Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

DOE PAGES

Rolison, John M.; Stirling, Claudine H.; Middag, Rob; ...

2018-02-19

We present that the chemical response of the Precambrian oceans to rising atmospheric O 2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shiftmore » in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS 2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the ‘Great Oxidation Event’ around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.« less

Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

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

Rolison, John M.; Stirling, Claudine H.; Middag, Rob

We present that the chemical response of the Precambrian oceans to rising atmospheric O 2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shiftmore » in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS 2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the ‘Great Oxidation Event’ around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise in atmospheric oxygen, contrary to other interpretations based on iron isotope systematics.« less

Fractionation of Fe isotopes by soil microbes and organic acids

USGS Publications Warehouse

Brantley, Susan L.; Liermann, Laura; Bullen, Thomas D.

2001-01-01

Small natural variations in Fe isotopes have been attributed to biological cycling. However, without understanding the mechanism of fractionation, it is impossible to interpret such variations. Here we show that the δ56Fe of Fe dissolved from a silicate soil mineral by siderophore-producing bacteria is as much as 0.8% lighter than bulk Fe in the mineral. A smaller isotopic shift is observed for Fe released abiotically by two chelates, and the magnitude of the shift increases with affinity of the ligand for Fe, consistent with a kinetic isotope effect during hydrolysis of Fe at the mineral surface. Fe dissolved abiotically without chelates shows no isotopic shift. The δ56Fe of the exchange fraction on soil grains is also lighter by ~0.6%-1% than Fe from both hornblende and iron oxyhydroxides. The kinetic isotope effect is therefore preserved in open systems such as soils. when recorded in the rock record, Fe isotopic fractionation could document Fe transport by organic molecules or by microbes where such entities were present in the geologic past.

Changes in the mean square charge radii and electromagnetic moments of neutron-deficient Bi isotopes

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

Barzakh, A. E., E-mail: barzakh@mail.ru; Batist, L. Kh.; Fedorov, D. V.

In-source laser spectroscopy experiments for neutron deficient bismuth isotopes at the 306.77 nm atomic transition were carried out at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility of Petersburg Nuclear Physics Institute (PNPI). New data on isotope shifts and hyperfine structure for {sup 189–198,} {sup 211}Bi isotopes and isomers were obtained. The changes in the mean-square charge radii and the magnetic moment values were deduced. Marked deviation from the nearly spherical behavior for ground states of bismuth isotopes at N < 109 is demonstrated, in contrast to the lead and thallium isotopic chains. The big isomer shift between Imore » = 1/2 (intruder) and I = 9/2 (normal) states for odd Bi isotopes (A = 193, 195, 197) was found.« less

Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations

NASA Technical Reports Server (NTRS)

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

1987-01-01

The relationship between the Nd isotopic composition in the Atlantic waters and the origin and circulation of the water masses was investigated. Samples were collected in the western North Atlantic between 7 and 54 deg N. The isotopic composition (Nd-143/Nd-144 ratios) showed extensive vertical structure at all locations. In regions where a thermocline was well-developed, large isotopic shifts were observed across the base of the thermocline, while regions without a thermocline were characterized by much more gradual shifts in isotopic composition with depth. The data reveal an excellent correlation between the Nd isotopic distribution in the western North Atlantic water column and the distribution of water masses identified from temperature and salinity measurements.

The Relationship Between the Zonal Mean ITCZ and Regional Precipitation during the mid-Holocene

NASA Astrophysics Data System (ADS)

Niezgoda, K.; Noone, D.; Konecky, B.

2017-12-01

Characteristics of the zonal mean Tropical Rain Belt (TRB, i.e. the ITCZ + the land-based monsoons) are often inferred from individual proxy records of precipitation or other hydroclimatic variables. However, these inferences can be misleading. Here, an isotope-enabled climate model simulation is used to evaluate metrics of the zonal mean ITCZ vs. regional hydrological characteristics during the mid-Holocene (MH, 6 kya). The MH provides a unique perspective on the relationship between the ITCZ and regional hydrology because of large, orbitally-driven shifts in tropical precipitation as well as a critical mass of proxy records. By using a climate model with simulated water isotopes, characteristics of atmospheric circulation and water transport processes can be inferred, and comparison with isotope proxies can be made more directly. We find that estimations of the zonal-mean ITCZ are insufficient for evaluating regional responses of hydrological cycles to forcing changes. For example, one approximation of a 1.5-degree northward shift in the zonal-mean ITCZ position during the MH corresponded well with northward shifts in maximum rainfall in tropical Africa, but did not match southward shifts in the tropical Pacific or longitudinal shifts in the Indian monsoon region. In many regions, the spatial distribution of water vapor isotopes suggests that changes in moisture source and atmospheric circulation were a greater influence on precipitation distribution, intensity, and isotope ratio than the average northward shift in ITCZ latitude. These findings reinforce the idea that using tropical hydrological proxy records to infer zonal-mean characteristics of the ITCZ may be misleading. Rather, tropical proxy records of precipitation, particularly those that record precipitation isotopes, serve as a guideline for regional hydrological changes while model simulations can put them in the context of zonal mean tropical convergence.

Penguin Proxies: Deciphering Millennial-Scale Antarctic Ecosystem Change using Amino Acid Stable Isotope Analysis.

NASA Astrophysics Data System (ADS)

Michelson, C.; McMahon, K.; Emslie, S. D.; Patterson, W. P.; McCarthy, M. D.; Polito, M. J.

2017-12-01

The Southern Ocean ecosystem is undergoing rapid environmental change due to ongoing and historic anthropogenic impacts such as climate change and marine mammal harvesting. These disturbances may have cascading effects through the Antarctic food webs, resulting in profound shifts in the sources and cycling of organic matter supporting higher-trophic organisms, such as penguins. For example, bulk stable isotope analyses of modern and ancient preserved penguin tissues suggest variations in penguin feeding ecology throughout the Holocene with dramatic isotopic shifts in the last 200 years. However, it is not clear whether these isotopic shifts resulted from changes at the base of the food web, dietary shifts in penguins, or some combination of both factors. Newly developed compound-specific stable nitrogen isotope analysis of individual amino acids (CSIA-AA) may provide a powerful new tool to tease apart these confounding variables. Stable nitrogen isotope values of trophic amino acids (e.g., glutamic acid) increase substantially with each trophic transfer in the food web, while source amino acid (e.g., phenylalanine) stable nitrogen isotope values remain relatively unchanged and reflect ecosystem baselines. As such, we can use this CSIA-AA approach to decipher between baseline and dietary shifts in penguins over time from modern and ancient eggshells of Pygoscelis penguins in the Antarctic Peninsula and the Ross Sea regions of Antarctica. In order to accurately apply this CSIA-AA approach, we first characterized the trophic fractionation factors of individual amino acids between diet and penguin consumers in a long-term controlled penguin feeding experiment. We then applied these values to modern and ancient eggshells from the Antarctic Peninsula and Ross Sea to evaluate shifts in penguin trophic dynamics as a function of climate and anthropogenic interaction throughout much of the Holocene. This work develops a cutting edge new molecular geochemistry approach applied to penguins as sensitive indicators of past environmental change in Antarctica.

Shape evolution for neutron-deficient bismuth isotopes studied by resonance laser ionization spectroscopy

NASA Astrophysics Data System (ADS)

Molkanov, P. L.; Barzakh, A. E.; Fedorov, D. V.; Ivanov, V. S.; Moroz, F. V.; Orlov, S. Yu.; Panteleev, V. N.; Seliverstov, M. D.; Volkov, Yu. M.

2017-11-01

In-source laser spectroscopy experiments for bismuth isotopes at the 306.77 nm atomic transition has been carried out at the IRIS (Investigation of Radioactive Isotopes at Synchrocyclotron) facility of Petersburg Nuclear Physics Institute. New data on isotope shifts for 189-198,211Bi isotopes and isomers have been obtained. The changes in the mean-square charge radii were deduced. The large isomer shift has been observed for the intruder isomer states of Bi with spin I = 1/2 ( A = 193, 195, 197). This testifies to the shape coexistence in these nuclei with the intruder isomer states more deformed than the ground states. Marked deviation from the nearly spherical behavior for ground states of the even-neutron Bi isotopes at N < 109 is demonstrated, in contrast to the Pb and Tl isotopic chains.

Geochemical structure of the Hawaiian plume: Sr, Nd, and Os isotopes in the 2.8 km HSDP-2 section of Mauna Kea volcano

NASA Astrophysics Data System (ADS)

Bryce, Julia G.; Depaolo, Donald J.; Lassiter, John C.

2005-09-01

Sr, Nd, and Os isotopic measurements were made on 110 Mauna Kea lava and hyaloclastite samples from the drillcore retrieved from the second phase of the Hawaii Scientific Drilling Project (HSDP-2). The samples come from depths of 255 to 3098 meters below sea level, span an age range from 200 to about 550-600 kyr, and represent an ordered record of the lava output from Mauna Kea volcano as it drifted a distance of about 40 km over the magma-producing region of the Hawaiian hot spot. The deepest (oldest) samples represent the time when Mauna Kea was closest to the center of the melting region of the Hawaiian plume. The Sr and Os isotopic ratios in HSDP-2 lavas show only subtle isotopic shifts over the ˜400 kyr history represented by the core. Neodymium isotopes (ɛNd values) increase systematically with decreasing age from an average value of nearly +6.5 to an average value of +7.5. This small change corresponds to subtle shifts in 87Sr/86Sr and 187Os/188Os isotope ratios, with small shifts of ɛHf, a large shift in 208Pb/204Pb and 208Pb/207Pb values, and with a very large shift in He isotope ratios from R/RA values of about 7-8 to values as high as 25. When Mauna Kea was closest to the plume core, the magma source did not have primitive characteristics for Nd, Sr, Pb, Hf, and Os isotopes but did have variable amounts of "primitive" helium. The systematic shifts in Nd, Hf, Pb, and He isotopes are consistent with radial isotopic zoning within the melting region of the plume. The melting region constitutes only the innermost, highest-temperature part of the thermally anomalous plume mantle. The different ranges of values observed for each isotopic system, and comparison of Mauna Kea lavas with those of Mauna Loa, suggest that the axial region of the plume, which has a radius of ˜20 km, is a mixture of recycled subducted components and primitive lower mantle materials, recently combined during the formational stages of the plume at the base of the mantle. The proportions of recycled and primitive components are not constant, and this requires there be longitudinal (vertical) heterogeneity within the core of the plume. The remainder of the plume, outside this plume "core zone," is less heterogeneous but distinct from upper mantle as represented by mid-ocean ridge basalt (MORB). The plume structure may provide a detailed view of mantle isotopic composition near the core-mantle boundary.

Infrared laser system

DOEpatents

Cantrell, Cyrus D.; Carbone, Robert J.; Cooper, Ralph S.

1977-01-01

An infrared laser system and method for isotope separation may comprise a molecular gas laser oscillator to produce a laser beam at a first wavelength, Raman spin flip means for shifting the laser to a second wavelength, a molecular gas laser amplifier to amplify said second wavelength laser beam to high power, and optical means for directing the second wavelength, high power laser beam against a desired isotope for selective excitation thereof in a mixture with other isotopes. The optical means may include a medium which shifts the second wavelength high power laser beam to a third wavelength, high power laser beam at a wavelength coincidental with a corresponding vibrational state of said isotope and which is different from vibrational states of other isotopes in the gas mixture.

Infrared laser system

DOEpatents

Cantrell, Cyrus D.; Carbone, Robert J.; Cooper, Ralph

1982-01-01

An infrared laser system and method for isotope separation may comprise a molecular gas laser oscillator to produce a laser beam at a first wavelength, Raman spin flip means for shifting the laser to a second wavelength, a molecular gas laser amplifier to amplify said second wavelength laser beam to high power, and optical means for directing the second wavelength, high power laser beam against a desired isotope for selective excitation thereof in a mixture with other isotopes. The optical means may include a medium which shifts the second wavelength high power laser beam to a third wavelength, high power laser beam at a wavelength coincidental with a corresponding vibrational state of said isotope and which is different from vibrational states of other isotopes in the gas mixture.

Trophic level and macronutrient shift effects associated with the weaning process in the Postclassic Maya.

PubMed

Williams, Jocelyn S; White, Christine D; Longstaffe, Fred J

2005-12-01

The weaning process was investigated at two Maya sites dominated by Postclassic remains: Marco Gonzalez (100 BC-AD 1350) and San Pedro (1400-AD 1650), Belize. Bone collagen and bioapatite were analyzed from 67 individuals (n < or = 6 years = 15, n > 6 years = 52). Five isotopic measures were used to reconstruct diet and weaning: stable nitrogen- and carbon-isotope ratios in collagen, stable carbon- and oxygen-isotope ratios in bioapatite, and the difference in stable carbon-isotope values of coexisting collagen and bioapatite. Nitrogen-isotope ratios in infant collagen from both sites are distinct from adult females, indicating a trophic level effect. Collagen-to-bioapatite differences in infant bone from both sites are distinct from adult females, indicating a shift in macronutrients. Oxygen-isotope ratios in infant bioapatite from both sites are also distinct from adult females, indicating the consumption of breast milk. Among infants, carbon- and nitrogen-isotope ratios vary, indicating death during different stages in the weaning process. The ethnohistoric and paleopathological literature on the Maya indicate cessation of breast-feeding between ages 3-4 years. Isotopic data from Marco Gonzalez and San Pedro also indicate an average weaning age of 3-4 years. Based on various isotopic indicators, weaning likely began around age 12 months. This data set is not only important for understanding the weaning process during the Postclassic, but also demonstrates the use of collagen-to-bioapatite spacing as an indicator of macronutrient shifts associated with weaning. 2005 Wiley-Liss, Inc.

Breath carbon stable isotope ratios identify changes in energy balance and substrate utilization in humans

USDA-ARS?s Scientific Manuscript database

Rapid detection of shifts in substrate utilization and energy balance would provide a compelling biofeedback tool to enable individuals to lose weight. In a pilot study, we tested whether the natural abundance of exhaled carbon stable isotope ratios (breath d13C values) reflects shifts between negat...

Spectroscopic Measurement of LEAD-204 Isotope Shift and LEAD-205 Nuclear Spin.

NASA Astrophysics Data System (ADS)

Schonberger, Peter

The isotope shift of ('204)Pb and the nuclear spin of 1.4 x 10('7)-y ('205)Pb was determined from a high -resolution optical measurement of the 6p('2) ('3)P(,o) -6p7s('3)P(,1)('o) 283.3-nm resonance line. The value of the shift, relative to ('208)Pb is -140.2(8) x 10('-3)cm(' -1), the negative sign indicating a shift to lower wave numbers. The precision is 3-4 times greater than that of previous measurements. The spin of ('205)Pb l = 5/2 was obtained from the measurement of the relative intensities of its three hyperfine components. This method of absorption spectroscopy determination of ground state nuclear spin is applicable to any stable or longlived isotope. High resolution optical absorption spectra were obtained with a 25.4cm diffraction grating in a 9.1m focal length Czerny-Turner spectrometer. A signal-averaging scanning technique was used to record the spectra. Increased precision in the isotope shift measurement was attained by using separated isotope samples of ('204)Pb and ('207)Pb. A controlled amount of the later was incorporated in the absorption cell to provide internal calibration by its 6p7s ('3)P(,1)('o) hfs separation. Absorption spectra were recorded for several optical thicknesses of the absorber. A single spin value of increased precision was derived from the entire set of combined data.

Methane flux and carbon isotope composition correlate to shifting plant and microbial communities along a permafrost thaw gradient

NASA Astrophysics Data System (ADS)

McCalley, C. K.; Mondav, R.; Chanton, J.; Crill, P. M.; Hodgkins, S. B.; Kim, E.; Rich, V. I.; Wehr, R.; Woodcroft, B. J.; Tyson, G. W.; Saleska, S. R.

2012-12-01

Methane flux from high latitude wetlands is a critical component of the global carbon budget and is highly sensitive to climate change, with observed and predicted increases as permafrost thaws. Microorganisms mediate wetland methane cycling, but connections between ecosystem-scale flux and underlying microbial dynamics are poorly understood. To address this gap we used isotopic (laser absorption spectrometry) and molecular (16S rRNA gene amplicon sequencing) techniques in a high latitude (68° N) wetland to investigate the relationship between microbial community composition and methane emissions across a permafrost thaw gradient. The transition from permafrost dominated, well drained palsas, through intermediate thaw sites dominated by Sphagnum spp., to wet sites with no underlying permafrost dominated by Eriophorum angustifolium is associated with substantial increases in methane emission. Across this thaw progression the carbon isotopic composition of emitted methane increased from -79.5 ‰ in the intermediate-thawing site to -66.4 ‰ in the thawed site, indicating a relative shift from CO2-reductive towards acetoclastic methanogenesis. Increases in methane flux under thaw were correlated with increasing abundance of methane-producing archaeal clades and increases in methane isotopic composition were associated with shifts in the archaeal community. While CO2 reducing methanogens were found throughout thawing and thawed sites, methanogens of the Methanosarcina (the order of Archaea that contains all known acetoclastic methanogens) were most associated with the fully thawed site. These results directly link microbial community composition to ecosystem scale changes in the magnitude and isotopic composition of methane emissions under permafrost thaw. If isotopic shifts of this magnitude are characteristic of methane dynamics under permafrost loss they should also become detectable in global atmospheric methane observations, providing a global scale tracer of shifting microbial communities associated with permafrost thaw.

Carbon and Nitrogen Isotopes from Top Predator Amino Acids Reveal Rapidly Shifting Ocean Biochemistry in the Outer California Current

PubMed Central

Ruiz-Cooley, Rocio I.; Koch, Paul L.; Fiedler, Paul C.; McCarthy, Matthew D.

2014-01-01

Climatic variation alters biochemical and ecological processes, but it is difficult both to quantify the magnitude of such changes, and to differentiate long-term shifts from inter-annual variability. Here, we simultaneously quantify decade-scale isotopic variability at the lowest and highest trophic positions in the offshore California Current System (CCS) by measuring δ15N and δ13C values of amino acids in a top predator, the sperm whale (Physeter macrocephalus). Using a time series of skin tissue samples as a biological archive, isotopic records from individual amino acids (AAs) can reveal the proximate factors driving a temporal decline we observed in bulk isotope values (a decline of ≥1 ‰) by decoupling changes in primary producer isotope values from those linked to the trophic position of this toothed whale. A continuous decline in baseline (i.e., primary producer) δ15N and δ13C values was observed from 1993 to 2005 (a decrease of ∼4‰ for δ15N source-AAs and 3‰ for δ13C essential-AAs), while the trophic position of whales was variable over time and it did not exhibit directional trends. The baseline δ15N and δ13C shifts suggest rapid ongoing changes in the carbon and nitrogen biogeochemical cycling in the offshore CCS, potentially occurring at faster rates than long-term shifts observed elsewhere in the Pacific. While the mechanisms forcing these biogeochemical shifts remain to be determined, our data suggest possible links to natural climate variability, and also corresponding shifts in surface nutrient availability. Our study demonstrates that isotopic analysis of individual amino acids from a top marine mammal predator can be a powerful new approach to reconstructing temporal variation in both biochemical cycling and trophic structure. PMID:25329915

Carbon and nitrogen isotopes from top predator amino acids reveal rapidly shifting ocean biochemistry in the outer California Current.

PubMed

Ruiz-Cooley, Rocio I; Koch, Paul L; Fiedler, Paul C; McCarthy, Matthew D

2014-01-01

Climatic variation alters biochemical and ecological processes, but it is difficult both to quantify the magnitude of such changes, and to differentiate long-term shifts from inter-annual variability. Here, we simultaneously quantify decade-scale isotopic variability at the lowest and highest trophic positions in the offshore California Current System (CCS) by measuring δ15N and δ13C values of amino acids in a top predator, the sperm whale (Physeter macrocephalus). Using a time series of skin tissue samples as a biological archive, isotopic records from individual amino acids (AAs) can reveal the proximate factors driving a temporal decline we observed in bulk isotope values (a decline of ≥1 ‰) by decoupling changes in primary producer isotope values from those linked to the trophic position of this toothed whale. A continuous decline in baseline (i.e., primary producer) δ15N and δ13C values was observed from 1993 to 2005 (a decrease of ∼4‰ for δ15N source-AAs and 3‰ for δ13C essential-AAs), while the trophic position of whales was variable over time and it did not exhibit directional trends. The baseline δ15N and δ13C shifts suggest rapid ongoing changes in the carbon and nitrogen biogeochemical cycling in the offshore CCS, potentially occurring at faster rates than long-term shifts observed elsewhere in the Pacific. While the mechanisms forcing these biogeochemical shifts remain to be determined, our data suggest possible links to natural climate variability, and also corresponding shifts in surface nutrient availability. Our study demonstrates that isotopic analysis of individual amino acids from a top marine mammal predator can be a powerful new approach to reconstructing temporal variation in both biochemical cycling and trophic structure.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Human-Induced Long-Term Shifts in Gull Diet from Marine to Terrestrial Sources in North America's Coastal Pacific: More Evidence from More Isotopes (δ2H, δ34S).

PubMed

Hobson, Keith A; Blight, Louise K; Arcese, Peter

2015-09-15

Measurements of naturally occurring stable isotopes in tissues of seabirds and their prey are a powerful tool for investigating long-term changes in marine foodwebs. Recent isotopic (δ(15)N, δ(13)C) evidence from feathers of Glaucous-winged Gulls (Larus glaucescens) has shown that over the last 150 years, this species shifted from a midtrophic marine diet to one including lower trophic marine prey and/or more terrestrial or freshwater foods. However, long-term isotopic patterns of δ(15)N and δ(13)C cannot distinguish between the relative importance of lower trophic-level marine foods and terrestrial sources. We examined 48 feather stable-hydrogen (δ(2)H) and -sulfur (δ(34)S) isotope values from this same 150-year feather set and found additional isotopic evidence supporting the hypothesis that gulls shifted to terrestrial and/or freshwater prey. Mean feather δ(2)H and δ(34)S values (± SD) declined from the earliest period (1860-1915; n = 12) from -2.5 ± 21.4 ‰ and 18.9 ± 2.7 ‰, respectively, to -35.5 ± 15.5 ‰ and 14.8 ± 2.4 ‰, respectively, for the period 1980-2009 (n = 12). We estimated a shift of ∼ 30% increase in dependence on terrestrial/freshwater sources. These results are consistent with the hypothesis that gulls increased terrestrial food inputs in response to declining forage fish availability.

Isotopic Evidence for Multi-stage Cosmic-ray Exposure Histories of Lunar Meteorites: Long Residence on the Moon and Short Transition to the Earth

NASA Astrophysics Data System (ADS)

Hidaka, Hiroshi; Sakuma, Keisuke; Nishiizumi, Kunihiko; Yoneda, Shigekazu

2017-06-01

It is known that most lunar meteorites have complicated cosmic-ray exposure experiences on the Moon and in space. In this study, cosmic-ray irradiation histories of six lunar meteorites, Dhofar 489, Northwest Africa 032 (NWA 032), NWA 479, NWA 482, NWA 2995, and NWA 5000, were characterized from neutron-captured isotopic shifts of Sm and Gd, and from the abundances of long-lived cosmogenic radionuclides like 10Be, 26Al, 36Cl, and 41Ca. Sm and Gd isotopic data of all of six meteorites show significant isotopic shifts of 149Sm-150Sm and 157Gd-158Gd caused by accumulation of neutron capture reactions due to cosmic-ray irradiation, corresponding to the neutron fluences of (1.3-9.6) × 1016 n cm-2. In particular, very large Sm and Gd isotopic shifts of NWA 482 are over those of a lunar regolith 70002, having the largest isotopic shifts among the Apollo regolith samples, corresponding to cosmic-ray exposure duration over 800 million years in the lunar surface (2π irradiation). Meanwhile, the concentrations of cosmogenic radionuclides for individual six meteorites show the short irradiation time less than one million years as their bodies in space (4π irradiation). Our data also support the results of previous studies, revealing that most of lunar meteorites have long exposure ages at shallow depths on the Moon and short transit times from the Moon to the Earth.

Theoretical study of the hyperfine-interaction constants and the isotope-shift factors for the 3 s21S0-3 s 3 p 3,1P1o transitions in Al+

NASA Astrophysics Data System (ADS)

Zhang, Tingxian; Xie, Luyou; Li, Jiguang; Lu, Zehuang

2017-07-01

We calculated the magnetic dipole and the electric quadrupole hyperfine interaction constants of 3 s 3 p 3,1P1o states and the isotope shift, including mass and field shift, factors for transitions from these two states to the ground state 3 s 2 1S0 in Al+ ions using the multiconfiguration Dirac-Hartree-Fock method. The effects of the electron correlations and the Breit interaction on these physical quantities were investigated in detail based on the active space approach. It is found that the core-core and the higher order correlations are considerable for evaluating the uncertainties of the atomic parameters concerned. The uncertainties of the hyperfine interaction constants in this work are less than 1.6%. Although the isotope shift factors are highly sensitive to the electron correlations, reasonable uncertainties were obtained by exploring the effects of the electron correlations. Moreover, we found that the relativistic nuclear recoil corrections to the mass shift factors are very small and insensitive to the electron correlations for Al+. These atomic parameters present in this work are valuable for extracting the nuclear electric quadrupole moments and the mean-square charge radii of Al isotopes.

Changing carbon isotope ratio of atmospheric carbon dioxide: implications for food authentication.

PubMed

Peck, William H; Tubman, Stephanie C

2010-02-24

Carbon isotopes are often used to detect the addition of foreign sugars to foods. This technique takes advantage of the natural difference in carbon isotope ratio between C(3) and C(4) plants. Many foods are derived from C(3) plants, but the low-cost sweeteners corn and sugar cane are C(4) plants. Most adulteration studies do not take into account the secular shift of the carbon isotope ratio of atmospheric carbon dioxide caused by fossil fuel burning, a shift also seen in plant tissues. As a result statistical tests and threshold values that evaluate authenticity of foods based on carbon isotope ratios may need to be corrected for changing atmospheric isotope values. Literature and new data show that the atmospheric trend in carbon isotopes is seen in a 36-year data set of maple syrup analyses (n = 246), demonstrating that published thresholds for cane or corn sugar adulteration in maple syrup (and other foods) have become progressively more lenient over time.

Natural trophic variability in a large, oligotrophic, near-pristine lake

USGS Publications Warehouse

Young, Talia; Jensen, Olaf P.; Weidel, Brian C.; Chandra, Sudeep

2015-01-01

Conclusions drawn from stable isotope data can be limited by an incomplete understanding of natural isotopic variability over time and space. We quantified spatial and temporal variability in fish carbon and nitrogen stable isotopes in Lake Hövsgöl, Mongolia, a large, remote, oligotrophic lake with an unusually species-poor fish community. The fish community demonstrated a high degree of trophic level overlap. Variability in δ13C was inversely related to littoral-benthic dependence, with pelagic species demonstrating more δ13C variability than littoral-benthic species. A mixed effects model suggested that space (sampling location) had a greater impact than time (collection year) on both δ13C and δ15N variability. The observed variability in Lake Hövsgöl was generally greater than isotopic variability documented in other large, oligotrophic lakes, similar to isotopic shifts attributed to introduced species, and less than isotopic shifts attributed to anthropogenic chemical changes such as eutrophication. This work complements studies on isotopic variability and changes in other lakes around the world.

Isotope Tales: Remaining Problems, Unsolvable Questions, and Gentle Successes

NASA Astrophysics Data System (ADS)

fogel, marilyn; bradley, christina; newsome, seth; filipp, fabian

2014-05-01

Earth's biomes function and adapt today as climate changes and ecosystems and the organisms within them adapt. Stable isotope biogeochemistry has had a major influence in understanding climate perturbations and continues to be an active area of research on many fronts. Banking on the success of compound specific stable isotope analyses of amino acids, nitrogen, carbon, and hydrogen isotopes continue to reveal subtle shifts in oceanic food webs and metabolic changes in microbes, plants, and animals. A biochemical understanding of exactly how organisms process and partition stable isotopes during metabolism remains unsolved, but is required if this field is to move beyond description to quantitation. Although the patterns of carbon and nitrogen isotopes are fairly well established in the common amino acids, we need to consider specifics: How do shifting metabolic pathways (metabolomics) influence the outcome of stable isotope partitioning? What influence does the gut microflora in animals have on isotopic labeling? What are the intramolecular isotope patterns of common amino acids and what do they tell us? What can be learned with other isotope systems, such as hydrogen? Results and ideas of how to move forward in this field will be presented starting at the molecular level and ending with ecosystems.

Metal isotope and density functional study of the tetracarboxylatodicopper(II) core vibrations

NASA Astrophysics Data System (ADS)

Drożdżewski, Piotr; Brożyna, Anna

2005-11-01

Vibrational spectra of tetrakis(acetato)diaquadicopper(II) complex have been deeply examined in order to provide a detailed description of dynamics of [Cu 2O 8C 4] core being a typical structural unit of most copper(II) carboxylates. Low frequency bands related to significant motions of metal atoms were detected by metal isotope substitution. Observed spectra and isotope shifts were reproduced in DFT calculations. For clear presentation of computed normal vibrations, a D 4h symmetry approximation was successfully applied. Basing on observed isotope shifts and calculation results, all skeletal vibrations have been analyzed including normal mode with the largest Cu ⋯Cu stretching amplitude assigned to Raman band at 178 cm -1.

Status of the TRIGA-LASER experiment

NASA Astrophysics Data System (ADS)

Gorges, C.; Kaufmann, S.; Geppert, Ch.; Krämer, J.; Sánchez, R.; Nörtershäuser, W.

2017-11-01

We report on the newly developed control system called TRITON and the new data acquisition called TILDA as well as on improved isotope shift measurements of the isotopes 40,42,44,48Ca in the 4 s 2S1/2 → 4 p 2P3/2 (D2) transition at the TRIGA-LASER experiment in Mainz using collinear laser spectroscopy. Well known isotope shift measurements in the 4 s 2S1/2 → 4 p 2P1/2 (D1) transition act as calibration points to reduce the uncertainties in the D2-line to provide reference values for the determination of nuclear charge radii and quadrupole moments of neutron rich calcium isotopes at COLLAPS.

Diode laser based resonance ionization mass spectrometric measurement of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1997-10-01

A diode laser based scheme for the isotopically selective excitation and ionization of strontium is presented. The double-resonance excitation 5s 21S 0→5s5p 3P 1→5s6s 3S 1 is followed by photoionization at 488 nm. The isotope shifts and hyperfine structure in the resonance transitions have been accurately measured for the stable isotopes and 90Sr, with the measurement of the 90Sr shifts using sub-pg samples. Analytical tests, using graphite crucible atomization, demonstrated 90Sr detection limits of 0.8 fg and overall (optical+mass spectrometer) isotopic selectivity of >10 10 against stable strontium.

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.

Variation in the isotopic composition of striped weakfish Cynoscion guatucupa of the Southwest Atlantic Ocean in response to dietary shifts.

PubMed

Viola, M N Paso; Riccialdelli, L; Jaureguizar, A; Panarello, H O; Cappozzo, H L

2018-05-01

The aim of this study was to analyze the isotopic composition in muscle of striped weakfish Cynoscion guatucupa from Southwest Atlantic Ocean in order to evaluate a possible variation in δ13C and δ15N in response to dietary shifts that occur as animals grow. We also explored for isotopic evidence of differences between sample locations. The results showed an agreement between isotope analysis and previous conventional studies. Differences in the isotope composition between sampling location were not observed. A positive relation exists between isotope values and total body length of the animals. The Cluster analysis defined three groups of size classes, validated by the MDS. Differences in the relative consumption of prey species in each size class were also observed performing isotope mixing models (SIAR). Variation in δ15N among size classes would be associated with the consumption of a different type of prey as animals grow. Small striped weakfish feed on small crustaceans and progressively increase their consumption of fish (anchovy, Engraulis anchoita), increasing by this way their isotope values. On the other hand, differences in δ13C values seemed to be related to age-class specific spatial distribution patterns. Therefore, large and small striped weakfish remain specialized but feeding on different prey at different trophic levels. These results contribute to the study of the diet of striped weakfish, improve the isotopic ecology models and highlight on the importance of accounting for variation in the isotopic composition in response to dietary shifts with the size of one of the most important fishery resources in the region.

Isotopically selective two-photon ionization of aniline in supersonic beams

NASA Astrophysics Data System (ADS)

Leutwyler, S.; Even, U.

1981-08-01

Tunable laser two-photon ionization of aniline cooled in supersonic expansions combined with TOF mass spectrometry reveal an isotopic shift of the vibronic origin at 2938 Å (ππ ∗; 1B 2← 1A 1 transition). The shift (+4.6 cm -1) is smaller than the rotational bandwidth and would be unobservable by laser-induced fluorescence.

