubated under anaerobic conditions, either with nitrite or nitrate. Gas samples were analyzed for N2O concentration and its isotopic signatures (SP, average δ15N, δ18O). To investigate O exchange, both treatments were also established with 18O-labelled water as a tracer in the medium. The Hypocreales strains showed O exchange mainly at NO2- reductase (Nir) with NO2- as electron acceptor and no additional O exchange at NO3- reductase (Nar) with NO3- as electron acceptor. The only Hypocreales species having higher O exchange with NO3- than with NO2- also showed O exchange at Nar. The Sordariales species tested seems capable of O exchange at NO reductase (Nor) additionally to O exchange at Nir with NO2-. The data will help to better interpret stable isotope values of N2O from soils. .[1] D. M. Kool, N. Wrage, O. Oenema, J. Dolfing, J. W. Van Groenigen. Oxygen exchange between (de)nitrification intermediates and H2O and its implications for source determination of NO?3- and N2O: a review. Rapid Commun. Mass Spec. 2007, 21, 3569. [2] L. Rohe, T.-H. Anderson, B. Braker, H. Flessa, A. Giesemann, N. Wrage-Mönnig, R. Well. Fungal Oxygen Exchange between

Fractionation of Nitrogen and Oxygen Isotopes and Roles of Bacteria during Denitrification

NASA Astrophysics Data System (ADS)

Kang, J.; Buyanjargal, A.; Jeen, S. W.

2017-12-01

Nitrate in groundwater can cause health and environmental problems when not properly treated. The purpose of this study was to develop a treatment method for nitrate in groundwater using organic carbon-based reactive mixtures (i.e., wood chips and gravel) through column experiments and to evaluate reaction mechanisms responsible for the treatment. The column experiments were operated for a total of 19 months. The results from the geochemical analyses for the experiments suggest that cultures of denitrifying bacteria used organic carbon while utilizing nitrate as their electron acceptor via denitrification process. Proteobacteria was the most abundant phylum in all samples, accounting for 45.7% of the bacterial reads, followed by Firmicutes (22.6%) and Chlorobi (10.6%). Bacilli, Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria_c consisted of 32, 30, 23, 11, and 2% of denitrifying bacteria class. The denitrification process caused fractionation of nitrogen and oxygen isotopes of nitrate while nitrate concentration decreased. When fitted to the Rayleigh's fractionation model, enrichment factors (ɛ) were 11.5‰ and 5.6‰ for 15N and 18O isotopes, respectively. Previous studies suggested that nitrogen isotope enrichment factors of denitrification are within the range of 4.7 to 40‰ and oxygen isotopic enrichment factors are between 8 and 18.3‰. This study shows that nitrate in groundwater can be effectively treated using passive treatment systems, such as permeable reactive barriers (PRBs), and denitrificaton is the dominant process reponsible for the removal of nitrate.

Oxygen Isotope Variability within Nautilus Shell Growth Bands

PubMed Central

2016-01-01

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

Oxygen isotope variability within Nautilus shell growth bands

DOE PAGES

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

2016-04-21

Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis ofmore » oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ 18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ 18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. In addition, to create the observed range of δ 18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands.« less

[Temporal and spatial variations of hydrogen and oxygen isotopes in Tuojia River and its influencing factors.

PubMed

Wu, Hong Bao; Zhao, Qiang; Qin, Xiao Bo; Gao, Qing Zhu; Lyu, Cheng Wen

2018-05-01

The characteristics of hydrogen and oxygen stable isotopes in river is important for regional hydrologic cycle research. To uncover water supply sources in subtropical agricultural basin from a perspective of stable isotopes, field measurements were conducted in four reaches (S 1 , S 2 , S 3 and S 4 ) of Tuojia River from April to August 2017. We analyzed the spatial and temporal variations in hydrogen and oxygen isotopes and deuterium excess parameters and their relationship with precipitation, altitude and water quality. Results showed that hydrogen and oxygen isotopes and deuterium excess values ranged from -43.17‰ to -26.43‰ (-35.50‰±5.44‰), -7.94‰ to -5.70‰ (-6.86‰±0.74‰), and 16.77‰ to 23.49‰ (19.39‰±1.95‰), respectively. Under the influence of monsoon circulation, hydrogen and oxygen isotopes showed substantial seasonal variation, with spring (δD: -29.88‰±3.31‰; δ 18 O: -6.18‰±0.57‰) > summer (δD: -39.25‰±2.65‰; δ 18 O: -7.32‰±0.42‰). The spatial distribution of hydrogen and oxygen isotopes values increased fluctuantly with the position from the sampling site to the river's source, with δD: S 1 ＜S 4 ＜S 3 ＜S 2 , and δ 18 O: S 1 ＜S 3 ＜S 4 ＜S 2 . The deuterium excess values had no significant temporal variation, while it spatially increased gradually with the river levels. The slope and intercept of water line in this river were smaller than that of the local meteoric water line, suggesting that precipitation was the primary water source for this river. At the seasonal scale, both δD and δ 18 O were significantly negatively correlated with water temperature (δD: r=-0.92; δ 18 O: r=-0.88) and δ 18 O was negatively correlated with altitude (r=-0.96). At spatial scale, δ 18 O had a significantly positive correlation with water temperature. The δD and δ 18 O had negative correlation with precipitation, but being not statistically significant.

Heterogenous Oxygen Isotopic Composition of a Complex Wark-Lovering Rim and the Margin of a Refractory Inclusion from Leoville

NASA Technical Reports Server (NTRS)

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

2014-01-01

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.

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

USGS Publications Warehouse

Balci, N.; Shanks, Wayne C.; Mayer, B.; Mandernack, K.W.

2007-01-01

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-08-01

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

Investigating the direct meltwater effect in oxygen-isotope records using an isotope-enabled Earth system model

NASA Astrophysics Data System (ADS)

Zhu, J.; Liu, Z.; Brady, E. C.; Otto-Bliesner, B. L.; Marcott, S. A.; Zhang, J.; Wang, X.; Noone, D.; Nusbaumer, J. M.; Wong, T. E.; Jahn, A.

2017-12-01

Oxygen isotopes (δ18O) in both terrestrial and marine paleoclimate archives have long been used to study the climate evolution of the late Quaternary. Based on the high-latitude "temperature effect" and the tropical "amount effect", the δ18O variations in ice cores and speleothems have been primarily interpreted as changes in surface air temperature and regional precipitation amount, respectively, although recent studies suggest that other climate processes may also play a role. However, one long-overlooked assumption for these climatic interpretations is that the δ18O variations in the terrestrial records can be exclusively explained by changes in climate variables. This assumption could be violated during past glacial meltwater events, as the meltwater discharged into the ocean by icebergs or surface runoff is considerably depleted in δ18O compared to the surface ocean. This depleted meltwater can significantly decrease the isotope composition of the seawater it deposits and propagate within the hydrological cycle to directly influence the δ18O values in adjacent precipitation (the direct effect), without involving any changes in the climate state (the indirect effect). Here, by conducting water isotope-enabled climate simulations, we aim to quantify the direct meltwater effect on the terrestrial δ18O records. We find that, for large meltwater events in the northern North Atlantic Ocean (e.g., around 0.25 Sv lasting 300 years), the direct meltwater effect contributes more than 15% and 35% of the total δ18O changes in the precipitation over Greenland and the eastern Brazil, respectively. Model simulations further demonstrate that the direct meltwater effect increases with the magnitude and duration of meltwater, and it is sensitive to both the location and the shape of the freshwater forcing. We argue that the direct meltwater effect on δ18O records could also be significant in other regions and for other terrestrial oxygen-isotope records, as long as the

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Covariance of oxygen and hydrogen isotopic composition in plant water: Species effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1989-12-01

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 {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leafmore » water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 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. 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.« less

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Oxygen Isotope Ratios of Magnetite in CI-Like Clasts from a Polymict Ureilite

NASA Technical Reports Server (NTRS)

Kita, N. T.; Defouilloy, C.; Goodrich, C. A.; Zolensky, M. E.

2017-01-01

Polymict ureilites contain a variety of Less than or equal to mm to cm sized non-ureilitic clasts, many of which can be identifed as chondritic and achondritic meteorite types. Among them, dark clasts have been observed in polymict ureilites that are similar to CI chondrites in mineralogy, containing phyllosilicates, magnetite, sulfide and carbonates. Bulk oxygen isotope analyses of a dark clast in Nilpena plot along the CCAM line and above the terrestrial fractionation line, on the O-poor extension of the main group ureilite trend and clearly different from bulk CI chondrites. One possible origins of such dark clast is that they represent aqueously altered precursors of ureilite parent body (UPB) that were preserved on the cold surface of the UPB. Oxygen isotope analyses of dark clasts are key to better understanding their origins. Oxygen isotope ratios of magnetite are of special interest because they reflect the compositions of the fluids in asteroidal bodies. In primitive chondrites, Delta O (= Delta O - 0.52× Delta O) values of magnetites are always higher than those of the bulk meteorites and represent minimum Delta O values of the initial O-poor aqueous fluids in the parent body. Previous SIMS analyses on magnetite and fayalite in dark clasts from the DaG 319 polymict ureilite were analytically difficult due to small grain sizes, though data indicated positive Delta O values of 3-4 per mille, higher than that of the dark clast in Nilpena (1.49per mille).

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oerter, Erik; Singleton, Michael; Davisson, Lee

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

DOE PAGES

Oerter, Erik; Singleton, Michael; Davisson, Lee

2017-10-22

The hydrogen and oxygen stable isotope composition (δ 2H and δ 18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ 2H and δ 18O values of liquid water samples with precision for δ 2H of ± 1.2‰, and for δ 18O of ± 0.17‰. For hydration waters in goethite, precision for δ 2H rangesmore » from ± 0.3‰ to 1.6‰, and for δ 18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ 2H and δ 18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ 2H values that reflect the hydrogen of the OH – phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ 18O values on goethite reflect the oxygen in OH – groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ 18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Triple oxygen and hydrogen isotopes of gypsum hydration water for quantitative paleo-humidity reconstruction

NASA Astrophysics Data System (ADS)

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

2018-01-01

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.

The pressure dependence of oxygen-isotope-exchange rates between solution and apical oxygens on the UO 2(OH) 4 2- ion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harley, Steven J.; Ohlin, C. Andre; Johnson, Rene L.

2011-04-06

The pressure dependence of isotope exchange rate was determined for apical oxygen atoms in the UO 2(OH) 4 2-(aq) ion. The results can be interpreted to indicate an associative character of the reaction.

Baseline shifts in coral skeletal oxygen isotopic composition: a signature of symbiont shuffling?

NASA Astrophysics Data System (ADS)

Carilli, J. E.; Charles, C. D.; Garren, M.; McField, M.; Norris, R. D.

2013-06-01

Decades-long records of the stable isotopic composition of coral skeletal cores were analyzed from four sites on the Mesoamerican Reef. Two of the sites exhibited baseline shifts in oxygen isotopic composition after known coral bleaching events. Changes in pH at the calcification site caused by a change in the associated symbiont community are invoked to explain the observed shift in the isotopic composition. To test the hypothesis that changes in symbiont clade could affect skeletal chemistry, additional coral samples were collected from Belize for paired Symbiodinium identification and skeletal stable isotopic analysis. We found some evidence that skeletal stable isotopic composition may be affected by symbiont clade and suggest this is an important topic for future investigation. If different Symbiodinium clades leave consistent signatures in skeletal geochemical composition, the signature will provide a method to quantify past symbiont shuffling events, important for understanding how corals are likely to respond to climate change.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Validation of chlorine and oxygen isotope ratio analysis to differentiate perchlorate sources and to document perchlorate biodegradation

USGS Publications Warehouse

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

2013-01-01

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.

Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.

2015-07-01

The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Femore » isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II) aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II) aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II) aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a

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

NASA Astrophysics Data System (ADS)

Trayler, Robin B.; Kohn, Matthew J.

2017-02-01

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

Risk Assessment of Mineral Groundwater Near Rogaška Slatina

NASA Astrophysics Data System (ADS)

Trcek, Branka; Leis, Albrecht

2017-10-01

Groundwater resources of mineral and thermo-mineral water are invaluable for planning a sustainable spatial and economic development of the Rogaška Slatina area, which requires a protection of this natural heritage. Numerous previous investigations of Rogaška groundwaters were subjects to balneology and to demands for larger exploitation quantities, that is why information are missing that are essential for definition of the Rogaška fractured aquifer system with mineral and thermo-mineral water and for its protection. The isotopic investigations of groundwaters stored in the Rogaška Slatina fractured aquifer system were performed aiming at answering open questions on the groundwater recharge and dynamics, on connections between different types of aquifers and on solute transport. Environmental isotopes 2H, 18O, 3H, 13C of dissolved inorganic carbon and 14C were analysed in mineral, thermo-mineral and spring waters. Results indicated the source and mechanism of groundwater recharge, its renewability, a transit time distribution, hydraulic interrelationships, the groundwater origin and its evolution due to effects of water-rock interaction. The mean residence time estimates of mineral and thermo- mineral water in the aquifer are between 3400 and 14000 years. On the other hand, the mixing processes between younger and older waters or mineral and spring waters are reflected as well as waters that infiltrated predominantly after the 1960s. These suggest the vulnerability of the research systems to man-made impacts. The presented results coupled with available information on a physical hydrogeology and water chemistry asses the optimal balance between the environmental protection and economic use of mineral water resources in the study area. They are essential for the protection strategy development of mineral and thermo-mineral water in the Rogaška Slatina area bringing together the state administration and local authorities and stakeholders.

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

NASA Astrophysics Data System (ADS)

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

1998-07-01

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

Oxygenation of Ediacaran Ocean recorded by iron isotopes

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

High-precision measurement of (186)Os/(188)Os and (187)Os/(188)Os: isobaric oxide corrections with in-run measured oxygen isotope ratios.

PubMed

Chu, Zhu-Yin; Li, Chao-Feng; Chen, Zhi; Xu, Jun-Jie; Di, Yan-Kun; Guo, Jing-Hui

2015-09-01

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.

Connection between ENSO and Asian Summer Monsoon Precipitation Oxygen Isotope

NASA Astrophysics Data System (ADS)

Cai, Z.; Tian, L.

2016-12-01

In an effort to understand the connection between El Niño Southern Oscillation (ENSO) and Asian Summer Monsoon (ASM) precipitation oxygen isotope, this study investigates the spatial and interannual patterns in summer (JJAS) monsoon precipitation δ18O and satellite water vapor isotope retrievals, especially those patterns associated with convection and vapor transport. Both precipitation and vapor isotope values exhibit a "V" shaped longitudinal pattern in their spatial variations, reflecting the gradual rainout and increase in convective intensity along vapor transport routes. In order to understand interannual variations, an ASM precipitation δ18O index (ASMOI) is introduced to measure the temporal variations in regional precipitation δ18O; and these variations are consistent with central Indo-Pacific convection and cloud-top height. The counter variations in the ASMOI in El Niño and La Niña years confirm the existence of a positive isotope- ENSO response (e.g., high values corresponding to warm phases) over the eastern Indian Ocean and southeastern Asia (80°E-120°E/10°S-30°N) as a response to changes in convection. However, JJAS vapor δD over the western Pacific (roughly east of 120oE) varies in opposition, due to the influence of water vapor transport. This opposite variation does not support the interpretation of precipitation isotope-ENSO relationship as changing proportion of vapor transported from different regions, but rather condensation processes associated with convection. These findings are important for studying past ASM and ENSO activity from various isotopic archives and have implications for the study of the atmospheric water cycle.

Laser Spectroscopic Study on Oxygen Isotope Effects in Ozone Surface Decomposition

NASA Astrophysics Data System (ADS)

Minissale, Marco; Boursier, Corinne; Elandaloussi, Hadj; Te, Yao; Jeseck, Pascal; Rouille, Christian; Zanon-Willette, Thomas; Janssen, Christof

2016-04-01

The isotope kinetics of ozone formation in the Chapman reaction [1] O + O2 + M → O3 + M (1) provides the primary example for a chemically induced oxygen isotope anomaly and is associated with large [2] and mass independent [3] oxygen isotope enrichments in the product molecule, linked to a symmetry selection in the ozone formation kinetics [4-5]. The isotopic composition of ozone and its transfer to other molecules is a powerful tracer in the atmospheric and biogeochemical sciences [6] and serves as a primary model for a possible explanation of the oxygen isotopic heterogeneity in the Solar system [7-8]. Recently, the isotope fractionation in the photolytic decomposition process O3 + hν → O2 + O (2) using visible light has been studied in detail [9-10]. Much less is currently known about the isotope fractionation in the dry deposition or in the gas phase thermal decomposition of ozone O3 + M → O2 + O +M. (3) Here we report on first spectroscopic studies of non-photolytic ozone decomposition using a cw-quantum cascade laser at 9.5 μm. The concentration of individual ozone isotopomers (16O3,16O16O17O, and 16O17O16O) in a teflon coated reaction cell is followed in real time at temperatures between 25 and 150 °C. Observed ozone decay rates depend on homogeneous (reaction (3)) processes in the gas phase and on heterogeneous reactions on the wall. A preliminary analysis reveals agreement with currently recommended ozone decay rates in the gas phase and the absence of a large symmetry selection in the surface decomposition process, indicating the absence of a mass independent fractionation effect. This result is in agreement with previous mass spectrometer (MS) studies on heterogeneous ozone formation on pyrex [11], but contradicts an earlier MS study [12] on ozone surface decomposition on pyrex and quartz. Implications for atmospheric chemistry will be discussed. [1] Morton, J., Barnes, J., Schueler, B. and Mauersberger, K. J. Geophys. Res. 95, 901 - 907 (1990

Cellular Metabolic Activity and the Oxygen and Hydrogen Stable Isotope Composition of Intracellular Water and Metabolites

NASA Astrophysics Data System (ADS)

Kreuzer-Martin, H. W.; Hegg, E. L.

2008-12-01

Intracellular water is an important pool of oxygen and hydrogen atoms for biosynthesis. Intracellular water is usually assumed to be isotopically identical to extracellular water, but an unexpected experimental result caused us to question this assumption. Heme O isolated from Escherichia coli cells grown in 95% H218O contained only a fraction of the theoretical value of labeled oxygen at a position where the O atom was known to be derived from water. In fact, fewer than half of the oxygen atoms were labeled. In an effort to explain this surprising result, we developed a method to determine the isotope ratios of intracellular water in cultured cells. The results of our experiments showed that during active growth, up to 70% of the oxygen atoms and 50% of the hydrogen atoms in the intracellular water of E. coli are generated during metabolism and can be isotopically distinct from extracellular water. The fraction of isotopically distinct atoms was substantially less in stationary phase and chilled cells, consistent with our hypothesis that less metabolically-generated water would be present in cells with lower metabolic activity. Our results were consistent with and explained the result of the heme O labeling experiment. Only about 40% of the O atoms on the heme O molecule were labeled because, presumably, only about 40% of the water inside the cells was 18O water that had diffused in from the culture medium. The rest of the intracellular water contained 16O atoms derived from either nutrients or atmospheric oxygen. To test whether we could also detect metabolically-derived hydrogen atoms in cellular constituents, we isolated fatty acids from log-phase and stationary phase E. coli and determined the H isotope ratios of individual fatty acids. The results of these experiments showed that environmental water contributed more H atoms to fatty acids isolated in stationary phase than to the same fatty acids isolated from log-phase cells. Stable isotope analyses of

New triple oxygen isotope data of bulk and separated fractions from SNC meteorites: Evidence for mantle homogeneity of Mars

NASA Astrophysics Data System (ADS)

Ali, Arshad; Jabeen, Iffat; Gregory, David; Verish, Robert; Banerjee, Neil R.

2016-05-01

We report precise triple oxygen isotope data of bulk materials and separated fractions of several Shergotty-Nakhla-Chassigny (SNC) meteorites using enhanced laser-assisted fluorination technique. This study shows that SNCs have remarkably identical Δ17O and a narrow range in δ18O values suggesting that these meteorites have assimilated negligibly small surface materials (<5%), which is undetectable in the oxygen isotope compositions reported here. Also, fractionation factors in coexisting silicate mineral pairs (px-ol and mask-ol) further demonstrate isotopic equilibrium at magmatic temperatures. We present a mass-dependent fractionation line for bulk materials with a slope of 0.526 ± 0.016 (1SE) comparable to the slope obtained in an earlier study (0.526 ± 0.013; Franchi et al. 1999). We also present a new Martian fractionation line for SNCs constructed from separated fractions (i.e., pyroxene, olivine, and maskelynite) with a slope of 0.532 ± 0.009 (1SE). The identical fractionation lines run above and parallel to our terrestrial fractionation line with Δ17O = 0.318 ± 0.016‰ (SD) for bulk materials and 0.316 ± 0.009‰ (SD) for separated fractions. The conformity in slopes and Δ17O between bulk materials and separated fractions confirm oxygen isotope homogeneity in the Martian mantle though recent studies suggest that the Martian lithosphere may potentially have multiple oxygen isotope reservoirs.

Devonian climate and reef evolution: Insights from oxygen isotopes in apatite

NASA Astrophysics Data System (ADS)

Joachimski, M. M.; Breisig, S.; Buggisch, W.; Talent, J. A.; Mawson, R.; Gereke, M.; Morrow, J. R.; Day, J.; Weddige, K.

2009-07-01

Conodonts, microfossils composed of carbonate-fluor apatite, are abundant in Palaeozoic-Triassic sediments and have a high potential to preserve primary oxygen isotope signals. In order to reconstruct the palaeotemperature history of the Devonian, the oxygen isotope composition of apatite phosphate was measured on 639 conodont samples from sequences in Europe, North America and Australia. The Early Devonian (Lochkovian; 416-411 Myr) was characterized by warm tropical temperatures of around 30 °C. A cooling trend started in the Pragian (410 Myr) with intermediate temperatures around 23 to 25 °C reconstructed for the Middle Devonian (397-385 Myr). During the Frasnian (383-375 Myr), temperatures increased again with temperatures to 30 °C calculated for the Frasnian-Famennian transition (375 Myr). During the Famennian (375-359 Myr), surface water temperatures slightly decreased. Reconstructed Devonian palaeotemperatures do not support earlier views suggesting the Middle Devonian was a supergreenhouse interval, an interpretation based partly on the development of extensive tropical coral-stromatoporoid communities during the Middle Devonian. Instead, the Devonian palaeotemperature record suggests that Middle Devonian coral-stromatoporoid reefs flourished during cooler time intervals whereas microbial reefs dominated during the warm to very warm Early and Late Devonian.

Using Oxygen Isotopic Values in Order to Infer Palaeoclimatic Differences between Northern and Central-Southern Greece

NASA Astrophysics Data System (ADS)

Michael, Dimitra-Ermioni; Dotsika, Elissavet

2017-12-01

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.

Oxygen isotope constraints on the alteration temperatures of CM chondrites

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

Could a secular increase in organic burial explain the rise of oxygen? Insights from a geological carbon cycle model constrained by the carbon isotope record

NASA Astrophysics Data System (ADS)

Krissansen-Totton, J.; Kipp, M.; Catling, D. C.

2017-12-01

The stable isotopes of carbon in marine sedimentary rock provide a window into the evolution of the Earth system. Conventionally, a relatively constant carbon isotope ratio in marine sedimentary rocks has been interpreted as implying constant organic carbon burial relative to total carbon burial. Because organic carbon burial corresponds to net oxygen production from photosynthesis, it follows that secular changes in the oxygen source flux cannot explain the dramatic rise of oxygen over Earth history. Instead, secular declines in oxygen sink fluxes are often invoked as causes for the rise of oxygen. However, constant fractional organic burial is difficult to reconcile with tentative evidence for low phosphate concentrations in the Archean ocean, which would imply lower marine productivity and—all else being equal—less organic carbon burial than today. The conventional interpretation of the carbon isotope record rests on the untested assumption that the isotopic ratio of carbon inputs into the ocean reflect mantle isotopic values throughout Earth history. In practice, differing rates of carbonate and organic weathering will allow for changes in isotopic inputs, as suggested by [1] and [2]. However, these inputs can not vary freely because large changes in isotopic inputs would induce secular trends in carbon reservoirs, which are not observed in the isotope record. We apply a geological carbon cycle model to all Earth history, tracking carbon isotopes in crustal, mantle, and ocean reservoirs. Our model is constrained by the carbon isotope record such that we can determine the extent to which large changes in organic burial are permitted. We find both constant organic burial and 3-5 fold increases in organic burial since 4.0 Ga can be reconciled with the carbon isotope record. Changes in the oxygen source flux thus need to be reconsidered as a possible contributor to Earth's oxygenation. [1] L. A. Derry, Organic carbon cycling and the lithosphere, in Treatise on

Seasonality of bottom water temperature in the northern North Sea reconstructed from the oxygen isotope composition of the bivalve Arctica islandica

NASA Astrophysics Data System (ADS)

Trofimova, Tamara; Andersson, Carin; Bonitz, Fabian

2017-04-01

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.

Using Nitrogen and Oxygen Isotope Compositions of Nitrate to Distinguish Contaminant Sources in Hanford Soil and Groundwater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conrad, Mark; Bill, Markus

2008-08-01

The nitrogen ({delta}{sup 15}N) and oxygen ({delta}{sup 18}O) isotopic compositions of nitrate in the environment are primarily a function of the source of the nitrate. The ranges of isotopic compositions for nitrate resulting from common sources are outlined in Figure 1 from Kendall (1998). As noted on Figure 1, processes such as microbial metabolism can modify the isotopic compositions of the nitrate, but the effects of these processes are generally predictable. At Hanford, nitrate and other nitrogenous compounds were significant components of most of the chemical processes used at the site. Most of the oxygen in nitrate chemicals (e.g., nitricmore » acid) is derived from atmospheric oxygen, giving it a significantly higher {delta}{sup 18}O value (+23.5{per_thousand}) than naturally occurring nitrate that obtains most of its oxygen from water (the {delta}{sup 18}O of Hanford groundwater ranges from -14{per_thousand} to -18{per_thousand}). This makes it possible to differentiate nitrate from Hanford site activities from background nitrate at the site (including most fertilizers that might have been used prior to the Department of Energy plutonium production activities at the site). In addition, the extreme thermal and chemical conditions that occurred during some of the waste processing procedures and subsequent waste storage in select single-shell tanks resulted in unique nitrate isotopic compositions that can be used to identify those waste streams in soil and groundwater at the site (Singleton et al., 2005; Christensen et al., 2007). This report presents nitrate isotope data for soil and groundwater samples from the Hanford 200 Areas and discusses the implications of that data for potential sources of groundwater contamination.« less

Paired N and O isotopic analysis of nitrate and nitrite in the Arabian Sea oxygen deficient zone

NASA Astrophysics Data System (ADS)

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

2017-03-01

The Arabian Sea is home to one of the three main oceanic oxygen deficient zones (ODZs). We present paired nitrogen (N) and oxygen (O) isotope measurements of nitrate (NO3-) and nitrite (NO2-) from the central Arabian Sea in order to understand the effects of N biogeochemistry on the distribution of these species in the low oxygen waters. Within the ODZ, NO2- accumulated in a secondary NO2- maximum (SNM), though the shape and magnitude of the SNM, along with the isotopic composition of NO3- and NO2-, were highly dependent on the location within the ODZ. We also explored water mass mixing within the Arabian Sea as an explanatory factor in the distribution of NO2- in the SNM. The intrusion of Persian Gulf Water at depth may influence the shape of the NO2- peak by introducing small amounts of dissolved oxygen (O2), favoring NO2- oxidation. There was also evidence that vertical mixing may play a role in shaping the top of the SNM peak. Finally, we present evidence for NO2- oxidation and NO2- reduction co-occurring within the ODZ, as has been previously suggested in the Arabian Sea, as well as in other ODZs. The decoupling of the N and O isotopes of NO3-, deviating from the expected 1:1 ratio for dissimilatory NO3- reduction, indicates that NO2- oxidation has a significant influence on the isotopic composition of NO3-. Additionally, the N isotopes of NO2- were generally fit well by Rayleigh curves for NO2- oxidation. However, the removal of dissolved inorganic nitrogen (DIN) within the domain reflects the importance of NO2- reduction to N2.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Thermophysiology of Tyrannosaurus rex: Evidence from Oxygen Isotopes.

PubMed

Barrick, R E; Showers, W J

1994-07-08

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

Coordinated Petrography and Oxygen Isotopic Compositions of Al-Rich Chondrules from CV3 Chondrites

NASA Astrophysics Data System (ADS)

Zhang, M. M.; Lin, Y. T.; Tang, G. Q.; Li, X. H.

2017-07-01

In this study, we coordinated the petrology, bulk compositions and oxygen isotope compositions of 12 ARCs from Allende and Leoville and Ningqiang chondrites in order to elucidate any potential genetic relationships between ARCs, CAIs and FMCs.

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

USGS Publications Warehouse

Truesdell, A.H.

1974-01-01

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

Oxygen Isotopes Archived in Subfossil Chironomids: Advancing a Promising Proxy for Lake Water Isotopes

NASA Astrophysics Data System (ADS)

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

2017-12-01

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.

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

PubMed

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

2011-03-04

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

Hydrogen and oxygen stable isotope ratios of milk in the United States.

PubMed

Chesson, Lesley A; Valenzuela, Luciano O; O'Grady, Shannon P; Cerling, Thure E; Ehleringer, James R

2010-02-24

Models of hydrogen and oxygen incorporation in human tissues recognize the impact of geographic location on the isotopic composition of fluid intake, but inputs can include nonlocal beverages, such as milk. Milk and cow drinking water were collected from dairies, and commercially available milk was purchased from supermarkets and fast food restaurants. It was hypothesized that milk water delta(2)H and delta(18)O values record geographic location information. Correlations between milk water isotope ratios and purchase location tap water were significant. However, the amount of variation in milk delta(2)H and delta(18)O values explained by tap water was low, suggesting a single estimation of fluid input isotope ratios may not always be adequate in studies. The delta(2)H and delta(18)O values of paired milk and cow drinking water were related, suggesting potential for geographical origin assignment using stable isotope analysis. As an application example, milk water delta(18)O values were used to predict possible regions of origin for restaurant samples.

Laboratory investigations of stable carbon and oxygen isotope ratio data enhance monitoring of CO2 underground

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Oxygen isotope fractionation between bird bone phosphate and drinking water.

PubMed

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

2017-06-01

Oxygen isotope compositions of bone phosphate (δ 18 O p ) 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 δ 18 O p values (from 9.8 to 22.5‰ V-SMOW) and the local rainfall δ 18 O w 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: δ 18 O w  = 1.119 (±0.040) δ 18 O p  - 24.222 (±0.644); R 2  = 0.98. The δ 18 O p -δ 18 O w 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 δ 18 O w 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.

Oxygen isotope fractionation between bird bone phosphate and drinking water

NASA Astrophysics Data System (ADS)

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

2017-06-01

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.

The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

NASA Astrophysics Data System (ADS)

von Sperber, C.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

2015-07-01

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

The oxygen isotope composition of phosphate released from phytic acid by the activity of wheat and Aspergillus niger phytase

NASA Astrophysics Data System (ADS)

Sperber, C. v.; Tamburini, F.; Brunner, B.; Bernasconi, S. M.; Frossard, E.

2015-03-01

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 (IP6) is an important form of Porg in many soils. The enzymatic hydrolysis of IP6 by phytase yields plant available inorganic phosphate (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 substrate were prepared. During the hydrolysis of IP6 by phytase, four Pi are released, and one oxygen atom from water is incorporated into each Pi. This incorporation of oxygen from water into Pi is subject to an apparent inverse isotopic fractionation (ϵ ∼ 6 to 10‰), which is similar to that imparted by acid phosphatase from potato during the hydrolysis of IP6 (ϵ ∼ 7‰) where less than three Pi are 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‰), again similar to values reported for acid phosphatases from potato and wheat germ. We attribute this similarity in ɛ 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 substrate-dependency of

Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Liu, Yun

2011-12-01

With a growing interest in small 17O-anomaly, there is a pressing need for the precise ratio, ln 17α/ln 18α, for a particular mass-dependent fractionation process (MDFP) (e.g., for an equilibrium isotope exchange reaction). This ratio (also denoted as " θ") can be determined experimentally, however, such efforts suffer from the demand of well-defined process or a set of processes in addition to high precision analytical capabilities. Here, we present a theoretical approach from which high-precision ratios for MDFPs can be obtained. This approach will complement and serve as a benchmark for experimental studies. We use oxygen isotope exchanges in equilibrium processes as an example. We propose that the ratio at equilibrium, θE ≡ ln 17α/ln 18α, can be calculated through the equation below: θa-bE=κa+(κa-κb){ln18βb}/{ln18α} where 18βb is the fractionation factor between a compound "b" and the mono-atomic ideal reference material "O", 18αa-b is the fractionation factor between a and b and it equals to 18βa/ 18βb and κ is a new concept defined in this study as κ ≡ ln 17β/ln 18β. The relationship between θ and κ is similar to that between α and β. The advantages of using κ include the convenience in documenting a large number of θ values for MDFPs and in estimating any θ values using a small data set due to the fact that κ values are similar among O-bearing compounds with similar chemical groups. Frequency scaling factor, anharmonic corrections and clumped isotope effects are found insignificant to the κ value calculation. However, the employment of the rule of geometric mean (RGM) can significantly affect the κ value. There are only small differences in κ values among carbonates and the structural effect is smaller than that of chemical compositions. We provide κ values for most O-bearing compounds, and we argue that κ values for Mg-bearing and S-bearing compounds should be close to their high temperature limitation (i.e., 0.5210 for

Digesting the data - Effects of predator ingestion on the oxygen isotopic signature of micro-mammal teeth

NASA Astrophysics Data System (ADS)

Barham, Milo; Blyth, Alison J.; Wallwork, Melinda D.; Joachimski, Michael M.; Martin, Laure; Evans, Noreen J.; Laming, Belinda; McDonald, Bradley J.

2017-11-01

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

A 62 ka record from the WAIS Divide ice core with annual resolution to 30 ka (so far)

NASA Astrophysics Data System (ADS)

Fudge, T. J.; Taylor, K.; McGwire, K.; Brook, E.; Sowers, T.; Steig, E.; White, J.; Vaughn, B.; Bay, R.; McConnell, J.; Waddington, E.; Conway, H.; Clow, G.; Cuffey, K.; Cole-Dai, J.; Ferris, D.; Severinghaus, J.

2012-04-01

Drilling of the West Antarctic Ice Sheet (WAIS) Divide ice core has been completed to a depth of 3400 m, about 60 meters above the bed. We present an annually resolved time scale for the most recent 30ka (to 2800 m) based on electrical conductivity measurements, called "timescale WDC06A-5". Below 2800 m the ice is dated by matching isotopes, methane, and/or dust records to other ice cores. Optical borehole logging provides stratigraphic ties to other cores for the bottom-most 75 m that was drilled in December 2011, and indicates the bottom-most ice has an age of 62 ka. The relatively young ice at depth is likely the result of basal melting. The inferred annual layer thickness of the deep ice is >1 cm, suggesting that annual layer counting throughout the entire core may be possible with continuous flow analysis of the ice core chemistry; however, the annual signal in the electrical measurements fades at about 30 ka. We compare the WDC06A-5 timescale through the glacial-interglacial transition with the Greenland GICC05 and GISP2 timescales via rapid variations in methane. We calculate a preliminary delta-age with: 1) accumulation rate inferred from the annual layer thicknesses and thinning functions computed with a 1-D ice flow model, and 2) surface temperature inferred from the low resolution d18O record and a preliminary borehole temperature profile. The WDC06A-5 timescale agrees with the GICC05 and GISP2 timescales to within decades at the 8.2k event and the ACR termination (Younger Dryas/Preboreal transition, 11.7 ka). This is within the delta-age and correlation uncertainties. At the rapid methane drop at ~12.8 ka, the WDC06A-5 timescale is ~150 years older than GICC05 and ~90 older than GISP2; while at ~14.8 ka, the timescales once again agree within the delta-age and correlation uncertainties. The cause of the age discrepancy at 12.8 ka is unclear. We also compare the WDC06A-5 timescale at Dansgaard-Oeschger events 3 and 4 (~27.5 and 29 ka) to the

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

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

Oxygen isotope reservoirs in the outer asteroid belt inferred from oxygen isotope systematics of chondrule olivines and isolated forsterite and olivine grains in Tagish Lake-type carbonaceous chondrites, WIS 91600 and MET 00432

NASA Astrophysics Data System (ADS)

Yamanobe, Masakuni; Nakamura, Tomoki; Nakashima, Daisuke

2018-03-01

To understand oxygen isotope ratios and redox conditions of the chondrule formation environments of the outer rigions of the asteroid belt, we analyzed major element concentrations and oxygen isotope ratios of olivine grains in chondrules, isolated forsterite, and isolated olivine from the WIS 91600 and MET 00432 carbonaceous chondrites, which are thought to have originated from D-type asteroids located in the outer asteroid belt. The oxygen isotope ratios of individual chondrules and isolated grains show a wide variation in δ18O from -9.9‰ to +9.1‰ along the carbonaceous chondrite anhydrous mineral (CCAM) and primitive chondrule mineral (PCM) lines. The Δ17O (= δ17O - 0.52 × δ18O) values of the measured objects increase with decreasing Mg#; i.e., FeO-poor objects (Mg# > 90; type I chondrules and isolated forsterites) mainly have Δ17O values of ca. -6‰, and FeO-rich objects (Mg# < 90; type II chondrules and isolated olivines) have Δ17O values ranging from -3‰ to +2‰. Similar trends are observed for ferromagnesian silicate particles from comet Wild2 and CR chondrite chondrules, particularly in terms of FeO-rich objects with Δ17O values ranging from -3‰ to +2‰. It is suggested that FeO-rich objects formed in the outer regions of the asteroid belt and were transported to the outer solar nebular regions where comet Wild2 formed.

The Pressure Dependence of Oxygen Isotope Exchange Rates Between Solution and Apical Oxygen Atoms on the [UO2(OH)4]2- Ion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harley, Steven J.; Ohlin, C. André; Johnson, Rene L.

2011-04-06

Under pressure: The pressure dependence of isotope exchange rate was determined for apical oxygen atoms in the [UO2(OH)4]2-(aq) ion (see picture). The results can be interpreted to indicate an associative character of the reaction.

Temperature and seawater isotopic controls on two stalagmite records since 83 ka from maritime Japan

NASA Astrophysics Data System (ADS)

Mori, Taiki; Kashiwagi, Kenji; Amekawa, Shota; Kato, Hirokazu; Okumura, Tomoyo; Takashima, Chiduru; Wu, Chung-Che; Shen, Chuan-Chou; Quade, Jay; Kano, Akihiro

2018-07-01

Millennial-scale interstadial Dansgaard-Oeschger (D-O) cycles and Heinrich (H) stadial events are pronounced paleoclimatic features during the last glacial period, which were first demonstrated in the North Atlantic region. These stadial and interstadial events are expressed in marine and terrestrial high-resolution records elsewhere in the world, but the magnitude and mode of the regional climate changes are still poorly quantified. Here we present new replicated stalagmite δ18O profiles from two caves in central Japan, which extend back to 83.4 ka. The records clearly display the H7 to H3 events, but not D-O cycles. An important feature of the two Japanese stalagmites is the small difference (∼2.9‰) in δ18O values between the mid-Holocene and the Last Glacial Maximum (LGM). Long-term trends of the stalagmite δ18O values at the more maritime site generally follow that of the δ18O record of seawater, which is responsible for ∼1.1‰ of the ∼2.9‰ difference between mid-Holocene and LGM. The remaining 1.8‰ in the difference can be accounted for by +9 °C of warming between the LGM and mid-Holocene and -3 °C cooling at H events, which are comparable with the previous estimates of land paleo-temperature in the Japanese Islands. The attenuated isotopic signal associated with D-O interstadials indicates that the warming in the Atlantic did not significantly transfer to the maritime Japan. These unique features of the isotopic records of the Japanese stalagmites are due to the geographic position at the vicinity of the moisture source, Kuroshio warm current.

Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts.

PubMed

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

2015-01-01

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.

CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

PubMed

Lyons, J R; Young, E D

2005-05-19

The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

Identification of Anthropogenic CO2 Using Triple Oxygen and Clumped Isotopes.

PubMed

Laskar, Amzad H; Mahata, Sasadhar; Liang, Mao-Chang

2016-11-01

Quantification of contributions from various sources of CO 2 is important for understanding the atmospheric CO 2 budget. Considering the number and diversity of sources and sinks, the widely used proxies such as concentration and conventional isotopic compositions (δ 13 C and δ 18 O) are not always sufficient to fully constrain the CO 2 budget. Additional constraints may help in understanding the mechanisms of CO 2 production and consumption. The anomaly in triple oxygen isotopes or 17 O excess (denoted by Δ 17 O) and molecules containing two rare isotopes, called clumped isotopes, are two recently developed tracers with potentials to independently constrain some important processes that regulate CO 2 in the atmosphere. The clumped isotope for CO 2 , denoted by Δ 47 , is the excess of 13 C 16 O 18 O over a random distribution of isotopes in a CO 2 molecule. We measured the concentrations of δ 13 C, δ 18 O, Δ 17 O, and Δ 47 in air CO 2 samples collected from the Hsuehshan tunnel (length: 12.9 km), and applied linear and polynomial regressions to obtain the fossil fuel end-members for all these isotope proxies. The other end-members, the values of all these proxies for background air CO 2 , are either assumed or taken as the values obtained over the tunnel and ocean. The fossil fuel (anthropogenic) CO 2 end-member values for δ 13 C, δ 18 O, Δ 17 O, and Δ 47 are estimated using the two component mixing approach: the derived values are -26.76 ± 0.25‰, 24.57 ± 0.33‰, -0.219 ± 0.021‰, and 0.267 ± 0.036‰, respectively. These four major CO 2 isotope tracers along with the concentration were used to estimate the anthropogenic contribution in the atmospheric CO 2 in urban and suburban locations. We demonstrate that Δ 17 O and Δ 47 have the potential to independently estimate anthropogenic contribution, and the advantages of these two over the conventional isotope proxies are discussed.