Sensing site-specific structural characteristics and chirality using vibrational circular dichroism of isotope labeled peptides.

PubMed

Keiderling, Timothy A

2017-12-01

Isotope labeling has a long history in chemistry as a tool for probing structure, offering enhanced sensitivity, or enabling site selection with a wide range of spectroscopic tools. Chirality sensitive methods such as electronic circular dichroism are global structural tools and have intrinsically low resolution. Consequently, they are generally insensitive to modifications to enhance site selectivity. The use of isotope labeling to modify vibrational spectra with unique resolvable frequency shifts can provide useful site-specific sensitivity, and these methods have been recently more widely expanded in biopolymer studies. While the spectral shifts resulting from changes in isotopic mass can provide resolution of modes from specific parts of the molecule and can allow detection of local change in structure with perturbation, these shifts alone do not directly indicate structure or chirality. With vibrational circular dichroism (VCD), the shifted bands and their resultant sign patterns can be used to indicate local conformations in labeled biopolymers, particularly if multiple labels are used and if their coupling is theoretically modeled. This mini-review discusses selected examples of the use of labeling specific amides in peptides to develop local structural insight with VCD spectra. © 2017 Wiley Periodicals, Inc.

Identifying stereoisomers by ab-initio calculation of secondary isotope shifts on NMR chemical shieldings.

PubMed

Böhm, Karl-Heinz; Banert, Klaus; Auer, Alexander A

2014-04-23

We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

Experimental determination of the field shift factor and the mass shift coefficient for the 1S0-3P1 spin-forbidden transition at 791 nm in neutral barium

NASA Astrophysics Data System (ADS)

Yu, Geng-Hua; Yan, Hui; Zhong, Jia-Qi; Liu, Hong; Zhu, Xiao-Ling; Yang, Wei

2018-01-01

The experimental measurements of the isotope shifts (ISs) for the 1S0-3P1 spin-forbidden transition at 791 nm in neutral barium have been carried out with a thermal barium atom beam. The hyperfine structure (HFS) constants a and b of the odd isotopes 137Ba and 135Ba for this transition have been extracted from the experimental results: a(137Ba) = 1149.9(1.0) MHz, b(137Ba)= -41.6(0.5) MHz, a(135Ba) = 1028.0(1.0) MHz, b(135Ba) = -27.5(0.5) MHz. The measured IS results with the reference isotope 138Ba are 183.7(1.0) MHz (137Ba-138Ba), 108.5(0.3) MHz (136Ba-138Ba) and 218.9(1.0) MHz (135Ba-138Ba). Our IS measurements are in good agreement with the previous experiments. The field shift (FS) factor Fk and the mass shift (MS) coefficient ΔKMS for this spin-forbidden transition have be determined experimentally as -3.19(4) GHz ṡ fm-2 and -242(20) GHz ṡ amu, respectively. The results provided herein could be used for further checks theoretically and experimentally, and could also contribute to the study on the nuclear structure of the barium isotopic nuclei.

Colloquium: Laser probing of neutron-rich nuclei in light atoms

NASA Astrophysics Data System (ADS)

Lu, Z.-T.; Mueller, P.; Drake, G. W. F.; Nörtershäuser, W.; Pieper, Steven C.; Yan, Z.-C.

2013-10-01

The neutron-rich He6 and He8 isotopes exhibit an exotic nuclear structure that consists of a tightly bound He4-like core with additional neutrons orbiting at a relatively large distance, forming a halo. Recent experimental efforts have succeeded in laser trapping and cooling these short-lived, rare helium atoms and have measured the atomic isotope shifts along the He4-He6-He8 chain by performing laser spectroscopy on individual trapped atoms. Meanwhile, the few-electron atomic structure theory, including relativistic and QED corrections, has reached a comparable degree of accuracy in the calculation of the isotope shifts. In parallel efforts, also by measuring atomic isotope shifts, the nuclear charge radii of lithium and beryllium isotopes have been studied. The techniques employed were resonance ionization spectroscopy on neutral, thermal lithium atoms and collinear laser spectroscopy on beryllium ions. Combining advances in both atomic theory and laser spectroscopy, the charge radii of these light halo nuclei have now been determined for the first time independent of nuclear structure models. The results are compared with the values predicted by a number of nuclear structure calculations and are used to guide our understanding of the nuclear forces in the extremely neutron-rich environment.

Simulated shifts in the mid-latitude storm tracks over the western US detected through isotopes in precipitation and vapor

NASA Astrophysics Data System (ADS)

Buenning, N. H.; Stott, L. D.; Kanner, L.; Yoshimura, K.

2013-12-01

One of the most robust features of climate model projections for the 21st century includes a poleward shift of middle latitude storm tracks in response to enhanced radiative forcing. This study evaluates how shifts in the middle latitude storm tracks over the North Pacific has been expressed in the stable isotopic composition of atmospheric vapor and precipitation in the past 60 years. Previous work has demonstrated how the isotopic composition of precipitation (δ18Op) in the Pacific Northwest and in atmospheric vapor (δ18Ov) across the western US reflects the large-scale atmospheric circulation. Thus, it is possible to use the isotopic composition of water in these regions to detect shifts in mid-latitude storm tracks. Results from the Isotope-incorporated Global Spectral Model (IsoGSM) are presented to better understand the recent low frequency variations in δ18O values over the western US. The IsoGSM simulations presented here were spectrally nudged every six hours to the NCEP/NCAR Reanalysis wind and temperature fields. The spectral nudging technique allows for realistic isotopic simulations that are consistent with observed large-scale mid-latitude storm systems. Model results suggest that δ18Op has risen over the Pacific Northwest and δ18Ov has increased across the western US since the 1950s (see Figure), an indication of more moisture advection from the tropics and less moisture transported from the middle latitudes. Water tagging simulations reveal that as δ18Ov increased in the western US, the fraction of vapor from the subtropics had also increased, while the fraction from the middle latitudes had decreased. Similarly, the tagging simulations resulted in increased subtropical precipitation falling in the Pacific Northwest and decreased precipitation from the middle latitudes. These model simulations suggest that a northward shift in storm tracks has already taken place over the last 60 years in the western US. Furthermore, the results underscore the potential of using isotopes in vapor and precipitation in certain regions of western North America to monitor middle latitude storm behavior as the climate warms.

Global Links to Local Carbon Cycling Perturbation

NASA Astrophysics Data System (ADS)

Chen, J.; Montanez, I. P.; Wang, X.; Qi, Y.

2016-12-01

Carbon cycle perturbations recorded by stable carbon isotope excursions (CIEs) play an important role in understanding climate, oceanography, and the biosphere through time. Recent studies, however, reveal the influence of regional processes on apparent global CIEs. Deconvolving local/regional from global processes imprinted in the carbon isotopic records of sedimentary successions requires integrated sedimentologic, stratigraphic, and geochemical study. Here we present coupled C and Sr isotopic records of diagenetically screened micrite and brachiopods from late Mississippian shallow-marine, carbonate platform and contemporaneous carbonate slope successions from the east Paleotethys Ocean region (South China). These records reveal distinctly different signatures of the depositional response to the onset of Carboniferous glaciation. C and Sr isotopic compositions of the platform carbonates exhibit systematic fluctuations in step with inferred sea-level changes captured by depositional cycles. CIEs in the platform succession can be correlated to the contemporaneous C isotope record from the Antler carbonate ramp (Idaho, USA). In contrast, slope carbonate and conodont isotopic records exhibit minimal variability interpreted to record the open-ocean seawater composition. The isotopic disparity between successions is interpreted to record the influence of local depositional, but not diagenetic, processes operating on the carbonate platform in response to glacioeustasy. Variability in the nature of coupled isotopic and inferred sea level fluctuations is interpreted to record stepwise onset of the late Paleozoic ice age in the late Mississippian. Initial large magnitude shifts in C and Sr isotopic compositions of late Visean to early Serpukhovian carbonates correspond to 1 to 2 myr-scale cycles driven by the buildup of continental glaciers. Subsequent decreased magnitude of isotopic shifts coincident with a shift to shorter duration and smaller magnitude sea-level fluctuations in the middle to late Serpukhovian interval is interpreted to record temporary retraction of the ice sheets in response to late Serpukhovian warming. Overall, the coupled stratigraphic and isotopic records indicate stepwise ice buildup prior to widespread glaciation across the mid-Carboniferous boundary.

The Fluctuating Bond Model, a Glue for Cuprate Superconductivity?

NASA Astrophysics Data System (ADS)

Newns, Dennis

2008-03-01

Twenty years of research have yet to produce a consensus on the origin of high temperature superconductivity (HTS). The mechanism of HTS - which originates in the CuO2 plane, common to all HTS families - can be constrained by some key experimental facts regarding superconducting and pseudogap behaviors. Superconductivity, involving a Tc of order 100 K, exhibits an unusual d-wave superconducting gap, with Fermi liquid nodal excitations, and an anomalous doping- dependent oxygen isotope shift. A ``pseudogap,'' also with d-symmetry, leads to a dip in the density of states below a characteristic temperature scale T^*, which has a negative isotope shift; we associate the pseudogap with the recently observed spatially inhomogeneous (nanometer- scale) C4 symmetry breaking. The isotope shifts and other evidence imply a key role for oxygen vibrations, but conventional BCS single-phonon coupling is essentially forbidden by symmetry and by the on-site Coulomb interaction U. In a novel approach, we introduce a model based on a strong, local, nonlinear interaction between electrons within the Cu-O-Cu bond in the CuO2 plane, and the oxygen vibrational degrees of freedom, termed the Fluctuating Bond Model (FBM) [D.M. Newns and C.C. Tsuei, Nature Physics 3, 184 (2007)]. In mean field the model predicts a phase manifesting broken C4 symmetry, with a d-type pseudogap, and an upper phase boundary in temperature, with a negative isotope shift, which we identify with T^*. An intrinsic d-wave pairing tendency is found, leading to a transition temperature dome and an anomalous isotope shift similar to that found experimentally. The softening in the oxygen vibrational frequency below Tc, seen in Raman and neutron spectra, has a natural explanation in the FBM. Recent ab initio calculations have been implemented which provide microscopic support for the model.

Isotonic similarities in isotope shifts from Hg to Ra.

NASA Astrophysics Data System (ADS)

Stroke, H. H.

2003-04-01

Isotope shifts (IS) in atomic spectra of heavy elements reflect largely the variation in of the nuclear charge distribution. Our early systematic measurements of IS for an extended range of stable and radioactive isotopes and nuclear isomers in Tl and Hg^1 showed that by displaying the relative IS, normalized to a chosen pair of isotopes, there was a striking similarity for the IS of isotones. This essentially divides out the electronic factor in the IS and allows the comparison of Δ for neighboring Z as N is varied. Following our further studies on Pb and Bi^2 and those on Fr at ISOLDE by the Orsay spectroscopy group^3, we found that the isotonic similarity extended to these elements. Since then, many additional measurements were made, principally at ISOLDE^4, extending to Ra the elements studied. The isotonic shift similarities persist from Z=80 to 88. We noted that the relative isotope and isomer shifts can be used to investigate the polarization of the nucleus by the added neutrons, a model used in a calculation by Barrett.^5 . The new data may serve further in this direction. ^1W,J.Tomlinson, H.H. Stroke, Nucl.Phys. 60, 614 (1964). ^2M. Barboza-Flores et al., Z.Phys. A 321, 85 (1985), ^3S. Liberman et al., Phys .Rev. A 22, 2732 (1980). ^4E,g. M.R. Pearson et al., J.Phys. G 26, 1829 (2000). ^5R.C. Barrett, Nucl. Phys. 88, 128 (1966).

Isotopic Evidence for Multi-stage Cosmic-ray Exposure Histories of Lunar Meteorites: Long Residence on the Moon and Short Transition to the Earth

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

Hidaka, Hiroshi; Sakuma, Keisuke; Nishiizumi, Kunihiko

It is known that most lunar meteorites have complicated cosmic-ray exposure experiences on the Moon and in space. In this study, cosmic-ray irradiation histories of six lunar meteorites, Dhofar 489, Northwest Africa 032 (NWA 032), NWA 479, NWA 482, NWA 2995, and NWA 5000, were characterized from neutron-captured isotopic shifts of Sm and Gd, and from the abundances of long-lived cosmogenic radionuclides like {sup 10}Be, {sup 26}Al, {sup 36}Cl, and {sup 41}Ca. Sm and Gd isotopic data of all of six meteorites show significant isotopic shifts of {sup 149}Sm–{sup 150}Sm and {sup 157}Gd–{sup 158}Gd caused by accumulation of neutron capturemore » reactions due to cosmic-ray irradiation, corresponding to the neutron fluences of (1.3–9.6) × 10{sup 16} n cm{sup −2}. In particular, very large Sm and Gd isotopic shifts of NWA 482 are over those of a lunar regolith 70002, having the largest isotopic shifts among the Apollo regolith samples, corresponding to cosmic-ray exposure duration over 800 million years in the lunar surface (2 π irradiation). Meanwhile, the concentrations of cosmogenic radionuclides for individual six meteorites show the short irradiation time less than one million years as their bodies in space (4 π irradiation). Our data also support the results of previous studies, revealing that most of lunar meteorites have long exposure ages at shallow depths on the Moon and short transit times from the Moon to the Earth.« less

Development of multicomponent hybrid density functional theory with polarizable continuum model for the analysis of nuclear quantum effect and solvent effect on NMR chemical shift.

PubMed

Kanematsu, Yusuke; Tachikawa, Masanori

2014-04-28

We have developed the multicomponent hybrid density functional theory [MC_(HF+DFT)] method with polarizable continuum model (PCM) for the analysis of molecular properties including both nuclear quantum effect and solvent effect. The chemical shifts and H/D isotope shifts of the picolinic acid N-oxide (PANO) molecule in chloroform and acetonitrile solvents are applied by B3LYP electron exchange-correlation functional for our MC_(HF+DFT) method with PCM (MC_B3LYP/PCM). Our MC_B3LYP/PCM results for PANO are in reasonable agreement with the corresponding experimental chemical shifts and isotope shifts. We further investigated the applicability of our method for acetylacetone in several solvents.

Application of carbon isotope stratigraphy to late miocene shallow marine sediments, new zealand.

PubMed

Loutit, T S; Kennett, J P

1979-06-15

A distinct (0.5 per mil) carbon-13/carbon-12 isotopic shift in the light direction has been identified in a shallow marine sedimentary sequence of Late Miocene age at Blind River, New Zealand, and correlated with a similar shift in Late Miocene Deep Sea Drilling Project sequences throughout the Indo-Pacific. A dated piston core provides an age for the shift of 6.2 +/- 0.1 million years. Correlations based on the carbon isotopic change require a revision of the previously established magnetostratigraphy at Blind River. The carbon shift at Blind River occurs between 6.2 and 6.3 +/- 0.1 million years before present. A new chronology provides an age for the evolutionary first appearance datum of Globorotalia conomiozea at 6.1 +/- 0.1 million years, the beginning of a distinct latest Miocene cooling event associated with the Kapitean stage at 6.2 +/- 0.1 million years, and the beginning of a distinct shallowing of water depths at 6.1 +/- 0.1 million years. The Miocene-Pliocene boundary as recognized in New Zealand is now dated at 5.3 +/- 0.1 million years. Extension of carbon isotope stratigraphy to other shallow Late Miocene sequences should provide an important datum for international correlation of Late Miocene shallow and deep marine sequences.

Measurement of isotope ratio of Ca{sup +} ions in a linear Paul Trap

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

Hashimoto, Y.; Minamino, K.; Nagamoto, D.

2009-03-17

Measurement of isotope ratios of Calcium is very useful in many fields. So we demonstrated the measurement of isotope ratios of {sup 40}Ca{sup +}(abundance 96.4%) to {sup 44}Ca{sup +}(2.09%) ions in a linear Paul trap with several laser lights tuning to the isotope shifts. And we found that the experimental parameters had large influences on the measurement of the isotope ratios.

Measurement of the isotope shift of the 63 P 1 ↔53 D 1 transition of ytterbium by using a diode oscillator fiber amplified laser

NASA Astrophysics Data System (ADS)

Lee, L.; Park, H.; Ko, K.-H.; Jeong, D.-Y.

2010-08-01

We demonstrated a Diode Oscillator Fiber Amplification (DOFA) system in order to study the 63 P 1 ↔53 D 1 (1539 nm) transition line of a neutral ytterbium atom that is accessed by the stepwise excitation of the ground state. The frequency of the DOFA system was doubled by a MgO:PPLN crystal for the resonant excitation of the 61 S 0 ↔63 P 1 transition. The frequency of the second harmonic beam was stabilized to the 61 S 0 ↔63 P 1 transition of each isotope with the stability of about 2 MHz. We performed absorption spectroscopy on the 63 P 1 ↔53 D 1 (1539 nm) transition after the velocity selective excitation by the frequency-doubled beam. The isotope shifts in the 63 P 1 ↔53 D 1 (1539 nm) transition were directly measured for the first time. The relative isotope shifts from 174Yb were measured as -105.8 MHz and 109.7 MHz for 176Yb and 172Yb, respectively.

Tracking the rise of eukaryotes to ecological dominance with zinc isotopes.

PubMed

Isson, Terry T; Love, Gordon D; Dupont, Christopher L; Reinhard, Christopher T; Zumberge, Alex J; Asael, Dan; Gueguen, Bleuenn; McCrow, John; Gill, Ben C; Owens, Jeremy; Rainbird, Robert H; Rooney, Alan D; Zhao, Ming-Yu; Stueeken, Eva E; Konhauser, Kurt O; John, Seth G; Lyons, Timothy W; Planavsky, Noah J

2018-06-05

The biogeochemical cycling of zinc (Zn) is intimately coupled with organic carbon in the ocean. Based on an extensive new sedimentary Zn isotope record across Earth's history, we provide evidence for a fundamental shift in the marine Zn cycle ~800 million years ago. We discuss a wide range of potential drivers for this transition and propose that, within available constraints, a restructuring of marine ecosystems is the most parsimonious explanation for this shift. Using a global isotope mass balance approach, we show that a change in the organic Zn/C ratio is required to account for observed Zn isotope trends through time. Given the higher affinity of eukaryotes for Zn relative to prokaryotes, we suggest that a shift toward a more eukaryote-rich ecosystem could have provided a means of more efficiently sequestering organic-derived Zn. Despite the much earlier appearance of eukaryotes in the microfossil record (~1700 to 1600 million years ago), our data suggest a delayed rise to ecological prominence during the Neoproterozoic, consistent with the currently accepted organic biomarker records. © 2018 John Wiley & Sons Ltd.

Isotope effect on electron-phonon interaction in the multiband superconductor MgB 2

DOE PAGES

Mou, Daixiang; Manni, Soham; Taufour, Valentin; ...

2016-04-07

We investigate the effect of isotope substitution on the electron-phonon interaction in the multiband superconductor MgB 2 using tunable laser-based angle-resolved photoemission spectroscopy. The kink structure around 70 meV in the σ band, which is caused by electron coupling to the E 2g phonon mode, is shifted to higher binding energy by ~3.5 meV in Mg 10B 2 and the shift is not affected by superconducting transition. Furthermore, these results serve as the benchmark for investigations of isotope effects in known, unconventional superconductors and newly discovered superconductors where the origin of pairing is unknown.

Reinterpreting the Early Cretaceous Sulfur Isotope Records: Implications for the Evolution of Seawater Chemistry

NASA Astrophysics Data System (ADS)

Mills, J. V.; Gomes, M. L.; Sageman, B. B.; Jacobson, A. D.; Hurtgen, M. T.

2013-12-01

The geologic record of the Cretaceous is punctuated by several periods of high organic carbon burial interpreted to represent global Ocean Anoxic Events (OAEs). In addition to the short-term (<1-Myr) changes in carbon (C) cycling associated with OAEs, evidence from a number of geochemical proxies has been interpreted to represent large-scale changes in ocean chemistry during the period. Specifically, the sulfur (S) isotope composition of early Cretaceous seawater sulfate as recorded in marine barite exhibits an ~5 permil shift in d34Ssulfate that persists for ~15Myr before returning to pre-excursion values. Superimposed upon this long-term shift in S-isotopes is OAE1a, the second major anoxic event recognized in the Cretaceous. Two hypotheses have been proposed to explain this S isotope perturbation: (1) massive evaporite deposition associated with rifting during the opening of the South Atlantic and a corresponding decrease in pyrite burial rates and (2) increased inputs of volcanic-derived S due to extensive LIP-volcanism. While there is geologic evidence for both evaporite deposition and enhanced hydrothermal activity, the relative influence of these potential driving factors remains largely unconstrained. Variation in the strontium (Sr) isotope composition of marine carbonates provides a tool for distinguishing between these influences. We examine the S isotope composition of carbonate-associated sulfate (CAS) spanning the Barremian through Aptian from Resolution Guyot (ODP Site 866) and compare the S isotope record to time equivalent records of carbon and strontium isotopes. Correlative changes in the C, S, and Sr cycles are observed: an ~5 permil shift in d34Ssulfate, which begins at the onset of OAE1a and continues after the positive d13Ccarb excursion, is accompanied by a contemporaneous, parallel shift in 87Sr/86Sr to unradiogenic values. The tight coupling observed between S and Sr throughout the interval is highly suggestive of a common driving mechanism and suggests that changes in the S-cycle were dominantly driven by increases in volcanism and hydrothermal activity. Constraints on S-cycle fluxes and implications for seawater chemistry will be discussed in the context of coupled S-Sr geochemical models.

Nonlinear detection of secondary isotopic chemical shifts in NMR through spin noise

PubMed Central

Pöschko, Maria Theresia; Rodin, Victor V.; Schlagnitweit, Judith; Müller, Norbert; Desvaux, Hervé

2017-01-01

The detection of minor species in the presence of large amounts of similar main components remains a key challenge in analytical chemistry, for instance, to obtain isotopic fingerprints. As an alternative to the classical NMR scheme based on coherent excitation and detection, here we introduce an approach based on spin-noise detection. Chemical shifts and transverse relaxation rates are determined using only the detection circuit. Thanks to a nonlinear effect in mixtures with small chemical shift dispersion, small signals on top of a larger one can be observed with increased sensitivity as bumps on a dip; the latter being the signature of the main magnetization. Experimental observations are underpinned by an analytical theory: the coupling between the magnetization and the coil provides an amplified detection capability of both small static magnetic field inhomogeneities and small NMR signals. This is illustrated by two-bond 12C/13C isotopic measurements. PMID:28067218

Estimating the Triple-Point Isotope Effect and the Corresponding Uncertainties for Cryogenic Fixed Points

NASA Astrophysics Data System (ADS)

Tew, W. L.

2008-02-01

The sensitivities of melting temperatures to isotopic variations in monatomic and diatomic atmospheric gases using both theoretical and semi-empirical methods are estimated. The current state of knowledge of the vapor-pressure isotope effects (VPIE) and triple-point isotope effects (TPIE) is briefly summarized for the noble gases (except He), and for selected diatomic molecules including oxygen. An approximate expression is derived to estimate the relative shift in the melting temperature with isotopic substitution. In general, the magnitude of the effects diminishes with increasing molecular mass and increasing temperature. Knowledge of the VPIE, molar volumes, and heat of fusion are sufficient to estimate the temperature shift or isotopic sensitivity coefficient via the derived expression. The usefulness of this approach is demonstrated in the estimation of isotopic sensitivities and uncertainties for triple points of xenon and molecular oxygen for which few documented estimates were previously available. The calculated sensitivities from this study are considerably higher than previous estimates for Xe, and lower than other estimates in the case of oxygen. In both these cases, the predicted sensitivities are small and the resulting variations in triple point temperatures due to mass fractionation effects are less than 20 μK.

First Principle Predictions of Isotopic Shifts in H2O

NASA Technical Reports Server (NTRS)

Schwenke, David W.; Kwak, Dochan (Technical Monitor)

2002-01-01

We compute isotope independent first and second order corrections to the Born-Oppenheimer approximation for water and use them to predict isotopic shifts. For the diagonal correction, we use icMRCI wavefunctions and derivatives with respect to mass dependent, internal coordinates to generate the mass independent correction functions. For the non-adiabatic correction, we use scaled SCF/CIS wave functions and a generalization of the Handy method to obtain mass independent correction functions. We find that including the non-adiabatic correction gives significantly improved results compared to just including the diagonal correction when the Born-Oppenheimer potential energy surface is optimized for H2O-16. The agreement with experimental results for deuterium and tritium containing isotopes is nearly as good as our best empirical correction, however, the present correction is expected to be more reliable for higher, uncharacterized levels.

What Drives Hydrogen Isotopic Variability Recorded by Biomarkers in Sediments of Lake Karakul, Pamir?

NASA Astrophysics Data System (ADS)

Aichner, B.; Mischke, S.; Pausata, F. S. R.; Werner, M.; Zhang, Q.; Heinecke, L.; Feakins, S. J.; Sachse, D.; Mahmoudov, Z.; Rajabov, I.

2017-12-01

Central Asia is a climate sensitive region located at the boundary of large scale atmospheric circulation systems. To examine glacial to interglacial hydrological changes in the region, we analysed the hydrogen isotopic composition (δD values) of n-alkanes in a 30-ka record from Lake Karakul, eastern Pamir (altitude: 3,915m, MAT: -3.9 °C, MAP: 82 mm). δD values of both aquatic and terrestrial compounds showed distinct trends throughout the studied time interval, with generally higher values during the glacial and lower values during the Holocene, and variability of up to 60‰. In particular shifts towards higher δD values were observed for aquatic biomarkers at ca. 30, 27, and 15 ka BP. Temperature and precipitation effects alone cannot explain the higher δD values during the glacial and the large isotopic amplitudes. To explain these observations we conducted a set of experiments using atmospheric models with embedded isotope modules (CAM3iso- and ECHAM5-wiso). We assume that terrestrial n-alkanes mainly record the isotopic signature of summer precipitation within the lower elevated parts of the Karakul Basin. Based on the model output we hypothesize that shifts between local and more distant vapour sources are the reason behind the trends within isotopic data. Data derived from aquatic biomarkers are more difficult to explain due to multiple influencing factors on δD of the lake water. Assuming that the lake water integrates an annual isotopic signal from the whole lake catchment, we suggest that a change in precipitation seasonality drives the large variability of hydrogen isotopic values. This is in agreement with the models, which suggest reduced winter (more negative δD) and slightly higher summer precipitation (more positive δD) during the glacial compared to the Holocene. Consequently, a net-increase of isotopically enriched inflow into the lake could explain the three distinct shifts towards higher δD values. Expansion of terrestrial vegetation, indicated by increasing biomarker concentrations, during these periods is another indicator for wetter summers in an arid environment. We conclude that δD values of terrestrial compounds reflect major shifts of vapour sources which are driven by insolation, while aquatic biomarkers are additionally influenced by changes of precipitation seasonality.

Iron isotopic fractionation between silicate mantle and metallic core at high pressure

PubMed Central

Liu, Jin; Dauphas, Nicolas; Roskosz, Mathieu; Hu, Michael Y.; Yang, Hong; Bi, Wenli; Zhao, Jiyong; Alp, Esen E.; Hu, Justin Y.; Lin, Jung-Fu

2017-01-01

The +0.1‰ elevated 56Fe/54Fe ratio of terrestrial basalts relative to chondrites was proposed to be a fingerprint of core-mantle segregation. However, the extent of iron isotopic fractionation between molten metal and silicate under high pressure–temperature conditions is poorly known. Here we show that iron forms chemical bonds of similar strengths in basaltic glasses and iron-rich alloys, even at high pressure. From the measured mean force constants of iron bonds, we calculate an equilibrium iron isotope fractionation between silicate and iron under core formation conditions in Earth of ∼0–0.02‰, which is small relative to the +0.1‰ shift of terrestrial basalts. This result is unaffected by small amounts of nickel and candidate core-forming light elements, as the isotopic shifts associated with such alloying are small. This study suggests that the variability in iron isotopic composition in planetary objects cannot be due to core formation. PMID:28216664

Carbon isotopic evidence for photosynthesis in Early Cambrian oceans

NASA Astrophysics Data System (ADS)

Surge, Donna M.; Savarese, Michael; Dodd, J. Robert; Lohmann, Kyger C.

1997-06-01

Were the first metazoan reefs ecologically similar to modern tropical reefs, enabling them to persist under oligotrophic conditions? We tested the hypothesis of ecological similarity by employing a geochemical approach. Petrography, cathodoluminescence, trace elements, and stable isotope analyses of primary precipitates of the Lower Cambrian Ajax Limestone, South Australia, indicate preservation of original C isotopic composition. All primary carbonate components exhibit C isotopic values similar to the composition of inorganically precipitated fibrous marine cements, suggesting that archaeocyaths and the calcimicrobe Epiphyton precipitated skeletal carbonate in equilibrium with ambient seawater in the absence of vital effects. Such data do not support the contention that archaeocyaths possessed photosymbionts. However, a +0.55‰ shift in δ13C occurs in reefs developed under shallower-water conditions relative to deeper reefs. This shift suggests the stratification of primary production in Early Cambrian oceans. The pattern is similar to that seen in the modern ocean, whereby significant photosynthesis modulates the C isotopic composition of the photic zone.

Mathematical, theoretical and experimental confirmations of IRS and IBS by R.M. Santilli

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

Kohale, Ritesh L.

The objective of present work is to put forward the Santilli’s experimental, physical and mathematical conception of IsoRedShift (IRS), IsoBlueShift (IBS) and NoIsoShift (NIS). Santilli has carried out a step-by step isotopic lifting of the physical laws of special relativity resulting in a new theory today specifically known Santilli isorelativity. In his 1991 hypothesis Santilli established the requirement to realize the light as electromagnetic waves propagating within a universal substratum. Furthermore Santilli has carried out a step-by step isotopic lifting of the physical laws of special relativity resulting in a new theory today specifically known Santilli isorelativity.

Molecular carbon isotope variations in core samples taken at the Permian-Triassic boundary layers in southern China

NASA Astrophysics Data System (ADS)

Wang, Ruiliang; Zhang, Shuichang; Brassell, Simon; Wang, Jiaxue; Lu, Zhengyuan; Ming, Qingzhong; Wang, Xiaomei; Bian, Lizeng

2012-07-01

Stable carbon isotope composition (δ13C) of carbonate sediments and the molecular (biomarker) characteristics of a continuous Permian-Triassic (PT) layer in southern China were studied to obtain geochemical signals of global change at the Permian-Triassic boundary (PTB). Carbonate carbon isotope values shifted toward positive before the end of the Permian period and then shifted negative above the PTB into the Triassic period. Molecular carbon isotope values of biomarkers followed the same trend at and below the PTB and remained negative in the Triassic layer. These biomarkers were acyclic isoprenoids, ranging from C15 to C40, steranes (C27 dominates) and terpenoids that were all significantly more abundant in samples from the Permian layer than those from the Triassic layer. The Triassic layer was distinguished by the dominance of higher molecular weight (waxy) n-alkanes. Stable carbon isotope values of individual components, including n-alkanes and acyclic isoprenoids such as phytane, isop-C25, and squalane, are depleted in δ13C by up to 8-10‰ in the Triassic samples as compared to the Permian. Measured molecular and isotopic variations of organic matter in the PT layers support the generally accepted view of Permian oceanic stagnation followed by a massive upwelling of toxic deep waters at the PTB. A series of large-scale (global) outgassing events may be associated with the carbon isotope shift we measured. This is also consistent with the lithological evidence we observed of white thin-clay layers in this region. Our findings, in context with a generally accepted stagnant Permian ocean, followed by massive upwelling of toxic deep waters might be the major causes of the largest global mass extinction event that occurred at the Permian-Triassic boundary.

Charge radii and electromagnetic moments of At-211195

NASA Astrophysics Data System (ADS)

Cubiss, J. G.; Barzakh, A. E.; Seliverstov, M. D.; Andreyev, A. N.; Andel, B.; Antalic, S.; Ascher, P.; Atanasov, D.; Beck, D.; Bieroń, J.; Blaum, K.; Borgmann, Ch.; Breitenfeldt, M.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Derkx, X.; De Witte, H.; Elseviers, J.; Fedorov, D. V.; Fedosseev, V. N.; Fritzsche, S.; Gaffney, L. P.; George, S.; Ghys, L.; Heßberger, F. P.; Huyse, M.; Imai, N.; Kalaninová, Z.; Kisler, D.; Köster, U.; Kowalska, M.; Kreim, S.; Lane, J. F. W.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Marsh, B. A.; Mitsuoka, S.; Molkanov, P. L.; Nagame, Y.; Neidherr, D.; Nishio, K.; Ota, S.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Revill, J. P.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Sandhu, K.; Schweikhard, L.; Sels, S.; Truesdale, V. L.; Van Beveren, C.; Van den Bergh, P.; Wakabayashi, Y.; Van Duppen, P.; Wendt, K. D. A.; Wienholtz, F.; Whitmore, B. W.; Wilson, G. L.; Wolf, R. N.; Zuber, K.