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

NASA Astrophysics Data System (ADS)

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

2003-04-01

Stable oxygen isotopic compositions of phosphate from mammal bones are commonly used in palaeoenvironmental reconstructions. However, preservation of the primary bone oxygen isotopic composition is of concern during post-mortem alteration. Particularly in studies of archaeological interest, bone samples are often obtained from contexts where they have been heated, either in middens, or near hearths. Hence, in addition to alteration resulting from natural diagenetic processes, burning may also have contributed to modification of the primary oxygen isotopic signal. Various techniques can be employed to evaluate the degree of preservation of bone during burning. Anthropologists commonly use colour comparisons (Munsell Colour Chart) to assess the temperature of burning. Recrystallization of the carbonated hydroxyapatite, i.e., bioapatite, in bone is more rigorously assessed using X-ray diffraction and infra-red spectroscopy. In this study, freshly deceased (6<8 months) white-tailed deer leg bones (Odocoileus virginianus) were collected from Pinery Provincial Park, Ontario, Canada. Each long bone was sectioned, incrementally burned, colour-typed, ground to a standardized grain-size (45<63mm), and analysed using differential thermal analysis (DTA), thermogravimetric analysis (TGA), rotating anode X-ray diffraction (XRD), and Fourier transform infra-red spectroscopy (FTIR). Heating temperatures ranged from 25 to 900^oC, increasing in intervals of 25^oC. Two major stages of weight loss were recorded in the DTA/TGA data, 25-260^oC representing dehydration, and 270-600^oC reflecting incineration of organic matter. The end-product (900^oC) resembled pure hydroxyapatite. XRD patterns of the bioapatite remained virtually unchanged from 25-250^oC, after which peak intensity, sharpness and the XRD crystallinity index (XRD CI) increased from 0.80 at 250^oC to 1.26 at 900^oC. FTIR patterns showed analogous behaviour, demonstrating minimal fluctuations in the FTIR crystallinity

Kinetic theory of oxygen isotopic exchange between minerals and water

USGS Publications Warehouse

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

1987-01-01

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

Growth patterns of an intertidal gastropod as revealed by oxygen isotope analysis

NASA Astrophysics Data System (ADS)

Bean, J. R.; Hill, T. M.; Guerra, C.

2007-12-01

The size and morphology of mollusk shells are affected by environmental conditions. As a result, it is difficult to assess growth rate, population age structure, shell morphologies associated with ontogenetic stages, and to compare life history patterns across various environments. Oxygen isotope analysis is a useful tool for estimating minimum ages and growth rates of calcium carbonate secreting organisms. Calcite shell material from members of two northern California populations of the intertidal muricid gastropod Acanthinucella spirata was sampled for isotopic analysis. Individual shells were sampled from apex to margin, thus providing a sequential record of juvenile and adult growth. A. spirata were collected from a sheltered habitat in Tomales Bay and from an exposed reef in Bolinas. Abiotic factors, such as temperature, wave exposure, and substrate consistency, and biotic composition differ significantly between these sites, possibly resulting in local adaptations and variation in life history and growth patterns. Shell morphology of A. spirata changes with age as internal shell margin thickenings of denticle rows associated with external growth bands are irregularly accreted. It is not known when, either seasonally and/or ontogentically, these thickenings and bands form or whether inter or intra-populational variation exists. Preliminary results demonstrate the seasonal oxygen isotopic variability present at the two coastal sites, indicating 5-6 degC changes from winter to summertime temperatures; these data are consistent with local intertidal temperature records. Analysis of the seasonal patterns indicate that: 1) differences in growth rate and seasonal growth patterns at different ontogenetic stages within populations, and 2) differences in growth patterns and possibly age structure between the two A. spirata populations. These findings indicate that isotopic analyses, in addition to field observations and morphological measurements, are necessary to

[Impacts of dominated landscape types on hydrogen and oxygen isotope effects of spring water in the Hani Rice Terraces].

PubMed

Jiao, Yuan Mei; Liu, Cheng Jing; Liu, Xin; Liu, Zhi Lin; Ding, Yin Ping

2017-07-18

Analysis of hydrogen and oxygen stable isotopes is an effective method to track the water cycle in watershed. Impact of landscape pattern on the isotope effects of spring water is a new interdisciplinary topic between landscape ecology and isotope hydrology. Taking the Quanfuzhuang River basin located in the core area of UNESCO World Cultural Heritage of Honghe Hani Rice Terrace as the object, collecting the monthly samples of 78 points of spring water and 39 precipitation at altitude of 1500 m (terraces), 1700 m (terraces) and 1900 m (forest) from March 2015 to March 2016, we analyzed the hydrogen and oxygen stable isotopes of water samples under the different landscape types. The results indicated that the dominated landscape types were forests and rice terraces, being 66.6% and 22.1% of the whole landscape area respectively, and they had a spatial vertical pattern of forest located at the mountain top and rice terraces at the down-slope. The correlation analysis showed that the spring water not only came from the precipitation, but also from other water sources which had a more positive δ 18 O and δD values, the spring water in up-slope forests mainly came from precipitation, while that in down-slope rice terraces came from precipitation, ri-ver water, rice terrace water and under ground water. Therefore, the mixing effects of spring water δ 18 O and δD were more significant in rice terraces. The overall altitude effect of the hydrogen and oxygen stable isotopes in spring water was obvious. The linear decreasing rates of δ 18 O and δD values were -0.125‰·(100 m) -1 and -0.688‰·(100 m) -1 , respectively. The deuterium surplus value increased with the altitude because of the impacts of landscape pattern and the local cycle of water isotopes. In summary, the dominant landscape types had a significant impact on the hydrogen and oxygen isotopes of spring water, which could be used as response indicator to reveal the impacts of landscape pattern on

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

A 150-ka-long record for the volcano-tectonic deformation of Central Anatolian Volcanic Province

NASA Astrophysics Data System (ADS)

Karabacak, Volkan; Tonguç Uysal, I.; Ünal-İmer, Ezgi; Mutlu, Halim; Zhao, Jian-xin

2017-04-01

The Anatolian Block represents one of the most outstanding examples of intra-plate deformation related to continental collision. Deformation related to the convergence of the Afro-Arabian continent toward north gives rise to widespread and intense arc volcanism in the Central Anatolia. All the usual studies on dating the volcano-tectonic deformation of the region are performed entirely on volcanic events of the geological record resulted in eruptions. However, without volcanic eruption, magma migration and related fluid pressurization also generate crustal deformation. In the current study has been funded by the Scientific and Technological Research Council of Turkey with the project no. 115Y497, we focused on fracture systems and their carbonate veins around the Ihlara Valley (Cappadocia) surrounded by well-known volcanic centers with latest activities of the southern Central Anatolian Volcanic Province. We dated 37 samples using the Uranium-series technique and analyzed their isotope systematics from fissure veins, which are thought to be controlled by the young volcanism in the region. Our detailed fracture analyses in the field show that there is a regional dilatation as a result of a NW-SE striking extension which is consistent with the results of recent GPS studies. The Uranium-series results indicate that fracture development and associated carbonate vein deposition occurred in the last 150 ka. Carbon and oxygen isotope systematics have almost remained unchanged in the studied time interval. Although veins in the region were precipitated from fluids primarily of meteoric origin, fluids originating from water-rock interaction also contribute for the deposition of carbonate veins. The age distribution indicates that the crustal deformation intensified during 7 different period at about 4.7, 34, 44, 52, 83, 91, 149 ka BP. Four of these periods (4.7, 34, 91, 149 ka BP) correspond to the volcanic activities suggested in the previous studies. The three crustal

Using thallium isotopes in the 2.63 Ga Jeerinah Formation from Hamersley Basin, Western Australia, to constrain ancient seafloor oxygenation

NASA Astrophysics Data System (ADS)

Holdaway, B. J.; Owens, J. D.; Nielsen, S.; Anbar, A. D.; Ostrander, C. M.

2017-12-01

Understanding the chemical and biological innovation and evolution of the global ocean is pivotal in understanding the processes for how early life on Earth and potentially habitable planets advanced. Previous research on early-Earth oxygenation has revealed a rise in atmospheric [O2] 2.32 billion years ago, coined the Great Oxidation Event, or GOE. Many lines of evidence, however, suggest continental oxidative weathering as early as 3.0 Ga, with possibilities of complementary ocean oxygenation. Modeling of the geochemical data suggests small oxygen "oases" prior to whiffs of O2, or even widespread oxygen-rich margins. However, constraining the extent and timing of oceanic oxygenation is difficult as proxies fall short in detecting early ocean oxygenation. Importantly, the formation and preservation of manganese (Mn) in the form of manganese-oxides requires an oxygenated water-column that penetrates the sediment-water interface. Until recently, tracking the global burial of Mn-oxides was very difficult, largely compounded by an incomplete ancient geologic record. Here we use thallium (Tl), a new and novel isotope system to better constrain marine [O2], specifically by constraining the global burial of Mn-oxides. Recently, it has been shown that modern seawater Tl isotope composition is faithfully recorded in anoxic to euxinic (anoxic and sulfidic) sediments. Nearly all isotopic inputs: riverine, dust, volcanic, hydrothermal, and benthic recycling of Tl into the ocean are constant with ɛ205Tl -2. In contrast, the two primary outputs impart significant fractionations, these outputs being the burial of Mn-oxides (ɛ205Tl +12) and altered oceanic crust (ɛ205Tl -10). Thus, seawater is mainly dictated by the mass balance of the outputs (Mn-oxides and altered oceanic crust) which, for short-term events, is likely driven by the amount of Mn-oxide burial. Tl isotope analyses of the dominantly euxinic 2.5 Ga Mt. McRae Shale from the Hamersley Basin, Western Australia

Hydroclimate variability of High Arctic Svalbard during the Holocene inferred from hydrogen isotopes of leaf waxes

NASA Astrophysics Data System (ADS)

Balascio, Nicholas L.; D'Andrea, William J.; Gjerde, Marthe; Bakke, Jostein

2018-03-01

The response of the Arctic hydrologic cycle to global warming includes changes in precipitation patterns and moisture availability associated with variable sea ice extent and modes of atmospheric circulation. Reconstructions of past hydroclimate changes help constrain the natural range of these systems, identify the manners in which they respond to different forcing mechanisms, and reveal their connections to other components of the climate system, all of which lead to a better understanding of present and future changes. Here we examine hydroclimate changes during the Holocene in the High Arctic archipelago of Svalbard by reconstructing the isotopic composition of precipitation. We measured the hydrogen isotopic composition (δD values) of leaf wax compounds (n-alkanes; C25-C31) in a sediment core from Lake Hakluytvatnet on the island of Amsterdamøya, northwest Spitsbergen. We interpret δD values of mid-chain (C25) and long-chain (C29, C31) length n-alkanes to represent changes in the isotopic composition of lake water and precipitation over the last 12.9 ka. After deglaciation of the catchment, water supply became restricted and the lake experienced significant evaporative isotopic enrichment indicating warmer conditions from 12.8 to 7.5 ka. The isotope values suggest an increase in the delivery of moisture from warmer sub-polar air masses between 12.8 and 9.5 ka, followed by generally warm, but unstable conditions between 9.5 and 7.5 ka, possibly indicating a response to meltwater forcing. Sedimentary evidence indicates a hiatus in deposition c. 7.5-5.0 ka, likely as a result of desiccation of the lake. At c. 5.0 ka lacustrine sedimentation resumed and over the last 5 ka there was a progressive increase in the influence of polar air masses and colder conditions, which culminated in an abrupt shift to colder conditions at c. 1.8 ka. This late Holocene cooling ended c. 0.18 ka, when isotopic data indicate warmer conditions and greater influence of moisture

Phosphorus cycling in forest ecosystems: insights from oxygen isotopes in phosphate

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Isotopic evolution of Mauna Loa Volcano: A view from the submarine southwest rift zone

NASA Astrophysics Data System (ADS)

Kurz, Mark D.; Kenna, T. C.; Kammer, D. P.; Rhodes, J. Michael; Garcia, Michael O.

New isotopic and trace element measurements on lavas from the submarine southwest rift zone (SWR) of Mauna Loa continue the temporal trends of subaerial Mauna Loa flows, extending the known compositional range for this volcano, and suggesting that many of the SWR lavas are older than any exposed on land. He and Nd isotopic compositions are similar to those in the oldest subaerial Mauna Loa lavas (Kahuku and Ninole Basalts), while 87Sr/86Sr ratios are slightly lower (as low as .7036) and Pb isotopes are higher (206Pb'204Pb up to 18.30). The coherence of all the isotopes suggests that helium behaves as an incompatible element, and that helium isotopic variations in the Hawaiian lavas are produced by melting and mantle processes, rather than magma chamber or metasomatic processes unique to the gaseous elements. The variations of He, Sr, and Nd are most pronounced in lavas of approximately 10 ka age range [Kurz and Kammer, 1991], but the largest Pb isotopic variation occurs earlier. These variations are interpreted as resulting from the diminishing contribution from the upwelling mantle plume material as the shield building ends at Mauna Loa. The order of reduction in the plume isotopic signature is inferred to be Pb (at >100 ka), He (at ˜14 ka), Sr (at ˜9 ka), and Nd (at ˜8 ka); the different timing may relate to silicate/melt partition coefficients, with most incompatible elements removed first, and also to concentration variations within the plume. Zr/Nb, Sr/Nb, and fractionation-corrected Nb concentrations, correlate with the isotopes and are significantly higher in some of the submarine SWR lavas, suggesting temporal variability on time scales similar to the Pb isotopes (i.e. ˜ 100 ka). Historical lavas define trace element and isotopic trends that are distinct from the longer term (10 to 100 ka) variations, suggesting that different processes cause the short term variability. The temporal evolution of Mauna Loa, and particularly the new data from the

Paleoclimate in continental northwestern Europe during the Eemian and early Weichselian (125-97 ka): insights from a Belgian speleothem

NASA Astrophysics Data System (ADS)

Vansteenberge, Stef; Verheyden, Sophie; Cheng, Hai; Edwards, R. Lawrence; Keppens, Eddy; Claeys, Philippe

2016-07-01

The last interglacial serves as an excellent time interval for studying climate dynamics during past warm periods. Speleothems have been successfully used for reconstructing the paleoclimate of last interglacial continental Europe. However, all previously investigated speleothems are restricted to southern Europe or the Alps, leaving large parts of northwestern Europe undocumented. To better understand regional climate changes over the past, a larger spatial coverage of European last interglacial continental records is essential, and speleothems, because of their ability to obtain excellent chronologies, can provide a major contribution. Here, we present new, high-resolution data from a stalagmite (Han-9) obtained from the Han-sur-Lesse Cave in Belgium. Han-9 formed between 125.3 and ˜ 97 ka, with interruptions of growth occurring at 117.3-112.9 and 106.6-103.6 ka. The speleothem was investigated for its growth, morphology and stable isotope (δ13C and δ18O) composition. The speleothem started growing relatively late within the last interglacial, at 125.3 ka, as other European continental archives suggest that Eemian optimum conditions were already present during that time. It appears that the initiation of Han-9 growth is caused by an increase in moisture availability, linked to wetter conditions around 125.3 ka. The δ13C and δ18O proxies indicate a period of relatively stable conditions after 125.3 ka; however, at 120 ka the speleothem δ18O registered the first signs of regionally changing climate conditions, being a modification of ocean source δ18O linked to an increase in ice volume towards the Marine Isotope Stage (MIS) 5e-5d transition. At 117.5 ka, drastic vegetation changes are recorded by Han-9 δ13C immediately followed by a cessation of speleothem growth at 117.3 ka, suggesting a transition to significantly dryer conditions. The Han-9 record covering the early Weichselian displays larger amplitudes in both isotope proxies and changes in stalagmite

Paleo-hydrological changes in the Chew Bahir area during the past 50 ka inferred from isotope signatures in aquatic microfossils

NASA Astrophysics Data System (ADS)

Junginger, Annett

2017-04-01

A major challenge in paleo-anthropology is to understand the impact of climatic changes on human evolution. The Hominin Sites and Paleo-lakes Drilling Project (HSPDP) is currently meeting that challenge by providing records that cover the last 3.7 Ma of paleoenvironmental change all located in close proximity to key paleo-anthropological findings in East Africa. One of the cored climatic archives comes from the Chew Bahir basin in southern Ethiopia, where duplicate sediment cores provide valuable insights about East African environmental variability during the last 550 ka. The lake basins in the eastern branch of the East African Rift System today contain mainly shallow and alkaline lakes. However, paleo-shorelines in the form of wave cut notches, shell beds, and beach ridges are common morphological evidences for deep freshwater lakes that have filled the basins up to their overflow level during pronounced humid episodes, such as the African Humid Period (15-5 ka). Unfortunately, further back in time, many of those morphological features disappear due to erosion and the estimation of paleo-water depths depend merely on qualitative proxies from core analyses. We here present a method that shows high potential to translate qualitative proxy signals from sediment core analyses to quantitative climate signals in the Ethiopian Rift. The method aims at water level reconstruction in the Chew Bahir basin using strontium isotope ratios (87Sr/86Sr, SIR) in lacustrine microfossils. SIR reflect the lithology of the drained catchment. SIR have changed pronouncedly when higher elevated paleo-lakes Abaya, Chamo and Awassa were overflowing into paleo-lake Chew Bahir. This new method may help to quantify paleo-lake levels beyond the past 20 ka and may also detect migrational barriers or routes due to the occurrence of synchronous large, connected and deep paleo-lakes.

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

USGS Publications Warehouse

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

2006-01-01

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

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

EPA Science Inventory

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

Assessing Pyrite-Derived Sulfate in the Mississippi River with Four Years of Sulfur and Triple-Oxygen Isotope Data.

PubMed

Killingsworth, Bryan A; Bao, Huiming; Kohl, Issaku E

2018-05-17

Riverine dissolved sulfate (SO 4 2- ) sulfur and oxygen isotope variations reflect their controls such as SO 4 2- reduction and reoxidation, and source mixing. However, unconstrained temporal variability of riverine SO 4 2- isotope compositions due to short sampling durations may lead to mischaracterization of SO 4 2- sources, particularly for the pyrite-derived sulfate load. We measured the sulfur and triple-oxygen isotopes (δ 34 S, δ 18 O, and Δ' 17 O) of Mississippi River SO 4 2- with biweekly sampling between 2009 and 2013 to test isotopic variability and constrain sources. Sulfate δ 34 S and δ 18 O ranged from -6.3‰ to -0.2‰ and -3.6‰ to +8.8‰, respectively. Our sampling period captured the most severe flooding and drought in the Mississippi River basin since 1927 and 1956, respectively, and a first year of sampling that was unrepresentative of long-term average SO 4 2- . The δ 34 S SO4 data indicate pyrite-derived SO 4 2- sources are 74 ± 10% of the Mississippi River sulfate budget. Furthermore, pyrite oxidation is implicated as the dominant process supplying SO 4 2- to the Mississippi River, whereas the Δ' 17 O SO4 data shows 18 ± 9% of oxygen in this sulfate is sourced from air O 2 .

Evaporation Induced Oxygen Isotope Fractionation in Impact Ejecta

NASA Astrophysics Data System (ADS)

Macris, C. A.; Young, E. D.; Kohl, I. E.; zur Loye, T. E.

2017-12-01

Tektites are natural glasses formed as quenched impact melt ejecta. Because they experienced extreme heating while entrained in a hot impact vapor plume, tektites allow insight into the nature of these ephemeral events, which play a critical role in planetary accretion and evolution. During tektite formation, the chemical and isotopic composition of parent materials may be modified by (1) vapor/liquid fractionation at high T in the plume, (2) incorporation of meteoric water at the target site, (3) isotope exchange with atmospheric oxygen (if present), or some combination of the three. Trends from O isotope studies reveal a dichotomy: some tektite δ18O values are 4.0-4.5‰ lower than their protoliths (Luft et al. 1987; Taylor & Epstein 1962), opposite in direction to a vaporization induced fractionation; increases in δ18O with decreasing SiO2 in tektites (Taylor & Epstein 1969) is consistent with vapor fractionation. Using an aerodynamic levitation laser furnace (e.g. Macris et al. 2016), we can experimentally determine the contributions of processes (1), (2) and (3) above to tektite compositions. We conducted a series of evaporation experiments to test process (1) using powdered tektite fused into 2 mm spheres and heated to 2423-2473 K for 50-90 s while levitated in Ar in the furnace. Mass losses were from 23 to 26%, reflecting evaporation of Si and O from the melt. The starting tektite had a δ18O value of 10.06‰ (±0.01 2se) and the residues ranged from 13.136‰ (±0.006) for the least evaporated residue to 14.30‰ (±0.02) for the most evaporated (measured by laser fluorination). The increase in δ18O with increasing mass loss is consistent with Rayleigh fractionation during evaporation, supporting the idea that O isotopes are fractionated due to vaporization at high T in an impact plume. Because atmospheric O2 and water each have distinctive Δ17O values, we should be able to use departures from our measured three-isotope fractionation law to evaluate

Isotope exchange in oxide-containing catalyst

NASA Technical Reports Server (NTRS)

Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

1989-01-01

A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

Forward Modeling of Oxygen Isotope Variability in Tropical Andean Ice Cores

NASA Astrophysics Data System (ADS)

Vuille, M. F.; Hurley, J. V.; Hardy, D. R.

2016-12-01

Ice core records from the tropical Andes serve as important archives of past tropical Pacific SST variability and changes in monsoon intensity upstream over the Amazon basin. Yet the interpretation of the oxygen isotopic signal in these ice cores remains controversial. Based on 10 years of continuous on-site glaciologic, meteorologic and isotopic measurements at the summit of the world's largest tropical ice cap, Quelccaya, in southern Peru, we developed a process-based physical forward model (proxy system model), capable of simulating intraseasonal, seasonal and interannual variability in delta-18O as observed in snow pits and short cores. Our results highlight the importance of taking into account post-depositional effects (sublimation and isotopic enrichment) to properly simulate the seasonal cycle. Intraseasonal variability is underestimated in our model unless the effects of cold air incursions, triggering significant monsoonal snowfall and more negative delta-18O values, are included. A number of sensitivity test highlight the influence of changing boundary conditions on the final snow isotopic profile. Such tests also show that our model provides much more realistic data than applying direct model output of precipitation delta-18O from isotope-enabled climate models (SWING ensemble). The forward model was calibrated with and run under present-day conditions, but it can also be driven with past climate forcings to reconstruct paleo-monsoon variability and investigate the influence of changes in radiative forcings (solar, volcanic) on delta-18O variability in Andean snow. The model is transferable and may be used to render a paleoclimatic context at other ice core locations.

Temperature and atmospheric CO2 concentration estimates through the PETM using triple oxygen isotope analysis of mammalian bioapatite

PubMed Central

Gehler, Alexander; Pack, Andreas

2016-01-01

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. PMID:27354522

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

PubMed

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

2009-06-01

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

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

EPA Science Inventory

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

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

The impact of moisture sources on the oxygen isotope composition of precipitation at a continental site in central Europe

NASA Astrophysics Data System (ADS)

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

2018-06-01

The stable isotope composition of precipitation records processes taking place within the hydrological cycle. Potentially, moisture sources are important controls on the stable isotope composition of precipitation, but studies focused on this topic are still scarce. We studied the moisture sources contributing to precipitation at Postojna (Slovenia) from 2009 to 2013. Back trajectory analyses were computed for the days with precipitation at Postojna. The moisture uptake locations were identified along these trajectories using standard hydrometeorological formulation. The moisture uptake locations were integrated in eight source regions to facilitate its comparison to the monthly oxygen isotope composition (δ18O values) of precipitation. Nearly half of the precipitation originated from continental sources (recycled moisture), and >40% was from central and western Mediterranean. Results show that moisture sources do not have a significant impact on the oxygen isotope composition at this site. We suggest that the large proportion of recycled moisture originated from transpiration rather than evaporation, which produced water vapour with less negative δ18O values. Thus the difference between the oceanic and local vapour source was reduced, which prevented the distinction of the moisture sources based on their oxygen isotope signature. Nevertheless, δ18O values of precipitation are partially controlled by climate parameters, which is of major importance for paleoclimate studies. We found that the main climate control on Postojna δ18O values of precipitation is the surface temperature. Amount effect was not recorded at this site, and the winter North Atlantic Oscillation (NAO) does not impact the δ18O values of precipitation. The Western Mediterranean Oscillation (WeMO) was correlated to oxygen stable isotope composition, although this atmospheric pattern was not a control. Instead we found that the link to δ18O values results from synoptic scenarios affecting We

An ion microprobe study of individual zircon phenocrysts from voluminous post-caldera rhyolites of the Yellowstone caldera

NASA Astrophysics Data System (ADS)

Watts, K. E.; Bindeman, I. N.; Schmitt, A. K.

2010-12-01

Following the formation of the Yellowstone caldera from the 640 ka supereruption of the Lava Creek Tuff (LCT), a voluminous episode of post-caldera volcanism filled the caldera with >600 km3 of low-δ18O rhyolite. Such low-δ18O signatures require remelting of 100s of km3 of hydrothermally altered (18O-depleted) rock in the shallow crust. We present a high resolution oxygen isotope and geochronology (U-Th and U-Pb) study of individual zircon crystals from seven of these voluminous post-caldera rhyolites in order to elucidate their genesis. Oxygen isotope and geochronology analyses of zircon were performed with an ion microprobe that enabled us to doubly fingerprint 25-30 µm diameter spots. Host groundmass glasses and coexisting quartz were analyzed in bulk for oxygen isotopes by laser fluorination. We find that zircons from the youngest (200-80 ka) post-caldera rhyolites have oxygen isotopic compositions that are in equilibrium with low-δ18O host groundmass glasses and quartz and are unzoned in oxygen and U-Th age. This finding is in contrast to prior work on older (500-250 ka) post-caldera rhyolites, which exhibit isotopic disequilibria and age zoning, including the presence of clearly inherited zircon cores. Average U-Th crystallization ages and δ18O zircon values for Pitchstone Plateau flow (81±7 ka, 2.8±0.2‰), West Yellowstone flow (118±8 ka, 2.8±0.1‰), Elephant Back flow (175±22 ka, 2.7±0.2‰) and Tuff of Bluff Point (176±20 ka, 2.7±0.1‰) are overlapping or nearly overlapping in age and identical in oxygen isotope composition within uncertainty (2 SE). New U-Pb geochronology and oxygen isotope data for the North Biscuit Basin flow establish that it has an age (188±33 ka) and δ18O signature (2.8±0.2‰) that is distinctive of the youngest post-caldera rhyolites. Conversely, the South Biscuit Basin flow has a heterogeneous zircon population with ages that range from 550-250 ka. In this unit, older and larger (200-400 µm) zircons have more

Can Lightning Produce Significant Levels of Mass-Independent Oxygen Isotopic Fractionation in Nebular Dust?

NASA Technical Reports Server (NTRS)

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

2012-01-01

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 .

Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

USGS Publications Warehouse

Kim, Sang-Tae; Gebbinck, Christa Klein; Mucci, Alfonso; Coplen, Tyler B.

2014-01-01

To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Ion Microprobe Measurements of Comet Dust and Implications for Models of Oxygen Isotope Heterogeneity in the Solar System

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

Late Quaternary palaeoenvironmental reconstruction from Lake Ohrid using stable isotopes

NASA Astrophysics Data System (ADS)

Lacey, Jack H.; Leng, Melanie J.; Francke, Alexander; Vogel, Hendrik; Zanchetta, Giovanni; Wagner, Bernd

2016-04-01

Lake Ohrid is a large, deep lake located on the Balkan Peninsula at the border between Macedonia and Albania, and is considered the oldest extant lake in Europe. An International Continental scientific Drilling Program (ICDP) deep drilling campaign was carried out in 2013 as part of the interdisciplinary Scientific Collaboration On Past Speciation Conditions in Lake Ohrid (SCOPSCO) project. Over 1500 m of sediment were recovered from six coring locations at the main target site in the central basin, where the maximum drill depth reached 569 m below the lake floor. Initial results indicate continuous lacustrine conditions over the past >1.2 Ma (Wagner et al., 2014). Here, we present oxygen and carbon isotope data (δ18O and δ13C) from carbonate from the upper 248 m of the SCOPSCO succession, which covers the last 640 ka, spanning marine isotope stages 15-1, according to an age model based on tephra and orbital tuning (Francke et al., 2015). Modern monitoring data show Lake Ohrid to be an evaporative system, where variations in δ18O of endogenic carbonate are primarily a function of changes in water balance, and δ13C largely reflects fluctuations in the amount of soil-derived CO2 and organic matter recycling. Our results indicate a trend from wetter to drier conditions through the Holocene, which is consistent with regional and hemispheric processes related to changes in insolation and progressive aridification. Over the last 640 ka, relatively stable climate conditions are inferred before ca. 450 ka, a transition to a wetter climate between ca. 400-250 ka, and a trend to drier climate after ca. 250 ka. Higher frequency, multi-millennial-scale oscillations observed during warm stages are most likely associated with regional climate change as a function of orbital forcing. This record is one of the most extensive and highly-resolved continental isotope records available, and emphasises the potential of Lake Ohrid as a valuable archive of long-term palaeoclimate and

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Distinguishing wild vs. stocked lake trout (Salvelinus namaycush) in Lake Ontario: Evidence from carbon and oxygen stable isotope values of otoliths

USGS Publications Warehouse

Schaner, T.; Patterson, W.P.; Lantry, B.F.; O'Gorman, R.

2007-01-01

We investigated the potential for using carbon and oxygen isotope values of otolith carbonate as a method to distinguish naturally produced (wild) lake trout (Salvelinus namaycush) from hatchery-reared lake trout in Lake Ontario. We determined δ 13C(CaCO3) and δ 18O(CaCO3) values of otoliths from juvenile fish taken from two hatcheries, and of otoliths from wild yearlings. Clear differences in isotope values were observed between the three groups. Subsequently we examined otoliths from large marked and unmarked fish captured in the lake, determining isotope values for regions of the otolith corresponding to the first year of life. Marked (i.e., stocked) fish showed isotope ratios similar to one of the hatchery groups, whereas unmarked fish, (wild fish or stocked fish that lost the mark) showed isotope ratios similar either to one of the hatchery groups or to the wild group. We interpret these data to suggest that carbon and oxygen isotope values can be used to determine the origin of lake trout in Lake Ontario, if a catalogue of characteristic isotope values from all candidate years and hatcheries is compiled.

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

USDA-ARS?s Scientific Manuscript database

The oxygen isotope ratio of water (18 O-H2O) and carbon dioxide (18 O-CO2) is an important signal of global change and can provide constraints on the coupled carbon-water cycle. Here, simultaneous observations of 18O-H2O (liquid and vapor phases) and 18 O-CO2 were used to investigate the relation be...

Ab initio study of nitrogen and position-specific oxygen kinetic isotope effects in the NO + O3 reaction

NASA Astrophysics Data System (ADS)

Walters, Wendell W.; Michalski, Greg

2016-12-01

Ab initio calculations have been carried out to investigate nitrogen (k15/k14) and position-specific oxygen (k17/k16O & k18/k16) kinetic isotope effects (KIEs) for the reaction between NO and O3 using CCSD(T)/6-31G(d) and CCSD(T)/6-311G(d) derived frequencies in the complete Bigeleisen equations. Isotopic enrichment factors are calculated to be -6.7‰, -1.3‰, -44.7‰, -14.1‰, and -0.3‰ at 298 K for the reactions involving the 15N16O, 14N18O, 18O16O16O, 16O18O16O, and 16O16O18O isotopologues relative to the 14N16O and 16O3 isotopologues, respectively (CCSD(T)/6-311G(d)). Using our oxygen position-specific KIEs, a kinetic model was constructed using Kintecus, which estimates the overall isotopic enrichment factors associated with unreacted O3 and the oxygen transferred to NO2 to be -19.6‰ and -22.8‰, respectively, (CCSD(T)/6-311G(d)) which tends to be in agreement with previously reported experimental data. While this result may be fortuitous, this agreement suggests that our model is capturing the most important features of the underlying physics of the KIE associated with this reaction (i.e., shifts in zero-point energies). The calculated KIEs will useful in future NOx isotopic modeling studies aimed at understanding the processes responsible for the observed tropospheric isotopic variations of NOx as well as for tropospheric nitrate.

Interpreting species-specific variation in tree-ring oxygen isotope ratios among three temperate forest trees

Treesearch

Xin Song; Kenneth S. Clark; Brent R. Helliker

2014-01-01

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

The activity-composition relationship of oxygen and hydrogen isotopes in aqueous salt solutions: III. Vapor-liquid water equilibration of NaCl solutions to 350°C

NASA Astrophysics Data System (ADS)

Horita, Juske; Cole, David R.; Wesolowski, David J.

1995-03-01

The effect of dissolved NaCl on equilibrium oxygen and hydrogen isotope fractionation factors between liquid water and water vapor was precisely determined in the temperature range from 130-350°C, using two different types of apparatus with static or dynamic sampling techniques of the vapor phase. The magnitude of the oxygen and hydrogen isotope effects of NaCl is proportional to the molality of liquid NaCl solutions at a given temperature. Dissolved NaCl lowers appreciably the hydrogen isotope fractionation factor between liquid water and water vapor over the entire temperature range. NaCl has little effect on the oxygen isotope fractionation factor at temperatures below about 200°C, with the magnitude of the salt effect gradually increasing from 200-350°C. Our results are at notable variance with those of Truesdell (1974) and Kazahaya (1986), who reported large oxygen and hydrogen isotope effects of NaCl with very complex dependencies on temperature and NaCl molality. Our high-temperature results have been regressed along with our previous results between 50 and 100°C (Horita et al., 1993a) and the low-temperature literature data to simple equations which are valid for NaCl solutions from 0 to at least 5 molal NaCl in the temperature range from 10-350°C. Our preliminary results of oxygen isotope fractionation in the system CaCO3-water ± NaCl at 300°C and 1 kbar are consistent with those obtained from the liquid-vapor equilibration experiments, suggesting that the isotope salt effects are common to systems involving brines and any other coexisting phases or species (gases, minerals, dissolved species, etc.). The observed NaCl isotope effects at elevated temperatures should be taken into account in the interpretation of isotopic data of brine-dominated natural systems.

Magnetic Mineral diagenesis in changing water environments in the Black Sea since ˜41.6 ka

NASA Astrophysics Data System (ADS)

Liu, Jiabo; Nowaczyk, Norbert; Frank, Ute; Arz, Helge

2017-04-01

Magnetic mineral diagenesis plays a key role in the global iron cycle. To understand the authigenic magnetic mineral formation by diagenesis is also fundamentally important for the interpretation of environmental magnetic as well as paleomagnetic signals. Core MSM33-55-1, recovered from the SW Black Sea, was subjected to rock-magnetic and SEM studies. The results demonstrate that four different magnetic mineral assemblages associated to specific water conditions can be observed. Between ˜41.6 ka and ˜19 ka, magnetite and greigite are alternatively in dominance in the sediment. Due to low organic matter input during the late MIS 3 and the last glacial maximum (LGM), oxygenated bottom water in the Black Sea was favourable for preserving detrital magnetite. Greigite in this interval have irregular shapes and assemble in spots, which were formed in a micro environment with limited sulfate availability. Between ˜19 ka and ˜16.5 ka, black layers were deposited as a result of organic matter accumulation induced by productivity blooming and riverine discharge soaring after the LGM. Hence less oxygenated bottom water conditions developed, and more fine grained greigite was formed. After melt-water pulse (MWP) events (˜16.5 ka), both primary productivity and the sea level were continuously rising until ˜8.3 ka, leading to the depletion of oxygen in bottom water. In addition to greigite, pyrite was also formed and gradually in dominance as approaching the Holocene. The influx of salt water masses from the Mediterranean Sea after ˜8.3 ka contributed to the establishment of the anoxic Black Sea, which resulted in the formation of ubiquitous frambiods of pyrite. Additionally, bacterial magnetic minerals are likely present in the sediment younger than ˜8.3 ka as indicated by rock magnetic results. In this paper, four different magnetic mineral assemblages, reflecting gradual changes from an oxic to an anoix Black Sea, were identified, yielding insights into the relation

Deglacial Western Equatorial Pacific pCO2 Reconstruction Using Boron Isotopes of Planktonic Foraminiferas

NASA Astrophysics Data System (ADS)

Kubota, K.; Yokoyama, Y.; Ishikawa, T.; Sagawa, T.; Ikehara, M.; Yamazaki, T.

2017-12-01

During the last deglaciation (ca. 19 - 11 ka), partial pressure of CO2 (pCO2) of the atmosphere increased by 80 μatm. Many paleoceanographers point out that the ocean had played an important role in atmospheric CO2 rise, since the ocean have 60 times larger capacity to store carbon compared to the atmosphere. However, evidence on where carbon was transferred from the ocean to the atmosphere is still lacking, hampering our understanding of global carbon cycles in glacial-interglacial timescales. Boron isotope of skeletons of marine calcifying organisms such as corals and foraminiferas can pin down where CO2 source/sink existed, because boron isotopes of marine calcium carbonates is dependent on seawater pH, from which pCO2 of the past seawater can be reconstructed. In previous studies using the boron isotope teqnique, Martinez-Boti et al. (2015, Nature) and Kubota et al. (2014, Scientific Reports) revealed that central and eastern parts of the equatorial Pacific acted as a CO2 source (i.e., CO2 emission) during the last deglaciation, suggesting the equatorial Pacific's contribution to atmospheric CO2 rise. However, some conflicting results have been confirmed in a marine sediment record from the western part of the equatorial Pacific (Palmer & Pearson, 2003, Science), making the conclusion elusive. In this presentation, we will show new results of Mg/Ca, oxygen isotope, and boron isotope measurements during the last 35 ka on two species of surface dwelling foraminiferas (Globigerinoides ruber and G. sacculifer) which was hand-picked separatedly from a well-dated marine sediment core recovered from the West Caroline Basin (KR05-15 PC01) (Yamazaki et al., 2008, GRL). From the new records, we will discuss how the equatorial Pacific behaved during the last deglaciation and how it related to the global carbon cycles.

Moisture transport across Canada: evidence from stable oxygen and deuterium isotope values of lakes and rivers

NASA Astrophysics Data System (ADS)

Oakley, J. R.; Patterson, W. P.

2008-12-01

Global warming models often contain a prediction of changes in precipitation, yet modern moisture cycling is poorly understood. Stable oxygen and deuterium isotope values of several thousand lake and river water samples collected from 2004 to 2008 throughout Canada and the Northern United States provide a means to evaluate variations in the movement of moisture across the northern North American continent. Our particular focus is on the moisture tracking in the province of Saskatchewan. The dominant moisture source for Saskatchewan is the Gulf of Mexico, though precipitation contains some water from the Pacific and Arctic Oceans as well. By sampling locations multiple times, we established time series of isotope variability that we can relate to meteorological variation. A series of cross-plots of oxygen to deuterium isotopes for each year exhibits an increase in slope from year to year that reflects an increase in humidity and/or precipitation throughout the Prairies from 2004 to 2008. We define the influence of temperature, precipitation and humidity on the change in slope for each suite of samples. Ultimately, by combining our evidence of moisture transport with a grid of long-term secular records from lakes, speleothems and tree-ring isotope variability, we can not only reconstruct changes in atmospheric circulation through time, but also better predict what will happen in the future under various global climate change scenarios.

Oxygen isotopic evidence for accretion of Earth's water before a high-energy Moon-forming giant impact.

PubMed

Greenwood, Richard C; Barrat, Jean-Alix; Miller, Martin F; Anand, Mahesh; Dauphas, Nicolas; Franchi, Ian A; Sillard, Patrick; Starkey, Natalie A

2018-03-01

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.

Isotopic fractionation of oxygen and carbon in decomposed lower-mantle inclusions in diamond

DOE PAGES

Kaminsky, Felix; Matzel, Jennifer; Jacobsen, Ben; ...

2015-07-25

Two carbonatitic mineral assemblages, calcite + wollastonite and calcite + monticellite, which are encapsulated in two diamond grains from the Rio Soriso basin in the Juina area, Mato Grosso State, Brazil, were studied utilizing the NanoSIMS technique. The assemblages were formed as the result of the decomposition of the lower-mantle assemblage calcite + CaSi-perovskite + volatile during the course of the diamond ascent under pressure conditions from 15 to less than 0.8 GPa. The oxygen and carbon isotopic compositions of the studied minerals are inhomogeneous. They fractionated during the process of the decomposition of primary minerals to very varying values:more » δ 18O from –3.3 to +15.4 ‰ SMOW and δ 13C from –2.8 to +9.3 ‰ VPDB. As a result, these values significantly extend the mantle values for these elements in both isotopically-light and isotopically-heavy areas.« less

Isotopic exchange in mineral-fluid systems. IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H 2O and layer silicate-H 2O systems

NASA Astrophysics Data System (ADS)

Cole, David R.