2018-05-01

Hyperfine-structure parameters and isotope shifts of At-211195 have been measured for the first time at CERN-ISOLDE, using the in-source resonance-ionization spectroscopy method. The hyperfine structures of isotopes were recorded using a triad of experimental techniques for monitoring the photo-ion current. The Multi-Reflection Time-of-Flight Mass Spectrometer, in connection with a high-resolution electron multiplier, was used as an ion-counting setup for isotopes that either were affected by strong isobaric contamination or possessed a long half-life; the ISOLDE Faraday cups were used for cases with high-intensity beams; and the Windmill decay station was used for short-lived, predominantly α -decaying nuclei. The electromagnetic moments and changes in the mean-square charge radii of the astatine nuclei have been extracted from the measured hyperfine-structure constants and isotope shifts. This was only made possible by dedicated state-of-the-art large-scale atomic computations of the electronic factors and the specific mass shift of atomic transitions in astatine that are needed for these extractions. By comparison with systematics, it was possible to assess the reliability of the results of these calculations and their ascribed uncertainties. A strong deviation in the ground-state mean-square charge radii of the lightest astatine isotopes, from the trend of the (spherical) lead isotopes, is interpreted as the result of an onset of deformation. This behavior bears a resemblance to the deviation observed in the isotonic polonium isotopes. Cases for shape coexistence have been identified in At,199197, for which a significant difference in the charge radii for ground (9 /2- ) and isomeric (1 /2+ ) states has been observed.

Stable isotope analysis of vertebrae reveals ontogenetic changes in habitat in an endothermic pelagic shark

PubMed Central

Carlisle, Aaron B.; Goldman, Kenneth J.; Litvin, Steven Y.; Madigan, Daniel J.; Bigman, Jennifer S.; Swithenbank, Alan M.; Kline, Thomas C.; Block, Barbara A.

2015-01-01

Ontogenetic changes in habitat are driven by shifting life-history requirements and play an important role in population dynamics. However, large portions of the life history of many pelagic species are still poorly understood or unknown. We used a novel combination of stable isotope analysis of vertebral annuli, Bayesian mixing models, isoscapes and electronic tag data to reconstruct ontogenetic patterns of habitat and resource use in a pelagic apex predator, the salmon shark (Lamna ditropis). Results identified the North Pacific Transition Zone as the major nursery area for salmon sharks and revealed an ontogenetic shift around the age of maturity from oceanic to increased use of neritic habitats. The nursery habitat may reflect trade-offs between prey availability, predation pressure and thermal constraints on juvenile endothermic sharks. The ontogenetic shift in habitat coincided with a reduction of isotopic niche, possibly reflecting specialization upon particular prey or habitats. Using tagging data to inform Bayesian isotopic mixing models revealed that adult sharks primarily use neritic habitats of Alaska yet receive a trophic subsidy from oceanic habitats. Integrating the multiple methods used here provides a powerful approach to retrospectively study the ecology and life history of migratory species throughout their ontogeny. PMID:25621332

Probing atomic Higgs-like forces at the precision frontier

NASA Astrophysics Data System (ADS)

Delaunay, Cédric; Ozeri, Roee; Perez, Gilad; Soreq, Yotam

2017-11-01

We propose a novel approach to probe new fundamental interactions using isotope shift spectroscopy in atomic clock transitions. As a concrete toy example we focus on the Higgs boson couplings to the building blocks of matter: the electron and the up and down quarks. We show that the attractive Higgs force between nuclei and their bound electrons, which is poorly constrained, might induce effects that are larger than the current experimental sensitivities. More generically, we discuss how new interactions between the electron and the neutrons, mediated via light new degrees of freedom, may lead to measurable nonlinearities in a King plot comparison between isotope shifts of two different transitions. Given state-of-the-art accuracy in frequency comparison, isotope shifts have the potential to be measured with sub-Hz accuracy, thus potentially enabling the improvement of current limits on new fundamental interactions. A candidate atomic system for this measurement requires two different clock transitions and four zero nuclear spin isotopes. We identify several systems that satisfy this requirement and also briefly discuss existing measurements. We consider the size of the effect related to the Higgs force and the requirements for it to produce an observable signal.

Light-Shifts of an Integrated Filter-Cell Rubidium Atomic Clock

DTIC Science & Technology

2015-05-25

the light-shift coefficient for two different rf- discharge lamps (i.e., a pure 87Rb lamp and a lamp filled with the natural Rb isotope abundance...for the Galileo Rb clock under the assumption of a natural (or 85Rb isotopically enriched) rf- discharge lamp for the Galileo clock. I...satellites [14]. 6.8347… GHz 85Rb Filter Cell Cell Resonance Photodiode Microwave Cavity 87Rb Discharge Lamp 87Rb & N2 Rb & Xe, Kr Optical Pumping 87Rb

Fossil mice and rats show isotopic evidence of niche partitioning and change in dental ecomorphology related to dietary shift in Late Miocene of Pakistan.

PubMed

Kimura, Yuri; Jacobs, Louis L; Cerling, Thure E; Uno, Kevin T; Ferguson, Kurt M; Flynn, Lawrence J; Patnaik, Rajeev

2013-01-01

Stable carbon isotope analysis in tooth enamel is a well-established approach to infer C3 and C4 dietary composition in fossil mammals. The bulk of past work has been conducted on large herbivorous mammals. One important finding is that their dietary habits of fossil large mammals track the late Miocene ecological shift from C3 forest and woodland to C4 savannah. However, few studies on carbon isotopes of fossil small mammals exist due to limitations imposed by the size of rodent teeth, and the isotopic ecological and dietary behaviors of small mammals to climate change remain unknown. Here we evaluate the impact of ecological change on small mammals by fine-scale comparisons of carbon isotope ratios (δ(13)C) with dental morphology of murine rodents, spanning 13.8 to ∼2.0 Ma, across the C3 to C4 vegetation shift in the Miocene Siwalik sequence of Pakistan. We applied in-situ laser ablation GC-IRMS to lower first molars and measured two grazing indices on upper first molars. Murine rodents yield a distinct, but related, record of past ecological conditions from large herbivorous mammals, reflecting available foods in their much smaller home ranges. In general, larger murine species show more positive δ(13)C values and have higher grazing indices than smaller species inhabiting the same area at any given age. Two clades of murine rodents experienced different rates of morphological change. In the faster-evolving clade, the timing and trend of morphological innovations are closely tied to consumption of C4 diet during the vegetation shift. This study provides quantitative evidence of linkages among diet, niche partitioning, and dental morphology at a more detailed level than previously possible.

Fossil Mice and Rats Show Isotopic Evidence of Niche Partitioning and Change in Dental Ecomorphology Related to Dietary Shift in Late Miocene of Pakistan

PubMed Central

Kimura, Yuri; Jacobs, Louis L.; Cerling, Thure E.; Uno, Kevin T.; Ferguson, Kurt M.; Flynn, Lawrence J.; Patnaik, Rajeev

2013-01-01

Stable carbon isotope analysis in tooth enamel is a well-established approach to infer C3 and C4 dietary composition in fossil mammals. The bulk of past work has been conducted on large herbivorous mammals. One important finding is that their dietary habits of fossil large mammals track the late Miocene ecological shift from C3 forest and woodland to C4 savannah. However, few studies on carbon isotopes of fossil small mammals exist due to limitations imposed by the size of rodent teeth, and the isotopic ecological and dietary behaviors of small mammals to climate change remain unknown. Here we evaluate the impact of ecological change on small mammals by fine-scale comparisons of carbon isotope ratios (δ13C) with dental morphology of murine rodents, spanning 13.8 to ∼2.0 Ma, across the C3 to C4 vegetation shift in the Miocene Siwalik sequence of Pakistan. We applied in-situ laser ablation GC-IRMS to lower first molars and measured two grazing indices on upper first molars. Murine rodents yield a distinct, but related, record of past ecological conditions from large herbivorous mammals, reflecting available foods in their much smaller home ranges. In general, larger murine species show more positive δ13C values and have higher grazing indices than smaller species inhabiting the same area at any given age. Two clades of murine rodents experienced different rates of morphological change. In the faster-evolving clade, the timing and trend of morphological innovations are closely tied to consumption of C4 diet during the vegetation shift. This study provides quantitative evidence of linkages among diet, niche partitioning, and dental morphology at a more detailed level than previously possible. PMID:23936324

A calcium isotope test of end-Permian ocean acidification using biogenic apatite

NASA Astrophysics Data System (ADS)

Hinojosa, J.; Brown, S. T.; DePaolo, D. J.; Paytan, A.; Shen, S.; Chen, J.; Payne, J.

2011-12-01

Submarine erosional truncation of uppermost Permian carbonate strata has been interpreted to reflect ocean acidification coincident with the end-Permian mass extinction. Although this scenario is consistent with carbon isotope and paleontological data, several alternative scenarios, such as ocean overturn or collapse of the biological pump, can also account for the carbon isotope and paleontological evidence. Calcium isotopes provide a geochemical proxy to test between acidification and alternative scenarios. Specifically, a negative shift in the calcium isotope composition (δ44/40Ca) of seawater is predicted under the acidification scenario but not the alternatives. The δ44/40Ca of carbonate rocks from south China exhibits a negative excursion of approximately 0.3%, but this shift could result from either a change in the δ44/40Ca of seawater or a change in carbonate mineralogy because calcite and aragonite exhibit substantially different fractionation factors relative to seawater. To test whether the negative shift in δ44/40Ca reflects seawater δ44/40Ca or carbonate mineralogy, we measured the δ44/40Ca of conodont microfossils (calcium hydroxyapatite) from the global stratotype section for the Permian-Triassic boundary at Meishan, China. The conodont δ44/40Ca record shows a negative excursion similar in stratigraphic position and magnitude to that previously observed in carbonate rocks. Parallel negative excursions in the δ44/40Ca of carbonate rocks and conodont microfossils cannot be accounted for by a change in carbonate mineralogy but are consistent with a negative shift in the δ44/40Ca of seawater. These data add further support for the ocean acidification scenario, pointing toward strong similarities between the greatest catastrophe in the history of animal life and anticipated global change during the 21st century.

Stable Isotopic Shifts in Fish Bones from Multiple Archeological Coastal Middens in Penobscot Bay, Maine

NASA Astrophysics Data System (ADS)

Harris, C.; Johnson, B.; Ambrose, W. G.; Bourque, B.; Dostie, P.; Crowley, E.

2010-12-01

The carbon and nitrogen stable isotope compositions of collagen extracted from well-preserved archeological fish bones has the potential to provide useful information on fish diets and food web dynamics over time. Previous work on the Turner Farm archaeological site in Penobscot Bay, Gulf of Maine, reveals significant shifts in fish diets have occurred since European colonization (post 1620’s). The objective of the present study was to analyze samples from other archaeological sites within Penobscot Bay to characterize the spatial extent of the isotopic shift measured at Turner Farm. Stratified cod, flounder, and sculpin bones were analyzed from eight coastal middens located approximately 50km apart from one another within Penobscot Bay. The bones were sampled from three time horizons (0kya, 0.5-1kya, and 2.2-2.4kya). All bone samples were demineralized in 0.2M HCl at 4°C for 2 to 7 days and then extracted in 0.25M NaOH at 4°C for 1 to 2 hours. After freeze-drying, the bulk isotopic composition of each sample was analyzed using the EA-IRMS. In all stratigraphic horizons analyzed, cod were more enriched in δ13C and δ15N than sculpin, and flounder were the most depleted in δ13C and δ15N . However, the isotopic offsets between the fish species decreased from 2.4kya to the present. The nitrogen isotope composition was relatively constant over time and space for all species, implying that trophic levels for the fishes analyzed have not changed significantly in Penobscot Bay for the last 2,400 years. The carbon isotope composition also appears to be constant spatially in Penobscot Bay, however, the modern signal was more depleted than the paleo signal in all three species. The difference between the modern and paleo δ13C is ~5‰ for cod and flounder, and ~9‰ for sculpin. These shifts may, in part, be explained by decreases in both primary producer and prey species diversity, as kelp forests replace eelgrass beds in the Gulf of Maine.

Macrophysical climate models and Holocene hunter-gatherer subsistence shifts in Central Texas, USA

NASA Astrophysics Data System (ADS)

Mauldin, R. P.; Munoz, C.

2013-12-01

We use stable carbon isotopic values from bone collagen, as well as carbon values from carbonate extracted from bone apatite from 69 prehistoric human skeletal samples to investigate past resource use and climate relationships over the Middle and Late Holocene in Central Texas. Bone samples come from seven archaeological sites and samples date from 6,900 BP to the close of the prehistoric sequence at about 350 BP. Carbon isotopes from these samples suggest four broad dietary trends. From 6,900 through about 3,800 BP, carbon isotopes suggest a gradual increase in the consumption of resources that ultimately use a C3 photosynthetic pathway. A decline in δ13C in both collagen and carbonate values follows, suggesting a decrease in C3 resource use through roughly 2,900 BP. A variable, but once again increasing pattern on C3 resource use by prehistoric hunter-gatherers is indicated in bone isotopes through about 1,000 BP. After that date, a decrease in C3 resource dependence, with hints at greater subsistence diversity, is suggested through the close of the sequence at 350 BP. To assess the impact of climate shifts on this isotopic pattern, we developed a series of macrophysical climate models (MCM) for several locations in Central Texas focusing on fall, winter, and early spring precipitation. This fall-spring rainfall should closely determine C3 production. If subsistence shifts are responding to climate-induced changes in resource availability, then the measured hunter-gatherer carbon isotope trends summarized above should pattern with C3 production as monitored by the modeled fall-spring precipitation values. For the Middle Holocene portion of the sequence, the precipitation models suggest increasing C3 production, consistent with increasing C3 dependence shown in the isotopic data. A decline in C3 production between 3,900 and 3,000 BP in the models is also consistent with the isotopic decline at that point. After 3,000 BP, however, the coupling between fall-spring rainfall pattern and the bone isotope patterns begin to break down. Precipitation models suggest an essentially flat or slightly increasing pattern of production, while the isotopic data show a rapid C3 increase, and then a decline. This divergence is especially the case late in the sequence, with isotopic patterns showing rapid decreases in C3 resource use that are not consistent with the macrophysical climate models. If the precipitation models are accurate, the Late Holocene pattern of resource use reflects additional elements (e.g., regional population density changes, mobility shifts, social alliances) that require investigation. Standardized values. Data point colors reflect distinct climate trends.

Isotope shift, nonlinearity of King plots, and the search for new particles

NASA Astrophysics Data System (ADS)

Flambaum, V. V.; Geddes, A. J.; Viatkina, A. V.

2018-03-01

We derive a mean-field relativistic formula for the isotope shift of an electronic energy level for arbitrary angular momentum; we then use it to predict the spectra of superheavy metastable neutron-rich isotopes belonging to the hypothetical island of stability. Our results may be applied to the search for superheavy atoms in astrophysical spectra using the known values of the transition frequencies for the neutron-deficient isotopes produced in the laboratory. An example of a relevant astrophysical system may be the spectra of the Przybylski's star where superheavy elements up to Z =99 have been possibly identified. In addition, it has been recently suggested to use the measurements of King plot nonlinearity in a search for hypothetical new light bosons. On the other hand, one can find the nonlinear corrections to the King plot arising already in the standard model framework. We investigate contributions to the nonlinearity arising from relativistic effects in the isotope field shift, the nuclear polarizability, and many-body effects. It is found that the nuclear polarizability contribution can lead to the significant deviation of the King plot from linearity. Therefore, the measurements of the nonlinearity of King plots may be applied to obtain the nuclear polarizability change between individual isotopes. We then proceed with providing a rough analytical estimate of the nonlinearity arising solely from the effect of a hypothetical scalar boson. Our predictions give theoretical limitations on the sensitivity of the search for new interactions and should help to identify the most suitable atoms for corresponding experiments.

Transfer of marine mercury to mountain lakes.

PubMed

Hansson, Sophia V; Sonke, Jeroen; Galop, Didier; Bareille, Gilles; Jean, Séverine; Le Roux, Gaël

2017-10-05

Stocking is a worldwide activity on geographical and historical scales. The rate of non-native fish introductions have more than doubled over the last decades yet the effect on natural ecosystems, in the scope of biologically mediated transport and biomagnification of Hg and Hg-isotopes, is unknown. Using geochemistry (THg) and stable isotopes (N, Sr and Hg), we evaluate natal origin and trophic position of brown trout (Salmo trutta fario), as well as mercury biomagnification trends and potential pollution sources to three high-altitude lakes. Farmed trout show Hg-isotope signatures similar to marine biota whereas wild trout shows Hg-isotope signatures typical of fresh water lakes. Stocked trout initially show Hg-isotope signatures similar to marine biota. As the stocked trout age and shifts diet to a higher trophic level, THg concentrations increase and the marine Hg isotope signatures, induced via farm fish feed, shift to locally produced MeHg with lower δ 202 Hg and higher Δ 199 Hg. We conclude that stocking acts a humanly induced biovector that transfers marine Hg to freshwater ecosystems, which is seen in the Hg-isotopic signature up to five years after stocking events occurred. This points to the need of further investigations of the role of stocking in MeHg exposure to freshwater ecosystems.

Theoretical analysis of geometry and NMR isotope shift in hydrogen-bonding center of photoactive yellow protein by combination of multicomponent quantum mechanics and ONIOM scheme

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

Kanematsu, Yusuke; Tachikawa, Masanori

2014-11-14

Multicomponent quantum mechanical (MC-QM) calculation has been extended with ONIOM (our own N-layered integrated molecular orbital + molecular mechanics) scheme [ONIOM(MC-QM:MM)] to take account of both the nuclear quantum effect and the surrounding environment effect. The authors have demonstrated the first implementation and application of ONIOM(MC-QM:MM) method for the analysis of the geometry and the isotope shift in hydrogen-bonding center of photoactive yellow protein. ONIOM(MC-QM:MM) calculation for a model with deprotonated Arg52 reproduced the elongation of O–H bond of Glu46 observed by neutron diffraction crystallography. Among the unique isotope shifts in different conditions, the model with protonated Arg52 with solventmore » effect reasonably provided the best agreement with the corresponding experimental values from liquid NMR measurement. Our results implied the availability of ONIOM(MC-QM:MM) to distinguish the local environment around hydrogen bonds in a biomolecule.« less

Allocate carbon for a reason: priorities are reflected in the ¹³C/¹²C ratios of plant lipids synthesized via three independent biosynthetic pathways.

PubMed

Zhou, Youping; Stuart-Williams, Hilary; Grice, Kliti; Kayler, Zachary E; Zavadlav, Saša; Vogts, Angela; Rommerskirchen, Florian; Farquhar, Graham D; Gessler, Arthur

2015-03-01

It has long been theorized that carbon allocation, in addition to the carbon source and to kinetic isotopic effects associated with a particular lipid biosynthetic pathway, plays an important role in shaping the carbon isotopic composition ((13)C/(12)C) of lipids (Park and Epstein, 1961). If the latter two factors are properly constrained, valuable information about carbon allocation during lipid biosynthesis can be obtained from carbon isotope measurements. Published work of Chikaraishi et al. (2004) showed that leaf lipids isotopic shifts from bulk leaf tissue Δδ(13)C(bk-lp) (defined as δ(13)C(bulkleaftissue)-δ(13)C(lipid)) are pathway dependent: the acetogenic (ACT) pathway synthesizing fatty lipids has the largest isotopic shift, the mevalonic acid (MVA) pathway synthesizing sterols the lowest and the phytol synthesizing 1-deoxy-D-xylulose 5-phosphate (DXP) pathway gives intermediate values. The differences in Δδ(13)C(bk-lp) between C3 and C4 plants Δδ(13)C(bk-lp,C4-C3) are also pathway-dependent: Δδ(13)C(ACT)(bk-lp,C4-C3) > Δδ(13)C(DXP(bk-lp,C4-C3) > Δδ(13)C(MVA)(bk-lp,C4-C3). These pathway-dependent differences have been interpreted as resulting from kinetic isotopic effect differences of key but unspecified biochemical reactions involved in lipids biosynthesis between C3 and C4 plants. After quantitatively considering isotopic shifts caused by (dark) respiration, export-of-carbon (to sink tissues) and photorespiration, we propose that the pathway-specific differences Δδ(13)C(bk-lp,C4-C3) can be successfully explained by C4-C3 carbon allocation (flux) differences with greatest flux into the ACT pathway and lowest into the MVA pathways (when flux is higher, isotopic shift relative to source is smaller). Highest carbon allocation to the ACT pathway appears to be tied to the most stringent role of water-loss-minimization by leaf waxes (composed mainly of fatty lipids) while the lowest carbon allocation to the MVA pathway can be largely explained by the fact that sterols act as regulatory hormones and membrane fluidity modulators in rather low concentrations. Copyright © 2014 Elsevier Ltd. All rights reserved.

On the interrelationship between temporal trends in. delta. sup 13 C,. delta. sup 18 O, and. delta. sup 34 S in the world ocean

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

Hoffman, A.; Gruszczynski, M.; Malkowski, K.

1991-05-01

The phenomena of (i) inverse correlation between the oceanic carbon and sulfur isotopic curves, and (ii) covariation between the oceanic carbon and oxygen isotopic curves at all their major excursions appear as paradoxes in the current paradigm of global biogeochemical cycles. These phenomena, however, are fully explicable by a model proposing that the ocean alternates between two general modes: stagnant, stratified, and net autotrophic (overfed) ocean, on the one hand, and vigorously mixed and net heterotrophic (hungry) ocean, on the other. This model is in fact strongly supported by the carbon isotopic evidence. The directions of change in the isotopicmore » ratios of carbon, oxygen, and sulfur should be different in the lower, anoxic box of a stratified ocean than in the upper, oxic box; whereas ocean destratification and mixing of the two boxes should lead to coeval shifts in the oceanic isotopic curves of these elements. The model has far-reaching implications for (i) the causal explanation of both secular trends and major shifts in the oceanic isotopic curves, and (ii) for the application of oxygen isotopic data for paleotemperature and paleoenvironment determinations.« less

Examination of an Oligocene Lacustrine Ecosystem Using C and N Stable Isotopes

NASA Astrophysics Data System (ADS)

Schweizer, M. K.; Wooller, M. J.; Toporski, J.; Fogel, M.; Steele, A.

2003-12-01

Stable isotopes of C and N are used to reconstruct the fossil Oligocene (25.8Ma) ecosystem at Lake Enspel, Westerwald, Germany. Enspel was a steep-sided, deep maar lake with anoxic bottom waters. Upon dying, terrestrial and aquatic organisms sank into the sediment where they were colonized by bacteria. These bacteria quickly became fossilized, preserving morphological detail and large amounts of organic matter from the original macroorganism. Carbon and nitrogen are sufficiently preserved in these fossils to permit stable isotope analysis. Stable isotopic signatures identify several trophic levels, including primary producers (terrigenous and aquatic plants, diatoms), primary consumers (tadpoles, some insects), and secondary consumers (carnivores such as fish). Primary producers are associated with depleted d13C and d15N values, primary consumers such as flies are one trophic shift higher, and fish are another shift higher. Signatures for the fish species show heavy-isotope enrichment correlated with increasing length, indicating an increasingly carnivorous diet. This study marks the first attempt to reconstruct a complete fossil ecosystem using stable isotope analysis, and confirms that techniques used to study modern food webs can be applied to extinct webs as well.

Isotopically Enriched C-13 Diamond Anvil as a Stress Sensor in High Pressure Experiments

NASA Astrophysics Data System (ADS)

Vohra, Yogesh; Qiu, Wei; Kondratyev, Andreiy; Velisavljevic, Nenad; Baker, Paul

2004-03-01

The conventional high pressure diamond anvils were modified by growing an isotopically pure C-13 diamond layer by microwave plasma chemical vapor deposition using methane/hydrogen/oxygen chemistry. The isotopically pure C-13 nature of the culet of the diamond anvil was confirmed by the Raman spectroscopy measurements. This isotopically engineered diamond anvil was used against a natural abundance diamond anvil for high pressure experiments in a diamond anvil cell. Spatial resolved Raman spectroscopy was used to measure the stress induced shift in the C-13 layer as well as the undelying C-12 layer to ultra high pressures. The observed shift and splitiing of the diamond first order Raman spectrum was correlated with the stress distribution in the diamond anvil cell. The experimental results will be compared with the finite element modeling results using NIKE-2D software in order to create a mathematical relationship between sets of the following parameters: vertical (z axis) distance; horizontal (r axis) distance; max shear stress, and pressure. The isotopically enriched diamond anvils offer unique opportunities to measure stress distribution in the diamond anvil cell devices.

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

Rasmussen, K.A.; Neumann, A.C.; Haddad, R.I.

The stable-isotope composition ({delta}{sup 13}C) of total organic carbon (TOC) was measured as a function of depth throughout a 217-cm-thick sequence of Holocene carbonate sediment within the Bight of Abaco lagoon, Little Bahama Bank. Biofacies and lithofacies analyses indicate progressive banktop submergence and paleoenvironmental response during Holocene sea-level rise. Stable-isotope values shift markedly from {minus}27.7{per thousand} within the 7900 B.P. paleosol at the base of the core to {minus}11.1{per thousand} at the present-day sediment-water interface. An abrupt excursion toward heavy-isotope values records the first establishment of Thalassia seagrass upon open-marine flooding. A multitracer approach, combining biofacies, lithofacies, and stable-isotope analysismore » of TOC confirms that the dramatic +17{per thousand} shift observed in {delta}{sup 13}C was a direct result of sea-level rise and associated environmental changes over the banktop; there is little evidence of spurious diagenetic overprint. Stable-isotope analyses of organic carbon may enhance the reconstruction of carbonate sequences by revealing a distinctive geochemical signature of banktop flooding, including the onset of growth of otherwise unpreservable Thalassia seagrass.« less

Effect of 10B isotope and vacancy defects on the phonon modes of two-dimensional hexagonal boron nitride

NASA Astrophysics Data System (ADS)

Sherajul Islam, Md.; Anindya, Khalid N.; Bhuiyan, Ashraful G.; Tanaka, Satoru; Makino, Takayuki; Hashimoto, Akihiro

2018-02-01

We report the details of the effects of the 10B isotope and those of B and N vacancies combined with the isotope on the phonon modes of two-dimensional hexagonal boron nitride (h-BN). The phonon density of states and localization problems are solved using the forced vibrational method, which is suitable for an intricate and disordered system. We observe an upward shift of Raman-active E2g-mode optical phonons (32 cm-1) for a 100% 10B isotope, which matches well with the experiment and simple harmonic oscillator model. However, a downward shift of E2g-mode phonons is observed for B or N vacancies and the combination of the isotope and vacancy-type disordered BN. Strong localized eigenmodes are found for all types of defects, and a typical localization length is on the order of ˜7 nm for naturally occurring BN samples. These results are very important for understanding the heat dissipation and electron transport properties of BN-based nanoelectronics.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

NASA Astrophysics Data System (ADS)

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; Hartig, K. C.; Phillips, M. C.

2018-06-01

Rapid, in-field, and non-contact isotopic analysis of solid materials is extremely important to a large number of applications, such as nuclear nonproliferation monitoring and forensics, geochemistry, archaeology, and biochemistry. Presently, isotopic measurements for these and many other fields are performed in laboratory settings. Rapid, in-field, and non-contact isotopic analysis of solid material is possible with optical spectroscopy tools when combined with laser ablation. Laser ablation generates a transient vapor of any solid material when a powerful laser interacts with a sample of interest. Analysis of atoms, ions, and molecules in a laser-produced plasma using optical spectroscopy tools can provide isotopic information with the advantages of real-time analysis, standoff capability, and no sample preparation requirement. Both emission and absorption spectroscopy methods can be used for isotopic analysis of solid materials. However, applying optical spectroscopy to the measurement of isotope ratios from solid materials presents numerous challenges. Isotope shifts arise primarily due to variation in nuclear charge distribution caused by different numbers of neutrons, but the small proportional nuclear mass differences between nuclei of various isotopes lead to correspondingly small differences in optical transition wavelengths. Along with this, various line broadening mechanisms in laser-produced plasmas and instrumental broadening generated by the detection system are technical challenges frequently encountered with emission-based optical diagnostics. These challenges can be overcome by measuring the isotope shifts associated with the vibronic emission bands from molecules or by using the techniques of laser-based absorption/fluorescence spectroscopy to marginalize the effect of instrumental broadening. Absorption and fluorescence spectroscopy probe the ground state atoms existing in the plasma when it is cooler, which inherently provides narrower lineshapes, as opposed to emission spectroscopy which requires higher plasma temperatures to be able to detect thermally excited emission. Improvements in laser and detection systems and spectroscopic techniques have allowed for isotopic measurements to be carried out at standoff distances under ambient atmospheric conditions, which have expanded the applicability of optical spectroscopy-based isotopic measurements to a variety of scientific fields. These technological advances offer an in-situ measurement capability that was previously not available. This review will focus on isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing knowledge/technological gaps identified from the current literature and suggestions for the future work.

Determining Timing and Magnitude of Dietary Shifts in Black Guillemots (Cepphus grylle) Using Stable Isotope Analysis of Flight Feathers

NASA Astrophysics Data System (ADS)

Kleese, M. C.; Boswell, K. M.; Divoky, G.; Barton, M. B.

2016-02-01

Recent decreases in Artic summer sea and increases in SST have caused changes in the marine ecosystems associated with ice-covered waters. A four-decade study of Black Guillemots (Cepphus grylle) on Cooper Island near Point Barrow, AK has shown that nestling quality and survival is linked to proximity to sea ice and SST. In recent years when sea ice retreats from the foraging area and SST increases to >4°C during the nestling period, parent guillemots have switched from their preferred prey, Arctic cod (Boreogadus saida), to less desirable fourhorn sculpin (Myoxocephalus quadricornis). The guillemots' shift from a cryopelagic fish to a nearshore demersal is hard to monitor through direct observation and we suggest a new method to assess the timing and magnitude of this dietary shift using stable isotope analysis of nestling flight feathers. Flight feathers (primaries, secondaries and tail feathers) provide a linear record of material incorporated into the body of the chick from the start of feather growth to fledging, a period of approximately 30 days. Arctic cod and fourhorn sculpin have distinctive diets and are reliant on different basal resources and should produce distinct isotopic signatures in guillemot tissues. We extracted vane tissues from sections of 30 black guillemot feathers grown in a breeding season that experienced an observed prey shift, and conducted stable carbon and nitrogen isotope analyses to determine whether such analyses could be used to assess the dietary shift linked with loss of sea ice and increasing SST. Most seabird populations are not as easily accessible as the guillemots of Cooper Island and thus observations of dietary composition are difficult to obtain. Development of a technique using nestling feathers to examine timing and magnitude of seasonal shifts in prey would preclude the need for daily observations and have great utility for monitoring the ecological effects of the continuing annual decrease in Arctic summer ice.

Laser-induced separation of hydrogen isotopes in the liquid phase

DOEpatents

Freund, Samuel M.; Maier, II, William B.; Beattie, Willard H.; Holland, Redus F.

1980-01-01

Hydrogen isotope separation is achieved by either (a) dissolving a hydrogen-bearing feedstock compound in a liquid solvent, or (b) liquefying a hydrogen-bearing feedstock compound, the liquid phase thus resulting being kept at a temperature at which spectral features of the feedstock relating to a particular hydrogen isotope are resolved, i.e., a clear-cut isotope shift is delineated, irradiating the liquid phase with monochromatic radiation of a wavelength which at least preferentially excites those molecules of the feedstock containing a first hydrogen isotope, inducing photochemical reaction in the excited molecules, and separating the reaction product containing the first isotope from the liquid phase.

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

USGS Publications Warehouse

Ellis, A.S.; Johnson, T.M.; Bullen, T.D.

2004-01-01

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto ??-Al2O3 and goethite is less than 0.04???. (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO42- was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in ??53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Reconstructing Past Vegetation Types During the Late Holocene Using Stable Carbon Isotopes of Leporids from Archaeological Sites in the American Southwest

NASA Astrophysics Data System (ADS)

Mauldin, R. P.; Munoz, C.; Kemp, L.; Hard, R.

2012-12-01

Stable carbon isotopes (δ13C) from bone collagen in leporids provide high-resolution vegetation reconstruction. Leporids [e.g., cottontails (Sylvilagus sp.), jackrabbits (Lepus sp.)] die young (ca. 2 years) and use small home ranges (< 1 km2). They consume a variety of vegetation, including plants that use both C3 and C4/CAM photosynthetic pathways. Leporids appear to focus on new growth as it becomes available throughout the year, perhaps as a function of water content. Their diet, and their bone collagen, provides a high-resolution view of the carbon isotopic values present in their local plant community. Here we provide an example of the use of leporid bone collagen for reconstruction of past vegetation types using data from several archaeological sites as well as modern collections. All samples are from a basin and range setting within the Chihuahuan Desert in far west Texas and southern New Mexico, USA. The sites span a period back to roughly 1350 BP. Isotopic patterns in leporid collagen show clear evidence of change in vegetation from around 775 BP to the modern period, with a dramatic shift of 4.2‰ in median δ13C values over this period in jackrabbit collagen and a 7.3‰ decrease in median carbon isotopic values in cottontail rabbits. These data suggest a significant increase in C3 plants in leporid diet, and by extension a relative increase in these plant types in the local environment sampled by leporids. This shift is consistent with historic accounts of more C3 mesquite, possibly because of historic land use and ranching practices in the 1800s. However, while this shift may have been accelerated by historic land use changes, our data suggest that the vegetation shift began several hundred years earlier during the prehistoric period. The prehistoric collagen isotopic record also shows increased sample variability through time in both species, suggesting that year-to-year variability in vegetation may have increased late in that sequence. Our results, then, clearly show the potential of leporids for high resolution tracking of vegetation shifts. As leporids are common in paleontological and archaeological sites throughout the temperate zones, their use as a vegetation and climate proxy has wide application.

A Stratigraphic Record from 16 Ma to Present of Compound-Specific Hydrogen Isotopes from northern Tibet: Implications for Paleoaltimetry and Paleoclimate of the Northern Tibetan Plateau

NASA Astrophysics Data System (ADS)

Zhuang, G.; Brandon, M. T.; Pagani, M.

2012-12-01

The paleotopographic evolution of Tibet remains a key issue in testing models for the formation of orogenic plateaus. Stable isotopes from paleosols and lake carbonates provide the primary tool for estimating paleotopography. Unfortunately, the deposits are strongly controlled by evaporation, which means that the surface waters from which they formed were shifted towards heavier isotopic compositions relative to initial (pre-evaporation) meteoric compositions. As a result, estimates from these settings probably represent a lower bound for paleotopography. We report here on new analyses of compound-specific hydrogen stable isotopes, which were determined for n-alkanes extracts from 36 samples from Neogene strata in the northern Tibetan Plateau. N-alkanes represent long-chain hydrocarbons, commonly formed as leaf waxes in terrestrial high plants. The advantage of this record is that it is linked to times when moisture transport was high and evaporation low, as required to allow for the plants to thrive. Distributions of n-alkanes show maxima at C27, C29, and C31 with high odd-over-even preference values, suggesting excellent preservation of lipid biomarkers from terrestrial high plants. The deuterium values highly co-vary between three compounds. Application of an apparent fractionation factor based on modern ground waters and soil-derived lipid biomarkers suggest a multiple-phase evolution of paleometeoric waters consistent with well-constrained tectonic and climatic histories in the northern Tibetan Plateau. For example, a ~60‰ negative shift in δD between 16-10 Ma correlates well with sedimentological and thermochronologic evidence for rapid erosion at that time. The magnitude of this isotopic shift is equivalent to an increase in elevation of 2 to 3 km, assuming that the isotopic composition of the moisture source remained constant during this time. An abrupt positive δD shift at ~10 Ma is consistent with studies supporting intensified aridity in central Asia, whereas a negative δD shift at ~6.5 Ma potentially reflects a change to more moist conditions related to the onset/intensified East Asia Summer Monsoon. The attainment of high elevations in northern Tibetan Plateau is synchronous with the attainment of maximum elevation in the south-central Tibetan Plateau and with the transition from dominant tectonic extrusion to distributed crustal shortening in the northern Tibetan Plateau.

Predissociation of oxygen in the B3Sigma(u)(-) state

NASA Technical Reports Server (NTRS)

Chiu, S. S.-L.; Cheung, A. S.-C.; Finch, M.; Jamieson, M. J.; Yoshino, K.; Dalgarno, A.; Parkinson, W. H.

1992-01-01

The predissociation linewidths and level shifts of vibrational levels of three oxygen isotopic molecules (O2)-16, (O-16)(O-18), and (O2)-18 arising from the interactions of the B3Sigma(u)(-) state with the four repulsive states 5Pi(u), 3Sigma(u)(+), 3Pi(u), and 1Pi(u) have been calculated. A set of parameters characterizing these interactions has been determined. Good agreement between calculated and experimental predissociation widths and shifts has been obtained for all the three isotopic molecules.

Quantum interference in laser spectroscopy of highly charged lithiumlike ions

NASA Astrophysics Data System (ADS)

Amaro, Pedro; Loureiro, Ulisses; Safari, Laleh; Fratini, Filippo; Indelicato, Paul; Stöhlker, Thomas; Santos, José Paulo

2018-02-01

We investigate the quantum interference induced shifts between energetically close states in highly charged ions, with the energy structure being observed by laser spectroscopy. In this work, we focus on hyperfine states of lithiumlike heavy-Z isotopes and quantify how much quantum interference changes the observed transition frequencies. The process of photon excitation and subsequent photon decay for the transition 2 s →2 p →2 s is implemented with fully relativistic and full-multipole frameworks, which are relevant for such relativistic atomic systems. We consider the isotopes 79+207Pb and 80+209Bi due to experimental interest, as well as other examples of isotopes with lower Z , namely 56+141Pr and 64+165Ho. We conclude that quantum interference can induce shifts up to 11% of the linewidth in the measurable resonances of the considered isotopes, if interference between resonances is neglected. The inclusion of relativity decreases the cross section by 35%, mainly due to the complete retardation form of the electric dipole multipole. However, the contribution of the next higher multipoles (e.g., magnetic quadrupole) to the cross section is negligible. This makes the contribution of relativity and higher-order multipoles to the quantum interference induced shifts a minor effect, even for heavy-Z elements.

Spectroscopy of the 1/2 2S → 3/2 2P transition in Yb ii: Isotope shifts, hyperfine splitting, and branching ratios

NASA Astrophysics Data System (ADS)

Feldker, T.; Fürst, H.; Ewald, N. V.; Joger, J.; Gerritsma, R.

2018-03-01

We report on spectroscopic results on the 1/2 2S → 3/2 2P transition in single trapped Yb+ ions. We measure the isotope shifts for all stable Yb+ isotopes except +173Yb, as well as the hyperfine splitting of the 3/2 2P state in +171Yb. Our results are in agreement with previous measurements but are a factor of 5-9 more precise. For the hyperfine constant A (3/2 2P)=875.4 (10 )MHz our results also agree with previous measurements but deviate significantly from theoretical predictions. We present experimental results on the branching ratios for the decay of the 3/2 2P state. We find branching fractions for the decay to the 3/2 2D state and 5/2 2D state of 0.17(1)% and 1.08(5)%, respectively, in rough agreement with theoretical predictions. Furthermore, we measured the isotope shifts of the 7/2 2F →1D[5/2 ] 5 /2 transition and determine the hyperfine structure constant for the 1D[5/2 ] 5 /2 state in +171Yb to be A (1D[5/2 ] 5 /2)=-107 (6 ) MHz .

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.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

Harilal, Sivanandan S.; Brumfield, Brian E.; LaHaye, Nicole L.

2018-04-20

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

DOE PAGES

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; ...

2018-04-20

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Lastly, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Lastly, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

DOE PAGES

Harilal, S. S.; Brumfield, B. E.; LaHaye, N. L.; ...

2018-06-01

This review article covers the present status of isotope detection through emission, absorption, and fluorescence spectroscopy of atoms and molecules in a laser-produced plasma formed from a solid sample. A description of the physics behind isotope shifts in atoms and molecules is presented, followed by the physics behind solid sampling of laser ablation plumes, optical methods for isotope measurements, the suitable physical conditions of laser-produced plasma plumes for isotopic analysis, and the current status. Finally, concluding remarks will be made on the existing gaps between previous works in the literature and suggestions for future work.

Fractionation of uranium isotopes in minerals screened by gamma spectrometry.

NASA Astrophysics Data System (ADS)

Geiger, Jeffrey L.; Baldwin, Austin M.; Blatchley, Charles C.

2008-03-01

At least two groups have reported finding shifts in the ratio of U-235/U-238 for sandstone, black shale, and other sedimentary samples using precision ICP-MS. These shifts were tentatively attributed to a recently predicted isotope effect based on nuclear volume that causes fractionation for U^IV-U^VI transitions. However, fractionation of high Z elements may be less likely an explanation than U-235 depletion induced by galactic cosmic ray neutrons. Isotope depletion in marine sediments could therefore be an indicator of changes in cosmic ray flux due to nearby supernovae, gamma-ray bursts, or longer term changes during the 62 million year cycle of the Sun above and below the galactic plane. We report using a less precise approach than ICP-MS, but one which can quickly screen samples to look for anomalies in isotope ratios, namely HPGe gamma ray spectrometry. Various levels of depletion were measured for uranium rich minerals, including brannerite, carnotite, and pitchblende, as well as coal and limestone samples.

Determination of nitrogen-15 isotope fractionation in tropine: evaluation of extraction protocols for isotope ratio measurement by isotope ratio mass spectrometry.

PubMed

Molinié, Roland; Kwiecień, Renata A; Silvestre, Virginie; Robins, Richard J

2009-12-01

N-Demethylation of tropine is an important step in the degradation of this compound and related metabolites. With the purpose of understanding the reaction mechanism(s) involved, it is desirable to measure the 15N kinetic isotope effects (KIEs), which can be accessed through the 15N isotope shift (Deltadelta15N) during the reaction. To measure the isotope fractionation in 15N during tropine degradation necessitates the extraction of the residual substrate from dilute aqueous solution without introducing artefactual isotope fractionation. Three protocols have been compared for the extraction and measurement of the 15N/14N ratio of tropine from aqueous medium, involving liquid-liquid phase partitioning or silica-C18 solid-phase extraction. Quantification was by gas chromatography (GC) on the recovered organic phase and delta15N values were obtained by isotope ratio measurement mass spectrometry (irm-MS). Although all the protocols used can provide satisfactory data and both irm-EA-MS and irm-GC-MS can be used to obtain the delta15N values, the most convenient method is liquid-liquid extraction from a reduced aqueous volume combined with irm-GC-MS. The protocols are applied to the measurement of 15N isotope shifts during growth of a Pseudomonas strain that uses tropane alkaloids as sole source of carbon and nitrogen. The accuracy of the determination of the 15N/14N ratio is sufficient to be used for the determination of 15N-KIEs. Copyright 2009 John Wiley & Sons, Ltd.

Photochemical isotope separation

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

1987-01-01

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

Laser isotope separation

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Boyer, Keith; Greiner, Norman R.

1988-01-01

A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

Isotope separation by laser means

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

1982-06-15

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

A Multi-proxy Approach to Using Cave Sediment Carbon Isotopes for Late Holocene Paleoenvironmental Reconstruction in Florida

NASA Astrophysics Data System (ADS)

Polk, J. S.; van Beynen, P.

2007-12-01

Carbon isotopes from cave sediments collected from Jennings Cave in Marion County, Florida were analyzed using a multi-proxy approach. Fulvic acids (FAs), humic acids (HAs), black carbon, phytoliths, and bulk organic matter were extracted from the sediments for carbon isotope analysis to determine periods of vegetation change caused by climatic influences during the Late Holocene (~\\ 2,800 years BP). The carbon isotope record ranges from -35‰ to -14‰, exhibiting variability of ~\\ -21‰, within the different proxies, which indicates changes between C3 and C4 vegetation. This likely indicates changes between a sub-tropical forested environment and more arid, grassy plains conditions. These changes in plant assemblages were in response to changes in available water resources, with increased temperatures and evapotranspiration leading to arid conditions and a shift toward less C3 vegetation (increased C4 vegetation) during the MWP. The cave sediment fulvic acid cabon isotopes record agrees well with ä13C values from a speleothem collected nearby that covers the same time period. Prolonged migration of the NAO and ITCZ affects precipitation in Florida and likely caused vegetation changes during these climatic shifts.

Isotope effect on superconductivity and Raman phonons of Pyrochlore Cd2Re2O7

NASA Astrophysics Data System (ADS)

Razavi, F. S.; Hajialamdari, M.; Reedyk, M.; Kremer, R. K.

2018-06-01

Cd2Re2O7 is the only α-Pyrochlore exhibiting superconductivity with a transition temperature (Tc) of ∼ 1 K. In this study, we present the effect of oxygen isotope (18O) as well as combined 18O and cadmium isotope (116Cd) substitution on the superconductivity and Raman scattering spectrum of Cd2Re2O7. The change of Tc and the energy gap Δ(T) are reported using various techniques including point contact spectroscopy. The shift in Raman phonon frequencies upon isotope substitution will be compared with measurement of the isotope effect on the superconducting transition temperature.

Nitrogen Isotope Evidence for a Shift in Eastern Beringian Nitrogen Cycle after the Terminal Pleistocene

NASA Astrophysics Data System (ADS)

Tahmasebi, F.; Longstaffe, F. J.; Zazula, G.

2016-12-01

The loess deposits of eastern Beringia, a region in North America between 60° and 70°N latitude and bounded by Chukchi Sea to the west and the Mackenzie River to the east, are a magnificent repository of Late Pleistocene megafauna fossils. The stable carbon and nitrogen isotope compositions of these fossils are measured to determine the paleodiet of these animals, and hence the paleoenvironment of this ecosystem during the Quaternary. For this approach to be most successful, however, requires consideration of possible changes in nutrient cycling and hence the carbon and nitrogen isotopic compositions of vegetation in this ecosystem. To test for such a shift following the terminal Pleistocene, we analyzed the stable carbon and nitrogen isotope compositions of modern plants and bone collagen of Arctic ground squirrels from Yukon Territory, and fossil plants and bones recovered from Late Pleistocene fossil Arctic ground squirrel nests. The data for modern samples provided a measure of the isotopic fractionation between ground squirrel bone collagen and their diet. The over-wintering isotopic effect of decay on typical forage grasses was also measured to evaluate its role in determining fossil plant isotopic compositions. The grasses showed only a minor change ( 0-1 ‰) in carbon isotope composition, but a major change ( 2-10 ‰) in nitrogen isotope composition over the 317-day experiment. Based on the modern carbon isotope fractionation between ground squirrel bone collagen and their diet, the modern vegetation carbon isotopic baseline provides a suitable proxy for the Late Pleistocene of eastern Beringia, after accounting for the Suess effect. However, the predicted nitrogen isotope composition of vegetation comprising the diet of fossil ground squirrels remains 2.5 ‰ higher than modern grasslands in this area, even after accounting for possible N-15 enrichment during decay. This result suggests a change in N cycling in this region since the Late Pleistocene.

FAST TRACK COMMUNICATION Accurate estimate of α variation and isotope shift parameters in Na and Mg+

NASA Astrophysics Data System (ADS)

Sahoo, B. K.

2010-12-01

We present accurate calculations of fine-structure constant variation coefficients and isotope shifts in Na and Mg+ using the relativistic coupled-cluster method. In our approach, we are able to discover the roles of various correlation effects explicitly to all orders in these calculations. Most of the results, especially for the excited states, are reported for the first time. It is possible to ascertain suitable anchor and probe lines for the studies of possible variation in the fine-structure constant by using the above results in the considered systems.

Laser isotope separation

DOEpatents

Robinson, C.P.; Reed, J.J.; Cotter, T.P.; Boyer, K.; Greiner, N.R.

1975-11-26

A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light is described. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

Photochemical isotope separation

DOEpatents

Robinson, C.P.; Jensen, R.J.; Cotter, T.P.; Greiner, N.R.; Boyer, K.

1987-04-28

A process is described for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium. 8 figs.

Benthic iron cycling in a high-oxygen environment: Implications for interpreting the Archean sedimentary iron isotope record.

PubMed

McCoy, V E; Asael, D; Planavsky, N

2017-09-01

The most notable trend in the sedimentary iron isotope record is a shift at the end of the Archean from highly variable δ 56 Fe values with large negative excursions to less variable δ 56 Fe values with more limited negative values. The mechanistic explanation behind this trend has been extensively debated, with two main competing hypotheses: (i) a shift in marine redox conditions and the transition to quantitative iron oxidation; and (ii) a decrease in the signature of microbial iron reduction in the sedimentary record because of increased bacterial sulfate reduction (BSR). Here, we provide new insights into this debate and attempt to assess these two hypotheses by analyzing the iron isotope composition of siderite concretions from the Carboniferous Mazon Creek fossil site. These concretions precipitated in an environment with water column oxygenation, extensive sediment pile dissimilatory iron reduction (DIR) but limited bacterial sulfate reduction (BSR). Most of the concretions have slightly positive iron isotope values, with a mean of 0.15‰ and limited iron isotope variability compared to the Archean sedimentary record. This limited variability in an environment with high DIR and low BSR suggests that these conditions alone are insufficient to explain Archean iron isotope compositions. Therefore, these results support the idea that the unusually variable and negative iron isotope values in the Archean are due to dissimilatory iron reduction (DIR) coupled with extensive water column iron cycling. © 2017 John Wiley & Sons Ltd.

Interpreting the Marine Calcium Isotope Record: Influence of Reef Builders

NASA Astrophysics Data System (ADS)

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

2008-12-01

The calcium isotopic composition of seawater as recorded in brachiopod shells varied substantially during the Paleozoic (Farkas et al. 2007, Geochim. Cosmochim. Acta, 71, 5117-5134). The most prominent feature of the record is an excursion to higher 44Ca/40Ca values that started during the Early Carboniferous and lasted until the Permian. The shift occurred shortly after the transition from a calcite-sea to an aragonite-sea (Sandberg 1983, Nature 305, 19-22; Stanley and Hardie 1998, Pal3, 144, 3-19). It therefore has been interpreted to reflect a change in the average calcium isotope fractionation of carbonates produced in the oceans. Aragonite is depleted by about 0.6 permil in 44Ca/40Ca compared to calcite (Gussone et al. 2005, Geochim. Cosmochim. Acta, 69, 4485-4494). Consequently a transient shift from calcite dominated to an aragonite dominated calcium carbonate sedimentation could have caused the observed 0.5 permil isotope shift. We compare the marine calcium isotope record with a new compilation of the Phanerozoic trends in the skeletal mineralogy of marine invertebrates (Kiessling et al. 2008, Nature Geoscience, 1, 527-530). The compilation is based on data collected in the PaleoReef database and the Paleobiology Database, which include information on Phanerozoic reef complexes and taxonomic collection data of Phanerozoic biota, respectively. We find a strong positive correlation between the calcium isotope ratios and the abundance of aragonitic reef builders from the Silurian until the Permian at a sample resolution of about 10 million years. The two records, however, diverge in the Triassic, when reefs were dominated by aragonite but the calcium isotope values remained at a relatively low level. We also find a good correlation between calcium isotopes and the proportion of aragonite in the general record of Phanerozoic biota. However, in this case the records start to diverge already in the latest Carboniferous. The observations suggest that the Paleozoic calcium isotope record was indeed strongly controlled by the skeletal mineralogy of the major carbonate producers. The collapse of the correlation in the late Paleozoic points to the evolution of new biocalcification mechanisms that allowed a more strict biological control of the calcium fluxes in the calcifying biota (sensu Gussone et al. 2006, Geology, 34, 625-628).

Abrupt Late Holocene Shift in Atmospheric Circulation Recorded by Mineral Dust in the Siple Dome Ice Core, Antarctica

NASA Astrophysics Data System (ADS)

Koffman, B. G.; Goldstein, S. L.; Kaplan, M. R.; Winckler, G.; Bory, A. J. M.; Biscaye, P.

2015-12-01

Atmospheric dust directly influences Earth's climate by altering the radiative balance and by depositing micronutrients in the surface ocean, affecting global biogeochemical cycling. In addition, mineral dust particles provide observational evidence constraining past atmospheric circulation patterns. Because dust can originate from both local and distant terrestrial sources, knowledge of dust provenance can substantially inform our understanding of past climate history, atmospheric transport pathways, and differences in aerosol characteristics between glacial and interglacial climate states. Dust provenance information from Antarctic ice cores has until now been limited to sites in East Antarctica. Here we present some of the first provenance data from West Antarctica. We use Sr-Nd isotopes to characterize dust extracted from late Holocene ice (~1000-1800 C.E.) from the Siple Dome ice core. The data form a tight array in Sr-Nd isotope space, with 87Sr/86Sr ranging between ~0.7087 and 0.7102, and ɛNd ranging between ~ -7 and -16. This combination is unique for Antarctica, with low Nd and low Sr isotope ratios compared to high-elevation East Antarctic sites, requiring a dust source from ancient (Archean to early Proterozoic) and unweathered continental crust, which mixes with young volcanic material. Both components are likely sourced from Antarctica. We also observe significant, systematic variability in Sr and Nd isotopic signatures through time, reflecting changes in the mixing ratio of these sources, and hypothesize that these changes are driven by shifts in circulation patterns. A large change occurs over about 10 years at ca. 1125 C.E. (ΔɛNd = +3 and Δ87Sr/86Sr = -0.0014). This shift coincides with changes in climate proxies in Southern Hemisphere paleoclimate records reflecting variability in the Westerlies. We therefore interpret the shift in dust provenance at Siple Dome to be related to larger-scale circulation changes. In general, the observed shifts in the particle source signatures indicate that dust transport pathways to and around the West Antarctic Ice Sheet are highly responsive to perturbations in atmospheric circulation, and can record rapid shifts in provenance.

Deviations from Born-Oppenheimer mass scaling in spectroscopy and ultracold molecular physics

NASA Astrophysics Data System (ADS)

Lutz, Jesse J.; Hutson, Jeremy M.

2016-12-01

We investigate Born-Oppenheimer breakdown (BOB) effects (beyond the usual mass scaling) for the electronic ground states of a series of homonuclear and heteronuclear alkali-metal diatoms, together with the Sr2 and Yb2 diatomics. Several widely available electronic structure software packages are used to calculate the leading contributions to the total isotope shift for commonly occurring isotopologs of each species. Computed quantities include diagonal Born-Oppenheimer corrections (mass shifts) and isotopic field shifts. Mass shifts dominate for light nuclei up to and including K, but field shifts contribute significantly for Rb and Sr and are dominant for Yb. We compare the ab initio mass-shift functions for Li2, LiK and LiRb with spectroscopically derived ground-state BOB functions from the literature. We find good agreement in the values of the functions for LiK and LiRb at their equilibrium geometries, but significant disagreement with the shapes of the functions for all 3 systems. The differences may be due to contributions of nonadiabatic terms to the empirical BOB functions. We present a semiclassical model for the effect of BOB corrections on the binding energies of near-threshold states and the positions of zero-energy Feshbach resonances.

Deuterium isotope effects on 13C and 15N chemical shifts of intramolecularly hydrogen-bonded enaminocarbonyl derivatives of Meldrum’s and Tetronic acid

NASA Astrophysics Data System (ADS)

Ullah, Saif; Zhang, Wei; Hansen, Poul Erik

2010-07-01

Secondary deuterium isotope effects on 13C and 15N nuclear shieldings in a series of cyclic enamino-diesters and enamino-esters and acyclic enaminones and enamino-esters have been examined and analysed using NMR and DFT (B3LYP/6-31G(d,p)) methods. One-dimensional and two-dimensional NMR spectra of enaminocarbonyl and their deuterated analogues were recorded in CDCl 3 and CD 2Cl 2 at variable temperatures and assigned. 1JNH coupling constants for the derivatives of Meldrum's and tetronic acids reveal that they exist at the NH-form. It was demonstrated that deuterium isotope effects, for the hydrogen bonded compounds, due to the deuterium substitution at the nitrogen nucleus lead to large one-bond isotope effects at nitrogen, 1Δ 15N(D), and two-bond isotope effects on carbon nuclei, 2ΔC(ND), respectively. A linear correlations exist between 2ΔC(ND) and 1Δ 15N(D) whereas the correlation with δNH is divided into two. A good agreement between the experimentally observed 2ΔC(ND) and calculated dσ 13C/dR NH was obtained. A very good correlation between calculated NH bond lengths and observed NH chemical shifts is found. The observed isotope effects are shown to depend strongly on Resonance Assisted Hydrogen bonding.

WILLAMETTE BASIN SURFACE WATER ISOSCAPE (18O AND 2H) FOR INTERPRETING TEMPORAL CHANGES OF SOURCE WATER WITHIN THE RIVER.

EPA Science Inventory

Understanding how water sources for rivers are shifting spatially over time will greatly aid our ability to understand climate impacts on rivers. Because stable isotopes of precipitation vary geographically, variation in the stable isotopes of river water can indicate source wat...

Ontogenetic shifts in the diet of plains hog-nosed snakes (Heterodon nasicus) revealed by stable isotope analysis.

PubMed

Durso, Andrew M; Mullin, Stephen J

2017-02-01

Wild snake diets are difficult to study using traditional methods, but stable isotopes offer several advantages, including integrating dietary information over time, providing data from individuals that have not fed recently, and avoiding bias towards slowly-digesting prey items. We used stable isotope signatures of carbon and nitrogen from scale tissue, red blood cells, and blood plasma to assess the diet of wild plains hog-nosed snakes (Heterodon nasicus) in Illinois. We developed Bayesian mixing models which, taken together, predicted that H. nasicus shifted from a juvenile diet predominantly (31-63%) composed of six-lined racerunners (Aspidoscelis sexlineatus) and their eggs to an adult diet predominantly (44-56%) composed of eggs of the aquatic turtles Chrysemys picta and Chelydra serpentina, with a contribution from toads (Anaxyrus sp.; 6-27%) during their adolescent years. These results agreed with sparse data from gut contents. Combining traditional and isotopic techniques for studying the diets of wild snakes can increase the utility of both types of data. Copyright © 2016 Elsevier GmbH. All rights reserved.

Dietary shift after 3600 cal yr BP and its influencing factors in northwestern China: Evidence from stable isotopes

NASA Astrophysics Data System (ADS)

Ma, Minmin; Dong, Guanghui; Jia, Xin; Wang, Hui; Cui, Yifu; Chen, Fahu

2016-08-01

Human diets rely on natural resource availability and can reflect social and cultural values. When environments, societies, and cultures change, diets may also shift. This study traced the extent of dietary change and the factors influencing such change. Through stable carbon and nitrogen isotopic analysis of late Neolithic and early Bronze Age human and animal bone collagen, we found that significant shifts in human diets were closely associated with intercontinental cultural exchanges in Eurasia and climate change in northwestern China. The isotopic evidence indicated that human diets mainly consisted of C4 foodstuffs (presumably millet and/or animals fed with C4 foods) around 4000 calibrated years before the present (cal yr BP), corresponding to the flourishing of millet agriculture in the context of the optimal climate conditions of the mid-Holocene. Subsequently, more C3 foods (probably wheat, barley, and animals fed with C3 foods) were added to human diets post-3600 cal yr BP when the climate became cooler and drier. Such dietary variation is also consistent with the increasing intensity of long-distance exchange after 4000 cal yr BP. While many factors can lead to human dietary shifts (e.g. climate change, population growth, cultural factors, and human migration), climate may have been a key factor in Gansu and Qinghai.

Dietary shift after 3600 cal yr BP and its influencing factors in northwestern China: Evidence from stable isotopes

NASA Astrophysics Data System (ADS)

Ma, Minmin; Dong, Guanghui; Jia, Xin; Wang, Hui; Cui, Yifu; Chen, Fahu

2017-04-01

:Human diets rely on natural resource availability and can reflect social and cultural values. When environments, societies, and cultures change, diets may also shift. This study traced the extent of dietary change and the factors influencing such change. Through stable carbon and nitrogen isotopic analysis of late Neolithic and early Bronze Age human and animal bone collagen, we found that significant shifts in human diets were closely associated with intercontinental cultural exchanges in Eurasia and climate change in northwestern China. The isotopic evidence indicated that human diets mainly consisted of C4 foodstuffs (presumably millet and/or animals fed with C4 foods) around 4000 calibrated years before the present (cal yr BP), corresponding to the flourishing of millet agriculture in the context of the optimal climate conditions of the mid-Holocene. Subsequently, more C3 foods (probably wheat, barley, and animals fed with C3 foods) were added to human diets post-3600 cal yr BP when the climate became cooler and drier. Such dietary variation is also consistent with the increasing intensity of long-distance exchange after 4000 cal yr BP. While many factors can lead to human dietary shifts (e.g. climate change, population growth, cultural factors, and human migration), climate may have been a key factor in Gansu and Qinghai.

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.

A Multiproxy Reconstruction of Holocene Southern Westerlies from the Auckland Islands

NASA Astrophysics Data System (ADS)

Nichols, J. E.; Moy, C. M.; Peteet, D. M.; Weiss, A.; Curtin, L. G.

2015-12-01

The strength and position of the Southern Hemisphere Westerly Wind belt plays an important role in our understanding of the global carbon cycle and glacial-interglacial climate change. We present a paleoclimate record that is primarily influenced by the strength and latitudinal position of the Southern Hemisphere Westerly Winds from a late Holocene lake sediment core and a peat core that spans the last 13,000 years, both obtained from New Zealand's subantarctic Auckland Islands (50°S, 166°E). Several proxy indicators contribute to our reconstruction. Hydrogen isotope ratios of specific organic molecules allow us to reconstruct the hydrogen isotope ratios of precipitation. Using macrofossil counts and the abundances of leaf wax biomarkers, we are able to estimate the moisture balance at our sites. Model simulations of the Westerlies and the rate and isotope ratios of precipitation allow us to interpret our proxy data as changes in the strength and position of the Westerly Winds. In our lacustrine sediment, we found that the Westerlies have been shifting southward since the Little Ice Age, consistent with modern observations of a southward shift. In the peatland sediment, we found a multi-millennial northward shift in the Westerlies during the middle Holocene. We will present further ongoing work that strengthens the chronology of Auckland Islands environmental change and integrates these results with vegetation shifts identified in pollen and macrofossil data.

Shifts in rotifer life history in response to stable isotope enrichment: testing theories of isotope effects on organismal growth

PubMed Central

2017-01-01

In ecology, stable isotope labelling is commonly used for tracing material transfer in trophic interactions, nutrient budgets and biogeochemical processes. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism growth and metabolism. This assumption is, however, challenged by theoretical considerations and experimental studies on kinetic isotope effects in vivo. Here, I demonstrate profound changes in life histories of the rotifer Brachionus plicatilis fed 15N-enriched algae (0.4–5.0 at%); i.e. at the enrichment levels commonly used in ecological studies. These findings support theoretically predicted effects of heavy isotope enrichment on growth, metabolism and ageing in biological systems and underline the importance of accounting for such effects when using stable isotope labelling in experimental studies. PMID:28405367

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

Spectroscopy of a Synthetic Trapped Ion Qubit

NASA Astrophysics Data System (ADS)

Hucul, David; Christensen, Justin E.; Hudson, Eric R.; Campbell, Wesley C.

2017-09-01

133Ba+ has been identified as an attractive ion for quantum information processing due to the unique combination of its spin-1 /2 nucleus and visible wavelength electronic transitions. Using a microgram source of radioactive material, we trap and laser cool the synthetic A =133 radioisotope of barium II in a radio-frequency ion trap. Using the same, single trapped atom, we measure the isotope shifts and hyperfine structure of the 62P1 /2↔62S1 /2 and 62P1 /2↔52D3 /2 electronic transitions that are needed for laser cooling, state preparation, and state detection of the clock-state hyperfine and optical qubits. We also report the 62P1 /2↔52D3 /2 electronic transition isotope shift for the rare A =130 and 132 barium nuclides, completing the spectroscopic characterization necessary for laser cooling all long-lived barium II isotopes.

Hydrological and vegetation shifts in the Wallacean region of central Indonesia since the Last Glacial Maximum

NASA Astrophysics Data System (ADS)

Wicaksono, Satrio A.; Russell, James M.; Holbourn, Ann; Kuhnt, Wolfgang

2017-02-01

Precipitation is the most important variable of Indonesian climate, yet there are substantial uncertainties about past and future hydroclimate dynamics over the region. This study explores vegetation and rainfall and associated changes in atmospheric circulation during the past 26,000 years in Wallacea, a biogeographical area in central Indonesia, wedged between the Sunda and Sahul shelves and known for its exceptionally high rainforest biodiversity. We use terrestrial plant biomarkers from sediment cores retrieved from Mandar Bay, off west Sulawesi, to reconstruct changes in Wallacean vegetation and climate since the Last Glacial Maximum (LGM). Enriched leaf wax carbon isotope (δ13Cwax) values recorded in Mandar Bay during the LGM, together with other regional vegetation records, document grassland expansion, implying a regionally dry, and possibly more seasonal, glacial climate. Depleted leaf wax deuterium isotope (δDwax) values in Mandar Bay during the LGM, and low reconstructed precipitation isotope compositions from nearby sites, reveal an intensified Austral-Asian summer monsoon circulation and a southward shift of the mean position of the Intertropical Convergence Zone, likely due to strong southern hemisphere summer insolation and the presence of large northern hemisphere ice sheets. Mandar Bay δ13Cwax was anti-correlated with δDwax during the LGM and the last deglaciation, but was positively correlated during most of the Holocene, indicating time-varying controls on the isotopic composition of rainfall in this region. The inundation event of the Sunda Shelf and in particular the opening of the Java Sea and Karimata Strait between 9.4 and 11.1 thousand years ago might have provided new moisture sources for regional convection and/or influenced moisture source trajectories, providing the trigger for shifts in atmospheric circulation and the controls on precipitation isotope compositions from the LGM to the Holocene.