2000-03-01

Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. We tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H 2O and layer silicate-H 2O at 300 and 350°C, respectively. Witherite (BaCO 3), strontianite (SrCO 3) and calcite (CaCO 3) were reacted with pure H 2O for different lengths of time (271-1390 h) at 300°C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H 2O for durations ranging from 132 to 3282 h at 350°C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. Changes in the mean grain diameters were particularly significant in experiments involving withertite, strontianite and biotite. The variations in the extent of oxygen isotope exchange were measured as a function of time, and fit to a pseudo-first order rate model that accounted for the change in surface area of the solid during reaction. The isotopic rates (ln r) for the carbonate-H 2O system are -20.75 ± 0.44, -18.95 ± 0.62 and -18.51 ± 0.48 mol O m -2 s -1 for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H 2O systems are -23.99 ± 0.89, -23.14 ± 0.74 and -22.40 ± 0.66 mol O m -2 s -1 for muscovite, biotite and chlorite, respectively. The rates for the carbonate-H 2O systems increase in order from calcite to strontianite to witherite. This order

Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands).

PubMed

Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

2016-10-01

Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ(18)Ocalc and δ(13)Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ(18)Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in (18)O relative to (16)O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ(18)Ocalc value of eggshell calcite to the δ(18)Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ(13)Ccalc and δ(18)Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ(13)Ccalc and high δ(18)Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands)

NASA Astrophysics Data System (ADS)

Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

2016-10-01

Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ18Ocalc and δ13Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ18Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in 18O relative to 16O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ18Ocalc value of eggshell calcite to the δ18Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ13Ccalc and δ18Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ13Ccalc and high δ18Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

Timescales for the evolution of oxygen isotope compositions in the solar nebula

NASA Astrophysics Data System (ADS)

Lyons, J. R.; Bergin, E. A.; Ciesla, F. J.; Davis, A. M.; Desch, S. J.; Hashizume, K.; Lee, J.-E.

2009-09-01

We review two models for the origin of the calcium-, aluminum-rich inclusion (CAI) oxygen isotope mixing line in the solar nebula: (1) CO self-shielding, and (2) chemical mass-independent fractionation (MIF). We consider the timescales associated with formation of an isotopically anomalous water reservoir derived from CO self-shielding, and also the vertical and radial transport timescales of gas and solids in the nebula. The timescales for chemical MIF are very rapid. CO self-shielding models predict that the Sun has Δ 17O SMOW ˜ -20‰ (Clayton, 2002), and chemical mass-independent fractionation models predict Δ 17O SMOW ˜0‰. Preliminary Genesis results have been reported by McKeegan et al. (McKeegan K. D., Coath C. D., Heber, V., Jarzebinski G., Kallio A. P., Kunihiro T., Mao P. H. and Burnett D. S. (2008b) The oxygen isotopic composition of captured solar wind: first results from the Genesis. EOS Trans. AGU 89(53), Fall Meet. Suppl., P42A-07 (abstr)) and yield a Δ 17O SMOW of ˜ -25‰, consistent with a CO self-shielding scenario. Assuming that subsequent Genesis analyses support the preliminary results, it then remains to determine the relative contributions of CO self-shielding from the X-point, the surface of the solar nebula and the parent molecular cloud. The relative formation ages of chondritic components can be related to several timescales in the self-shielding theories. Most importantly the age difference of ˜1-3 My between CAIs and chondrules is consistent with radial transport from the outer solar nebula (>10 AU) to the meteorite-forming region, which supports both the nebular surface and parent cloud self-shielding scenarios. An elevated radiation field intensity is predicted by the surface shielding model, and yields substantial CO photolysis (˜50%) on timescales of 0.1-1 My. An elevated radiation field is also consistent with the parent cloud model. The elevated radiation intensities may indicate solar nebula birth in a medium to large

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

PubMed Central

Lightfoot, Emma; O’Connell, Tamsin C.

2016-01-01

Oxygen isotope analysis of archaeological skeletal remains is an increasingly popular tool to study past human migrations. It is based on the assumption that human body chemistry preserves the δ18O of precipitation in such a way as to be a useful technique for identifying migrants and, potentially, their homelands. In this study, the first such global survey, we draw on published human tooth enamel and bone bioapatite data to explore the validity of using oxygen isotope analyses to identify migrants in the archaeological record. We use human δ18O results to show that there are large variations in human oxygen isotope values within a population sample. This may relate to physiological factors influencing the preservation of the primary isotope signal, or due to human activities (such as brewing, boiling, stewing, differential access to water sources and so on) causing variation in ingested water and food isotope values. We compare the number of outliers identified using various statistical methods. We determine that the most appropriate method for identifying migrants is dependent on the data but is likely to be the IQR or median absolute deviation from the median under most archaeological circumstances. Finally, through a spatial assessment of the dataset, we show that the degree of overlap in human isotope values from different locations across Europe is such that identifying individuals’ homelands on the basis of oxygen isotope analysis alone is not possible for the regions analysed to date. Oxygen isotope analysis is a valid method for identifying first-generation migrants from an archaeological site when used appropriately, however it is difficult to identify migrants using statistical methods for a sample size of less than c. 25 individuals. In the absence of local previous analyses, each sample should be treated as an individual dataset and statistical techniques can be used to identify migrants, but in most cases pinpointing a specific homeland should

Oxygen isotope systematics of chondrules in the Murchison CM2 chondrite and implications for the CO-CM relationship

NASA Astrophysics Data System (ADS)

Chaumard, Noël; Defouilloy, Céline; Kita, Noriko T.

2018-05-01

High-precision oxygen three-isotope measurements of olivine and pyroxene were performed on 29 chondrules in the Murchison CM2 chondrite by secondary ion mass spectrometry (SIMS). The oxygen isotope ratios of analyzed chondrules all plot very close to the primitive chondrule minerals (PCM) line. In each of 24 chondrules, the olivine and/or pyroxene grains analyzed show indistinguishable oxygen isotope ratios. Exceptions are minor occurrences of isotopically distinguished relict olivine grains, which were found in nine chondrules. The isotope homogeneity of these phenocrysts is consistent with a co-magmatic crystallization of olivine and pyroxene from the final chondrule melts and a significant oxygen isotope exchange between the ambient gas and the melts. Homogeneous type I chondrules with Mg#'s of 98.9-99.5 have host chondrule Δ17O values ranging from -6.0‰ to -4.1‰, with one exception (Δ17O: -1.2‰; Mg#: 99.6). Homogeneous chondrules with Mg#'s <96, including four type II chondrules (Mg# ∼65-70), have Δ17O values of around -2.5‰. Five type I chondrules (Mg# ≥99) have internally heterogeneous oxygen isotope ratios with Δ17O values ranging from -6.5‰ to -4.0‰, similar to those of host chondrule values. These heterogeneous chondrules have granular or porphyritic textures, convoluted outlines, and contain numerous metal grains dispersed within fine-grained silicates. This is consistent with a low degree of melting of the chondrule precursors, possibly because of a low temperature of the melting event and/or a shorter duration of melting. The Δ17O values of relict olivine grains in nine chondrules range from -17.9‰ to -3.4‰, while most of them overlap the range of the host chondrule values. Similar to those reported from multiple carbonaceous chondrites (Acfer 094, Y-82094, CO, and CV), the Δ17O ∼ -5‰ and high Mg# (≥99) chondrules, which might derive from a reduced reservoir with limited dust enrichments (∼50 × Solar System), dominate

HIGH ARSENIC CONCENTRATIONS AND ENRICHED SULFUR AND OXYGEN ISOTOPES IN A FRACTURED-BEDROCK GROUND-WATER SYSTEM

EPA Science Inventory

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...

The oxygen isotope partition function ratio of water and the structure of liquid water

USGS Publications Warehouse

O'Neil, J.R.; Adami, L.H.

1969-01-01

By means of the CO2-equilibration technique, the temperature dependence and absolute values of the oxygen isotope partition function ratio of liquid water have been determined, often at 1?? intervals, from -2 to 85??. A linear relationship between In (Q2/Q1) (H2O) and T-1 was obtained that is explicable in terms of the Bigeleisen-Mayer theory of isotopic fractionation. The data are incompatible with conventional, multicomponent mixture models of water because liquid water behaves isotopically as a singly structured homogeneous substance over the entire temperature range studied. A two-species model of water is proposed in which approximately 30% of the hydrogen bonds in ice are broken on melting at 0?? and in which this per cent of monomer changes by only a small amount over the entire liquid range. Because of the high precision and the fundamental property determined, the isotopic fractionation technique is particularly well suited to the detection of thermal anomalies. No anomalies were observed and those previously reported are ascribed to under-estimates of experimental error.

Sediment geochemical records of productivity and oxygen depletion along the margin of western North America during the past 60,000 years: teleconnections with Greenland Ice and the Cariaco Basin

USGS Publications Warehouse

Dean, W.E.

2007-01-01

Many sediment records from the margins of the Californias (Alta and Baja) collected in water depths between 60 and 1200 m contain anoxic intervals (laminated sediments) that can be correlated with interstadial intervals as defined by the oxygen-isotope composition of Greenland ice (Dansgaard-Oeschger, D-O, cycles). These intervals include all or parts of Oxygen Isotope Stage 3 (OIS3; 60-24 cal ka), the Bo??lling/Allero??d warm interval (B/A; 15-13 cal ka), and the Holocene. This study uses organic carbon (Corg) and trace-element proxies for anoxia and productivity, namely elevated concentrations and accumulation rates of molybdenum and cadmium, in these laminated sediments to suggest that productivity may be more important than ventilation in producing changes in bottom-water oxygen (BWO) conditions on open, highly productive continental margins. The main conclusion from these proxies is that during the last glacial interval (LGI; 24-15 cal ka) and the Younger Dryas cold interval (YD; 13-11.6 cal ka) productivity was lower and BWO levels were higher than during OIS3, the B/A, and the Holocene on all margins of the Californias. The Corg and trace-element profiles in the LGI-B/A-Holocene transition in the Cariaco Basin on the margin of northern Venezuela are remarkably similar to those in the transition on the northern California margin. Correlation between D-O cycles in Greenland ice with gray-scale measurements in varved sediments in the Cariaco Basin also is well established. Synchronous climate-driven changes as recorded in the sediments on the margins of the Californias, sediments from the Cariaco Basin, and in the GISP-2 Greenland ice core support the hypothesis that changes in atmospheric dynamics played a major role in abrupt climate change during the last 60 ka. Millennial-scale cycles in productivity and oxygen depletion on the margins of the Californias demonstrate that the California Current System was poised at a threshold whereby perturbations of

Oxygen and nitrogen isotope effects duing nitrification and denitrification occuring in Midwesern soils

NASA Astrophysics Data System (ADS)

Michalski, G. M.; Wilkens, B.; Sanchez, A. V.; Yount, J.

2017-12-01

The processes of nitrification and denitrification are key steps in the biogeochemical cycling of N and are a main control on ecosystem productivity. These processes are ephemeral and often difficult to assess across wide spatial and temporal scales. Natural abundance stable isotopes are a way of potentially assessing these two processes across multiple scales. We have conducted incubation experiments to assess the N and O isotope effects occurring during denitrification in soils typical of the Midwestern United States. Nitrification was examined by incubating soils amended with ammonium (with a known δ15N) mixed with H2O and O2 that had different δ18O values and then measured the δ15N and δ18O of the product nitrate. The fraction of nitrate oxygen arising from H2O and O2 was determined along with the N and O kinetic isotope effect (KIE). For denitrification, nitrate with a known δ15N, δ17O, and δ18O, was incubated in anaerobic soils from 12-48 hours. The residual nitrate was analyzed for isotope change and the KIE for O and N as well as exchange with H2O was determined. These data can be useful for interpreting nitrate isotopes in agricultural fields as a way off assessing nitrification and denitrification is agricultural ecosystems such as the IML-CZO.

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

USGS Publications Warehouse

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

1984-01-01

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

Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

USGS Publications Warehouse

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

2009-01-01

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.

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Microanalyzing Metasomatism: Correlative Microanalysis of Trace Elements and Oxygen Isotopes in the Franciscan

NASA Astrophysics Data System (ADS)

Goltz, A. E.; Hoover, W. F.; Page, F. Z.; Moreira, H.; Storey, C.; Kitajima, K.; Valley, J. W.

2017-12-01

Mélange fluids play a vital role in metamorphic processes; however, because of the complexity of the mélange, the fluid signals are hard to isolate. Microanalysis of Heavy Rare Earth Elements (HREE) in garnet has the potential to be a powerful tool in understanding the nature of these fluids. When coupled to oxygen isotope analysis, HREE signals may be attributed to an internal or external fluid source. This study pairs microanalysis of HREE and oxygen isotopes in garnet to reveal the origin of HREE enrichment events in two rocks (02WC1 and 02WC4) from the Ward Creek area of the Franciscan Complex. 02WC1 is an intergrown epidote-blueschist and eclogite, with the assemblage omph + ep + glc + gt + sph ± rt ± ab. Its whole-rock major element composition is similar to altered oceanic crust. Two generations of epidote are evident: the first Mn-rich, the other Mn-poor. Garnets have prograde zoning profiles with high spessartine contents ( 40%) in their cores, are unzoned in oxygen isotopes from core (9.6±0.4‰, 2SD, VSMOW) to rim (9.8±0.4‰), and have HREE peaks in their mantles. 02WC4 is also banded with zones of differing epidote content and overall assemblage ep + gt + hbl + omph + sph ± phg ± chl. The whole rock composition of 02WC4 is unusual; it is broadly basaltic but is also SiO2 poor (41.95%) and Cr and Ni rich (675 and 182 ppm, respectively). Epidote shows two generations with higher (cores) and lower (rims) Mn content. Garnet cores are high in spessartine ( 50%), and some garnet mantles have pronounced Mn and Fe plateaux. Garnets are zoned in oxygen isotopes from core (10.2±0.6‰) to rim (6.9±0.4‰). There is one HREE peak in the mantle, coincident with high values of δ18O and one in the rims corresponding to lower values of δ18O. The HREE peaks that occur in high δ18O areas throughout 02WC1 and 02WC4 are likely internally derived within the sample. Mn annuli in garnets and dissolution textures in epidote cores implicate epidote dehydration as

δ18O water isotope in the iLOVECLIM model (version 1.0) - Part 3: A paleoperspective based on present-day data-model comparison for oxygen stable isotopes in carbonates

NASA Astrophysics Data System (ADS)

Caley, T.; Roche, D. M.

2013-03-01

Oxygen stable isotopes (18O) are among the most usual tools in paleoclimatology/paleoceanography. Simulation of oxygen stable isotopes allows testing how the past variability of these isotopes in water can be interpreted. By modelling the proxy directly in the model, the results can also be directly compared with the data. Water isotopes have been implemented in the global three-dimensional model of intermediate complexity iLOVECLIM allowing fully coupled atmosphere-ocean simulations. In this study, we present the validation of the model results for present day climate against global database for oxygen stable isotopes in carbonates. The limitation of the model together with the processes operating in the natural environment reveal the complexity of use the continental calcite 18O signal of speleothems for a data-model comparison exercise. On the contrary, the reconstructed surface ocean calcite δ18O signal in iLOVECLIM does show a very good agreement with late Holocene database (foraminifers) at the global and regional scales. Our results indicate that temperature and the isotopic composition of the seawater are the main control on the fossil δ18O signal recorded in foraminifer shells and that depth habitat and seasonality play a role but have secondary importance. We argue that a data-model comparison for surface ocean calcite δ18O in past climate, such as the last glacial maximum (≈21 000 yr), could constitute an interesting tool for mapping the potential shifts of the frontal systems and circulation changes throughout time. Similarly, the potential changes in intermediate oceanic circulation systems in the past could be documented by a data (benthic foraminifers)-model comparison exercise whereas future investigations are necessary in order to quantitatively compare the results with data for the deep ocean.

A 600-ka Arctic sea-ice record from Mendeleev Ridge based on ostracodes

USGS Publications Warehouse

Cronin, Thomas M.; Polyak, L.V.; Reed, D.; Kandiano, E. S.; Marzen, R. E.; Council, E. A.

2013-01-01

Arctic paleoceanography and sea-ice history were reconstructed from epipelagic and benthic ostracodes from a sediment core (HLY0503-06JPC, 800 m water depth) located on the Mendeleev Ridge, Western Arctic Ocean. The calcareous microfaunal record (ostracodes and foraminifers) covers several glacial/interglacial cycles back to estimated Marine Isotope Stage 13 (MIS 13, ∼500 ka) with an average sedimentation rate of ∼0.5 cm/ka for most of the stratigraphy (MIS 5–13). Results based on ostracode assemblages and an unusual planktic foraminiferal assemblage in MIS 11 dominated by a temperate-water species Turborotalita egelida show that extreme interglacial warmth, high surface ocean productivity, and possibly open ocean convection characterized MIS 11 and MIS 13 (∼400 and 500 ka, respectively). A major shift in western Arctic Ocean environments toward perennial sea ice occurred after MIS 11 based on the distribution of an ice-dwelling ostracode Acetabulastoma arcticum. Spectral analyses of the ostracode assemblages indicate sea ice and mid-depth ocean circulation in western Arctic Ocean varied primarily at precessional (∼22 ka) and obliquity (∼40 ka) frequencies.

Closed system oxygen isotope redistribution in igneous CAIs upon spinel dissolution

NASA Astrophysics Data System (ADS)

Aléon, Jérôme

2018-01-01

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.

Distribution of oxygen isotopes in the water masses of Drake Passage and the South Atlantic

NASA Astrophysics Data System (ADS)

Meredith, Michael P.; Grose, Katie E.; McDonagh, Elaine L.; Heywood, Karen J.; Frew, Russell D.; Dennis, Paul F.

1999-09-01

Measurements of the ratio of stable isotopes of oxygen (18O and 16O) from samples collected on World Ocean Circulation Experiment sections SR1b (eastern Drake Passage) and A11 (Punta Arenas to Cape Town) are used, together with hydrographic data, to deduce information about the formation and variability of South Atlantic and Southern Ocean water masses. The Drake Passage surface waters south of the Polar Front (PF) are isotopically light (δ18O around -0.4‰) owing to the influence of meteoric waters. The salinity and δ18O of the A11 surface waters yield an apparent freshwater end-member which is much isotopically lighter than the local precipitation, thus advection of these waters from farther south dominates over local effects in determining the surface water properties. The Drake Passage section shows unusual proximity of the two main fronts of the Antarctic Circumpolar Current (the PF and Subantarctic Front (SAF)), and we observe cold, fresh, and isotopically light water derived from the temperature-minimum Winter Water at the SAF. This water is of the correct density to freshen the intermediate water north of the SAF and thus play a role in the formation of the comparatively fresh Antarctic Intermediate Water (AAIW) of the South Atlantic. This confirms the role of Antarctic water in forming the South Atlantic variety of AAIW. Across the A11 section the oxygen isotope and salinity data at the AAIW core show very similar traces, with waters in the Malvinas Current loop showing lowest values of both. At the eastern boundary of the South Atlantic, the input of Red Sea Water from east of South Africa is observed via the presence of anomalously isotopically heavy AAIW. We deduce potentially significant temporal variability in the isotopic composition of Weddell Sea Deep Water (WSDW) by comparing the Drake Passage data to earlier data covering the outflow of the Weddell Sea. The A11 data show WSDW consistent with such variability, indicating that its effects could

An 8,000 year oxygen isotope record of hydroclimatic change from Paradise Lake, central British Columbia

NASA Astrophysics Data System (ADS)

Hillman, A. L.; Abbott, M. B.; Steinman, B. A.; Pompeani, D. P.; Cwiklik, J. P.