Isotopic Investigation of Contemporary and Historic Changes in Penguin Trophic Niches and Carrying Capacity of the Southern Indian Ocean

PubMed Central

Jaeger, Audrey; Cherel, Yves

2011-01-01

A temperature-defined regime shift occurred in the 1970s in the southern Indian Ocean, with simultaneous severe decreases in many predator populations. We tested a possible biological link between the regime shift and predator declines by measuring historic and contemporary feather isotopic signatures of seven penguin species with contrasted foraging strategies and inhabiting a large latitudinal range. We first showed that contemporary penguin isotopic variations and chlorophyll a concentration were positively correlated, suggesting the usefulness of predator δ13C values to track temporal changes in the ecosystem carrying capacity and its associated coupling to consumers. Having controlled for the Suess effect and for increase CO2 in seawater, δ13C values of Antarctic penguins and of king penguins did not change over time, while δ13C of other subantarctic and subtropical species were lower in the 1970s. The data therefore suggest a decrease in ecosystem carrying capacity of the southern Indian Ocean during the temperature regime-shift in subtropical and subantarctic waters but not in the vicinity of the Polar Front and in southward high-Antarctic waters. The resulting lower secondary productivity could be the main driving force explaining the decline of subtropical and subantarctic (but not Antarctic) penguins that occurred in the 1970s. Feather δ15N values did not show a consistent temporal trend among species, suggesting no major change in penguins’ diet. This study highlights the usefulness of developing long-term tissue sampling and data bases on isotopic signature of key marine organisms to track potential changes in their isotopic niches and in the carrying capacity of the environment. PMID:21311756

Isotopic investigation of contemporary and historic changes in penguin trophic niches and carrying capacity of the southern Indian ocean.

PubMed

Jaeger, Audrey; Cherel, Yves

2011-02-02

A temperature-defined regime shift occurred in the 1970s in the southern Indian Ocean, with simultaneous severe decreases in many predator populations. We tested a possible biological link between the regime shift and predator declines by measuring historic and contemporary feather isotopic signatures of seven penguin species with contrasted foraging strategies and inhabiting a large latitudinal range. We first showed that contemporary penguin isotopic variations and chlorophyll a concentration were positively correlated, suggesting the usefulness of predator δ¹³C values to track temporal changes in the ecosystem carrying capacity and its associated coupling to consumers. Having controlled for the Suess effect and for increase CO₂ in seawater, δ¹³C values of Antarctic penguins and of king penguins did not change over time, while δ¹³C of other subantarctic and subtropical species were lower in the 1970s. The data therefore suggest a decrease in ecosystem carrying capacity of the southern Indian Ocean during the temperature regime-shift in subtropical and subantarctic waters but not in the vicinity of the Polar Front and in southward high-Antarctic waters. The resulting lower secondary productivity could be the main driving force explaining the decline of subtropical and subantarctic (but not Antarctic) penguins that occurred in the 1970s. Feather δ¹⁵N values did not show a consistent temporal trend among species, suggesting no major change in penguins' diet. This study highlights the usefulness of developing long-term tissue sampling and data bases on isotopic signature of key marine organisms to track potential changes in their isotopic niches and in the carrying capacity of the environment.

Isotope shifts in the 7 s →8 s transition of francium: Measurements and comparison to ab initio theory

NASA Astrophysics Data System (ADS)

Kalita, M. R.; Behr, J. A.; Gorelov, A.; Pearson, M. R.; DeHart, A. C.; Gwinner, G.; Kossin, M. J.; Orozco, L. A.; Aubin, S.; Gomez, E.; Safronova, M. S.; Dzuba, V. A.; Flambaum, V. V.

2018-04-01

We observe the electric-dipole forbidden 7 s →8 s transition in the francium isotopes Fr-211208 and 213Fr using a two-photon excitation scheme. We collect the atoms online from an accelerator and confine them in a magneto-optical trap for the measurements. In combination with previous measurements of the 7 s →7 p1 /2 transition we perform a King plot analysis. We compare the thus-determined ratio of the field shift constants (1.228 ± 0.019) to results obtained from new ab initio calculations (1.234 ± 0.010).

HFS and isotope shift in the atomic spectrum of205Pb

NASA Astrophysics Data System (ADS)

Barboza-Flores, M.; Redi, O.; Schönberger, P.; Stroke, H. H.; Naumann, R. A.

1987-06-01

The hfs of205Pb in the 283.3-nm resonance line and its isotope shift (IS) have been measured in absorption with the use of dispersive spectroscopy. A new method for calibration and analysis, when internal standards are not available is described. The results are: hfs interaction constants A=70.3(5)×10-3 cm-1, B=-0.6(1.1)×10-3 cm-1,205Pb-208Pb IS=-123.9(2.0)×10-3 cm-1. The derived nuclear magnetic dipole moment, μ=0.704(5) μ N is in good agreement with values calculated with a nuclear configuration mixing model.

Stable isotopes reveal habitat-related diet shifts in facultative deposit-feeders

NASA Astrophysics Data System (ADS)

Rossi, Francesca; Baeta, Alexandra; Marques, João C.

2015-01-01

Seagrass patches interspersed in a sediment matrix may vary environmental conditions and affect feeding habits of consumers and food-web structure. This paper investigates diet shifts between bare sediments and a Zostera noltei (Hornemann, 1832) meadow for three facultative deposit-feeding macrofaunal consumers, notably the bivalve Scrobicularia plana (da Costa, 1778), the polychaete Hediste diversicolor (O.T. Müller, 1776), and the gastropod Hydrobia ulvae (Pennant, 1778). In July 2008, one eelgrass meadow and two bare sediment locations were chosen in the Mondego estuary (40° 08″ N, 8° 50‧ W, Portugal) and sampled for stable isotope signatures (δ13C and δ15N) of macrofauna consumers and some of their potential basal food sources, such as sedimentary organic matter (SOM), microphytobenthos (MPB), seagrass shoots, leaves and seaweeds laying on the surface sediment. The δ15N of H. diversicolor was 3‰ higher in the eelgrass meadow than in bare sediment, indicating a change of trophic position, whereas the Bayesian stable-isotope mixing model showed that S. plana assimilated more macroalgal detritus than microphytobenthos in the eelgrass bed. Such habitat-related diet shifts have the potential to change structure and spatial dynamics of benthic food webs.

Stable Carbon Isotope Evidence and Quantification of Reductive Dechlorination of Chlorinated Ethenes at Kelly AFB, TX

NASA Astrophysics Data System (ADS)

Morrill, P.; Lacrampe-Couloume, G.; Slater, G.; Sleep, B.; Edwards, E.; McMaster, M.; Major, D.; Sherwood Lollar, B.

2002-12-01

Cis-1, 2-dichloroethene (cDCE) was the primary volatile organic compound (VOC) after biostimulation of a perchloroethene (PCE) plume in a pilot test at Kelly Air Force Base (AFB) in San Antonio Texas. A stable natural microbial consortium, KB-1, shown in laboratory experiments to reduce chlorinated ethenes to non-toxic ethene was added in a pilot test area (PTA). After the addition of KB-1 stable carbon isotope values were measured for each chlorinated ethene to verify the occurrence of reductive dechlorination and quantify the extent of cDCE degradation. After bioaugmentation with KB-1, PCE, TCE and cDCE concentrations declined, while VC concentrations increased and subsequently decreased, as ethene became the dominant transformation product measured. Shifts in carbon isotopic values up to 2.7 permil, 6.4 permil, 10.9 permil and 10.6 permil were observed for PCE, TCE, cDCE and VC respectively. These isotopic shifts are consistent with the effects of biodegradation observed during laboratory and field studies. Most notably, isotopic enrichment trends characteristic of reductive dechlorination were detectable in the parent compounds before measurable concentrations of daughter products VC and ethene were produced. These results illustrate the advantage of using the more sensitive compound specific isotope analysis to confirm degradation in addition to the traditional method of monitoring the appearance of degradation products. Fractionation factors obtained from laboratory studies were used in conjunction with isotope data measured in the field to estimate the extent of cDCE degraded. It is estimated that within a 44 day period, 37 to 48 percent of the cDCE was reductively dechlorinated. Independent biodegradation estimates using data from a bromide tracer test, a groundwater flow model, and concentration analyses were all in good agreement with the isotope degradation estimate.

An evaporite-based high-resolution sulfur isotope record of Late Permian and Triassic seawater sulfate

NASA Astrophysics Data System (ADS)

Bernasconi, Stefano M.; Meier, Irene; Wohlwend, Stephan; Brack, Peter; Hochuli, Peter A.; Bläsi, Hansruedi; Wortmann, Ulrich G.; Ramseyer, Karl

2017-05-01

Variations in the sulfur isotope composition of dissolved marine sulfate through time reflect changes in the global sulfur cycle and are intimately related to changes in the carbon and oxygen cycles. A large shift in the sulfur isotope composition of sulfate at the Permian/Triassic boundary has been recognized for long time and a number of studies were carried out to understand the causes and significance of this shift. However, data for the Middle and Late Triassic are very sparse and the stratigraphic evolution of the sulfur isotope composition of seawater is poorly constrained due to the small number of samples analyzed and/or due to the limited stratigraphic intervals studied. Moreover, in the last few years the Triassic timescale has significantly changed due to a wealth of new radiometric and stratigraphic data. In this study we show that for the Late Permian and the Triassic it is possible to obtain a precise reconstruction of the evolution of the sulfur cycle, for parts of it at sub-million year resolution, by analyzing exclusively gypsum and anhydrite deposits. We base our reconstruction on new data from the Middle and Late Triassic evaporites of Northern Switzerland and literature data from evaporites from Germany, Austria, Italy and the Middle East. We propose a revised correlation between the well-dated marine Tethyan sections in northern Italy and the evaporites from Northern Switzerland and from the Germanic Basin calibrated to the newest radiometric absolute age scale. This new correlation allows for a precise dating of the evaporites and constructing a composite sulfur isotope evolution of seawater sulfate from the latest Permian (Lopingian Epoch) to the Norian. We show that a rapid positive shift of approximately 24‰ at the Permian-Triassic boundary can be used to constrain seawater sulfate concentrations in the range of 2-6 mM, thus higher than previous estimates but with less rapid changes. Finally, we discuss two possible evolution scenarios for the Middle Triassic negative shift to values of 15‰ that subsequently remain constant during the Late Triassic.

Modeling the Impact of Forest and Peat Fires on Carbon-Isotopic Compositions of Cretaceous Atmosphere and Vegetation

NASA Astrophysics Data System (ADS)

Finkelstein, D. B.; Pratt, L. M.

2004-12-01

Prevalence of wildfires or peat fires associated with seasonally dry conditions in the Cretaceous is supported by recent studies documenting the widespread presence of pyrolytic polycyclic aromatic hydrocarbons and fusinite. Potential roles of CO2 emissions from fire have been overlooked in many discussions of Cretaceous carbon-isotope excursions (excluding K-P boundary discussions). Enhanced atmospheric CO2 levels could increase fire frequency through elevated lightning activity. When biomass or peat is combusted, emissions of CO2 are more negative than atmospheric CO2. Five reservoirs (atmosphere, vegetation, soil, and shallow and deep oceans), and five fluxes (productivity, respiration, litter fall, atmosphere-ocean exchange, and surface-deep ocean exchange) were modeled as a closed system. The size of the Cretaceous peat reservoir was estimated by compilation of published early Cretaceous coal resources. Initial pCO2 was assumed to be 2x pre-industrial atmospheric levels (P.A.L.). Critical variables in the model are burning efficiency and post-fire growth rates. Assuming 1% of standing terrestrial biomass is consumed by wildfires each year for ten years (without combustion of peat), an increase of atmospheric CO2 (from 2.0 to 2.2x P.A.L.) and a negative carbon isotope excursion (-1.2 ‰ ) are recorded by both atmosphere and new growth. Net primary productivity linked to the residence time of the vegetation and soil reservoirs results in a negative isotope shift followed by a broad positive isotope excursion. Decreasing the rate of re-growth dampens this trailing positive shift and increases the duration of the excursion. Post-fire pCO2 and new growth returned to initial values after 72 years. Both negative and positive isotope excursions are recorded in the model in surface ocean waters. Exchange of CO2 with the surface- and deep-ocean dampens the isotopic shift of the atmosphere. Excursions are first recorded in the atmosphere (and new growth), followed by the ocean, vegetation, and soil reservoirs. Ten to twenty five-year cycles of drought and fire are not recorded as individual excursions in the soil reservoir as the rate of transfer between the vegetation and soil reservoirs homogenizes the signal. A wildfire-modeled excursion does not propagate a geologically significant excursion through time. Combustion of a peat reservoir is necessary to drive and validate a geologically and isotopically significant excursion. Assuming 0.5% of the standing early Cretaceous peat reservoir is consumed by fire for each year for ten years coupled with the earlier scenario, the atmospheric CO2 increases from 2.0 to 3.1x P.A.L., atmosphere, vegetation, and the surface ocean record a negative carbon isotope excursion of -5.1 ‰ , -3.8 ‰ and -1.8 ‰ respectively, with a duration of 741 years. Increasing the size of the vegetation reservoir translates the excursions from the centennial to millennial scale. For example, doubling the vegetation reservoir (from 1.4 to 2.8E+16 gC) for a 25 year global peat conflagration (0.5% combusted each year) results in a CO2 increase from 2.0 to 4.0x P.A.L., and the atmosphere, vegetation, and the surface ocean reservoirs with a negative carbon isotope excursion of -5.7 ‰ , -8.7 ‰ and -2.3 ‰ respectively. Addition of carbonaceous aerosols (black carbon and polycyclic aromatic hydrocarbons) to pelagic marine sediments could potentially serve as a high-resolution record of ancient fires and firmly tie isotopic shifts to paleofires.

A precise few-nucleon size difference by isotope shift measurements of helium

NASA Astrophysics Data System (ADS)

Rezaeian, Nima Hassan

We perform high precision measurements of an isotope shift between the two stable isotopes of helium. We use laser excitation of the 23 S1 -- 23P0 transition at 1083 .... in a metastable beam of 3He and 4He atoms. A newly developed tunable laser frequency selector along with our previous electro-optic frequency modulation technique provides extremely reliable, adaptable, and precise frequency and intensity control. The intensity control contributes negligibly to overall experimental uncertainty by selecting (t selection < 50 ) and stabilizing the intensity of the required sideband and eliminating (˜10-5) the unwanted frequencies generated during the modulation of 1083 nm laser carrier frequency. The selection technique uses a MEMS based fiber switch (tswitch ≈ 10 ms) and several temperature stabilized narrow band (˜3 GHz) fiber gratings. A fiber based optical circulator and an inline fiber amplifier provide the desired isolation and the net gain for the selected frequency. Also rapid (˜2 sec.) alternating measurements of the 23 S1 -- 23P0 interval for both species of helium is achieved with a custom fiber laser for simultaneous optical pumping. A servo-controlled retro-reflected laser beam eliminates residual Doppler effects during the isotope shift measurement. An improved detection design and software control makes negligible subtle potential biases in the data collection. With these advances, combined with new internal and external consistency checks, we are able to obtain results consistent with the best previous measurements, but with substantially improved precision. Our measurement of the 23S 1 -- 23P0 isotope shift between 3He and 4He is 31 097 535.2 (5)kHz. The most recent theoretic calculation combined with this measuremen. yields a new determination for nuclear size differences between 3He and 4He: Deltarc = 0.292 6 (1)exp (8)th(52)expfm, with a precision of less than a part in 104 coming from the experimental uncertainty (first parenthesis), and a part in 10 3 coming from theory. This value is consistent with electron scattering measurement, but a factor of 10 more precise. It is inconsistent (4 sigma) with a recent isotope shift measurement on another helium transition (2 1S0 -- 23 S1). Comparisons with ongoing muonic helium measurements may provide clues to the origin of what is currently called the proton puzzle: electronic and muonic measurements of the proton size do not agree. In the future, the experimental improvements described here can be used for higher precision tests of atomic theory and quantum electrodynamics, as well as an important atomic physics source of the fine structure constant.

Evaporation induced 18O and 13C enrichment in lake systems: A global perspective on hydrologic balance effects

NASA Astrophysics Data System (ADS)

Horton, Travis W.; Defliese, William F.; Tripati, Aradhna K.; Oze, Christopher

2016-01-01

Growing pressure on sustainable water resource allocation in the context of global development and rapid environmental change demands rigorous knowledge of how regional water cycles change through time. One of the most attractive and widely utilized approaches for gaining this knowledge is the analysis of lake carbonate stable isotopic compositions. However, endogenic carbonate archives are sensitive to a variety of natural processes and conditions leaving isotopic datasets largely underdetermined. As a consequence, isotopic researchers are often required to assume values for multiple parameters, including temperature of carbonate formation or lake water δ18O, in order to interpret changes in hydrologic conditions. Here, we review and analyze a global compilation of 57 lacustrine dual carbon and oxygen stable isotope records with a topical focus on the effects of shifting hydrologic balance on endogenic carbonate isotopic compositions. Through integration of multiple large datasets we show that lake carbonate δ18O values and the lake waters from which they are derived are often shifted by >+10‰ relative to source waters discharging into the lake. The global pattern of δ18O and δ13C covariation observed in >70% of the records studied and in several evaporation experiments demonstrates that isotopic fractionations associated with lake water evaporation cause the heavy carbon and oxygen isotope enrichments observed in most lakes and lake carbonate records. Modeled endogenic calcite compositions in isotopic equilibrium with lake source waters further demonstrate that evaporation effects can be extreme even in lake records where δ18O and δ13C covariation is absent. Aridisol pedogenic carbonates show similar isotopic responses to evaporation, and the relevance of evaporative modification to paleoclimatic and paleotopographic research using endogenic carbonate proxies are discussed. Recent advances in stable isotope research techniques present unprecedented opportunities to overcome the underdetermined nature of stable isotopic data through integration of multiple isotopic proxies, including dual element 13C-excess values and clumped isotope temperature estimates. We demonstrate the utility of applying these multi-proxy approaches to the interpretation of paleohydroclimatic conditions in ancient lake systems. Understanding past, present, and future hydroclimatic systems is a global imperative. Significant progress should be expected as these modern research techniques become more widely applied and integrated with traditional stable isotopic proxies.

Paleohydrologic change across the Paleocene-Eocene Thermal Maximum, Bighorn Basin, WY

NASA Astrophysics Data System (ADS)

Baczynski, A. A.; McInerney, F. A.; Wing, S. L.; Kraus, M. J.

2013-12-01

One of the uncertainties in accurately predicting future climate change involves how the hydrologic cycle will respond to increasing pCO2 and temperature. Quantifying the relationship between carbon cycle perturbations and the hydrologic cycle in the geologic past is crucial to understanding and accurately modeling how anthropogenic carbon emissions will affect future changes in the hydrologic cycle. Records of paleohydrologic response to global warming in the geologic past are rare, particularly for continental interiors, where climate model projections of precipitation are highly uncertain. Here we examine hydrogen isotope ratios of leaf waxes as a tool for reconstructing paleohydrologic change in the continental interior of North America across the Paleocene-Eocene Thermal Maximum (PETM), an abrupt, transient episode of extreme global warming ~56 Ma. New hydrogen isotope measurements of leaf-wax n-alkanes from the southeastern Bighorn Basin, Wyoming record two positive shifts during the PETM. n-Alkane δD values first shift to more positive values just after the onset of the carbon isotope excursion and then again higher up in the body of the carbon isotope excursion, with a return to slightly more negative δD values in between. Paleobotanical, paleopedologic, and isotope data from the same field area have suggested that the Bighorn Basin may have experienced a drier or more seasonally dry climate during the PETM. Mean annual precipitation estimates based on paleosol major oxides, soil wetness assessed using the soil morphology index, and an aridity proxy based on differences in δ18O values of tooth enamel in aridity-sensitive and aridity-insensitive mammals each independently suggest a potential two-phase drying within the PETM interval. Similarly, the hydrogen isotope record could reflect two periods of drying, with a return to slightly wetter conditions in between. However, leaf-wax hydrogen isotope ratios reflect not only source water hydrogen isotope values but also deuterium-enrichment resulting from soil evaporation and transpiration. Interpretation of hydrogen isotope records requires consideration of both of these factors. To examine the potential roles of changes in source water isotopic composition and transpirational D-enrichment, we compare the hydrogen isotope ratios of leaf waxes with the oxygen isotope ratios of tooth enamel from Coryphodon, a large herbivore and an obligate drinker. The Coryphodon tooth enamel δ18O record enables us to constrain shifts in surface water isotope values. Relative humidity of paleoenvironments can then be explored using a modified Craig-Gordon model for transpirational D-enrichment. Preliminary calculations suggest that relative humidity increased during the PETM, contrary to the drying suggested by all other aridity proxies. One possibility is that leaf waxes record only the relative humidity at the time of leaf formation. Therefore, the n-alkane δD record could reflect an increase in seasonality of precipitation, with greater relative humidity during the early growing season. To evaluate the validity of this approach, we will systematically examine the assumptions involved in using hydrogen isotope ratios of leaf waxes as a paleoaridity index to evaluate paleohydrologic changes in the Bighorn Basin during the PETM.

Stalagmite geochemistry and the timing of the last interglacial-glacial transition in Central Europe (NE Hungary)

NASA Astrophysics Data System (ADS)

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

2009-04-01

Speleothems can provide accurate chronologies for reconstructions of climate change by combination of U/Th dating and climate-related geochemical compositions. Geochemical studies of speleothems from Central Europe are mostly based on stable C and O isotope analyses, thus, complex geochemical studies combining isotope and trace element measurements are needed for more reliable climate models for this transitional area between oceanic and continental regions. We present stable H-C-O isotope and trace element records obtained on speleothems covering the Last Interglacial (MIS 5e) and the transition to MIS 5d. A stalagmite from Baradla Cave grew from 127.5 to 110 ka. Accelerated growth rates have been detected by U/Th age data in the 127 to 126 ka and 119 to 117 ka parts. Trace element compositions and 230Th/232Th ratios suggest changes in the hydrological regime, whereby early calcite precipitates formed in fissures during the dry and cold glacial period were dissolved by the starting flux of infiltrating meteoric water (producing elevated dissolved ion concentration but low detrital Th component), then the increasing amount of dripwater during the interglacial period resulted in trace element dilution. Temperature and precipitation amount variations are also reflected by the stable isotope compositions. Oxygen isotope composition shows a continuous increase from 127.5 ka until about 118 ka most probably related to temperature rise, whereas C isotope values are shifted in negative direction suggesting increasing humidity in accordance with trace element contents. The presumably warmest period at ca. 118 ka is associated with rather arid climate as indicated by peak d18O values coinciding with the highest dD values of fluid inclusion water. This is followed by a pronounced negative shift in both O and H isotope values, similarly to recent Alpine studies (Meyer et al., 2008), most probably related to cooling. Hydrogen isotope compositions of fluid inclusion water evaluated together with calculated oxygen isotope compositions of water indicate warming and increasing significance of summer precipitation at the latest period of the last interglacial, then increasing importance of winter precipitation and/or changes in oceanic source composition during the cooling phase. The good agreement with other (Alpine and marine) records indicate a synchronous climate change. However, after a negative shift in the wet/warm phase (increasing soil activity), C isotope values start to increase already at about 119 ky BP, warning to the use of the two isotope systems as event correlation tools. In conclusion, our combined isotope and trace element study indicate a complex pattern of temperature and humidity variations during and right after the Last Interglacial. Acknowledgements — This study was financially supported by the Hungarian Scientific Research Fund (OTKA T 049713). Measurements of U-Th isotopic compositions and and 230Th dates were supported by the National Science Council grants (94-2116-M002-012, 97-2752-M002-004-PAE & -005-PAE to C.C.S.). [Meyer, M.; Spötl, C.; Mangini, A. (2008): The demise of the Last Interglacial recorded in isotopically dated speleothems from the Alps. Quaternary Science Reviews, 27, 476-496.

Deuterium isotope effect on 13C chemical shifts of tetrabutylammonium salts of Schiff bases amino acids.

PubMed

Rozwadowski, Z

2006-09-01

Deuterium isotope effects on 13C chemical shift of tetrabutylammonium salts of Schiff bases, derivatives of amino acids (glycine, L-alanine, L-phenylalanine, L-valine, L-leucine, L-isoleucine and L-methionine) and various ortho-hydroxyaldehydes in CDCl3 have been measured. The results have shown that the tetrabutylammonium salts of the Schiff bases amino acids, being derivatives of 2-hydroxynaphthaldehyde and 3,5-dibromosalicylaldehyde, exist in the NH-form, while in the derivatives of salicylaldehyde and 5-bromosalicylaldehyde a proton transfer takes place. The interactions between COO- and NH groups stabilize the proton-transferred form through a bifurcated intramolecular hydrogen bond. Copyright (c) 2006 John Wiley & Sons, Ltd.

Fin whales as bioindicators of multi-decadal change in carbon and oxygen stable isotope shifts in the North Atlantic.

PubMed

Borrell, A; Saiz, L; Víkingsson, G A; Gaufier, P; López Fernández, A; Aguilar, A

2018-07-01

Global changes, and particularly the massive release of CO 2 to the atmosphere and subsequent global warming, have altered the baselines of carbon and oxygen stable isotopic ratios. Temporal shifts in these baselines can be advantageously monitored through cetacean skin samples because these animals are highly mobile and therefore integrate in their tissues the heterogeneity of local environmental signals. In this study, we examine variation of δ 13 C and δ 18 O values in the skin of fin whales sampled over three decades in two different North Atlantic feeding grounds: west Iceland and northwest Spain. These locations are situated about 2700 km apart and thus represent a wide latitudinal range within the North Atlantic Ocean. The δ 13 C decrease in both areas is attributed to the burning of fossil fuels and increased deforestation worldwide, the so-called Suess effect. The dissimilarity in the magnitude of the shift between the two areas is coincidental with previous information on local shifts and lies within the ranges of variation observed. δ 18 O values experienced a minimal, yet significant change in fin whales from W Iceland (a decline of -0.44‰ between 1986 and 2013) but not in those from NW Spain. This is in concordance with a higher rise in temperatures in the former area than in the latter. The study validates the use of cetacean skin to monitor temporal and geographical shifts in stable isotopic values and alerts that, when applying this tool to ecological research, comparisons between sample sets should take into account temporal and latitudinal scales. Copyright © 2018 Elsevier Ltd. All rights reserved.

Laser cooling and imaging of individual radioactive +90Sr ions

NASA Astrophysics Data System (ADS)

Jung, Kyunghun; Iwata, Yoshihiro; Miyabe, Masabumi; Yamamoto, Kazuhiro; Yonezu, Tomohisa; Wakaida, Ikuo; Hasegawa, Shuichi

2017-10-01

We have developed an apparatus integrating resonance-ionization, ion-trap, and laser-cooling techniques for an ultratrace radioactive isotope 90Sr analysis. Trapped +90Sr isotope ions were laser cooled, and their 4 d 3/2 2D →5 p 1/2 2P transition isotope shift was experimentally measured to be -281 (17 ) MHz by comparing individual spectra of +88Sr and +90Sr ions. Crystallization of +90Sr was carried out using the resonance frequency value confirmed in our experiment, and then +90Sr individual ions were successfully observed.

Carbon stable isotopic composition of soluble sugars in Tillandsia epiphytes varies in response to shifts in habitat.

PubMed

Goode, Laurel K; Erhardt, Erik B; Santiago, Louis S; Allen, Michael F

2010-07-01

We studied C stable isotopic composition (delta(13)C) of bulk leaf tissue and extracted sugars of four epiphytic Tillandsia species to investigate flexibility in the use of crassulacean acid metabolism (CAM) and C(3) photosynthetic pathways. Plants growing in two seasonally dry tropical forest reserves in Mexico that differ in annual precipitation were measured during wet and dry seasons, and among secondary, mature, and wetland forest types within each site. Dry season sugars were more enriched in (13)C than wet season sugars, but there was no seasonal difference in bulk tissues. Bulk tissue delta(13)C differed by species and by forest type, with values from open-canopied wetlands more enriched in (13)C than mature or secondary forest types. The shifts within forest habitat were related to temporal and spatial changes in vapor pressure deficits (VPD). Modeling results estimate a possible 4% increase in the proportional contribution of the C(3) pathway during the wet season, emphasizing that any seasonal or habitat-mediated variation in photosynthetic pathway appears to be quite moderate and within the range of isotopic effects caused by variation in stomatal conductance during assimilation through the C(3) pathway and environmental variation in VPD. C isotopic analysis of sugars together with bulk leaf tissue offers a useful approach for incorporating short- and long-term measurements of C isotope discrimination during photosynthesis.

Carbon stable isotopic composition of soluble sugars in Tillandsia epiphytes varies in response to shifts in habitat

PubMed Central

Erhardt, Erik B.; Santiago, Louis S.; Allen, Michael F.

2010-01-01

We studied C stable isotopic composition (δ13C) of bulk leaf tissue and extracted sugars of four epiphytic Tillandsia species to investigate flexibility in the use of crassulacean acid metabolism (CAM) and C3 photosynthetic pathways. Plants growing in two seasonally dry tropical forest reserves in Mexico that differ in annual precipitation were measured during wet and dry seasons, and among secondary, mature, and wetland forest types within each site. Dry season sugars were more enriched in 13C than wet season sugars, but there was no seasonal difference in bulk tissues. Bulk tissue δ13C differed by species and by forest type, with values from open-canopied wetlands more enriched in 13C than mature or secondary forest types. The shifts within forest habitat were related to temporal and spatial changes in vapor pressure deficits (VPD). Modeling results estimate a possible 4% increase in the proportional contribution of the C3 pathway during the wet season, emphasizing that any seasonal or habitat-mediated variation in photosynthetic pathway appears to be quite moderate and within the range of isotopic effects caused by variation in stomatal conductance during assimilation through the C3 pathway and environmental variation in VPD. C isotopic analysis of sugars together with bulk leaf tissue offers a useful approach for incorporating short- and long-term measurements of C isotope discrimination during photosynthesis. PMID:20155286

Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption.

PubMed

Höhener, Patrick; Yu, Xianjing

2012-03-15

Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from -0.13±0.04‰ (benzene) to -0.52±0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between -2.4 and -9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from -19±5.4‰ (benzene) to -64±30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for (13)C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants. Copyright © 2011 Elsevier B.V. All rights reserved.

Carbon isotopic shift and its cause at the Wuchiapingian-Changhsingian boundary in the Upper Permian at the Zhaojiaba section, South China: Evidences from multiple geochemical proxies

NASA Astrophysics Data System (ADS)

Wei, Hengye; Yu, Hao; Wang, Jianguo; Qiu, Zhen; Xiang, Lei; Shi, Guo

2015-06-01

The Late Permian environmental change, connecting the Guadalupian-Lopingian (G-L) (Middle-Upper Permian) boundary mass extinction and the Permain-Triassic (P-Tr) boundary mass extinction, has attracted more and more attentions. A significant negative shift for carbon isotope had been found at the Wuchiapingian-Changhsingian (W-C) boundary in the Upper Permian recently. However, the cause(s) of this negative excursion is still unknown. To resolve this problem, we analyzed the bulk organic carbon isotope, total organic carbon (TOC) content, pyritic sulfur (Spy) content, major element concentrations, and molecular organic biomarkers in the Wujiaping and Dalong formations in the Upper Permian from the Zhaojiaba section in western Hubei province, South China. Our results show that (1) there was a significant negative excursion in organic carbon isotopes at the W-C boundary and again a negative excursion at the top of Changhsingian stage; (2) the significant negative excursion at the W-C boundary was probably a global signal and mainly caused by the low primary productivity; and (3) the negative carbon isotope excursion at the top of Changhsingian was probably caused by the Siberian Traps eruptions. A decline in oceanic primary productivity at the W-C boundary probably represents a disturbance of the marine food web, leading to a vulnerable ecosystem prior to the P-Tr boundary mass extinction.

A new serial pooling method of shifted tree ring blocks to construct millennia long tree ring isotope chronologies with annual resolution.

PubMed

Boettger, Tatjana; Friedrich, Michael

2009-03-01

The study presents a new serial pooling method of shifted tree ring blocks for the building of isotope chronologies. This method combines the advantages of traditional 'serial' and 'intertree' pooling, and can be recommended for the construction of sub-regional long isotope chronologies with sufficient replication, and on annual resolution, especially for the case of extremely narrow tree rings. For Scots pines (Pinus sylvestris L., Khibiny Low Mountains, NW Russia) and Silver firs (Abies alba Mill., Franconia, Southern Germany), serial pooling of five consecutive tree rings seems appropriate because the species- and site-specific particularities lead to blurs of climate linkages in their tree rings for the period up to ca. five years back. An equivalent to a five-year running means that curve gained on the base annual data sets of single trees can be derived from the analysis of yearly shifted five-year blocks of consecutive tree rings, and therefore, with approximately 20% of the expense. Good coherence of delta(13)C- and delta(18)O-values between calculated means of annual total rings or late wood data and means of five-year blocks of consecutive total tree rings analysed experimentally on most similar material confirms this assumption.

Compound-specific amino acid isotopic analyses of invertebrates in the Chukchi Sea: New insights on food web dynamics

NASA Astrophysics Data System (ADS)

Zhang, M.; Cooper, L. W.; Biasatti, D. M.; Kedra, M.; Grebmeier, J. M.

2016-02-01

Food web dynamics in the Chukchi Sea have been previously evaluated using bulk analysis of stable carbon and nitrogen isotopes of organisms. However, recent advances in compound-specific stable isotope analysis of amino acids indicate the potential to better identify the contributions of different dietary sources (e.g., pelagic vs. benthic, ice algae vs. phytoplankton) and to resolve complexities of food web structure that are difficult to address with bulk isotope analysis. Here we combine amino acid δ13C and δ15N data measured from primary producers and tissues of bivalves, polychaetes and other benthic invertebrates collected during two cruises in the summer of 2013 and 2015 in the Pacific Arctic. The results showed spatial variation of carbon isotope values in amino acids with difference up to 6 per mil for each individual species or taxa studied, indicating a shift in the food-web baseline geographically. Furthermore, the spatial variation in isotopic values was related to environmental factors, specifically sea ice extent, and total organic carbon, total organic nitrogen and the carbon/nitrogen ratio of the organic fractions of surface sediments. Results also indicated that trophic levels, as estimated by differences in the nitrogen isotope composition of glutamic acid and phenylalanine [Δ15Nglu-phe (δ15Nglu - δ15Nphe)], varied spatially by 0.5 to 1.5 trophic levels for certain species or taxa such as Macoma calcarea, Maldanidae and Ampelisca, indicating trophic level shifts that were associated with the food quality of organic matter in the organic fraction of the sediments. These results can be potentially used to predict future food web change in this high latitude marine system that is known for its ecological importance and on-going environmental changes, including warming and sea ice decline.

Long-Term Precipitation Isotope Ratios (δ18O, δ2H, d-excess) in the Northeast US Reflect Atlantic Ocean Warming and Shifts in Moisture Sources

NASA Astrophysics Data System (ADS)

Puntsag, T.; Welker, J. M.; Mitchell, M. J.; Klein, E. S.; Campbell, J. L.; Likens, G.

2014-12-01

The global water cycle is exhibiting dramatic changes as global temperatures increase resulting in increases in: drought extremes, flooding, alterations in storm track patterns with protracted winter storms, and greater precipitation variability. The mechanisms driving these changes can be difficult to assess, but the spatial and temporal patterns of precipitation water isotopes (δ18O, δ2H, d-excess) provide a means to help understand these water cycle changes. However, extended temporal records of isotope ratios in precipitation are infrequent, especially in the US. In our study we analyzed precipitation isotope ratio data from the Hubbard Brook Experimental Forest in New Hampshire that has the longest US precipitation isotope record, to determine: 1) the monthly composited averages and trends from 1967 to 2012 (45 years); ; 2) the relationships between abiotic properties such as local temperatures, precipitation type, storm tracks and isotope ratio changes; and 3) the influence of regional shifts in moisture sources and/or changes in N Atlantic Ocean water conditions on isotope values. The seasonal variability of Hubbard Brook precipitation isotope ratios is consistent with other studies, as average δ18O values are ~ -15‰ in January and ~ -5 ‰ in July. However, over the 45 year record there is a depletion trend in the δ 18O values (becoming isotopically lighter with a greater proportion of 16O), which coupled with less change in δ 2H leads to increases in d-excess values from ~ -10‰ around 1970 to greater than 10‰ in 2009. These changes occurred during a period of warming as opposed to cooling local temperatures indicating other processes besides temperature are controlling long-term water isotope traits in this region. We have evidence that these changes in precipitation isotope traits are controlled in large part by an increases in moisture being sourced from a warming N Atlantic Ocean that is providing evaporated, isotopically-depleted precipitation to the region. Thus, the warming of the N Atlantic Ocean appears to influence the climate and the precipitation isotopes of Northeastern coastal regions and could be a larger water source to watersheds in this North American region.

Rovibrational bound states of SO2 isotopologues. II: Total angular momentum J = 11-20

NASA Astrophysics Data System (ADS)

Kumar, Praveen; Poirier, Bill

2015-11-01

In a two-part series, the rovibrational bound states of SO2 are investigated in comprehensive detail, for all four stable sulfur isotopes 32-34,36S. All low-lying rovibrational energy levels-both permutation-symmetry-allowed and not allowed-are computed, for all values of total angular momentum in the range J = 0-20. The calculations have carried out using the ScalIT suite of parallel codes. The present study (Paper II) examines the J = 11-20 rovibrational levels, providing symmetry and rovibrational labels for every computed state, relying on a new lambda-doublet splitting technique to make completely unambiguous assignments. Isotope shifts are analyzed, as is the validity of ;J-shifting; as a predictor of rotational fine structure. Among other ramifications, this work will facilitate understanding of mass-independent fractionation of sulfur isotopes (S-MIF) observed in the Archean rock record-particularly as this may have arisen from self shielding. S-MIF, in turn is highly relevant in the broader context of understanding the ;oxygen revolution;.

Cu isotopes in marine black shales record the Great Oxidation Event

PubMed Central

Rodríguez, Nathalie P.; Partin, Camille A.; Andersson, Per; Weiss, Dominik J.; El Albani, Abderrazak; Rodushkin, Ilia; Konhauser, Kurt O.

2016-01-01

The oxygenation of the atmosphere ∼2.45–2.32 billion years ago (Ga) is one of the most significant geological events to have affected Earth’s redox history. Our understanding of the timing and processes surrounding this key transition is largely dependent on the development of redox-sensitive proxies, many of which remain unexplored. Here we report a shift from negative to positive copper isotopic compositions (δ65CuERM-AE633) in organic carbon-rich shales spanning the period 2.66–2.08 Ga. We suggest that, before 2.3 Ga, a muted oxidative supply of weathering-derived copper enriched in 65Cu, along with the preferential removal of 65Cu by iron oxides, left seawater and marine biomass depleted in 65Cu but enriched in 63Cu. As banded iron formation deposition waned and continentally sourced Cu became more important, biomass sampled a dissolved Cu reservoir that was progressively less fractionated relative to the continental pool. This evolution toward heavy δ65Cu values coincides with a shift to negative sedimentary δ56Fe values and increased marine sulfate after the Great Oxidation Event (GOE), and is traceable through Phanerozoic shales to modern marine settings, where marine dissolved and sedimentary δ65Cu values are universally positive. Our finding of an important shift in sedimentary Cu isotope compositions across the GOE provides new insights into the Precambrian marine cycling of this critical micronutrient, and demonstrates the proxy potential for sedimentary Cu isotope compositions in the study of biogeochemical cycles and oceanic redox balance in the past. PMID:27091980

Millennial-scale isotope records from a wide-ranging predator show evidence of recent human impact to oceanic food webs

PubMed Central

Wiley, Anne E.; Ostrom, Peggy H.; Welch, Andreanna J.; Fleischer, Robert C.; Gandhi, Hasand; Southon, John R.; Stafford, Thomas W.; Penniman, Jay F.; Hu, Darcy; Duvall, Fern P.; James, Helen F.

2013-01-01

Human exploitation of marine ecosystems is more recent in oceanic than near shore regions, yet our understanding of human impacts on oceanic food webs is comparatively poor. Few records of species that live beyond the continental shelves date back more than 60 y, and the sheer size of oceanic regions makes their food webs difficult to study, even in modern times. Here, we use stable carbon and nitrogen isotopes to study the foraging history of a generalist, oceanic predator, the Hawaiian petrel (Pterodroma sandwichensis), which ranges broadly in the Pacific from the equator to near the Aleutian Islands. Our isotope records from modern and ancient, radiocarbon-dated bones provide evidence of over 3,000 y of dietary stasis followed by a decline of ca. 1.8‰ in δ15N over the past 100 y. Fishery-induced trophic decline is the most likely explanation for this sudden shift, which occurs in genetically distinct populations with disparate foraging locations. Our isotope records also show that coincident with the apparent decline in trophic level, foraging segregation among petrel populations decreased markedly. Because variation in the diet of generalist predators can reflect changing availability of their prey, a foraging shift in wide-ranging Hawaiian petrel populations suggests a relatively rapid change in the composition of oceanic food webs in the Northeast Pacific. Understanding and mitigating widespread shifts in prey availability may be a critical step in the conservation of endangered marine predators such as the Hawaiian petrel. PMID:23671094

Millennial-scale isotope records from a wide-ranging predator show evidence of recent human impact to oceanic food webs.

PubMed

Wiley, Anne E; Ostrom, Peggy H; Welch, Andreanna J; Fleischer, Robert C; Gandhi, Hasand; Southon, John R; Stafford, Thomas W; Penniman, Jay F; Hu, Darcy; Duvall, Fern P; James, Helen F

2013-05-28

Human exploitation of marine ecosystems is more recent in oceanic than near shore regions, yet our understanding of human impacts on oceanic food webs is comparatively poor. Few records of species that live beyond the continental shelves date back more than 60 y, and the sheer size of oceanic regions makes their food webs difficult to study, even in modern times. Here, we use stable carbon and nitrogen isotopes to study the foraging history of a generalist, oceanic predator, the Hawaiian petrel (Pterodroma sandwichensis), which ranges broadly in the Pacific from the equator to near the Aleutian Islands. Our isotope records from modern and ancient, radiocarbon-dated bones provide evidence of over 3,000 y of dietary stasis followed by a decline of ca. 1.8‰ in δ(15)N over the past 100 y. Fishery-induced trophic decline is the most likely explanation for this sudden shift, which occurs in genetically distinct populations with disparate foraging locations. Our isotope records also show that coincident with the apparent decline in trophic level, foraging segregation among petrel populations decreased markedly. Because variation in the diet of generalist predators can reflect changing availability of their prey, a foraging shift in wide-ranging Hawaiian petrel populations suggests a relatively rapid change in the composition of oceanic food webs in the Northeast Pacific. Understanding and mitigating widespread shifts in prey availability may be a critical step in the conservation of endangered marine predators such as the Hawaiian petrel.

Shifting diet, shifting culture? A bioarchaeological approach to island dietary development on Iron-Age Öland, Baltic Sea.

PubMed

Wilhelmson, Helene

2017-06-01

The diet and subsistence in Iron-Age Öland is debated as earlier studies and different archaeological sources seemingly provide conflicting interpretations. The objectives of this study are therefore to: (i) add new insights on diet and (ii) investigate the chronological variation in detail. It is common in studies of diet to investigate differences between datasets defined by archaeological periods (determined by artefact typology), but it is rare to explore whether these dietary changes are, in fact, well correlated with these temporal categories or not. Stable isotope analysis of 108 individuals and 25 animals was used to interpret diet in comparison with data from earlier studies. Different values of TLE (Trophic Level Effect) for δ 15 N were compared for interpretations of diet. Of the 108 individuals, 42 were subjected to 14 C analysis in this study. The isotopes from Iron-Age animals on Öland indicate that the local, contemporary ecology is specific. The human isotope values show chronological development both when pooled in chronological groups by typology and by more specific 14 C chronology. The new samples of animals as well as the use of 5‰ TLE for δ 15 N values results in the diet reinterpreted as mainly domesticate-based, with at least two shifts in diet occurring in the Iron Age. The use of 14 C dates in connection with the stable isotope results indicates a dietary transition occurring between 200 BC and AD 200, a date range that spans two typologically determined time periods. © 2017 Wiley Periodicals, Inc.

Strontium isotopic evidence of shifting inflows to Eocene Lake Uinta in the Laramide foreland of Utah

NASA Astrophysics Data System (ADS)

Davis, S. J.; Wiegand, B. A.; Chamberlain, C. P.

2007-12-01

Isotopic records from the Uinta basin in Utah are evidence of an evolving landscape during the early Cenozoic. Combined with studies of provenance and paleoflow, oxygen and carbon isotopic results have recently been interpreted to reflect changes in hydrology and catchment hypsometry as the basin responded to developing relief in the foreland. We now present strontium isotope data from lacustrine limestones indicating significant and rapid (< 1 my) shifts in the source of inflowing surface waters. Provenance of Eocene sediments has been used to argue that water spilling south from an overfilled Lake Gosiute in the Greater Green River basin caused a highstand of the lake in the Piceance Creek basin, which in turn overtopped the Douglas Creek Arch and connected with Lake Uinta in the Uinta basin. The lake highstand was extremely productive, and resulted in the deposition of the rich "Mahogany zone" oil shales. New data shows that the 87Sr/86Sr ratio of lacustrine limestones collected in the Uinta basin is generally low (< 0.7105) for most of the Eocene, but spikes higher (to 0.7122) in samples of the Main Body of the Green River Formation near and within the Mahogany zone. We interpret this data to reflect a period of input of water from Lake Gosiute, where that lake's catchments included exposed basement that was much more radiogenic. The strontium data further supports the interpretation that intraforeland basin development in the central North American Cordillera was largely controlled by shifting drainage patterns as the landscape responded to ongoing Laramide tectonism.

Informational Aspects of Isotopic Diversity in Biology and Medicine

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2004-10-01

Use of stable and radioactive isotopes in biology and medicine is intensive, yet informational aspects of isotopes as such are largely neglected (A.A.Berezin, J.Theor.Biol.,1992). Classical distinguishability (``labelability'') of isotopes allows for pattern generation dynamics. Quantum mechanically advantages of isotopicity (diversity of stable isotopes) arise from (almost perfect) degeneracy of various isotopic configurations; this in turn allows for isotopic sweeps (hoppings) by resonance neutron tunneling (Eccles mechanism). Isotopic variations of de Broglie wavelength affect quantum tunneling, diffusivity, magnetic interactions (e.g. by Lorentz force), etc. Ergodicity principle (all isoenergetic states are eventually accessed) implies possibility of fast scanning of library of morphogenetic patterns (cf metaphors of universal ``Platonic'' Library of Patterns: e.g. J.L.Borges, R.Sheldrake) with subsequent Darwinian reinforcement (e.g. by targeted mutations) of evolutionary advantageous patterns and structures. Isotopic shifts in organisms, from viruses and protozoa to mammalians, (e.g. DNA with enriched or depleted C-13) are tools to elucidate possible informational (e.g. Shannon entropy) role of isotopicity in genetic (e.g. evolutionary and morphological), dynamical (e.g. physiological and neurological) as well as medical (e.g. carcinogenesis, aging) aspects of biology and medicine.

Rapidly Assessing Changes in Bone Mineral Balance Using Natural Stable Calcium Isotopes

NASA Technical Reports Server (NTRS)

Morgan, J. L. L.; Gordon, G. W.; Romaniello, S. J.; Skulan, J. L.; Smith, S. M.; Anbar, A. D.

2011-01-01

We demonstrate that variations in the Ca isotope ratios in urine rapidly and quantitatively reflect changes in bone mineral balance. This variation occurs because bone formation depletes soft tissue of light Ca isotopes, while bone resorption releases that isotopically light Ca back into soft tissue. In a study of 12 individuals confined to bed rest, a condition known to induce bone resorption, we show that Ca isotope ratios shift in a direction consistent with net bone loss after just 7 days, long before detectible changes in bone density occur. Consistent with this interpretation, the Ca isotope variations track changes observed in N-teleopeptide, a bone resorption biomarker, while bone-specific alkaline phosphatase, a bone formation biomarker, is unchanged. Ca isotopes can in principle be used to quantify net changes in bone mass. Ca isotopes indicate an average loss of 0.62 +/- 0.16 % in bone mass over the course of this 30-day study. The Ca isotope technique should accelerate the pace of discovery of new treatments for bone disease and provide novel insights into the dynamics of bone metabolism.

Using n-alkane records to constrain carbon cycle - hydrological cycle coupling: Case study from the Northern Hemisphere mid-latitudes during the PETM

NASA Astrophysics Data System (ADS)

Krishnan, S.; Pagani, M.; Tipple, B. J.

2010-12-01

The early Eocene was a warmer world compared to the present and is characterized by rising temperatures interspersed with rapid hyperthermal events. During the largest of these rapid warming events; the Paleocene-Eocene Thermal Maximum (PETM), proxy records suggest that sea surface temperatures (SST) rose by 3-5 deg. C in the tropics (Zachos et al., 2003, Tripati and Elderfield, 2004), >5 deg. C in the Arctic (Sluijs et al., 2006) and perhaps has high as 9 deg. C in some sub-Antarctic regions (Kennett and Stott, 1991; Thomas et al., 1999). This warming is believed to be the result of massive input of 13C-depleted carbon into the ocean-atmosphere system, evidenced by the large negative carbon isotope excursion (CIE) and carbonate dissolution associated with the event. However, there are several questions regarding the exact mechanism of warming and feedbacks between the carbon cycle and climate. Did climate shift prior to the main event that led to the release of isotopically light carbon? Do we observe consistent leads or lags between changes in carbon isotopes and hydrological conditions during warm intervals? This study aims to reconstruct hydrological changes in the in the Northern Hemisphere mid-latitudes during the PETM using terrestrial biomarkers. Terrestrial biomarkers, such leaf-wax lipids stored in sediments, have the unique advantage of recording carbon and hydrogen isotopic compositions of atmospheric CO2 (modified by plant fractionation) and precipitation (modified by plant fractionation and evapotranspiration), allowing evaluation of the relative timing of carbon and hydrogen isotopic (i.e., climate) shifts. In this study, we compile and present three mid-latitude PETM records from the Northern Hemisphere, i.e. Alamedilla (Spain), Cicogna and Forada (Italy). The Cicogna and Forada sections are located in the Belluno basin (~12 km apart). Preliminary results do not indicate any significant pre-excursion hydrogen isotope changes at Cicogna, while at Forada we observe a pre-excursion shift toward more positive values. Comparison of the mean-weighted isotopic trends (to account for vegetation changes) indicates that the carbon and hydrogen isotopic compositions shift simultaneously at the start of the CIE at Cicogna and Forada and remain coupled during the latter part of the recovery. However, the most depleted values in δD do not coincide with the most negative δ13C values, suggesting that the response time of the hydrological cycle was slower than the carbon isotopic excursion. The δD trends appear to diverge from δ13C records during the initial recovery period. This difference in response and response times between the initial perturbation and recovery enable us to constrain the timing and mechanism of feedbacks. A third section (Alamedilla), located at lower latitude, will be used to test these hypotheses. The timing and average magnitudes of δD changes at these three sites will be extrapolated to infer precipitation trends during the late Paleocene, peak PETM, and early Eocene for this region and will be useful for future data-model comparisons.

Atmospheric studies of C2 white dwarfs

NASA Astrophysics Data System (ADS)

Swanson, Steven Roger

Model atmosphere and line formation calculations for the delta nu = + 1 Swan bands of the C2 molecule are presented for seven white dwarfs and are compared to high resolution optical spectra. Limits on the C-12 to C-13 ratio are computed for highly pressure broadened lines and are used to analyze the observed spectra for any sign of absorption by the (C-12)(C-13) molecule. The metal abundances in cool white dwarf atmospheres and the usefulness of the determination of the C-12 to C-13 ratio are discussed. The line center shift and the pressure broadening are used to determine a value for the van der Waals interaction constant, C6. This is done using a detailed line modelling program which explicitly includes approximately 2000 rotational transition lines within the vibrational bands, in conjunction with atmospheric models calculated by the LUCIFER atmosphere modelling program. The isotopic shift of the vibrational and rotational lines is also included in the model to compare the detectability of various C-12 to C-13 ratios. The line models fit the observed spectra with varying degrees of accuracy. One star, WD0548-001, shows an unusually small pressure shift and broadening for the high pressures that the atmospheric model predicts. The results show that only in the hottest stars with the least pressure broadened lines in this study can the isotopic effect be seen. With the data available, the best limit on the C-12 to C-13 ratio is a minimum of 40 for WD0856 + 331. The models show that even for very high signal to noise data, the isotopic shift in the Swan bands in very cool white dwarfs would be difficult to separate from the pressure broadening effects. It is shown that the isotopic ratio is high enough to rule out the possibility that the carbon is a relic from previous CNO burning.

Backbone dynamics of a model membrane protein: measurement of individual amide hydrogen-exchange rates in detergent-solubilized M13 coat protein using /sup 13/C NMR hydrogen/deuterium isotope shifts

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

Henry, G.D.; Weiner, J.H.; Sykes, B.D.

Hydrogen-exchange rates have been measured for individual assigned amide protons in M13 coat protein, a 50-residue integral membrane protein, using a /sup 13/C nuclear magnetic resonance (NMR) equilibrium isotope shift technique. The locations of the more rapidly exchanging amides have been determined. In D/sub 2/O solutions, a peptide carbonyl resonance undergoes a small upfield isotope shift (0.08-0.09 ppm) from its position in H/sub 2/O solutions; in 1:1 H/sub 2/O/D/sub 2/O mixtures, the carbonyl line shape is determined by the exchange rate at the adjacent nitrogen atom. M13 coat protein was labeled biosynthetically with /sup 13/C at the peptide carbonyls ofmore » alanine, glycine, phenylalanine, proline, and lysine, and the exchange rates of 12 assigned amide protons in the hydrophilic regions were measured as a function of pH by using the isotope shift method. This equilibrium technique is sensitive to the more rapidly exchanging protons which are difficult to measure by classical exchange-out experiments. In proteins, structural factors, notably H bonding, can decrease the exchange rate of an amide proton by many orders of magnitude from that observed in the freely exposed amides of model peptides such as poly(DL-alanine). With corrections for sequence-related inductive effects, the retardation of amide exchange in sodium dodecyl sulfate solubilized coat protein has been calculated with respect to poly(DL-alanine). The most rapidly exchanging protons, which are retarded very little or not at all, are shown to occur at the N- and C-termini of the molecule. A model of the detergent-solubilized coat protein is constructed from these H-exchange data which is consistent with circular dichroism and other NMR results.« less

Stable isotopic compositions of carbon in vegetation and soil organic matter along the bioclimatic transect, North Caucasus

NASA Astrophysics Data System (ADS)

Kovda, Irina; Morgun, Evgeny; Golubeva, Natalia

2010-05-01

Stable isotopic composition of carbon in plant species and soil organic matter was investigated along the bioclimatic transect in the North Caucasus. The aim of this research was to find the possible shift of stable isotopic composition of carbon reflecting the gradual successive changes of landscapes connected with the changes of climatic conditions (temperature, precipitation, air humidity) at a various absolute heights above sea level i.e. along the vertical zonation. The study site was located in the North Caucasus near Arkhiz, Big Zelentchuk valley (43o33-40'N; 41o16-27'E). Soil and vegetation samples were collected along Precaucasus and Caucasus slopes at an absolute heights interval of 1280 - 2065 m. Soils are formed at eluvo-deluvium of noncarbonated silicate massive rocks under warm temperate climate with MAT 4-5oC and MAP ~ 860 mm and more. Samples of vegetation (whole grasses and tree leaves) represented several altitudinal vegetation belts including forest and subalpine belts with coniferous (pine, spruce, fir), mixed coniferous-deciduous (fir + beech), broad-leaved (beech, maple), small-leaved (birch, aspen) forests, elfin birch wood and subalpine meadows. Stable isotope composition of carbon was determined using IRMS Finnigan Delta V+. Stable isotopic composition of vegetal species ranges from -33.04 to -27.29 o/oo with the general trend of lighter δ13С with the decreasing of absolute heights. The most heavier δ13С = ~ -27o/oo were found in subalpine meadow plants, while at a smaller altitudes in the forest belt δ13С shifts to ~ 30-31, and up to ~ - 32-33o/oo. More clear regularities were found for vegetation specimens grouped into three categories such as "trees", "grasses" and "litter". δ13С of each category clearly shifts to the lighter values with the decrease of absolute heights i.e from subalpine meadows to spruce-broad-leaved forests. δ13С shift is about 2,49o/oo for trees, 1,75-4,92 o/oo for grasses and ~ 1,8 o/oo for the litter. The complimentary determination of δ15N have shown large variability from -3,59 to + 18,24o/oo which corresponds with the expected large variation of δ15N of plant debris and general trend of lighter δ15N during the decomposition. δ13С of soil organic matter varies from -28.92 to -24.99 o/oo. The similar trend for lighter stable isotopic composition of carbon at a lower absolute heights i.e. in forest belt was found for soil organic matter. The whole picture of δ13С values in soil samples is quite complicated and needs further investigation. As a result, the isotopic characteristic of carbon and nitrogen in vegetal specimens, and carbon in soil organic matter were obtained along a bioclimatic topocatena. The general trend of lighter C isotopic composition was found. It is known that lighter isotopic composition correlates with cooler and/or wetter climate. While the temperature gradually decreases upward, the changes of precipitation are not linear. Further research is needed to better explain the variation of stable isotopic compositions in dependence of those climatic factors. This research was supported by the Presidium of Russian Academy of Sciences, Program 14

Lamb shifts and hyperfine structure in 6Li+ and 7Li+: Theory and experiment

NASA Astrophysics Data System (ADS)

Riis, E.; Sinclair, A. G.; Poulsen, O.; Drake, G. W. F.; Rowley, W. R. C.; Levick, A. P.

1994-01-01

High-precision laser-resonance measurements accurate to +/-0.5 MHz or better are reported for transitions among the 1s2s 3S1-1s2p 3PJ hyperfine manifolds for each of J=0, 1, and 2 in both 6Li+ and 7Li+. A detailed analysis of hyperfine structure is performed for both the S and P states, using newly calculated values for the magnetic dipole and electric quadrupole coupling constants, and the hyperfine shifts subtracted from the measurements. The resulting transition frequencies are then analyzed on three different levels. First, the isotope shifts in the fine-structure splittings are calculated from the relativistic reduced mass and recoil terms in the Breit interaction, and compared with experiment at the +/-0.5-MHz level of accuracy. This comparison is particularly significant because J-independent theoretical uncertainties reduce through cancellation to the +/-0.01-MHz level. Second, the isotope shifts in the full transition frequencies are used to deduce the difference in rms nuclear radii. The result is Rrms(6Li)-Rrms(7Li)=0.15+/-0.01 fm, in agreement with nuclear scattering data, but with substantially improved accuracy. Third, high-precision calculations of the low-order non-QED contributions to the transition frequencies are subtracted from the measurements to obtain the residual QED shifts. The isotope-averaged and spin-averaged effective shift for 7Li+ is 37 429.40+/-0.39 MHz, with an additional uncertainty of +/-1.5 MHz due to finite nuclear size corrections. The accuracy of 11 parts per million is the best two-electron Lamb shift measurement in the literature, and is comparable to the accuracies achieved in hydrogen. Theoretical contributions to the two-electron Lamb shift are discussed, including terms of order (αZ)4 recently obtained by Chen, Cheng, and Johnson [Phys. Rev. A 47, 3692 (1993)], and the results used to extract a QED shift for the 2 3S1 state. The result of 30 254+/-12 MHz is shown to be in good accord with theory (30 250+/-30 MHz) when two-electron corrections to the Bethe logarithm are taken into account by a 1/Z expansion method.

The end-Permian regression in the western Tethys: sedimentological and geochemical evidence from offshore the Persian Gulf, Iran

NASA Astrophysics Data System (ADS)

Tavakoli, Vahid; Naderi-Khujin, Mehrangiz; Seyedmehdi, Zahra

2018-04-01

Detailed sedimentological and geochemical records across the Permian-Triassic boundary (PTB) in five offshore wells of the central Persian Gulf served to interpret the end-Permian sea-level change in this region. A decrease in sea level at the PTB was established by petrographical and geochemical study of the boundary. Thin sections showed that Upper Permian strata are composed of dolomite with minor anhydrite, changing into limestone in Lower Triassic sediments. Brine dilution toward the boundary supports sea-level fall in the Permian-Triassic transition, reflected by a decrease in anhydrite content and a shallowing-upward trend from lagoonal to peritidal facies. Isotopic changes at the boundary are in favor of sea-level fall. Changes in both carbon (from about 4 to -1‰) and oxygen (from 2 to -5‰) stable isotopes show negative excursions. The shift in carbon isotope values is a global phenomenon and is interpreted as resulting from carbonate sediment interaction with 12C-rich waters at the end-Permian sea-level fall. However, the oxygen isotope shift is attributed to the effect of meteoric waters with negative oxygen isotope values. The increase in strontium isotope ratios is also consistent with the high rate of terrestrial input at the boundary. The effect of meteoric conditions during diagenesis is evident from vuggy and moldic porosities below the PTB. The following transgression at the base of the Triassic is evident from the presence of reworked fossils and intraclasts resulting from deposition from agitated water.

Evaluating climate controls on isotopic shifts in high-altitude forests during the Last Interglacial

NASA Astrophysics Data System (ADS)

Insel, N.; Berkelhammer, M. B.; Sturm, C.; Karimova, G.

2016-12-01

Forests play a significant role in the global carbon cycle, and influence climate through their effect on albedo and latent heat flux. Predicting the response of these ecosystems to climate change is complicated by competing influences between rising CO2, warming, and shifts in hydrology such as timing, rate, and type of precipitation. A key to detection and prediction of future regional and global changes of modern ecosystems lies in understanding the causes and characteristics of historical variations at the ecosystem level. The Last Interglacial (LIG: 130 to 116 ka) is the most recent period in Earth's history when growing season temperature exceeded those of today. In this study, we are using isotope-enabled regional climate model (REMOiso) simulations under LIG (115ka, 125 ka and 135 ka) and modern forcings to evaluate climate controls on boreal forest in the western US. In particular, we investigate (1) changes in moisture sources and moisture transport, (2) changes in the annual and seasonal extent and duration of precipitation, and (3) temperature variations to explore how ecosystem carbon and water fluxes change under coupled temperature and precipitation variability. Eemian wood samples from the Rocky Mountains in Colorado show a progressive increase in the 18O seasonal cycle that may be related to trees utilizing isotopically enriched monsoonal moisture. However, Eemian climate simulations (125ka) incorporate orbital forcings that result in stronger seasonal changes in temperature, precipitation, and snow cover in comparison to today, while annual anomalies are small. The seasonal shift in climate affects the water availability and the length of growing season for Eemian plants. Model results indicate only a very slight increase in monsoonal moisture transport from the south, resulting in slightly wetter conditions in western Colorado, but slightly drier conditions in the eastern part. Preliminary results suggest that changes in the North American monsoon system were not sufficient to explain the observed isotopic enrichment in Eemian wood samples. Current isotope simulations address changes in the seasonal isotopic cycle in the precipitation during the Eemian and will allow us to distinguish tree's reliance on summer or winter moisture sources more clearly.

Accounting for cyanide and its degradation products at three Nevada gold mines; constraints from stable C- and N-isotopes

USGS Publications Warehouse

Johnson, C.A.; Grimes, D.J.; Rye, R.O.

1998-01-01

An understanding of the fate of cyanide (CN-) in mine process waters is important for addressing environmental concerns and for taking steps to minimize reagent costs. The utility of stable isotope methods in identifying cyanide loss pathways has been investigated in case studies at three Nevada gold mines. Freshly prepared barren solutions at the mines have cyanide d15N and d13C values averaging -4 ? and -36 ?, respectively, reflecting the nitrogen and carbon sources used by commercial manufacturers, air and natural gas methane. Pregnant solutions returning from ore heaps display small isotopic shifts to lower d15N and d13C values. The shifts are similar to those observed in laboratory experiments where cyanide was progressively precipitated as a cyanometallic compound, and are opposite in sign and much smaller in magnitude than the shifts observed in experiments where HCN was offgassed. Offgassing is inferred to be a minor cyanide loss mechanism in the heap leach operations at the three mines, and precipitation as cyanometallic compounds, and possibly coprecipitation with ferric oxides, is inferred to be an important loss mechanism. Isotopic analysis of dissolved inorganic carbon (DIC) shows that uptake of high d13C air CO2 has been important in many barren and pregnant solutions. However, DIC in reclaim pond waters at all three mines has low d13C values of -28 to -34 ? indicating cyanide breakdown either by hydrolysis or by other chemical pathways that break the C-N bond. Isotope mass balance calculations indicate that about 40 % of the DIC load in the ponds, at a minimum, was derived from cyanide breakdown. This level of cyanide hydrolysis accounts for 14-100 % of the dissolved inorganic nitrogen species present in the ponds. Overall, isotope data provide quantitative evidence that only minor amounts of cyanide are lost via offgassing and that significant amounts are destroyed via hydrolysis and related pathways. The data also highlight the possibility that significant cyanide may be either retained in the ore heaps or destroyed via other chemical pathways.