2013-12-01

Climate in the Pacific Northwest over the Holocene has primarily been controlled by the position of the Aleutian Low (AL), which is interconnected to the Pacific Decadal Oscillation (PDO) and the El Nino Southern Oscillation (ENSO). Stable isotopes of authigenic calcite precipitated from lake water and archived as lake sediment can be used to reconstruct changes in precipitation/evaporation (P/E) balance over timescales ranging from individual years to millennia. Several records of this type from southern British Columbia and northern Washington (e.g., Castor and Cleland Lakes), as well as from the southern Yukon Territory (e.g., Marcella and Rantin Lakes) have been produced, but few records from between these two regions exist. Here, we present a record of δ18O and δ13C measurements of authigenic calcite from Paradise Lake, British Columbia (54.68259°N, 122.61154°W), a surficially closed basin, groundwater throughflow lake located in the central interior of British Columbia. A total of 14 AMS radiocarbon dates were used to provide age control for the Paradise Lake record. In sediment from 8,000-4,500 years BP, oxygen isotope values vary around a mean value of -18.0‰. From 4,500-2,000 years BP, a general trend towards more positive oxygen isotope values occurs, with increased variability in both δ18O and δ13C. A gradual shift of ~2‰ in δ18O measurements (to a mean value of -16.0‰) occurs over the last 2,000 years of the record, likely due to lower lake levels. The large magnitude mean state shifts in oxygen isotopes over the last 8,000 years are similar to that observed in the Marcella Lake record (Anderson et al., 2007), although they are of a smaller magnitude. We hypothesize that significant groundwater throughflow at Paradise Lake likely causes a muted hydrologic and isotopic response to climate forcing relative to Marcella Lake, which has more isotopically enriched water and loses a greater proportion of water via evaporation. The Paradise lake �

Mid-Brunhes magnetic excursions in marine isotope stages 9, 13, 14, and 15 (286, 495, 540, and 590 ka) at North Atlantic IODP Sites U1302/3, U1305, and U1306

NASA Astrophysics Data System (ADS)

Channell, J. E. T.

2017-02-01

Integrated Ocean Drilling Program (IODP) Site U1302/3 (Orphan Knoll, off Newfoundland) recorded magnetic excursions in marine isotope stages (MIS) 9a (at 286 ka) and 13a (at 495 ka). Sites U1306 and U1305 (Eirik Drift, off SE Greenland) record excursions in MIS 14a/b (at 540 ka) and 15b/c (at 590 ka). In the excursion intervals, magnetic measurements of continuous "u-channel" samples from multiple holes within site are augmented by measurements of cubic (8 cm3) discrete samples. The excursions lie in relative paleointensity (RPI) minima at each site and in RPI reference stacks, and correspond to dated intervals of 10Be overproduction in other deep-sea sediment records. Although observed at multiple holes at each site, and from u-channel and discrete samples, the excursions are not observed at all three sites, and often at only one of the three sites. Sporadic recording of these magnetic excursions, and excursions in general, is attributed to a combination of filtering by the process of acquisition of detrital remanent magnetization (DRM), postdepositional overprint of weak excursion magnetizations, the millennial or even centennial duration of directional excursions, and nonuniform sedimentation rates at these timescales in North Atlantic sediment drifts.

Origin of oxygen in sulfate during pyrite oxidation with water and dissolved oxygen: an in situ horizontal attenuated total reflectance infrared spectroscopy isotope study.

PubMed

Usher, Courtney R; Cleveland, Curtis A; Strongin, Daniel R; Schoonen, Martin A

2004-11-01

FeS2 (pyrite) is known to react with water and dissolved molecular oxygen to form sulfate and iron oxyhydroxides. This process plays a large role in the environmentally damaging phenomenon known as acid mine drainage. An outstanding scientific issue has been whether the oxygen in the sulfate and oxyhydroxide product was derived from water and/or dissolved oxygen. By monitoring the reaction in situ with horizontal attenuated total reflectance infrared spectroscopy, it was found that when using 18O isotopically substituted water, the majority of the infrared absorbance due to sulfate product red-shifted approximately 70 cm(-1) relative to the absorbance of sulfate using H(2)16O as a reactant. Bands corresponding to the iron oxyhydroxide product did not shift. These results indicate water as the primary source of oxygen in the sulfate product, while the oxygen atoms in the iron oxyhydroxide product are obtained from dissolved molecular oxygen.

{Carbon and oxygen isotope signals from marine ostracod calcite - results from present and past oceans}

NASA Astrophysics Data System (ADS)

Bornemann, A.; Speijer, R. P.

2009-04-01

Systematic stable isotope studies on ostracod calcite are generally rare, in particular for marine taxa only the work of DIDIÉ & BAUCH (2002) provides first clues towards an improved understanding of ostracod stable isotope data in paleoceanography. Here we present analyses from recent near surface sediments from the Gulf of Taranto, the Levantine Basin (15 ka, both Mediterranean Sea) and the Paleocene of Tunisia (southern Tethyan margin). Data are compared to those from selected benthic foraminiferal taxa from which the living habitat and the isotopic disequilibria from ambient sea-water are well known. In addition, size fractions of monospecific samples have been studied in order to test whether a size/mass dependent change exists with respect to the isotopic composition of the carapace calcite. Calcification of ostracod carapaces is a very rapid process, which often takes place within a few hours and the obtained signal provides only a snap-shot of the prevailing paleoceanographic conditions. Multiple mono-specific measurements show therefore a much higher variability than benthic foraminifera, but may give a more complete picture of the seasonal changes. Our study confirms the findings of DIDIÉ & BAUCH (2002) and others (for non-marine taxa) that ostracod calcite displays a positive species-specific deviation from the sea-water ^18O composition between 0.5 and 1.5 per mil with an intra-specific variability of less than 0.5 per mil. In contrast ^13C values cover a huge range with an off-set from sea-water of up to -5 per mil and show a high intra-specific variability of up to 2 per mil. Size-fraction data show no systematic change, although a statistically significant positive covariance between ^18O and ^13C has been observed. This covariance consists of a slope similar to a kinetic controlled fractionation as has been described from asymbiotic planktic foraminifera (Globigerina bulloides) and corals (MCCONNAUGHEY, 1989; SPERO & LEA, 1996). This suggests that

Composite δ13C and petrographic 195-355 ka record from Frasassi cave (central Italy) stalagmites: investigating drivers of speleothem calcite carbon isotope signals.

NASA Astrophysics Data System (ADS)

Vanghi, V.; Borsato, A.; Frisia, S.; Drysdale, R.; Hellstrom, J. C.; Bajo, P.; Montanari, A.

2016-12-01

Carbon isotope ratio of speleothem calcite is known to be a proxy for climate-dependent soil CO2 production. One of the paradigms is that, ideally, C stable isotope incorporation occurred in equilibrium. Yet, the process of degassing in the cave commonly results in δ13C values more positive than theoretically expected for speleothems formed in temperate-humid settings. Fabrics then provide the benchmark to unravel local, regional and global significance of speleothem δ13C. The δ13C time-series from two precisely U-Th dated Frasassi stalagmites covering the interval from 195 ka to 355 ka (Marine Isotope Stages 7 - 10) were interpreted on the basis of the sequence of fabrics. Columnar fabrics indicated deposition under constant kinetic fractionation, whereby δ13C shifts through time reflected a combination of atmospheric CO2 concentration changes and soil efficiency variability, controlled by regional mean annual temperature. Given that the δ13C values are constantly more-positive-than-expected because of the effect of degassing, shifts to more positive δ13C values above a baseline of -7 permil during glacials are here interpreted as driven by low soil efficiency and higher contribution of atmospheric CO2 (Breecker et al. 2012, Borsato et al. 2015). The comparison of high resolution δ13C curves with atmospheric pCO2 and benthic δ18O records further suggests that hemispheric temperature changes driven by insolation modulated the δ13C shifts above or below the baseline. Thus, a -3‰ shift from glacial to interglacial at terminations IV and III is here ascribed to changes in atmospheric pCO2 (Schubert and Jahren 2012). More open fabrics mark warmer conditions and increased soil productivity and are associated with more negative δ13C. In conclusion, only by coupling petrography and geochemical properties the global and local drivers of δ13C anomalies in stalagmites from this deep cave could be distinguished. Borsato et al. (2015), Earth Surface Processes and

Correlated carbon and oxygen isotope signatures in eclogitic diamonds with coesite inclusions: A SIMS investigation of diamonds from Guaniamo, Argyle and Orapa mines

NASA Astrophysics Data System (ADS)

Schulze, D. J.; Page, Z.; Harte, B.; Valley, J.; Channer, D.; Jaques, L.

2006-12-01

Using ion microprobes and secondary-ion mass spectrometry we have analyzed the carbon and oxygen isotopic composition of eclogite-suite diamonds and their coesite inclusions, respectively, from three suites of diamonds of Proterozoic age. Extremely high (for the mantle) oxygen isotope values (delta 18O of +10.2 to +16.9 per mil VSMOW) are preserved in coesites included in eclogitic diamonds from Guaniamo, Venezuela (Schulze et al., Nature, 2003), providing compelling evidence for an origin of their eclogite hosts by subduction of sea water altered ocean floor basalts. In situ SIMS analyses of their host diamonds yield carbon isotope values (delta 13C) of -12 to -18 per mil PDB. SIMS analyses of coesite inclusions from Argyle, Australia diamonds previously analyzed by combustion methods for d13C composition (Jaques et al., Proc. 4th Kimb. Conf, 1989), also yield anomalously high d18O values (+6.8 to +16.0 per mil VSMOW), that correlate with the anomalously low carbon isotope values (-10.3 to -14.1 per mil PDB). One coesite-bearing diamond from Orapa, Botswana analyzed in situ by SIMS has a d18O value of the coesite of +8.5 per mil VSMOW and a d13C value of the adjacent diamond host of -9.0 per mil PDB. A second Orapa stone has a SIMS carbon isotope compositional range of d13C = -14 to -16 per mil PDB, but the coesite is too small for ion probe analysis. At each of these localities, carbon isotope values of coesite-bearing diamonds that are lower than typical of mantle carbon are correlated with oxygen isotope compositions of included coesites that are substantially above the common mantle oxygen isotope range. Such results are not in accord with diamond genesis models involving formation of eclogitic diamonds from igneous melts undergoing fractionation in the mantle or by crystallization from primordial inhomogeneities in Earth's mantle. By analogy with the oxygen isotope compositions of altered ocean floor basalts and Alpine (subduction zone) eclogites they are

Late Proterozoic rise in atmospheric oxygen concentration inferred from phylogenetic and sulphur-isotope studies

NASA Technical Reports Server (NTRS)

Canfield, D. E.; Teske, A.

1996-01-01

The evolution of non-photosynthetic sulphide-oxidizing bacteria was contemporaneous with a large shift in the isotopic composition of biogenic sedimentary sulphides between 0.64 and 1.05 billion years ago. Both events were probably driven by a rise in atmospheric oxygen concentrations to greater than 5-18% of present levels--a change that may also have triggered the evolution of animals.

Oxygen isotopic evidence for accretion of Earth’s water before a high-energy Moon-forming giant impact

PubMed Central

Barrat, Jean-Alix; Sillard, Patrick; Starkey, Natalie A.

2018-01-01

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

Oxygen-isotope, X-ray-diffraction and scanning-electron-microscope examinations of authigenic-layer-silicate minerals from Mississippian and Pennsylvanian sandstones in the Michigan Basin

USGS Publications Warehouse

Zacharias, K.F.; Sibley, D.F.; Westjohn, D.B.; Weaver, T. L.

1993-01-01

Oxygen-isotope compositions of authigenic-layer silicates (<2-micrometer fraction) extracted from Mississippian and Pennsylvanian sandstones in the Lower Peninsula of Michigan were determined. Petrographic and 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.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Automated system measuring triple oxygen and nitrogen isotope ratios in nitrate using the bacterial method and N2 O decomposition by microwave discharge.

PubMed

Hattori, Shohei; Savarino, Joel; Kamezaki, Kazuki; Ishino, Sakiko; Dyckmans, Jens; Fujinawa, Tamaki; Caillon, Nicolas; Barbero, Albane; Mukotaka, Arata; Toyoda, Sakae; Well, Reinhard; Yoshida, Naohiro

2016-12-30

Triple oxygen and nitrogen isotope ratios in nitrate are powerful tools for assessing atmospheric nitrate formation pathways and their contribution to ecosystems. N 2 O decomposition using microwave-induced plasma (MIP) has been used only for measurements of oxygen isotopes to date, but it is also possible to measure nitrogen isotopes during the same analytical run. The main improvements to a previous system are (i) an automated distribution system of nitrate to the bacterial medium, (ii) N 2 O separation by gas chromatography before N 2 O decomposition using the MIP, (iii) use of a corundum tube for microwave discharge, and (iv) development of an automated system for isotopic measurements. Three nitrate standards with sample sizes of 60, 80, 100, and 120 nmol were measured to investigate the sample size dependence of the isotope measurements. The δ 17 O, δ 18 O, and Δ 17 O values increased with increasing sample size, although the δ 15 N value showed no significant size dependency. Different calibration slopes and intercepts were obtained with different sample amounts. The slopes and intercepts for the regression lines in different sample amounts were dependent on sample size, indicating that the extent of oxygen exchange is also dependent on sample size. The sample-size-dependent slopes and intercepts were fitted using natural log (ln) regression curves, and the slopes and intercepts can be estimated to apply to any sample size corrections. When using 100 nmol samples, the standard deviations of residuals from the regression lines for this system were 0.5‰, 0.3‰, and 0.1‰, respectively, for the δ 18 O, Δ 17 O, and δ 15 N values, results that are not inferior to those from other systems using gold tube or gold wire. An automated system was developed to measure triple oxygen and nitrogen isotopes in nitrate using N 2 O decomposition by MIP. This system enables us to measure both triple oxygen and nitrogen isotopes in nitrate with comparable precision

Chondrule heritage and thermal histories from trace element and oxygen isotope analyses of chondrules and amoeboid olivine aggregates

NASA Astrophysics Data System (ADS)

Jacquet, Emmanuel; Marrocchi, Yves

2017-12-01

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.

Inter-laboratory calibration of new silver orthophosphate comparison materials for the stable oxygen isotope analysis of phosphates.

PubMed

Halas, Stanislaw; Skrzypek, Grzegorz; Meier-Augenstein, Wolfram; Pelc, Andrzej; Kemp, Helen F

2011-03-15

Stable oxygen isotope compositions (δ(18)O values) of two commercial and one synthesized silver orthophosphate reagents have been determined on the VSMOW scale. The analyses were carried out in three different laboratories: lab (1) applying off-line oxygen extraction in the form of CO(2) which was analyzed on a dual inlet and triple collector isotope ratio mass spectrometer, while labs (2) and (3) employed an isotope ratio mass spectrometer coupled to a high-temperature conversion/elemental analyzer (TC/EA) where Ag(3)PO(4) samples were analyzed as CO in continuous flow mode. The δ(18)O values for the proposed new comparison materials were linked to the generally accepted δ(18)O values for Vennemann's TU-1 and TU-2 standards as well as for Ag(3)PO(4) extracted from NBS120c. The weighted average δ(18)O(VSMOW) values for the new comparison materials UMCS-1, UMCS-2 and AGPO-SCRI were determined to be + 32.60 (± 0.12), + 19.40 (± 0.12) and + 14.58 (± 0.13)‰, respectively. Copyright © 2011 John Wiley & Sons, Ltd.

Temperature history of Coregonus artedi in the St. Marys River, Laurentian Great Lakes, inferred from oxygen isotopes in otoliths

USGS Publications Warehouse

Joukhadar, Zeina; Patterson, W.P.; Todd, T.N.; Smith, G.R.

2002-01-01

The population of Coregonus artedi in the St. Marys River, between lakes Superior and Huron, was sampled and otoliths were analyzed for oxygen isotopic composition to determine whether the fish are residents in the St. Marys River and its warm bays or migrants to and from cold Lake Huron. Otoliths were extracted, sectioned, and growth ring-specific samples of calcium carbonate were milled to obtain samples for determination of oxygen isotope ratios (18O values). The 18O values of calcium carbonate (CaCO3) in accretionary structures such as otoliths allow calculation of growth temperatures of the fish, because of differential fractionation of oxygen isotopes at different temperatures. Growth temperatures of 10 St. Marys River lake herring were compared with lake and catch data as well as growth temperatures of lake herring collected from Lake Huron and other ciscoes from the Great Lakes. Results of this analysis indicate that these fish remained in the bays of the St. Marys River for their entire life history. After their second year they grew at average temperatures between 11 C and 13 C, consistent with temperature in the warmer bays of the St. Marys River and 6 C higher than expected for growth of this species in Lake Huron.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars.

PubMed

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

2010-11-23

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.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars

PubMed Central

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

2010-01-01

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 17O (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 O3 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. PMID:21059939

Carbon, nitrogen and oxygen isotope fractionation during food cooking: Implications for the interpretation of the fossil human record.

PubMed

Royer, Aurélien; Daux, Valérie; Fourel, François; Lécuyer, Christophe

2017-08-01

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.

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

NASA Astrophysics Data System (ADS)

Lee, Charles Chi-Woo

2000-11-01

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

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

DOE PAGES

Simon, Justin I.; Matzel, Jennifer E. P.; Simon, Steven B.; ...

2016-05-02

Oxygen isotopic variations across the outer margins and Wark–Lovering (WL) rims of a diverse suite of six coarse-grained Types A and B refractory inclusions from both oxidized and reduced CV3 chondrites suggest that CAIs originated from a 16O-rich protosolar gas reservoir and were later exposed to both relatively 17,18O-rich and 16O-rich reservoirs. The O-isotope profiles of CAIs can be explained by changes in the composition of gas near the protoSun or the migration of CAIs through a heterogeneous nebula. Variability within the inclusion interiors appears to have been set prior to WL rim growth. Modeling the isotopic zoning profiles asmore » diffusion gradients between inclusion interiors and edges establishes a range of permissible time–temperature combinations for their exposure in the nebula. At mean temperatures of 1400 K, models that match the isotope gradients in the inclusions yield timescales ranging from 5 × 10 3 to 3 × 10 5 years. Assuming CAIs originated with a relatively 16O-rich (protosolar) isotopic composition, differences among the melilite interiors and the isotopic gradients in their margins imply the existence of a number of isotopically distinct reservoirs. In addition, evidence at the edges of some CAIs for subsequent isotopic exchange may relate to the beginning of rim formation. In the WL rim layers surrounding the interiors, spinel is relatively 16O-rich but subtly distinct among different CAIs. Melilite is often relatively 16O-poor, but rare relatively 16O-rich grains also exist. Pyroxene generally exhibits intermediate O-isotope compositions and isotopic zoning. Olivine in both WL and accretionary rims, when present, is isotopically heterogeneous. The extreme isotopic heterogeneity among and within individual WL rim layers and in particular, the observed trends of outward 16O-enrichments, suggest that rims surrounding CAIs contained in CV3 chondrites, like the inclusions themselves, formed from a number of isotopically distinct

A Simple Mechanism for Fractionating Oxygen Isotopes in the Solar Nebula

NASA Technical Reports Server (NTRS)

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

2009-01-01

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

Correlation and Stacking of Relative Paleointensity and Oxygen Isotope Data

NASA Astrophysics Data System (ADS)

Lurcock, P. C.; Channell, J. E.; Lee, D.

2012-12-01

The transformation of a depth-series into a time-series is routinely implemented in the geological sciences. This transformation often involves correlation of a depth-series to an astronomically calibrated time-series. Eyeball tie-points with linear interpolation are still regularly used, although these have the disadvantages of being non-repeatable and not based on firm correlation criteria. Two automated correlation methods are compared: the simulated annealing algorithm (Huybers and Wunsch, 2004) and the Match protocol (Lisiecki and Lisiecki, 2002). Simulated annealing seeks to minimize energy (cross-correlation) as "temperature" is slowly decreased. The Match protocol divides records into intervals, applies penalty functions that constrain accumulation rates, and minimizes the sum of the squares of the differences between two series while maintaining the data sequence in each series. Paired relative paleointensity (RPI) and oxygen isotope records, such as those from IODP Site U1308 and/or reference stacks such as LR04 and PISO, are warped using known warping functions, and then the un-warped and warped time-series are correlated to evaluate the efficiency of the correlation methods. Correlations are performed in tandem to simultaneously optimize RPI and oxygen isotope data. Noise spectra are introduced at differing levels to determine correlation efficiency as noise levels change. A third potential method, known as dynamic time warping, involves minimizing the sum of distances between correlated point pairs across the whole series. A "cost matrix" between the two series is analyzed to find a least-cost path through the matrix. This least-cost path is used to nonlinearly map the time/depth of one record onto the depth/time of another. Dynamic time warping can be expanded to more than two dimensions and used to stack multiple time-series. This procedure can improve on arithmetic stacks, which often lose coherent high-frequency content during the stacking process.

Oxygen isotopic composition of chondritic interplanetary dust particles: A genetic link between carbonaceous chondrites and comets

NASA Astrophysics Data System (ADS)

Aléon, J.; Engrand, C.; Leshin, L. A.; McKeegan, K. D.