The nature of abrupt climate change during the last glacial period from detailed isotopic records from the NGRIP ice core

NASA Astrophysics Data System (ADS)

Popp, T. J.; Svensson, A.; Steffensen, J. P.; Johnsen, S. J.; White, J. W. C.

2009-04-01

Isotopic and chemical impurity records from Greenland ice cores with sub-annual resolution across three fast climate transitions of the last deglacial termination reveal complex patterns of environmental change for the onset of Greenland Interstadial 1 (GI-1 or Bølling), the onset of Greenland Stadial 1 (GS-1 or Younger Dryas), and the onset of the Holocene. In the NGRIP ice core each of these transitions is initiated by a 1-3 year mode shift in deuterium excess, which is a proxy for the Greenland precipitation moisture source. These mode shifts in deuterium excess are decoupled in time from the isotopic (deuterium and oxygen-18) transitions from which they are derived. In general the abrupt isotopic transitions follow the corresponding deuterium excess shifts and span decades rather than years. Similar data from GISP2 confirms the clear deuterium excess mode shifts for transitions from cold states to warm states; however the abrupt deuterium excess transition at the onset of GS-1 is not expressed in a similar way at GISP2. Ironically, it appears that this cooling at the beginning of the Younger Dryas, for which we have theories of the triggering event, is less clearly recorded than warming events, the triggering of which is still poorly understood. Along with other available paleo-data, these results indicate that the sum of an abrupt climate change is composed of multiple responses from different parts of the climate system. These responses can be separated by as little as a single year to a few decades and the collection of these responses result in a variety of abrupt transitions giving each a unique anatomy. Here we expand this type of analysis with new isotope, deuterium excess, and accumulation rate time series from NGRIP across the abrupt transitions associated with several interstadial events of the Last Glacial period (Dansgaard-Oeschger events). Indeed the temporal phasing of deuterium excess and the isotopic content of the ice can vary from one event to the next and emerging patterns may depend on the conditions associated with specific events such as Heinrich Events and ice volume boundary conditions. Together with modeling and chemical impurity data, these patterns will provide clues to the timing and origin of ocean and atmospheric changes that comprise an abrupt climate change. The emerging picture indicates that abrupt climate changes have both a temporal and geographic anatomy that can change from one event to the next in how they are recorded across Greenland.

Tracing Pleistocene to Holocene meltwater events and provenance of sediments in Baffin Bay using radiogenic isotope signals

NASA Astrophysics Data System (ADS)

Kirillova, Valeriia; Kasemann, Simone A.; Lucassen, Friedrich

2016-04-01

Large meltwater discharge is the principal carrier of detritus from the continent into the ocean and the dispersion of this detritus by ocean currents is a measure for the spatially focused addition of freshwater in the ocean in the high latitude areas. To trace Greenland ice sheet dynamics and freshwater routing during late Pleistocene to Holocene climate transition, we generate strontium (Sr), neodymium (Nd) and lead (Pb) isotope records on sediment cores in the Baffin Bay: GeoTÜ SL 170, covering the last 18.000 years of climate history and GeoTÜ SL 174, covering 40.000 years. Sr, Nd and Pb isotopes are used as proxies for the provenance of continental detritus and seawater sources. Isotope analyses were performed on two separated fractions from the sedimentary core material: the chemically leached fraction and the remaining detritus. Leachates are supposed to represent Fe-Mn coatings formed on the surface of the sediment grains and to reflect the bottom water signal. The detrital fraction acts as a tracer for the meltwater event and weathering regime of the nearby continental masses. For the detrital fraction of the core SL 170, a pronounced shift can be observed in all three isotope systems at ˜ 12 ka, what coincides with the Younger Dryas cold event. For the detrital fraction the 87Sr/86Sr is around ˜0,72 before the event and reaches up to ˜0,74 after. Nd isotope composition (ɛNd) changed from ˜-26 to ˜-32. The shift suggests a change in the continental sources from West and West-South Greenland to the Baffin Island and Canadian Archipelago. It can be explained by the ice sheet melting processes. The 206Pb/204Pb values for the detrital fraction range from ˜17 before the shift to ˜18 after. On the contrary, the leachates show pronounced radiogenic signatures with values changing from ˜21 to ˜23. The reason for such an unusual high values is most likely in the composition of the leached material, which doesn't seem to show the presence of Fe-Mn coatings as was suggested before. The work on the second core SL 174 is in progress. Up to now the results show similar patterns for isotope ratios as in the case of SL 170.

Insights into Paleogene biogeochemistry from coupled carbon and sulfur isotopes in foraminiferal calcite.

NASA Astrophysics Data System (ADS)

Rennie, V.; Paris, G.; Abramovitch, S.; Sessions, A. L.; Adkins, J. F.; Turchyn, A. V.

2014-12-01

The Paleogene witnessed large-scale environmental changes, including the beginning of long-term Cenozoic cooling. The carbon isotope composition of foraminiferal calcite suggests a major reorganization of the carbon cycle over the Paleogene, with enhanced organic carbon burial in the Paleocene, and subsequent oxidation of this organic carbon or increased volcanism throughout the Eocene. The sulfur cycle is linked to the carbon cycle via the breakdown of organic carbon during bacterial sulfate reduction. Over geological time, carbon and sulfur isotopic shifts are often coupled due to enhanced pyrite burial being coupled to enhanced organic carbon burial, and enhanced pyrite weathering being coupled to enhanced organic carbon weathering. However, over the Paleogene, carbon and sulfur isotopes are fully decoupled, with the sulfur isotope record showing only one major shift in the early Eocene, after most of the carbon isotope variability is complete. One complication of interpreting the evolution of the sulfur cycle over the Cenozoic, is the fact that the mineral proxies used (typically barite) may not be temporally coincident with those used to reconstruct the carbon cycle (typically carbonate). Furthermore, these minerals are preserved in different locations, and therefore often must be extracted from different sediment cores in different ocean basins, leading to age-model uncertainty when the records are merged. To properly ascertain the phasing between early Cenozoic changes in the carbon cycle and the sulfur cycle, we would ideally measure all isotope records on the same mineral. A new sulfur isotope analytical technique [1] has been optimised for foraminiferal calcite as a proxy for seawater δ34SSO4. The δ34SSO4 in foraminiferal calcite can then be tied to records of carbon isotopes from stratigraphically identical samples, resolving previous age model uncertainties. We present coupled carbon and sulfur isotope records from the same core over the early-to-mid Eocene, to better resolve the relative timing of changes in the carbon and sulfur cycles. We use a numerical model to explore the environmental changes necessary for the observed evolution in both the carbon and sulfur cycles. [1] Paris et al, 2013 Chemical Geology, 345, 50-61

Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

2017-04-01

In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

Use of Multiple Isotopic Systems to Interpret Ecosystem Processes in Hawaii

NASA Astrophysics Data System (ADS)

Chadwick, O.; Derry, L.; Vitousek, P.

2007-12-01

The Hawaiian Islands are an excellent natural laboratory for studying the way in which ecosystems develop and function under varying climates. The mantle-derived basalt parent material provides a constant reaction matrix, the trade winds provide an asymmetric climate pattern that means that the same-age lava flows can be studied under different forcing factors, the relatively few plant species that made it to Hawaii provide a simplified biotic influence on substrate. In essence, we find that the geochemical evolution of basalt weathering provides shifting boundary conditions that constrain ecosystem potentialities, and allows us to apply a number of isotopic systems to enhance the specificity of our interpretation of ecosystem processes. We have applied the following isotopes to assist us in understanding the processes that impact ecosystems: O, C, Sr, Ca, N, Si and Be, and are presently exploring the use of S and Mg. We use these isotopic systems within a matrix of controls that allows us to focus on specific questions. The isotopic signatures from different isotopic systems can define climate- response patterns that are non-linear with each defining different threshold and plateau in rainfall space. Measurement of these isotopic systems allows us to evaluate multiple chemical behaviors at once and to evaluate expected responses to perturbations to any of these tracers in response to past or future changes in climate or other ecosystem drives such as land cover change. For instance, based on deep-soil samples, the plants that grew before humans reached Hawaii have C13 values that drop from -14 per mil to -26 per mil as rainfall increases from 200 mm to 3000 mm. Today the surface-soil values remain close to -14 per mil throughout the rainfall gradient due to the introduction of C4 grasses for pasture. Along the same rainfall gradient, Sr isotopes demonstrate that as C3 plants began to predominate there was a fundmental shift in nutrients supplied from rocks to those supplied by rainfall.

Bulk and compound-specific isotope analysis of long-chain n-alkanes from a 85,000 year sediment core from Lake Peten Petén Itzá, Guatemala

NASA Astrophysics Data System (ADS)

Mays, J.; Brenner, M.; Curtis, J. H.; Curtis, K.; Hodell, D. A.; Correa-Metrio, A.; Escobar, J.; Dutton, A. L.; Zimmerman, A. R.; Guilderson, T. P.

2013-12-01

Sediment core PI-6 from Lake Petén Itzá, Guatemala possesses an 85-ka record of climate from lowland Central America. Variations in sediment lithology suggest large, abrupt changes in precipitation during the last glacial and deglacial periods, and into the early Holocene. Study of cores from nearby Lake Quexil demonstrated the utility of using the carbon isotopic composition of leaf wax n-alkanes to infer changes in terrestrial vegetation (Huang et al. 2001). Forty-nine samples were taken from composite Petén Itzá core PI-6 to measure carbon isotopes of bulk organic carbon and long-chain n alkanes. Changes in δ13C values indicate shifts in the relative proportion of C3 to C4 biomass. The record shows largest δ13C variations are associated with Heinrich Events. Carbon isotope values in sediments deposited during the Last Glacial Maximum (LGM) indicate moderate precipitation and little rainfall fluctuation. The deglacial was a period of pronounced climate variability, e.g. the Bölling-Allerod and Younger Dryas. Arid times of the deglacial were inferred from samples with the greatest δ13C values in organic matter, reflecting the largest proportion of C4 plants. Such inferences are supported by stable isotope measurements on ostracod shells and analysis of pollen from the same sample depths in core PI-6. Carbon stable isotope measures on bulk organic carbon and n alkane compounds show similar trends throughout the record and the C:N ratio of Petén Itzá sediments indicates a predominantly allochthonous source for bulk organic matter. Hence, isotope measures on bulk organic carbon (δ13CTOC) in sediments from this lake are sufficient to infer climate-driven shifts in vegetation, making n-alkane extraction and isotope analysis superfluous.

Shifting material source of Chinese Loess since ~2.7 Ma reflected by Sr isotopic composition.

PubMed

Zhang, Wenfang; Chen, Jun; Li, Gaojun

2015-05-21

Deciphering the sources of eolian dust on the Chinese Loess Plateau (CLP) is fundamental to reconstruct paleo-wind patterns and paleo-environmental changes. Existing datasets show contradictory source evolutions of eolian dust on the CLP, both on orbital and tectonic timescales. Here, the silicate Sr and Nd isotopic compositions of a restricted grain size fraction (28-45 μm) were measured to trace the source evolution of the CLP since ~2.7 Ma. Our results revealed an unchanged source on orbital timescales but a gradual source shift from the Qilian Mountains to the Gobi Altay Mountains during the past 2.7 Ma. Both tectonic uplift and climate change may have played important roles for this shift. The later uplift of the Gobi Altay Mountains relative to the Qilian Mountains since 5 ± 3 Ma might be responsible for the increasing contribution of Gobi materials to the source deserts in Alxa arid lands. Enhanced winter monsoon may also facilitate transportation of Gobi materials from the Alxa arid lands to the CLP. The shifting source of Asian dust was also reflected in north Pacific sediments. The finding of this shifting source calls for caution when interpreting the long-term climate changes based on the source-sensitive proxies of the eolian deposits.

Diode-laser-based RIMS measurements of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1998-12-01

Double- and triple-resonance excitation schemes for the ionization of strontium are presented. Use of single-mode diode lasers for the resonance excitations provides a high degree of optical isotopic selectivity: with double-resonance, selectivity of >104 for 90Sr against the stable Sr isotopes has been demonstrated. Measurement of lineshapes and stable isotope shifts in the triple-resonance process indicate that optical selectivity should increase to ˜109. When combined with mass spectrometer selectivity this is sufficient for measurement of 90Sr at background environmental levels. Additionally, autoionizing resonances have been investigated for improving ionization efficiency with lower power lasers.

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.

Cenozoic changes in atmospheric lead recorded in central Pacific ferromanganese crusts

NASA Astrophysics Data System (ADS)

Klemm, Veronika; Reynolds, Ben; Frank, Martin; Pettke, Thomas; Halliday, Alex N.

2007-01-01

The possible sources of pre-anthropogenic Pb contributed to the world's oceans have been the focus of considerable study. The role of eolian dust versus riverine inputs has been of particular interest. With better calibration of isotopic records from central Pacific ferromanganese crusts using Os isotope stratigraphy it now appears that deep water Pb isotopic compositions were effectively homogeneous over a distance of 5000 km for the past 80 Myr. The composition shifted slightly from high 206Pb/ 204Pb ratios in the range of 18.87 ± 0.02 before 65 Ma to lower values of 18.62 ± 0.02 by 45 Ma and then gradually increased again very slightly to the present day ratio of 18.67 ± 0.02. The regional homogeneity provides evidence of a dominant well-mixed atmospheric source the most likely candidate for which is volcanic aerosols contributed either directly or as soluble condensates on eolian dust. The slight shift in Pb isotope composition of deep waters in the central Pacific between 65 and 45 Ma may be the result of a regional- or perhaps global-scale change in the sources of volcanic exhalations and volcanic activity caused by an increase in the importance of melting and assimilation of older continental crustal components over the Cenozoic.

Stable isotope evidence for increasing dietary breadth in the European mid-Upper Paleolithic

PubMed Central

Richards, Michael P.; Pettitt, Paul B.; Stiner, Mary C.; Trinkaus, Erik

2001-01-01

New carbon and nitrogen stable isotope values for human remains dating to the mid-Upper Paleolithic in Europe indicate significant amounts of aquatic (fish, mollusks, and/or birds) foods in some of their diets. Most of this evidence points to exploitation of inland freshwater aquatic resources in particular. By contrast, European Neandertal collagen carbon and nitrogen stable isotope values do not indicate significant use of inland aquatic foods but instead show that they obtained the majority of their protein from terrestrial herbivores. In agreement with recent zooarcheological analyses, the isotope results indicate shifts toward a more broad-spectrum subsistence economy in inland Europe by the mid-Upper Paleolithic period, probably associated with significant population increases. PMID:11371652

Stable isotope evidence for increasing dietary breadth in the European mid-Upper Paleolithic.

PubMed

Richards, M P; Pettitt, P B; Stiner, M C; Trinkaus, E

2001-05-22

New carbon and nitrogen stable isotope values for human remains dating to the mid-Upper Paleolithic in Europe indicate significant amounts of aquatic (fish, mollusks, and/or birds) foods in some of their diets. Most of this evidence points to exploitation of inland freshwater aquatic resources in particular. By contrast, European Neandertal collagen carbon and nitrogen stable isotope values do not indicate significant use of inland aquatic foods but instead show that they obtained the majority of their protein from terrestrial herbivores. In agreement with recent zooarcheological analyses, the isotope results indicate shifts toward a more broad-spectrum subsistence economy in inland Europe by the mid-Upper Paleolithic period, probably associated with significant population increases.

Probing the structure of the stable Xe isotopes with inelastic neutron scattering

NASA Astrophysics Data System (ADS)

Peters, Erin E.; Ross, Timothy J.; Crider, Benjamin P.; Yates, Steven W.

2018-05-01

The stable isotopes of xenon, which have attracted interest for a number of reasons, span a transitional region that evolves from γ-soft structures for the lighter mass isotopes to nearly spherical 136Xe with a closed neutron shell. The nature of this transition, which is gradual, is not well understood. To provide detailed spectroscopic information on the Xe isotopes, we have studied 130,132,134,136Xe at the University of Kentucky Accelerator Laboratory using inelastic neutron scattering and γ-ray detection. These measurements yielded γ-ray angular distributions, branching ratios, multipole mixing ratios, and level lifetimes (from the Doppler-shift attenuation method), which allowed the determination of reduced transition probabilities and provided insight into the structure of these nuclei.

Isotopic and Geochemical Fingerprinting of a Polygonal Arctic Ecosystem

NASA Astrophysics Data System (ADS)

Throckmorton, H.; Heikoop, J. M.; Newman, B. D.; Wilson, C. J.; Wullschleger, S. D.

2015-12-01

Arctic tundra contain large C stocks and may be an important source of CO2 and CH4 over the next century due to a rapidly changing climate, degrading permafrost, and redistribution of water across high latitude landscapes. This presentation synthesizes geochemical and isotopic data and examines vertical and lateral factors and processes critical to predicting the C, N, and water balance of tundra ecosystems. Stable water isotope analyses (delta 2H and delta 18O) indicate that summer rain is the dominant source for active layer groundwater, with melting seasonal ice contributing to deeper pore waters in late summer. Microtopography and water table effects on geochemistry were apparent from a comprehensive spatial examination of active layer biogeochemistry, showing a number of significant differences in the concentrations of cations and anions for high- vs. low-centered polygons, microtopographic features (polygonal centers vs. troughs), and with depth. Results have implications for future nutrient availability with projected permafrost degradation and landscape evolution, suggesting greater availability of limiting nutrients (sulfate, phosphate, and nitrate) where polygons undergo a shift from low- to high-centered. Nitrate isotopes (delta 15N and delta 18O) indicated a predominantly microbial source for nitrate in high centered polygons active layers. However, atmospheric nitrate was preserved in permafrost, and may serve as a potential indicator of permafrost degradation. Additionally, results suggest that older, deeper C sources may be promoting a shift in methanogenic pathway, from predominantly acetoclastic to hydrogenotrophic. This mechanistic shift is attributed to the source and quality of available organic substrate. Overall, results showed substantial lateral and vertical variability in biogeochemical, biogeophysical, and hydrological processes across microtopographic- to landscape scales that needs to be accounted for in fine and intermediate scale models.

Modelled rainfall skill assessment against a 1000-year time/space isotope dendro-climatology for southern Africa

NASA Astrophysics Data System (ADS)

Woodborne, Stephan; Hall, Grant; Zhang, Qiong

2016-04-01

Palaeoclimate reconstruction using isotopic analysis of tree growth increments has yielded a 1000-year record of rainfall variability in southern Africa. Isotope dendro-climatology reconstructions from baobab trees (Adansonia digitata) provide evidence for rainfall variability from the arid Namib Desert and the Limpopo River Valley. Isotopic analysis of a museum specimen of a yellowwood tree (Podocarps falcatus) yields another record from the southwestern part of the subcontinent. Combined with the limited classic denro-climatologies available in the region these records yield palaeo-rainfall variability in the summer and winter rainfall zones as well as the hyper-arid zone over the last 1000 years. Coherent shifts in all of the records indicate synoptic changes in the westerlies, the inter-tropical convergence zone, and the Congo air boundary. The most substantial rainfall shift takes place at about 1600 CE at the onset of the Little Ice Age. Another distinctive feature of the record is a widespread phenomenon that occurs shortly after 1810 CE that in southern Africa corresponds with a widespread social upheaval known as the Difequane or Mfekane. Large scale forcing of the system includes sea-surface temperatures in the Agulhas Current, the El Nino Southern Oscillation and the Southern Annular Mode. The Little Ice Age and Mfekane climate shifts result from different forcing mechanisms, and the rainfall response in the different regions at these times do not have a fixed phase relationship. This complexity provides a good scenario to test climate models. A first order (wetter versus drier) comparison between each of the tree records and a 1000-year palaeoclimate model simulation for the Little Ice Age and Mfekane transitions demonstrates a generally good correspondence.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence.

PubMed

Berhanu, Tesfaye A; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S K; Johnson, Matthew S; Savarino, Joël

2014-06-28

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ((15)N, (17)O, and (18)O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ(15)N, δ(18)O, and Δ(17)O). From these measurements an average photolytic isotopic fractionation of (15)ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of (15)ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of (14)NO3 (-) and (15)NO3 (-) in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

NASA Astrophysics Data System (ADS)

Berhanu, Tesfaye A.; Meusinger, Carl; Erbland, Joseph; Jost, Rémy; Bhattacharya, S. K.; Johnson, Matthew S.; Savarino, Joël

2014-06-01

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. ["Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry," J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate (15N, 17O, and 18O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ15N, δ18O, and Δ17O). From these measurements an average photolytic isotopic fractionation of 15ɛ = (-15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of 15ɛ = (-47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from -40 to -74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of 14NO3- and 15NO3- in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.

Selenium stable isotope investigation into selenium biogeochemical cycling in a lacustrine environment: Sweitzer Lake, Colorado.

PubMed

Clark, Scott K; Johnson, Thomas M

2010-01-01

We present a comprehensive set of Se concentration and isotope ratio data collected over a 3-yr period from dissolved, sediment-hosted, and organically bound Se in a Se-contaminated lake and littoral wetland. Median isotope ratios of these various pools of Se spanned a narrow isotopic range (delta80/76Se(SRM-3149)) = 1.14-2.40 per thousand). Selenium (VI) reduction in the sediments is an important process in this system, but its isotopic impact is muted by the lack of direct contact between surface waters and reduction sites within sediments. This indicates that using Se isotope data as an indicator of microbial or abiotic Se oxyanion reduction is not effective in this or other similar systems. Isotopic data suggest that most Se(IV) in the lake originates from oxidation of organically bound Se rather than directly through Se(VI) reduction. Mobilization of Se(VI) from bedrock involves only a slight isotopic shift. Temporally constant isotopic differences observed in Se(VI) from two catchment areas suggest the potential for tracing Se(VI) from different source areas. Phytoplankton isotope ratios are close to those of the water, with a small depletion in heavy isotopes (0.56 per thousand). Fish tissues nearly match the phytoplankton, being only slightly depleted in the heavier isotopes. This suggests the potential for Se isotopes as migration indicators. Volatile, presumably methylated Se was isotopically very close to median values for phytoplankton and macrophytes, indicating a lack of isotopic fractionation during methylation.

Drought Sensitivity of the Carbon Isotope Composition of Leaf Dark-Respired CO2 in C3 (Leymus chinensis) and C4 (Chloris virgata and Hemarthria altissima) Grasses in Northeast China

PubMed Central

Zhong, Shangzhi; Chai, Hua; Xu, Yueqiao; Li, Yan; Ma, Jian-Ying; Sun, Wei

2017-01-01

Whether photosynthetic pathway differences exist in the amplitude of nighttime variations in the carbon isotope composition of leaf dark-respired CO2 (δ13Cl) and respiratory apparent isotope fractionation relative to biomass (ΔR,biomass) in response to drought stress is unclear. These differences, if present, would be important for the partitioning of C3-C4 mixed ecosystem C fluxes. We measured δ13Cl, the δ13C of biomass and of potential respiratory substrates and leaf gas exchange in one C3 (Leymus chinensis) and two C4 (Chloris virgata and Hemarthria altissima) grasses during a manipulated drought period. For all studied grasses, δ13Cl decreased from 21:00 to 03:00 h. The magnitude of the nighttime shift in δ13Cl decreased with increasing drought stress. The δ13Cl values were correlated with the δ13C of respiratory substrates, whereas the magnitude of the nighttime shift in δ13Cl strongly depended on the daytime carbon assimilation rate and the range of nighttime variations in the respiratory substrate content. The ΔR,biomass in the C3 and C4 grasses varied in opposite directions with the intensification of the drought stress. The contribution of C4 plant-associated carbon flux is likely to be overestimated if carbon isotope signatures are used for the partitioning of ecosystem carbon exchange and the δ13C of biomass is used as a substitute for leaf dark-respired CO2. The detected drought sensitivities in δ13Cl and differences in respiratory apparent isotope fractionation between C3 and C4 grasses have marked implications for isotope partitioning studies at the ecosystem level. PMID:29375587

Identification of energy consumption and nutritional stress by isotopic and elemental analysis of urine in bonobos (Pan paniscus).

PubMed

Deschner, Tobias; Fuller, Benjamin T; Oelze, Vicky M; Boesch, Christophe; Hublin, Jean-Jacques; Mundry, Roger; Richards, Michael P; Ortmann, Sylvia; Hohmann, Gottfried

2012-01-15

A mounting body of evidence suggests that changes in energetic conditions like prolonged starvation can be monitored using stable isotope ratios of tissues such as bone, muscle, hair, and blood. However, it is unclear if urinary stable isotope ratios reflect a variation in energetic condition, especially if these changes in energetic condition are accompanied by shifts in dietary composition. In a feeding experiment conducted on captive bonobos (Pan paniscus), we monitored urinary δ(13)C, δ(15)N, total C (carbon), total N (nitrogen), and C/N ratios and compared these results with glucocorticoid levels under gradually changing energy availability and dietary composition. Measurements of daily collected urine samples over a period of 31 days showed that while shifts in urinary isotope signatures of δ(13)C and δ(15)N as well as total C were best explained by changes in energy consumption, urinary total N excretion as well as the C/N ratios matched the variation in dietary composition. Furthermore, when correcting for fluctuations in dietary composition, the isotope signatures of δ(13)C and δ(15)N as well as total C correlated with urinary glucocorticoid levels; however, the urinary total N and the C/N ratio did not. These results indicate for the first time that it is possible to non-invasively explore specific longitudinal records on animal energetic conditions and dietary compositions with urinary stable isotope ratios and elemental compositions, and this research provides a strong foundation for investigating how ecological factors and social dynamics affect feeding habits in wild animal populations such as primates. Copyright © 2011 John Wiley & Sons, Ltd.

Duration of and decoupling between carbon isotope excursions during the end-Triassic mass extinction and Central Atlantic Magmatic Province emplacement

NASA Astrophysics Data System (ADS)

Yager, Joyce A.; West, A. Joshua; Corsetti, Frank A.; Berelson, William M.; Rollins, Nick E.; Rosas, Silvia; Bottjer, David J.

2017-09-01

Changes in δ13Ccarb and δ13Corg from marine strata occur globally in association with the end-Triassic mass extinction and the emplacement of the Central Atlantic Magmatic Province (CAMP) during the break up of Pangea. As is typical in deep time, the timing and duration of these isotopic excursions has remained elusive, hampering attempts to link carbon cycle perturbations to specific processes. Here, we report δ13Ccarb and δ13Corg from Late Triassic and Early Jurassic strata near Levanto, Peru, where intercalated dated ash beds permit temporal calibration of the carbon isotope record. Both δ13Ccarb and δ13Corg exhibit a broad positive excursion through the latest Triassic into the earliest Jurassic. The first order positive excursion in δ13Corg is interrupted by a negative shift noted in many sections around the world coincident with the extinction horizon. Our data indicate that the negative excursion lasts 85 ± 25 kyrs, longer than inferred by previous studies based on cyclostratigraphy. A 260 ± 80 kyr positive δ13Corg shift follows, during which the first Jurassic ammonites appear. The overall excursion culminates in a return to pre-perturbation carbon isotopic values over the next 1090 ± 70 kyrs. Via chronologic, isotopic, and biostratigraphic correlation to other successions, we find that δ13Ccarb and δ13Corg return to pre-perturbation values as CAMP volcanism ceases and in association with the recovery of pelagic and benthic biota. However, the initiation of the carbon isotope excursion at Levanto predates the well-dated CAMP sills from North America, indicating that CAMP may have started earlier than thought based on these exposures, or that the onset of carbon cycle perturbations was not related to CAMP.

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.

Intrapopulation variability in the timing of ontogenetic habitat shifts in sea turtles revealed using δ15N values from bone growth rings

PubMed Central

Turner Tomaszewicz, Calandra N.; Seminoff, Jeffrey A.; Peckham, S. Hoyt; Avens, Larisa; Kurle, Carolyn M.

2016-01-01

Summary Determining location and timing of ontogenetic shifts in the habitat use of highly migratory species, along with possible intrapopulation variation in these shifts, is essential for understanding mechanisms driving alternate life histories and assessing overall population trends. Measuring variations in multi-year habitat use patterns is especially difficult for remote oceanic species.To investigate the potential for differential habitat use among migratory marine vertebrates, we measured the naturally occurring stable nitrogen isotope (δ15N) patterns that differentiate distinct ocean regions to create a “regional isotope characterization”, analyzed the δ15N values from annual bone growth layer rings from dead-stranded animals, then combined the bone and regional isotope data to track individual animal movement patterns over multiple years.We used humeri from juvenile North Pacific loggerhead turtles (Caretta caretta), animals that undergo long migrations across the North Pacific Ocean (NPO), using multiple discrete regions as they develop to adulthood. Typical of many migratory marine species, ontogenetic changes in habitat use throughout their decades-long juvenile stage is poorly understood, but each potential habitat has unique foraging opportunities and spatially explicit natural and anthropogenic threats that could affect key life history parameters.We found a bimodal size/age distribution in the timing that juveniles underwent an ontogenetic habitat shift from the oceanic central North Pacific (CNP) to the neritic east Pacific region near the Baja California Peninsula (BCP) (42.7±7.2 vs. 68.3±3.4 cm carapace length, 7.5±2.7 vs. 15.6±1.7 years). Important to the survival of this population, these disparate habitats differ considerably in their food availability, energy requirements, and threats, and these differences can influence life history parameters such as growth, survival, and future fecundity. This is the first evidence of alternative ontogenetic shifts and habitat use patterns for juveniles foraging in the eastern NPO.We combine two techniques, skeletochronology and stable isotope analysis, to reconstruct multi-year habitat use patterns of a remote migratory species, linked to estimated ages and body sizes of individuals, to reveal variable ontogeny during the juvenile life stage that could drive alternate life histories and that has the potential to illuminate the migration patterns for other species with accretionary tissues. PMID:28075017

Probing New Long-Range Interactions by Isotope Shift Spectroscopy

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

Berengut, Julian C.; Budker, Dmitry; Delaunay, Cédric

We explore a method to probe new long- and intermediate-range interactions using precision atomic isotope shift spectroscopy. We develop a formalism to interpret linear King plots as bounds on new physics with minimal theory inputs. We focus only on bounding the new physics contributions that can be calculated independently of the standard model nuclear effects. We apply our method to existing Ca + data and project its sensitivity to conjectured new bosons with spin-independent couplings to the electron and the neutron using narrow transitions in other atoms and ions, specifically, Sr and Yb. Future measurements are expected to improve themore » relative precision by 5 orders of magnitude, and they can potentially lead to an unprecedented sensitivity for bosons within the 0.3 to 10 MeV mass range.« less

Probing New Long-Range Interactions by Isotope Shift Spectroscopy.

PubMed

Berengut, Julian C; Budker, Dmitry; Delaunay, Cédric; Flambaum, Victor V; Frugiuele, Claudia; Fuchs, Elina; Grojean, Christophe; Harnik, Roni; Ozeri, Roee; Perez, Gilad; Soreq, Yotam

2018-03-02

We explore a method to probe new long- and intermediate-range interactions using precision atomic isotope shift spectroscopy. We develop a formalism to interpret linear King plots as bounds on new physics with minimal theory inputs. We focus only on bounding the new physics contributions that can be calculated independently of the standard model nuclear effects. We apply our method to existing Ca^{+} data and project its sensitivity to conjectured new bosons with spin-independent couplings to the electron and the neutron using narrow transitions in other atoms and ions, specifically, Sr and Yb. Future measurements are expected to improve the relative precision by 5 orders of magnitude, and they can potentially lead to an unprecedented sensitivity for bosons within the 0.3 to 10 MeV mass range.

Probing New Long-Range Interactions by Isotope Shift Spectroscopy

DOE PAGES

Berengut, Julian C.; Budker, Dmitry; Delaunay, Cédric; ...