2009-08-01

Oxygen isotopes were measured in four chondritic hydrated interplanetary dust particles (IDPs) and five chondritic anhydrous IDPs including two GEMS-rich particles (Glass embedded with metal and sulfides) by a combination of high precision and high lateral resolution ion microprobe techniques. All IDPs have isotopic compositions tightly clustered around that of solar system planetary materials. Hydrated IDPs have mass-fractionated oxygen isotopic compositions similar to those of CI and CM carbonaceous chondrites, consistent with hydration of initially anhydrous protosolar dust. Anhydrous IDPs have small 16O excesses and depletions similar to those of carbonaceous chondrites, the largest 16O variations being hosted by the two GEMS-rich IDPs. Coarse-grained forsteritic olivine and enstatite in anhydrous IDPs are isotopically similar to their counterparts in comet Wild 2 and in chondrules suggesting a high temperature inner solar system origin. The small variations in the 16O content of GEMS-rich IDPs suggest that most GEMS either do not preserve a record of interstellar processes or the initial interstellar dust is not 16O-rich as expected by self-shielding models, although a larger dataset is required to verify these conclusions. Together with other chemical and mineralogical indicators, O isotopes show that the parent-bodies of carbonaceous chondrites, of chondritic IDPs, of most Antarctic micrometeorites, and comet Wild 2 belong to a single family of objects of carbonaceous chondrite chemical affinity as distinct from ordinary, enstatite, K- and R-chondrites. Comparison with astronomical observations thus suggests a chemical continuum of objects including main belt and outer solar system asteroids such as C-type, P-type and D-type asteroids, Trojans and Centaurs as well as short-period comets and other Kuiper Belt Objects.

Oxygen Isotope Calibration Study of Modern Diatoms in Freshwater Environments: Implications for Biogenic Silica as a Paleoclimate Proxy

NASA Astrophysics Data System (ADS)

Dodd, J. P.; Sharp, Z. D.; Fawcett, P.

2008-12-01

Oxygen isotope values of biogenic silica from diatom frustules are a commonly used proxy in freshwater and marine environments, and provide a valuable archive of paleoclimatic information such as temperature and water cycle processes. Advances in analytical techniques have made oxygen isotope measurements of diatom silica more robust; however, to date, there are multiple published fractionation factors for biogenic silica, with no general consensus on which is 'correct.' Previous studies (e.g. Moschen et al, 2005) demonstrated that there is no difference in SiO2-H2O fractionation between different size fractions of diatoms and, therefore, no species-dependent effects. The SiO2-H2O fractionation factors observed in laboratory grown diatoms analyzed by Brandriss et al. (1998) and modern lacustrine diatoms (Moschen et al., 2005) are in close agreement (τ = -0.2‰/°C) and are defined by the equations 1000lnα SiO2-H2O = 15.56 (103 T-1) - 20.92 and 1000lnα SiO2-H2O = 20.5 (103 T-1) - 36.2, respectively. However, these studies are not in agreement with other published SiO2-H2O fractionation factors for biogenic silica in marine and freshwater environments. In order to effectively utilize diatom δ18O values as a climate proxy, it is necessary to understand how oxygen isotopes are fractionated during silica frustule formation and identify potential errors in δ18O values obtained through different analytic/purification processes. Here we present oxygen isotope data from modern diatom species collected from a wide variety of natural riverine and lacustrine environments in northern New Mexico, USA. Temperatures at collection sites ranged from 5.5°C to 37.8°C. Preliminary isotope data indicate a SiO2-H2O fractionation factor identical to Brandriss et al. (1998). Additional experiments were undertaken to examine the effect of differing chemical purification techniques (i.e. HNO3, H2O2, and NaOH) on modern diatoms to see if processing techniques might affect the δ18O

The oxygen side of sulfate constrains global biospheric productivity in the mid-Phanerozoic

NASA Astrophysics Data System (ADS)

Wing, B. A.

2009-12-01

Recent work has read in the oxygen side of sulfate a record of CO2 concentrations and extreme environments on Neoproterozoic Earth [1, 2]. The connection between CO2 levels and total isotopic composition of mineral proxies for marine sulfate was motivated by an empirical correlation between CO2 concentrations and in 17O anomalies in samples of atmospheric gases preserved as bubbles in ice cores [3,4]. The 17O anomaly in atmospheric O2 has been interpreted to originate primarily from stratospheric photochemical cycles of O3, O2, and CO2 [3, 4]. Both CO2 and O3 form the 17O-enriched partners for the 17O-depleted O2 and, given a fixed atmospheric lifetime for O2, isotopic mass balance dictates that increasing CO2 levels will drive larger relative 17O deficits in O2. With a photochemically-calibrated relationship between the relative 17O anomaly in atmospheric O2 and atmospheric CO2 levels [1], the amount of CO2 in an ancient atmosphere can be directly estimated from the isotopic record of atmospheric O2 bound up in the oxygen side of sulfate. Although they are correlated, the relative 17O anomaly in atmospheric O2 is not only a function of atmospheric CO2 levels. Photosynthetic O2 is characterized by isotopically ‘normal’ oxygen sourced from the global hydrosphere [3]. Increased photosynthetic O2 production, therefore, dilutes the isotopic anomaly found in atmospheric O2. Measurements of the 17O anomaly in O2 from ice cores allow global changes in global biosphere productivity to be traced back to 60 ka ago [3, 4]. Applying similar analysis to recent datasets of the 17O anomaly in marine sulfates [1] and atmospheric CO2 levels [5] produces quantitative global biospheric productivity estimates for the time interval from 310 to 240 Ma ago. Although the time resolution is coarse, much of the mid-Phanerozoic was characterized by global biospheric productivity similar in magnitude to the average global biospheric productivity for the last 10 ka. Counterintuitively

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Deuterium and oxygen-18 isotope effects on nucleophilic displacement by water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.

1981-01-01

Kinetic deuterium isotope effects (k/sub H/sub 2/O//k/sub D/sub 2/O/) have been measured for nucleophilic attack by water at primary alkyl carbon (S-methylthiophenium ion (MeTh+), methyl trifluoromethane-sulfonate (MeOTf), methyl and ethyl perchlorate (MeOClO/sub 3/, EtOClO/sub 3/)) in aprotic solvents (acetonitrile (MeCN) and tetrahydrothiophene-1, 1-dioxide (TMSO/sub 2/; solfolane)) and L/sub 2/O. In L/sub 2/O solvent k/sub H/sub 2/O//k/sub D/sub 2/O/ is significantly greater than unity while it is reduced to near unity in aprotic solvents. The oxygen-18 isotope effect has also been observed to be 1.002 +- 0.004 for the reaction of MeTh/sup +/ with dilute H/sub 2/O in TMSO/sub 2/ atmore » 35/sup 0/C. For the reaction of MeTh/sup +/ and MeOClO/sub 3/ in aprotic solvents the chemical reaction kinetics are discussed.« less

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

The stable oxygen isotopic ratio of carbon dioxide can potentially track fundamental indicators of environmental change such as the balance between photosynthesis and respiration on regional to global scales. The Stable Isotope Laboratory (SIL) at the Institute of Arctic and Alpine Research (INSTAAR), University of Colorado at Boulder, has measured the stable isotopes of atmospheric carbon dioxide from more than 60 NOAA/Earth System Research Laboratory (ESRL) air flask-sampling sites since the early 1990s. If air is sampled without drying, oxygen can exchange between carbon dioxide and water in the flasks, entirely masking the desired signal. An attempt to investigate how water vapor is affecting the δ18O signal is accomplished by comparing the SIL measurements with specific humidity, calculated from the National Climatic Data Center (NCDC) global integrated surface hourly temperature and dew point database, at the time of sampling. Analysis of sites where samples have been collected initially without drying, and subsequently with a drying kit, in conjunction with the humidity data, has led to several conclusions. Samples that initially appear isotopically unaltered, in that their δ18O values are within the expected range, are being subtly influenced by the water vapor in the air. At Bermuda and other tropical to semi-tropical sites, the 'wet' sampling values have a seasonal cycle that is strongly anti-correlated to the specific humidity, while the 'dry' values have a seasonal cycle that is shifted earlier than the specific humidity cycle by 1-2 months. The latter phasing is expected given the seasonal phasing between climate over the ocean and land, while the former is consistent with a small, but measurable isotope exchange in the flasks. In addition, we note that there is a strong (r > 0.96) correlation between the average specific humidity and the percent of rejected samples for 'wet' sampling. This presents an opportunity for determining a threshold of

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Workshop on Oxygen in the Terrestrial Planets

NASA Technical Reports Server (NTRS)

2004-01-01

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in

Robust 24 ± 6 ka 40Ar/39Ar age of a low-potassium tholeiitic basalt in the Lassen region of NE California

USGS Publications Warehouse

Turrin, Brent D.; Muffler, L. J. Patrick; Clynne, Michael A.; Champion, Duane E.

2007-01-01

40Ar/39Ar ages on the Hat Creek Basalt (HCB) and stratigraphically related lava flows show that latest Pleistocene tholeiitic basalt with very low K2O can be dated reliably. The HCB underlies ∼ 15 ka glacial gravel and overlies four andesite and basaltic andesite lava flows that yield 40Ar/39Ar ages of 38 ± 7 ka (Cinder Butte; 1.65% K2O), 46 ± 7 ka (Sugarloaf Peak; 1.85% K2O), 67 ± 4 ka (Little Potato Butte; 1.42% K2O) and 77 ± 11 ka (Potato Butte; 1.62% K2O). Given these firm age brackets, we then dated the HCB directly. One sample (0.19% K2O) clearly failed the criteria for plateau-age interpretation, but the inverse isochron age of 26 ± 6 ka is seductively appealing. A second sample (0.17% K2O) yielded concordant plateau, integrated (total fusion), and inverse isochron ages of 26 ± 18, 30 ± 20 and 24 ± 6 ka, all within the time bracket determined by stratigraphic relations; the inverse isochron age of 24 ± 6 ka is preferred. As with all isotopically determined ages, confidence in the results is significantly enhanced when additional constraints imposed by other isotopic ages within a stratigraphic context are taken into account.

Lumped parameter, isotopic model simulations of closed-basin lake response to drought in the Pacific Northwest and implications for lake sediment oxygen isotope records.

NASA Astrophysics Data System (ADS)

Steinman, B. A.; Rosenmeier, M.; Abbott, M.

2008-12-01

The economy of the Pacific Northwest relies heavily on water resources from the drought-prone Columbia River and its tributaries, as well as the many lakes and reservoirs of the region. Proper management of these water resources requires a thorough understanding of local drought histories that extends well beyond the instrumental record of the twentieth century, a time frame too short to capture the full range of drought variability in the Pacific Northwest. Here we present a lumped parameter, mass-balance model that provides insight into the influence of hydroclimatological changes on two small, closed-basin systems located in north- central Washington. Steady state model simulations of lake water oxygen isotope ratios using modern climate and catchment parameter datasets demonstrate a strong sensitivity to both the amount and timing of precipitation, and to changes in summertime relative humidity, particularly at annual and decadal time scales. Model tests also suggest that basin hypsography can have a significant impact on lake water oxygen isotope variations, largely through surface area to volume and consequent evaporative flux to volume ratio changes in response to drought and pluvial sequences. Additional simulations using input parameters derived from both on-site and National Climatic Data Center historical climate datasets accurately approximate three years of continuous lake observations (seasonal water sampling and continuous lake level monitoring) and twentieth century oxygen isotope ratios in sediment core authigenic carbonate recovered from the lakes. Results from these model simulations suggest that small, closed-basin lakes in north-central Washington are highly sensitive to changes in the drought-related climate variables, and that long (8000 year), high resolution records of quantitative changes in precipitation and evaporation are obtainable from sediment cores recovered from water bodies of the Pacific Northwest.

Iron and oxygen isotope fractionation during iron UV photo-oxidation: Implications for early Earth and Mars

NASA Astrophysics Data System (ADS)

Nie, Nicole X.; Dauphas, Nicolas; Greenwood, Richard C.

2017-01-01

Banded iron formations (BIFs) contain appreciable amounts of ferric iron (Fe3+). The mechanism by which ferrous iron (Fe2+) was oxidized into Fe3+ in an atmosphere that was globally anoxic is highly debated. Of the three scenarios that have been proposed to explain BIF formation, photo-oxidation by UV photons is the only one that does not involve life (the other two are oxidation by O2 produced by photosynthesis, and anoxygenic photosynthesis whereby Fe2+ is directly used as electron donor in place of water). We experimentally investigated iron and oxygen isotope fractionation imparted by iron photo-oxidation at a pH of 7.3. The iron isotope fractionation between precipitated Fe3+-bearing lepidocrocite and dissolved Fe2+ follows a Rayleigh distillation with an instantaneous 56Fe/54Fe fractionation factor of + 1.2 ‰. Such enrichment in the heavy isotopes of iron is consistent with the values measured in BIFs. We also investigated the nature of the mass-fractionation law that governs iron isotope fractionation in the photo-oxidation experiments (i.e., the slope of the δ56Fe-δ57Fe relationship). The experimental run products follow a mass-dependent law corresponding to the high-T equilibrium limit. The fact that a ∼3.8 Gyr old BIF sample (IF-G) from Isua (Greenland) falls on the same fractionation line confirms that iron photo-oxidation in the surface layers of the oceans was a viable pathway to BIF formation in the Archean, when the atmosphere was largely transparent to UV photons. Our experiments allow us to estimate the quantum yield of the photo-oxidation process (∼0.07 iron atom oxidized per photon absorbed). This yield is used to model iron oxidation on early Mars. As the photo-oxidation proceeds, the aqueous medium becomes more acidic, which slows down the reaction by changing the speciation of iron to species that are less efficient at absorbing UV-photons. Iron photo-oxidation in centimeter to meter-deep water ponds would take months to years to

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Palaeotemperature estimation in the Holsteinian Interglacial (MIS 11) based on oxygen isotopes of aquatic gastropods from eastern Poland

NASA Astrophysics Data System (ADS)

Szymanek, Marcin

2017-12-01

For quantitative estimation of past water temperature of four Holsteinian (MIS 11) palaeolakes from eastern Poland, the oxygen isotope palaeothermometer was applied to shells of the aquatic gastropods Viviparus diluvianus and Valvata piscinalis. The δ18O composition of their shells demonstrated the average growth-season water temperatures during the mesocratic stage of the interglacial (Ortel Królewski Lake), during its climatic optimum - the Carpinus-Abies Zone (Ossówka-Hrud, Roskosz and Szymanowo Lakes), and in the post-optimum (Szymanowo Lake). The calculation was based on δ18OShell values and the δ18OWater assumed for the Holsteinian from the modern oxygen isotope composition of precipitation and the expected amount of evaporative enrichment. The mean oxygen isotope palaeotemperatures of Ortel Królewski lake waters were in the range of 18.1-21.9°C and were uniform for the Taxus and Pinus-Larix zones. Ossówka-Hrud and Roskosz Lakes had mean temperatures of 17.4-21.0°C during the climatic optimum, whereas the temperature of Szymanowo lake waters was estimated at 20.6-21.7°C at that time. These values are concordant with the pollen-inferred July air temperatures noted during the Holsteinian in eastern Poland. Relatively high values of 25°C in the post-optimum noted at Szymanowo were connected with the presence of a shallow and warm isolated bay indicated by pollen and mollusc records.

Ka Band Objects: Observation and Monitoring (KaBOOM)

NASA Astrophysics Data System (ADS)

Geldzahler, B.

2012-09-01

NASA has embarked on a path that will enable the implementation of a high power, high resolution X/Ka band radar system using widely spaced 12m antennas to better track and characterize near Earth objects and orbital debris. This radar system also has applications for cost effective space situational awareness. We shall demonstrate Ka band coherent uplink arraying with real-time atmospheric compensation using three 12m antennas at the Kennedy Space Center (KSC). Our proposed radar system can complement and supplement the activities of the Space Fence. The proposed radar array has the advantages of filling the gap between dusk and dawn and offers the possibility of high range resolution (4 cm) and high spatial resolution (?10 cm at GEO) when used in a VLBI mode. KSC was chosen because [a] of reduced implementation costs, [b] there is a lot of water vapor in the air (not Ka band friendly), and [c] the test satellites have a low elevation adding more attenuation and turbulence to the demonstration. If Ka band coherent uplink arraying can be made to work at KSC, it will work anywhere. We expect to rebaseline X-band in 2013, and demonstrate Ka band uplink arraying in 2014.

Oxygen isotope fractionations across individual leaf carbohydrates in grass and tree species.

PubMed

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

2017-08-01

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.

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

PubMed Central

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

PubMed

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

2017-01-25

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

Cross-continental triple oxygen isotope analysis of tropospheric CO2

NASA Astrophysics Data System (ADS)

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

2016-12-01

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, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by 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 an alternative constraint on the strengths of the associated cycles involving CO2. Here, we report more than one year of data obtained from Taiwan (Taipei), South China Sea, and USA (Pasadena, CA and Palos Verdes, CA). On average, the D17O values from these locations are similar and show no significant influence from the 2014-2016 El Nino event, in contrast to what has been reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Implications for utilizing the new tracer D17O for carbon cycling studies will be made.

Reduced ENSO Variability at the LGM Revealed by an Isotope-Enabled Earth System Model

NASA Technical Reports Server (NTRS)

Zhu, Jiang; Liu, Zhengyu; Brady, Esther; Otto-Bliesner, Bette; Zhang, Jiaxu; Noone, David; Tomas, Robert; Nusbaumer, Jesse; Wong, Tony; Jahn, Alexandra;

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

NASA Astrophysics Data System (ADS)

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

1991-04-01

Oxygen isotope records and glaciomarine sediments indicate at least an intermittent presence of large continental ice sheets on Antarctica since the earliest Oligocene (circa 35 Ma). The growth and decay of ice sheets during the Oligocene to modern "ice house world" caused glacioeustatic sea level changes. The early Eocene was an ice-free "greenhouse world," but it is not clear if ice sheets existed during the middle to late Eocene "doubt house world." Benthic foraminiferal δ18O records place limits on the history of glaciation, suggesting the presence of ice sheets at least intermittently since the earliest Oligocene. The best indicator of ice growth is a coeval increase in global benthic and western equatorial planktonic δ18O records. Although planktonic isotope records from the western equatorial regions are limited, subtropical planktonic foraminifera may also record such ice volume changes. It is difficult to apply these established principles to the Cenozoic δ18O record because of the lack of adequate data and problems in stratigraphic correlations that obscure isotope events. We improved Oligocene to Miocene correlations of δ18O records and erected eight oxygen isotope zones (Oi1-Oi2, Mi1-Mi6). Benthic foraminiferal δ18O increases which are associated with the bases of Zones Oil (circa 35.8 Ma), Oi2 (circa 32.5 Ma), and Mil (circa 23.5 Ma) can be linked with δ18O increases in subtropical planktonic foraminifera and with intervals of glacial sedimentation on or near Antarctica. Our new correlations of middle Miocene benthic and western equatorial planktonic δ18O records show remarkable agreement in timing and amplitude. We interpret benthic-planktonic covariance to reflect substantial ice volume increases near the bases of Zones Mi2 (circa 16.1 Ma), Mi3 (circa 13.6 Ma), and possibly Mi5 (circa 11.3 Ma). Possible glacioeustatic lowerings are associated with the δ18O increases which culminated with the bases of Zone Mi4 (circa 12.6 Ma) and Mi6 (circa 9

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

NASA Technical Reports Server (NTRS)

Schmidt, Gavin A.

1999-01-01

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

Trial application of oxygen and carbon isotope analysis in tooth enamel for identification of past-war victims for discriminating between Japanese and US soldiers.

PubMed

Someda, Hidetoshi; Gakuhari, Takashi; Akai, Junko; Araki, Yoshiyuki; Kodera, Tsutomu; Tsumatori, Gentaro; Kobayashi, Yasushi; Matsunaga, Satoru; Abe, Shinichi; Hashimoto, Masatsugu; Saito, Megumi; Yoneda, Minoru; Ishida, Hajime

2016-04-01

Stable isotope analysis has undergone rapid development in recent years and yielded significant results in the field of forensic sciences. In particular, carbon and oxygen isotopic ratios in tooth enamel obtained from human remains can provide useful information for the crosschecking of morphological and DNA analyses and facilitate rapid on-site prescreening for the identification of remains. This study analyzes carbon and oxygen isotopic ratios in the tooth enamel of Japanese people born between 1878 and 1930, in order to obtain data for methodological differentiation of Japanese and American remains from the Second World War. The carbon and oxygen isotopic ratios in the tooth enamel of the examined Japanese individuals are compared to previously reported data for American individuals (born post WWII), and statistical analysis is conducted using a discrimination method based on a logistic regression analysis. The discrimination between the Japanese and US populations, including Alaska and Hawaii, is found to be highly accurate. Thus, the present method has potential as a discrimination technique for both populations for use in the examination of mixed remains comprising Japanese and American fallen soldiers. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Oxygen isotope ranking of late Eocene and Oligocene planktonic foraminifers: Implications for Oligocene sea-surface temperatures and global ice-volume

USGS Publications Warehouse

Poore, R.Z.; Matthews, R.K.

1984-01-01

Oxygen isotope analyses of late Eocene and Oligocene planktonic foraminifers from low and middle latitude sites in the Atlantic Basin show that different species from the same samples can yield significantly different isotopic values. The range of isotopic values observed between species is greatest at low-latitudes and declines poleward. Many planktonic foraminifers exhibit a systematic isotopic ranking with respect to each other and can therefore be grouped on the basis of their isotopic ranking. The isotopic ranking of some taxa, however, appears to vary geographically and/or through time. Isotopic and paleontologic data from DSDP Site 522 indicate that commonly used isotopic temperature scales underestimate Oligocene sea surface temperatures. We suggest these temperature scales require revision to reflect the presence of Oligocene glaciation. Comparison of isotopic and paleontologic data from Sites 522, 511 and 277 suggests cold, low-salinity surface waters were present in high southern latitudes during the early Oligocene. Lowsalinity, high latitude surface waters could be caused by Eocene/Oligocene paleogeography or by the production of warm saline bottom water. ?? 1984.

Abundances in red giant stars - Carbon and oxygen isotopes in carbon-rich molecular envelopes

NASA Technical Reports Server (NTRS)

Wannier, P. G.; Sahai, R.

1987-01-01

Millimeter-wave observations have been made of isotopically substituted CO toward the envelopes of 11 carbon-rich stars. In every case, C-13O was detected and model calculations were used to estimate the C-12/C-13 abundance ratio. C-17O was detected toward three, and possibly four, envelopes, with sensitive upper limits for two others. The CO-18 variant was detected in two envelopes. New results include determinations of oxygen isotopic ratios in the two carbon-rich protoplanetary nebulae CRL 26688 and CRL 618. As with other classes of red giant stars, the carbon-rich giants seem to be significantly, though variably, enriched in O-17. These results, in combination with observations in interstellar molecular clouds, indicate that current knowledge of stellar production of the CNO nuclides is far from satisfactory.

Carbon and oxygen isotopic composition of coal and carbon dioxide derived from laboratory coal combustion: A preliminary study

USGS Publications Warehouse

Warwick, Peter D.; Ruppert, Leslie F.

2016-01-01

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 http://www.esrl.noaa.gov/gmd/outreach/isotopes/c13tellsus.html). 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

High-resolution analysis of Quaternary calcretes: a coupled stable isotope and micromorphological approach

NASA Astrophysics Data System (ADS)

Adamson, Kathryn; Candy, Ian; Whitfield, Liz

2015-04-01

Pedogenic calcretes are abundant in arid and semi-arid regions, and they are widely used as proxy records of palaeoclimatic change. Calcrete oxygen (δ18O) and carbon (δ13C) isotopic signatures are indicative of temperature, aridity, or vegetation at the time of calcrete formation. Their microfabrics also reflect carbonate formation mechanisms in response to the prevailing environmental conditions. Many studies have explored calcrete micromorphology or stable isotope composition, but these techniques have not yet been applied simultaneously. This co-analysis is important as it allows us to establish whether calcrete morphology directly reflects environmental change. This study tests the potential of combining these analyses to examine the relationships between calcrete microfabrics, their isotopic signals, and Quaternary climate change. Calcretes from four river terraces of the Rio Alias in southeast Spain have been analysed in detail. On the basis of morphostratigraphic correlation (Maher et al., 2007) and Uranium-series ages (Candy et al., 2005), these span the period from 304 ± 26 ka (MIS 9) to the Holocene. The oldest profiles have therefore been exposed to multiple glacial-interglacial cycles. A total of 37 micromorphological profiles have been used to extract stable oxygen and carbon isotopic indicators from 77 microfacies. The morphological and isotopic complexity of the calcrete profiles increases with progressive age. The oldest samples display multiple calcretisation phases, and their microfabrics have a larger isotopic range than the younger samples. Alpha (non-biogenic) fabrics have higher δ13C and δ18O values than beta (biogenic) fabrics. Strong positive covariance between δ13C and δ18O within all profiles suggests that both isotopes are responding to the same environmental parameter. We suggest that this is relative aridity. The study demonstrates that the detailed co-analysis of calcrete micromorphology and stable isotope signatures allows

The source of phosphate in the oxidation zone of ore deposits: Evidence from oxygen isotope compositions of pyromorphite

NASA Astrophysics Data System (ADS)

Burmann, Fabian; Keim, Maximilian F.; Oelmann, Yvonne; Teiber, Holger; Marks, Michael A. W.; Markl, Gregor

2013-12-01

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

Oxygen isotope heterogeneity and disequilibria of olivine crystals in large volume Holocene basalts from Iceland: Evidence for magmatic digestion and erosion of Pleistocene hyaloclastites

NASA Astrophysics Data System (ADS)

Bindeman, Ilya; Gurenko, Andrey; Sigmarsson, Olgeir; Chaussidon, Marc

2008-09-01

This work considers petrogenesis of the largest Holocene basaltic fissure eruptions of Iceland, which are also the largest in the world: Laki (1783-84 AD, 15 km 3), Eldgjá (934 AD, 18 km 3), Veidivötn (900, 1480 AD, multiple eruptions, >2 km 3), Núpahraun (ca. 4000 BP, >1 km 3) and Thjórsárhraun (ca 8000 BP, >20 km 3). We present oxygen isotope laser fluorination analyses of 55 individual and bulk olivine crystals, coexisting individual and bulk plagioclase phenocrysts, and their host basaltic glasses with average precision of better than 0.1‰ (1SD). We also report O isotope analyses of cores and rims of 61 olivine crystals by SIMS with average precision on single spots of 0.24‰ (1SD) in 13 samples coupled with electron microprobe data for major and trace elements in these olivines. Within each individual sample, we have found that basaltic glass is relatively homogeneous with respect to oxygen isotopes, plagioclase phenocrysts exhibit crystal to crystal variability, while individual olivines span from the values in equilibrium with the low-δ 18O matrix glass to those being three permil higher in δ 18O than the equilibrium. Olivine cores with maximum value of 5.2‰ are found in many of these basalts and suggest that the initial magma was equilibrated with normal-δ 18O mantle. No olivines or their intracrystalline domains are found with bulk or spot value higher than those found in MORB olivines. The δ 18O variability of 0.3-3‰ exists for olivine grains from different lavas, and variable core-to-rim oxygen isotopic zoning is present in selected olivine grains. Many olivines in the same sample are not zoned, while a few grains are zoned with respect to oxygen isotopes and exhibit small core-to-core variations in Fe-Mg, Ni, Mn, Ca. Grains that are zoned in both Mg# and δ 18O exhibit positive correlation of these two parameters. Electron microprobe analysis shows that most olivines equilibrated with the transporting melt, and thin Fe-richer rim is

Long-Term (4 mo) Oxygen Isotope Exchange Experiment between Zircon and Hydrothermal Fluid

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Schmitt, A. K.; Lundstrom, C.; Golledge, S.

2013-12-01

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1981-01-01

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

Patterns of mortality among South Florida Manatees: Evidence from oxygen, sulfur and deuterium stable isotopes

NASA Astrophysics Data System (ADS)

MacAvoy, S. E.; Bacalan, V.; Kazantseva, M.; Rhodes, J.; Kim, K.

2012-12-01

The Florida manatee (Trichechus manatus latirostris) is an endangered marine mammal whose coastal habitat has been heavily altered by human development. Sources of mortality include anthropogenic and environmental causes. Necropsies were completed on 75 deceased individuals, and tissues, including bone samples, were collected for later analysis. This study investigates the utility of manatee bone stable oxygen (δ18O), sulfur (δ34S) and deuterium (δD) for determining where the animals lived (which may not be where they where their bodies were recovered), and the relative importance of marine versus freshwater for the individual animals. The isotopes can provide a "geochemical map" showing the distribution of mortality, aiding in the evaluation of geographical patterns in mortality. The δ18O signatures of the bones ranged from 14 to 18.5‰, with no significant difference between male and female mean values. δ18O significantly decreased with increasing latitude (p=.0016), a trend positively correlated with coastal Florida seawater δ18O literature values obtained from the NASA Global Seawater Oxygen-18 Database (http://data.giss.nasa.gov/o18data/) and the EAIA stable isotope database (http://www.univie.ac.at/cartography/project/wiser/). Bone δ34S indicated the influence of marine versus coastal freshwater dietary sources on the animals. Most individuals showed 34S-depleted signatures, which indicated a non-marine sulfur source; however some individuals clearly had taken up marine sulfate (mean 4.9 ± 3.7‰, range 0.8 to 13.8‰). Deuterium values were not available at the time this abstract was written, however we hypothesize that those values will co-vary with δ18O. We conclude that manatee diets are based on both marine and freshwater sources, but freshwater sources exert more influence. Marine water and manatee δ18O co-vary with latitude, suggesting that stable oxygen isotopes may be useful indicators of the latitude where manatees lived.

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

NASA Astrophysics Data System (ADS)

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

2004-12-01

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

Precise oxygen and hydrogen isotope determination in nanoliter quantities of speleothem inclusion water by cavity ring-down spectroscopic techniques

NASA Astrophysics Data System (ADS)

Uemura, Ryu; Nakamoto, Masashi; Asami, Ryuji; Mishima, Satoru; Gibo, Masakazu; Masaka, Kosuke; Jin-Ping, Chen; Wu, Chung-Che; Chang, Yu-Wei; Shen, Chuan-Chou

2016-01-01

Speleothem inclusion-water isotope compositions are a promising new climatic proxy, but their applicability is limited by their low content in water and by analytical challenges. We have developed a precise and accurate isotopic technique that is based on cavity ring-down spectroscopy (CRDS). This method features a newly developed crushing apparatus, a refined sample extraction line, careful evaluation of the water/carbonate adsorption effect. After crushing chipped speleothem in a newly-developed crushing device, released inclusion water is purified and mixed with a limited amount of nitrogen gas in the extraction line for CRDS measurement. We have measured 50-260 nL of inclusion water from 77 to 286 mg of stalagmite deposits sampled from Gyokusen Cave, Okinawa Island, Japan. The small sample size requirement demonstrates that our analytical technique can offer high-resolution inclusion water-based paleoclimate reconstructions. The 1σ reproducibility for different stalagmites ranges from ±0.05 to 0.61‰ for δ18O and ±0.0 to 2.9‰ for δD. The δD vs. δ18O plot for inclusion water from modern stalagmites is consistent with the local meteoric water line. The 1000 ln α values based on calcite and fluid inclusion measurements from decades-old stalagmites are in agreement with the data from present-day farmed calcite experiment. Combination of coeval carbonate and fluid inclusion data suggests that past temperatures at 9-10 thousand years ago (ka) and 26 ka were 3.4 ± 0.7 °C and 8.2 ± 2.4 °C colder than at present, respectively.

Silicon in Mars' Core: A Prediction Based on Mars Model Using Nitrogen and Oxygen Isotopes in SNC Meteorites

NASA Technical Reports Server (NTRS)

Mohapatra, R. K.; Murty, S. V. S.

2002-01-01

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.

Can oxygen stable isotopes be used to track precipitation moisture source in vascular plant-dominated peatlands?

NASA Astrophysics Data System (ADS)

Amesbury, Matthew J.; Charman, Dan J.; Newnham, Rewi M.; Loader, Neil J.; Goodrich, Jordan; Royles, Jessica; Campbell, David I.; Keller, Elizabeth D.; Baisden, W. Troy; Roland, Thomas P.; Gallego-Sala, Angela V.

2015-11-01

Variations in the isotopic composition of precipitation are determined by fractionation processes which occur during temperature- and humidity-dependent phase changes associated with evaporation and condensation. Oxygen stable isotope ratios have therefore been frequently used as a source of palaeoclimate data from a variety of proxy archives, which integrate this signal over time. Applications from ombrotrophic peatlands, where the source water used in cellulose synthesis is derived solely from precipitation, have been mostly limited to Northern Hemisphere Sphagnum-dominated bogs, with few in the Southern Hemisphere or in peatlands dominated by vascular plants. New Zealand (NZ) provides an ideal location to undertake empirical research into oxygen isotope fractionation in vascular peatlands because single taxon analysis can be easily carried out, in particular using the preserved root matrix of the restionaceous wire rush (Empodisma spp.) that forms deep Holocene peat deposits throughout the country. Furthermore, large gradients are observed in the mean isotopic composition of precipitation across NZ, caused primarily by the relative influence of different climate modes. Here, we test whether δ18O of Empodisma α-cellulose from ombrotrophic restiad peatlands in NZ can provide a methodology for developing palaeoclimate records of past precipitation δ18O. Surface plant, water and precipitation samples were taken over spatial (six sites spanning >10° latitude) and temporal (monthly measurements over one year) gradients. A link between the isotopic composition of root-associated water, the most likely source water for plant growth, and precipitation in both datasets was found. Back-trajectory modelling of precipitation moisture source for rain days prior to sampling showed clear seasonality in the temporal data that was reflected in root-associated water. The link between source water and plant cellulose was less clear, although mechanistic modelling predicted mean

Assessment of nitrogen and oxygen isotopic fractionation during nitrification and its expression in the marine environment.

PubMed

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

2011-01-01

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.

Isotopic Evidence for C4 Grass Expansion During the Last Glacial Maximum and Younger Dryas in Northern Australia

NASA Astrophysics Data System (ADS)

Johnson, B. J.; Wakeham, S.; Gelinas, Y.; Luly, J.; Miller, G.

2004-12-01

In northern and central Australia, late Quaternary records of terrestrial environmental change are rare due to generally poor preservation of pollen grains and a derth of long-term, continuous lacustrine sedimentary deposits. The Wombe mound spring in the Keep River National Park, Northern Territory, is an organic mound and isolated patch of monsoon vine thicket thought to have formed tens of thousands of years ago. In an effort to obtain a record of paleovegetation and fire history from northern Australia, a 3.4 m sediment core was recovered from the Wombe mound spring and subject to multiple types of analyses. The core represents a continuous depositional sequence with radiocarbon ages spanning the last 35 ka cal years (hereafter referred to as 35 ka). Paleovegetation was reconstructed using a combination of pollen and carbon isotopes in bulk sediment and higher plant leaf wax (HPLW) lipid biomarkers. The fire history was reconstructed from paired graphitic black carbon (GBC) and polycyclic aromatic hydrocarbon (PAH) analyses of the core sediments. Between 35 and 11 ka, the bulk organic carbon (OC) isotope data fluctuate between -22 and -15%, with the most isotopically enriched values measured at 11.4 ka. Between 12.3 and 6.8 ka, OC isotope values decrease by 13%, and remain steady from 6.8 ka to the present at -28%. There are two distinct peaks of isotopic enrichment in the higher plant leaf wax biomarkers. These two peaks coincide with the Last Glacial Maximum (LGM; 21 ka) and the Younger Dryas (YD; 11.4 ka) and represent maximum increases in C4 grasses relative to C3 plants. Relative increases in C4 grasses during the LGM in other parts of the tropics (i.e., Sacred Lake, Mt. Kenya) have been attributed to the competitive advantage of C4 plants relative to C3 plants under reduced atmospheric pCO2 and is likely the cause for C4 expansion in northern Australia. The increase in C4 grasses during the YD is reflected in the bulk sediment and HPLW isotope data and is

Anatomy of the thriple oxygen isotope Terrestrial Fractionatoin Line

NASA Astrophysics Data System (ADS)

Sharp, Z. D.; Pack, A.

2017-12-01

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

Relationship between the hydrogen and oxygen isotopes of deer bone and their use in the estimation of relative humidity

NASA Astrophysics Data System (ADS)

Cormie, A. B.; Luz, B.; Schwarcz, H. P.

1994-08-01

The hydrogen isotopic ratio of bone collagen (δDb) and the oxygen isotopic ratio of bone phosphate (δ 18Ob) from North American white-tailed deer are each related to both the isotopic ratio of local rain and relative humidity during the growing season. The humidity corrected bone δDb and δ 18Ob are highly correlated with each other with a correlation coefficient of 0.962. The regression slope of this equation (8.0) reflects the δD vs. δ 18O slope of meteoric water when we use a model which assumes that bone oxygen derives from leaf water rather than from drinking or environmental water. Therefore, growing season rain is the likely source of bone H and O. The effects of humidity are significantly greater for δ 18Ob than for δDb. Relative humidity (RH) can be estimated with moderate accuracy (± 6%) from a combination of bone phosphate δ 18Ob and collagen δDb and δ 15Nb. This indicates some potential benefits of using fossil bone for evaluating palaeohumidity. The estimate of RH improves to ± 4% when only data from warm climate areas are considered. It appears that for cold climate areas of North America, there may be a discrepancy between the actual leaf water values and the leaf water isotopic values predicted on the basis of the leaf water models used here. It seems possible that the further study of bone isotopic values may lead to a better understanding of how the average leaf water values of an area are related to local environment.

Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

NASA Technical Reports Server (NTRS)

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

2012-01-01

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.

Nitrogen and Triple Oxygen Isotopic Analyses of Atmospheric Particulate Nitrate over the Pacific Ocean

NASA Astrophysics Data System (ADS)

Kamezaki, Kazuki; Hattori, Shohei; Iwamoto, Yoko; Ishino, Sakiko; Furutani, Hiroshi; Miki, Yusuke; Miura, Kazuhiko; Uematsu, Mitsuo; Yoshida, Naohiro

2017-04-01

Nitrate plays a significant role in the biogeochemical cycle. Atmospheric nitrate (NO3- and HNO3) are produced by reaction precursor as NOx (NO and NO2) emitted by combustion, biomass burning, lightning, and soil emission, with atmospheric oxidants like ozone (O3), hydroxyl radical (OH), peroxy radical and halogen oxides. Recently, industrial activity lead to increases in the concentrations of nitrogen species (NOx and NHy) throughout the environment. Because of the increase of the amount of atmospheric nitrogen deposition, the oceanic biogeochemical cycle are changed (Galloway et al., 2004; Kim et al., 2011). However, the sources and formation pathways of atmospheric nitrate are still uncertain over the Pacific Ocean because the long-term observation is limited. Stable isotope analysis is useful tool to gain information of sources, sinks and formation pathways. The nitrogen stable isotopic composition (δ15N) of atmospheric particulate NO3- can be used to posses information of its nitrogen sources (Elliott et al., 2007). Triple oxygen isotopic compositions (Δ17O = δ17O - 0.52 ×δ18O) of atmospheric particulate NO3- can be used as tracer of the relative importance of mass-independent oxygen bearing species (e.g. O3, BrO; Δ17O ≠ 0 ‰) and mass-dependent oxygen bearing species (e.g. OH radical; Δ17O ≈ 0 ‰) through the formation processes from NOx to NO3- in the atmosphere (Michalski et al., 2003; Thiemens, 2006). Here, we present the isotopic compositions of atmospheric particulate NO3- samples collected over the Pacific Ocean from 40˚ S to 68˚ N. We observed significantly low δ15N values for atmospheric particulate NO3- on equatorial Pacific Ocean during both cruises. Although the data is limited, combination analysis of δ15N and Δ17O values for atmospheric particulate NO3- showed the possibility of the main nitrogen source of atmospheric particulate NO3- on equatorial Pacific Ocean is ammonia oxidation in troposphere. Furthermore, the Δ17O values

Oxygen isotope thermometry of quartz-Al2SiO5veins in high-grade metamorphic rocks on Naxos island (Greece)

NASA Astrophysics Data System (ADS)

Putlitz, Benita; Valley, John; Matthews, Alan; Katzir, Yaron

2002-04-01

Diffusion models predict that peak metamorphic temperatures are best recorded by the oxygen isotope fractionation between minerals in a bi-mineralic rock in which a refractory accessory mineral with slow oxygen diffusion rate is modally minor to a mineral with a faster diffusion rate. This premise is demonstrated for high-grade metamorphism on the island of Naxos, Greece, where quartz-kyanite oxygen isotope thermometry from veins in high-grade metamorphic pelites gives temperatures of 635-690 °C. These temperatures are in excellent agreement with independent thermometry for the regional M2 peak metamorphic conditions and show that the vein minerals isotopically equilibrated at the peak of metamorphism. Quartz-sillimanite fractionations in the same veins give similar temperatures (680+/-35 °C) and suggest that the veins grew near to the kyanite-sillimanite boundary, corresponding to pressures of 6.5 to 7.5 kbar for temperatures of 635-685 °C. By contrast, quartz-kyanite and quartz-biotite pairs in the host rocks yield lower temperature estimates than the veins (590-600 and 350-550 °C, respectively). These lower apparent temperatures are also predicted from calculations of diffusional resetting in the polyphase host-rock system. The data demonstrate that bimineralic vein assemblages can be used as accurate thermometers in high-temperature rocks whereas retrograde exchange remains a major problem in many polymineralic rocks.