2018-02-26

We explore a method to probe new long- and intermediate-range interactions using precision atomic isotope shift spectroscopy. We develop a formalism to interpret linear King plots as bounds on new physics with minimal theory inputs. We focus only on bounding the new physics contributions that can be calculated independently of the standard model nuclear effects. We apply our method to existing Ca + data and project its sensitivity to conjectured new bosons with spin-independent couplings to the electron and the neutron using narrow transitions in other atoms and ions, specifically, Sr and Yb. Future measurements are expected to improve themore » relative precision by 5 orders of magnitude, and they can potentially lead to an unprecedented sensitivity for bosons within the 0.3 to 10 MeV mass range.« less

Vibronic effects in the 1.4-eV optical center in diamond

NASA Astrophysics Data System (ADS)

Iakoubovskii, Konstantin; Davies, Gordon

2004-12-01

We report optical absorption and luminescence measurements on the 1.4-eV center in diamond. We show that the zero-phonon lines have a temperature-dependent Ni-isotope shift, that the isotopic shifts induced by carbon and nickel are opposite in sign, and that a local vibronic mode is present in the absorption spectrum but not in luminescence. The microscopic properties of the center are successfully analyzed with the Ludwig-Woodbury theory (LWT), revealing that the Ni+ ion in the 1.4-eV center only weakly interacts with the diamond lattice. The importance of vibronic effects in the LWT analysis is experimentally demonstrated. It is believed that similar effects can account for the discrepancies previously encountered in modeling other 3d9 impurities in semiconductors.

Late-Glacial to Late-holocene Shifts in Global Precipitation Delta(sup 18)O

NASA Technical Reports Server (NTRS)

Jasechko, S.; Lechler, A.; Pausata, F.S.R.; Fawcett, P.J.; Gleeson, T.; Cendon, D.I.; Galewsky, J.; LeGrande, A. N.; Risi, C.; Sharp, Z. D.;

Size-dependent trophic patterns of pallid sturgeon and shovelnose sturgeon in a large river system

USGS Publications Warehouse

French, William E.; Graeb, Brian D. S.; Bertrand, Katie N.; Chipps, Steven R.; Klumb, Robert A.

2013-01-01

This study compared patterns of δ15N and δ13C enrichment of pallid sturgeon Scaphirhynchus albus and shovelnose sturgeon S. platorynchus in the Missouri River, United States, to infer their trophic position in a large river system. We examined enrichment and energy flow for pallid sturgeon in three segments of the Missouri River (Montana/North Dakota, Nebraska/South Dakota, and Nebraska/Iowa) and made comparisons between species in the two downstream segments (Nebraska/South Dakota and Nebraska/Iowa). Patterns in isotopic composition for pallid sturgeon were consistent with gut content analyses indicating an ontogenetic diet shift from invertebrates to fish prey at sizes of >500-mm fork length (FL) in all three segments of the Missouri River. Isotopic patterns revealed shovelnose sturgeon did not experience an ontogenetic shift in diet and used similar prey resources as small (<500-mm FL) pallid sturgeon in the two downstream segments. We found stable isotope analysis to be an effective tool for evaluating the trophic position of sturgeons within a large river food web.

Matrix isolation infrared spectroscopic studies and density functional theory calculations of the MNN, (MN)2 (M = Y and La), and Y3NN molecules.

PubMed

Teng, Yun-Lei; Xu, Qiang

2008-04-24

The reactions of yttrium and lanthanum with dinitrogen were reinvestigated. Laser-ablated yttrium and lanthanum atoms were co-deposited at 4 K with dinitrogen in excess argon, and the low-temperature reactions of Y and La with N2 in solid argon were studied using infrared spectroscopy. The reaction products YNN, (YN)2, LaNN, and (LaN)2 were formed in the present experiments and characterized on the basis of 14N/15N isotopic shifts, mixed isotope splitting patterns, stepwise annealing, change of reagent concentration and laser energy, and comparison with theoretical predictions. Some assignments were made based on a previous report. Density functional theory calculations were performed on these systems to identify possible reaction products. The agreement between experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts of the MNN and (MN)2 (M = Y and La) molecules supports the identification of these molecules from the matrix infrared spectra. Plausible reaction mechanisms were proposed for the formation of these molecules along with tentative identification of the Y3NN molecule.

Towards laser spectroscopy of the proton-halo candidate boron-8

NASA Astrophysics Data System (ADS)

Maaß, Bernhard; Müller, Peter; Nörtershäuser, Wilfried; Clark, Jason; Gorges, Christian; Kaufmann, Simon; König, Kristian; Krämer, Jörg; Levand, Anthony; Orford, Rodney; Sánchez, Rodolfo; Savard, Guy; Sommer, Felix

2017-11-01

We propose to determine the nuclear charge radius of 8B by high-resolution laser spectroscopy. 8B (t 1/2 = 770 ms) is perhaps the best candidate of a nucleus exhibiting an extended proton wave-function or "one-proton-halo" in a more descriptive picture. Laser spectroscopic measurements of the isotope shift will be used to probe the change in nuclear charge radius along the three boron isotopes 8B, 10B and 11B. The change in nuclear charge radius directly correlates with the extent of the proton wave function. In-flight production and preparation of sufficient yields of 8B ions at low energies is provided by the Argonne Tandem Linac Accelerator System (ATLAS) at Argonne National Laboratory (ANL) in Chicago, IL, USA. Subsequently, the ions will be guided through a charge exchange cell for neutralization and the fluorescence signal of the atoms which interact with the resonant laser light will be detected. The charge radius can then be extracted from the measured isotope shift by employing highly accurate atomic theory calculations of this five-electron system which are carried out presently.

Hyperfine structure and isotope shift of /sup 208/Bi in the 3067-A resonance line

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

Lamontagne, J.J.

1982-01-01

The hyperfine structure of /sup 208/Bi (I = 5) was measured using the 3067 A spectral line from the 6p/sup 2/7s (/sup 4/P/sub 1/2/) - 6p/sup 3/ (/sup 4/S/sub 3/2/) transition. After production of the isotope at the Princeton University Cyclotron, chemical separation, and mass separation, some 10/sup 12/ atoms were used to produce an absorption spectrum. The monochromator, Czerny-Turner design), had a 9.1 m focal length with a 25 cm diffraction grating used in autocollimation near 63/sup 0/. The spectrum was recorded on photographic plates. Measurements were made of the position of the components. From these the value /supmore » 208/A (/sup 4/P/sub 1/2) = 166 (1.5) mK was obtained. Neglecting hyperfine anomalies this gives /sup 208/A (/sup 4/S/sub 3/2/) = 15.07 (.1). The isotope shift /sup 208/Bi-/sup 208/Bi was measured to be 50.58 (7.5) mK.« less

An isotopic study of the Coso, California, geothermal area

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

Fournier, R.O.; Thompson, J.M.

1982-10-01

Thirty-nine water samples were collected from the Coso geothermal system and vicinity and were analyzed for major chemical constituents and deltaD and delta/sup 18/O. Non-thermal ground waters from the Coso Range were found to be isotopically heavier than non-thermal ground waters from the Sierra Nevada to the west. The deltaD value for the deep thermal water at Coso is similar to that of the Sierra water, suggesting that the major recharge for the hydrothermal system comes from the Sierra Nevada rather than from local precipitation on the Coso Range. The delta/sup 18/O values of the thermal water are about 7/supmore » 0//00 heavier than those of the Sierra water. This shift in delta/sup 18/O is the result of water-rock reaction at high temperatures, and the magnitude of the shift indicates that the ratio of rock to total water has been large for the system up to its present stage of development. The isotopic data are compatible with the geochemical model previously proposed by Fournier.« less

Isotopic Changes During Digestion: Protein

NASA Astrophysics Data System (ADS)

Tuross, N.

2013-12-01

Nutrient and hydrological inputs traverse a complicated route of pH, enzymatic and cellular processes in digestion in higher animals. The end products of digestion are the starting products for biosynthesis that are often used to interpret past life-ways. Using an artificial gut system, the isotopic changes (dD, d18O, d13C and d15N) of protein are documented. Three separate protein sources are subjected to the conditions, chemical and enzymatic, found in the stomach and upper small intestine with only a small shift in the oxygen isotopic composition of the proteins observed. Middle to lower small intestine parameters produced both greater isotopic effects and significantly lower molecular weight products. The role of the gastric enterocyte and the likely involvement of the internal milieu of this cell in the isotopic composition of amino acids that are transported to the liver are reported.

Laser ablation molecular isotopic spectroscopy (LAMIS) towards the determination of multivariate LODs via PLS calibration model of 10B and 11B Boric acid mixtures

NASA Astrophysics Data System (ADS)

Harris, C. D.; Profeta, Luisa T. M.; Akpovo, Codjo A.; Johnson, Lewis; Stowe, Ashley C.

2017-05-01

A calibration model was created to illustrate the detection capabilities of laser ablation molecular isotopic spectroscopy (LAMIS) discrimination in isotopic analysis. The sample set contained boric acid pellets that varied in isotopic concentrations of 10B and 11B. Each sample set was interrogated with a Q-switched Nd:YAG ablation laser operating at 532 nm. A minimum of four band heads of the β system B2∑ -> Χ2∑transitions were identified and verified with previous literature on BO molecular emission lines. Isotopic shifts were observed in the spectra for each transition and used as the predictors in the calibration model. The spectra along with their respective 10/11B isotopic ratios were analyzed using Partial Least Squares Regression (PLSR). An IUPAC novel approach for determining a multivariate Limit of Detection (LOD) interval was used to predict the detection of the desired isotopic ratios. The predicted multivariate LOD is dependent on the variation of the instrumental signal and other composites in the calibration model space.

Cretaceous-Tertiary boundary in the Antarctic: Climatic cooling precedes biotic crisis

NASA Technical Reports Server (NTRS)

Stott, Lowell D.; Kennett, James P.

1988-01-01

Stable isotopic investigations were conducted on calcareous microfossils across two deep sea Cretaceous-Tertiary boundary sequences on Maud Rise, Weddell Sea, Antarctica. The boundary is taken at the level of massive extinctions in calcareous planktonic microfossils, and coincides with a sharp lithologic change from pure calcareous ooze to calcareous ooze with a large volcanic clay component. The uppermost Maestrichtian is marked by a long-term decrease in delta value of 0 to 18 which spans most of the lower and middle A. mayaroensis Zone and represents a warming trend which culminated in surface water temperatures of about 16 C. At approximately 3 meters below the K-T boundary this warming trend terminates abruptly and benthic and planktonic isotopic records exhibit a rapid increase in delta value of 0 to 18 that continues up to the K-T boundary. The trend towards cooler surface water temperatures stops abruptly at the K-T boundary and delta value of 0 to 18 values remain relatively stable through the Paleocene. Comparison of the Antarctic sequence with the previously documented deep sea records in the South Atlantic reveal shifts of similar magnitude in the latest Maestrichtian. It is indicated that the Southern Ocean underwent the most significant, and apparently permanent, climatic change. The latest Cretaceous oxygen isotopic shift recorded at Maud Rise and other deep sea sites is similar in magnitude to large positive delta valve of 0 to 18 shifts in the middle Eocene, at the Eocene/Oligocene boundary and in the middle Miocene that marked large scale climatic transitions which ultimately lead to cryospheric development of the Antarctic. The climatic shift at the end of the Cretaceous represents one of the most significant climatic transitions recorded in the latest Phanerozoic and had a profound effect on global climate as well as oceanic circulation.

Shifts in the trophic base of intermittent stream food webs

USGS Publications Warehouse

Dekar, Matthew P.; Magoulick, Daniel D.; Huxel, G.R.

2009-01-01

Understanding spatial and temporal variation in the trophic base of stream food webs is critical for predicting population and community stability, and ecosystem function. We used stable isotope ratios (13C/12C, and 15N/14N) to characterize the trophic base of two streams in the Ozark Mountains of northwest Arkansas, U.S.A. We predicted that autochthonous resources would be more important during the spring and summer and allochthonous resources would be more important in the winter due to increased detritus inputs from the riparian zone during autumn leaf drop. We predicted that stream communities would demonstrate increased reliance on autochthonous resources at sites with larger watersheds and greater canopy openness. The study was conducted at three low-order sites in the Mulberry River Drainage (watershed area range: 81-232 km2) seasonally in 2006 and 2007. We used circular statistics to examine community-wide shifts in isotope space among fish and invertebrate consumers in relation to basal resources, including detritus and periphyton. Mixing models were used to quantify the relative contribution of autochthonous and allochthonous energy sources to individual invertebrate consumers. Significant isotopic shifts occurred but results varied by season and site indicating substantial variation in the trophic base of stream food webs. In terms of temporal variation, consumers shifted toward periphyton in the summer during periods of low discharge, but results varied during the interval between summer and winter. Our results did not demonstrate increased reliance on periphyton with increasing watershed area or canopy openness, and detritus was important at all the sites. In our study, riffle-pool geomorphology likely disrupted the expected spatial pattern and stream drying likely impacted the availability and distribution of basal resources.

Mid- to late Holocene climate-driven regime shifts inferred from diatom, ostracod and stable isotope records from Lake Son Kol (Central Tian Shan, Kyrgyzstan)

NASA Astrophysics Data System (ADS)

Schwarz, Anja; Turner, Falko; Lauterbach, Stefan; Plessen, Birgit; Krahn, Kim J.; Glodniok, Sven; Mischke, Steffen; Stebich, Martina; Witt, Roman; Mingram, Jens; Schwalb, Antje

2017-12-01

Arid Central Asia represents a key region for understanding climate variability and interactions in the Northern Hemisphere. Patterns and mechanisms of Holocene climate change in arid Central Asia are, however, only partially understood. Multi-proxy data combining diatom, ostracod, sedimentological, geochemical and stable isotope analyses from a ca. 6000-year-old lake sediment core from Son Kol (Central Kyrgyzstan) show distinct and repeated changes in species assemblages. Diatom- and ostracod-inferred conductivity shifts between meso-euhaline and freshwater conditions suggest water balance and regime shifts. Organism-derived data are corroborated by stable isotope, mineralogical and geochemical records, underlining that Son Kol was affected by strong lake level fluctuations of several meters. The δ13Ccarb/δ18Ocarb correlation shows repeated switchovers from a closed to an open lake system. From 6000 to 3800 and 3250 to 1950 cal. yr BP, Son Kol was a closed basin lake with higher conductivities, increased nutrient availability and a water level located below the modern outflow. Son Kol became again a hydrologically open lake at 3800 and 1950 cal. yr BP. Comparisons to other local and regional paleoclimate records indicate that these regime shifts were largely controlled by changing intensity and position of the Westerlies and the Siberian Anticyclone that triggered changes in the amount of winter precipitation. A strong influence of the Westerlies ca. 5000-4400, 3800-3250 and since 1950 cal. yr BP enhanced the amount of precipitation during spring, autumn and winter, whereas cold and dry winters prevailed during phases with a strong Siberian Anticyclone and southward shifted Westerlies at ca. 6000-5000, 4400-3800 and 3250-1950 cal. yr BP. Similarities between variations in winter precipitation at Son Kol and records of the predominant NAO-mode further suggest a teleconnection between wet (dry) winter climate in Central Asia and a positive (negative) NAO-mode. Thus, this study identifies climate fluctuations as the main driver for hydrological regime shifts in Son Kol controlling physicochemical conditions and consequently causing abrupt species assemblage changes. This emphasizes the importance of multi-proxy approaches to identify triggers, thresholds and cascades of aquatic ecosystem transformations.

Palaeo-equatorial temperatures and carbon-cycle evolution at the Triassic- Jurassic boundary: A stable isotope perspective from shallow-water carbonates from the UAE

NASA Astrophysics Data System (ADS)

Honig, M. R.; John, C. M.

2013-12-01

The Triassic-Jurassic boundary was marked by global changes including carbon-cycle perturbations and the opening of the Atlantic Ocean. These changes were accompanied by one of the major extinction events of the Phanerozoic. The carbon-cycle perturbations have been recorded in carbon isotope curves from bulk carbonates, organic carbon and fossil wood in several Tethyan locations and have been used for chemostratigraphic purposes. Here we present data from shallow-marine carbonates deposited on a homoclinal Middle Eastern carbonate ramp (United Arab Emirates). Our site was located at the equator throughout the Late Triassic and the Early Jurassic, and this study provides the first constraints of environmental changes at the low-latitudes for the Triassic-Jurassic boundary. Shallow-marine carbonate depositional systems are extremely sensitive to palaeoenvironmental changes and their usefulness for chemostratigraphy is being debated. However, the palaeogeographic location of the studied carbonate ramp gives us a unique insight into a tropical carbonate factory at a time of severe global change. Stable isotope measurements (carbon and oxygen) are being carried out on micrite, ooids and shell material along the Triassic-Jurassic boundary. The stable isotope results on micrite show a prominent negative shift in carbon isotope values of approximately 2 ‰ just below the inferred position of the Triassic-Jurassic boundary. A similar isotopic trend is also observed across the Tethys but with a range of amplitudes (from ~2 ‰ to ~4 ‰). These results seem to indicate that the neritic carbonates from our studied section can be used for chemostratigraphic purposes, and the amplitudes of the carbon isotope shifts provide critical constraints on the magnitude of carbon-cycle perturbations at low latitudes across the Triassic-Jurassic boundary. Seawater temperatures across the Triassic-Jurassic boundary will be constrained using the clumped isotope palaeo-thermometer applied to blocky calcite, bulk carbonate, oyster shells and echinoids. Assuming a pristine depositional signal can be extracted from one of the components, clumped isotopes will either shed light on the palaeoenvironmental conditions and the isotopic composition of a tropical ocean during the Late Triassic / Early Jurassic, or on the diagenetic history of the platform. We gratefully acknowledge funding from Qatar Petroleum, Shell, and Qatar Science & Technology Park.

Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.

PubMed

Gourgiotis, Alkiviadis; Ducasse, Thomas; Barker, Evelyne; Jollivet, Patrick; Gin, Stéphane; Bassot, Sylvain; Cazala, Charlotte

2017-02-15

High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of 29 Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O 2 as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO + and SiO 2 + ion species was performed, and we found that SiO + ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO 3 ). For SiO 2 + , no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e. 28 Si 16 O 18 O + , 30 Si 16 O 16 O + ). The developed method was validated by measuring a series of reference solutions with different 29 Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0.2%, <0.5% and <0.6%, respectively. These performances meet the requirements of the studies of nuclear glasses alteration and open up possibilities to use this method for precise determination of silicon content in natural samples by Isotope Dilution. Copyright © 2016 Elsevier B.V. All rights reserved.

Fractionation of Cu and Mo isotopes caused by vapor-liquid partitioning, evidence from the Dahutang W-Cu-Mo ore field

NASA Astrophysics Data System (ADS)

Yao, Junming; Mathur, Ryan; Sun, Weidong; Song, Weile; Chen, Huayong; Mutti, Laurence; Xiang, Xinkui; Luo, Xiaohong

2016-05-01

The study presents δ65Cu and δ97Mo isotope values from cogenetic chalcopyrite and molybdenite found in veins and breccias of the Dahutang W-Cu-Mo ore field in China. The samples span a 3-4 km range. Both isotopes show a significant degree of fractionation. Cu isotope values in the chalcopyrite range from -0.31‰ to +1.48‰, and Mo isotope values in the molybdenite range from -0.03‰ to +1.06‰. For the cogenetic sulfide veined samples, a negative slope relationship exists between δ65Cu and δ97Mo values, which suggest a similar fluid history. Rayleigh distillation models the vein samples' change in isotope values. The breccia samples do not fall on the trend, thus indicating a different source mineralization event. Measured fluid inclusion and δD and δ18O data from cogenetic quartz indicate changes in temperature, and mixing of fluids do not appear to cause the isotopic shifts measure. Related equilibrium processes associated with the partitioning of metal between the vapor-fluid in the hydrothermal system could be the probable cause for the relationship seen between the two isotope systems.

Lifetime measurement of neutron-rich even-even molybdenum isotopes

NASA Astrophysics Data System (ADS)

Ralet, D.; Pietri, S.; Rodríguez, T.; Alaqeel, M.; Alexander, T.; Alkhomashi, N.; Ameil, F.; Arici, T.; Ataç, A.; Avigo, R.; Bäck, T.; Bazzacco, D.; Birkenbach, B.; Boutachkov, P.; Bruyneel, B.; Bruce, A. M.; Camera, F.; Cederwall, B.; Ceruti, S.; Clément, E.; Cortés, M. L.; Curien, D.; De Angelis, G.; Désesquelles, P.; Dewald, M.; Didierjean, F.; Domingo-Pardo, C.; Doncel, M.; Duchêne, G.; Eberth, J.; Gadea, A.; Gerl, J.; Ghazi Moradi, F.; Geissel, H.; Goigoux, T.; Goel, N.; Golubev, P.; González, V.; Górska, M.; Gottardo, A.; Gregor, E.; Guastalla, G.; Givechev, A.; Habermann, T.; Hackstein, M.; Harkness-Brennan, L.; Henning, G.; Hess, H.; Hüyük, T.; Jolie, J.; Judson, D. S.; Jungclaus, A.; Knoebel, R.; Kojouharov, I.; Korichi, A.; Korten, W.; Kurz, N.; Labiche, M.; Lalović, N.; Louchart-Henning, C.; Mengoni, D.; Merchán, E.; Million, B.; Morales, A. I.; Napoli, D.; Naqvi, F.; Nyberg, J.; Pietralla, N.; Podolyák, Zs.; Pullia, A.; Prochazka, A.; Quintana, B.; Rainovski, G.; Reese, M.; Recchia, F.; Reiter, P.; Rudolph, D.; Salsac, M. D.; Sanchis, E.; Sarmiento, L. G.; Schaffner, H.; Scheidenberger, C.; Sengele, L.; Singh, B. S. Nara; Singh, P. P.; Stahl, C.; Stezowski, O.; Thoele, P.; Valiente Dobon, J. J.; Weick, H.; Wendt, A.; Wieland, O.; Winfield, J. S.; Wollersheim, H. J.; Zielinska, M.; PreSPEC Collaboration

2017-03-01

Background: In the neutron-rich A ≈100 mass region, rapid shape changes as a function of nucleon number as well as coexistence of prolate, oblate, and triaxial shapes are predicted by various theoretical models. Lifetime measurements of excited levels in the molybdenum isotopes allow the determination of transitional quadrupole moments, which in turn provides structural information regarding the predicted shape change. Purpose: The present paper reports on the experimental setup, the method that allowed one to measure the lifetimes of excited states in even-even molybdenum isotopes from mass A =100 up to mass A =108 , and the results that were obtained. Method: The isotopes of interest were populated by secondary knock-out reaction of neutron-rich nuclei separated and identified by the GSI fragment separator at relativistic beam energies and detected by the sensitive PreSPEC-AGATA experimental setup. The latter included the Lund-York-Cologne calorimeter for identification, tracking, and velocity measurement of ejectiles, and AGATA, an array of position sensitive segmented HPGe detectors, used to determine the interaction positions of the γ ray enabling a precise Doppler correction. The lifetimes were determined with a relativistic version of the Doppler-shift-attenuation method using the systematic shift of the energy after Doppler correction of a γ -ray transition with a known energy. This relativistic Doppler-shift-attenuation method allowed the determination of mean lifetimes from 2 to 250 ps. Results: Even-even molybdenum isotopes from mass A =100 to A =108 were studied. The decays of the low-lying states in the ground-state band were observed. In particular, two mean lifetimes were measured for the first time: τ =29 .7-9.1+11.3 ps for the 4+ state of 108Mo and τ =3 .2-0.7+0.7 ps for the 6+ state of 102Mo. Conclusions: The reduced transition strengths B (E 2 ) , calculated from lifetimes measured in this experiment, compared to beyond-mean-field calculations, indicate a gradual shape transition in the chain of molybdenum isotopes when going from A =100 to A =108 with a maximum reached at N =64 . The transition probabilities decrease for 108Mo which may be related to its well-pronounced triaxial shape indicated by the calculations.

Similar mid-depth Atlantic water mass provenance during the Last Glacial Maximum and Heinrich Stadial 1

NASA Astrophysics Data System (ADS)

Howe, Jacob N. W.; Huang, Kuo-Fang; Oppo, Delia W.; Chiessi, Cristiano M.; Mulitza, Stefan; Blusztajn, Jurek; Piotrowski, Alexander M.

2018-05-01

The delivery of freshwater to the North Atlantic during Heinrich Stadial 1 (HS1) is thought to have fundamentally altered the operation of Atlantic meridional overturning circulation (AMOC). Although benthic foraminiferal carbon isotope records from the mid-depth Atlantic show a pronounced excursion to lower values during HS1, whether these shifts correspond to changes in water mass proportions, advection, or shifts in the carbon cycle remains unclear. Here we present new deglacial records of authigenic neodymium isotopes - a water mass tracer that is independent of the carbon cycle - from two cores in the mid-depth South Atlantic. We find no change in neodymium isotopic composition, and thus water mass proportions, between the Last Glacial Maximum (LGM) and HS1, despite large decreases in carbon isotope values at the onset of HS1 in the same cores. We suggest that the excursions of carbon isotopes to lower values were likely caused by the accumulation of respired organic matter due to slow overturning circulation, rather than to increased southern-sourced water, as typically assumed. The finding that there was little change in water mass provenance in the mid-depth South Atlantic between the LGM and HS1, despite decreased overturning, suggests that the rate of production of mid-depth southern-sourced water mass decreased in concert with decreased production of northern-sourced intermediate water at the onset of HS1. Consequently, we propose that even drastic changes in the strength of AMOC need not cause a significant change in South Atlantic mid-depth water mass proportions.

Linking Specific Heterotrophic Bacterial Populations to Bioreduction of Uranium and Nitrate in Contaminated Subsurface Sediments by Using Stable Isotope Probing▿†

PubMed Central

Akob, Denise M.; Kerkhof, Lee; Küsel, Kirsten; Watson, David B.; Palumbo, Anthony V.; Kostka, Joel E.

2011-01-01

Shifts in terminal electron-accepting processes during biostimulation of uranium-contaminated sediments were linked to the composition of stimulated microbial populations using DNA-based stable isotope probing. Nitrate reduction preceded U(VI) and Fe(III) reduction in [13C]ethanol-amended microcosms. The predominant, active denitrifying microbial groups were identified as members of the Betaproteobacteria, whereas Actinobacteria dominated under metal-reducing conditions. PMID:21948831

Discrimination of carbon and nitrogen isotopes from milk to serum and vibrissae in Alaska Steller sea lions (Eumetopias jubatus)

USGS Publications Warehouse

Stegall, V.K.; Farley, Sean D.; Rea, Lorrie D.; Pitcher, K.W.; Rye, R.O.; Kester, C.L.; Stricker, C.A.; Bern, C.R.

2008-01-01

Knowledge of diet-tissue stable isotope discrimination is required to properly interpret stable isotope values and to identify possible diet shifts, such as might be expected from nursing through weaning. This study compared ??13C and ??15N of paired serum and vibrissal roots with those of ingested milk (n = 52) from free-ranging Steller sea lion (Eumetopias jubatus (Schreber, 1776)) pups (1-11 months) and juveniles (14-27 months) to estimate diet-tissue discrimination. Mean 15N enrichment from ingested milk to serum was 2.1??? ?? 0.6%??? and ??15N at the root of the vibrissae (representing current growth) were not significantly different from serum values. Milk was enriched for mean 13C by 5.0??? ?? 1.0%??? and 7.3??? ?? 1.2??? relative to serum and vibrissal roots, respectively, which was due to the presence of 13C-depleted lipids in milk. This was confirmed by lipid extraction from a subset of milk and serum samples, resulting in a 5.8??? ?? 1.0??? change only in milk. This study established that vibrissal roots and serum are reflective of a milk diet with approximately 2.0??? 15N enrichment, and vibrissal roots reflect serum and lipid-extracted milk values with approximately 2.0??? 13C enrichment. These discrimination factors are important to establish for stable isotope studies assessing diet shifts. ?? 2008 NRC.

Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark

NASA Astrophysics Data System (ADS)

Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.

2014-12-01

Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

Changes in erosion and ocean circulation recorded in the Hf isotopic compositions of North Atlantic and Indian Ocean ferromanganese crusts

USGS Publications Warehouse

Piotrowski, Alexander M.; Lee, Der-Chuen; Christensen, John N.; Burton, Kevin W.; Halliday, Alex N.; Hein, James R.; Günther, Detlef

2000-01-01

High-resolution Hf isotopic records are presented for hydrogenetic Fe–Mn crusts from the North Atlantic and Indian Oceans. BM1969 from the western North Atlantic has previously been shown to record systematically decreasing Nd isotopic compositions from about 60 to ∼4 Ma, at which time both show a rapid decrease to unradiogenic Nd composition, thought to be related to the increasing influence of NADW or glaciation in the northern hemisphere. During the Oligocene, North Atlantic Hf became progressively less radiogenic until in the mid-Miocene (∼15 Ma) it reached +1. It then shifted gradually back to an ϵHf value of +3 at 4 Ma, since when it has decreased rapidly to about −1 at the present day. The observed shifts in the Hf isotopic composition were probably caused by variation in intensity of erosion as glaciation progressed in the northern hemisphere. Ferromanganese crusts SS663 and 109D are from about 5500 m depth in the Indian Ocean and are now separated by ∼2300 km across the Mid-Indian Ridge. They display similar trends in Hf isotopic composition from 20 to 5 Ma, with the more northern crust having a composition that is consistently more radiogenic (by ∼2 ϵHf units). Paradoxically, during the last 20 Ma the Hf isotopic compositions of the two crusts have converged despite increased separation and subsidence relative to the ridge. A correlatable negative excursion at ∼5 Ma in the two records may reflect a short-term increase in erosion caused by the activation of the Himalayan main central thrust. Changes to unradiogenic Hf in the central Indian Ocean after 5 Ma may alternatively have been caused by the expanding influence of NADW into the Mid-Indian Basin via circum-Antarctic deep water or a reduction of Pacific flow through the Indonesian gateway. In either case, these results illustrate the utility of the Hf isotope system as a tracer of paleoceanographic changes, capable of responding to subtle changes in erosional regime not readily resolved using other isotope systems.

Precision Isotope Shift Measurements in Calcium Ions Using Quantum Logic Detection Schemes.

PubMed

Gebert, Florian; Wan, Yong; Wolf, Fabian; Angstmann, Christopher N; Berengut, Julian C; Schmidt, Piet O

2015-07-31

We demonstrate an efficient high-precision optical spectroscopy technique for single trapped ions with nonclosed transitions. In a double-shelving technique, the absorption of a single photon is first amplified to several phonons of a normal motional mode shared with a cotrapped cooling ion of a different species, before being further amplified to thousands of fluorescence photons emitted by the cooling ion using the standard electron shelving technique. We employ this extension of the photon recoil spectroscopy technique to perform the first high precision absolute frequency measurement of the 2D(3/2)→2P(1/2) transition in calcium, resulting in a transition frequency of f=346 000 234 867(96)  kHz. Furthermore, we determine the isotope shift of this transition and the 2S(1/2)→2P(1/2) transition for 42Ca+, 44Ca+, and 48Ca+ ions relative to 40Ca+ with an accuracy below 100 kHz. Improved field and mass shift constants of these transitions as well as changes in mean square nuclear charge radii are extracted from this high resolution data.

Regime shifts in the northern North Atlantic during the past 6,000 years: A record of seabird population size and precipitation isotopes on Bjørnøya, Svalbard

NASA Astrophysics Data System (ADS)

D'Andrea, W. J.; Hormes, A.; Bakke, J.; Nicolaisen, L.

2015-12-01

The northeastern North Atlantic Ocean, and the Norwegian and Greenland Seas are subject to large hydrographic changes. These variations can influence oceanic heat transport to the Arctic, meridional overturning circulation, and atmospheric circulation patterns and thereby impact global climate patterns. Marine records suggest that numerous large-scale changes in the hydrography of the northern North Atlantic took place during the middle to late Holocene. Here, we report a record of nitrogen and hydrogen isotope measurements from a lake sediment core from Bjørnøya, Svalbard (74.38°N, 19.02°E) that documents major regime shifts in the climate of the northern North Atlantic during the past 6,000 years. Bjørnøya is the nesting ground for one of the largest seabird populations in the North Atlantic. As top predators in the marine ecosystem, seabirds (and their guano) are enriched in 15N; during spring and summer months they deliver this isotopically enriched nitrogen to their nesting area. We developed a record of seabird population changes on Bjørnøya based on the bulk nitrogen isotope composition of sediments in a core collected from lake Ellasjøen. The record reveals multiple multicentennial scale changes in δ15N values (varying between ~8-12‰) that track past changes in the size of seabird populations. From the same sediment core, we also developed a record of δD of precipitation, by measuring δD values of sedimentary n-alkanes. Past intervals with the largest inferred bird populations correspond with the most enriched δD of precipitation, which we interpret to represent a more Atlantic climate. Periods with reduced seabird populations correspond with intervals having more negative δD of precipitation and representing a more Arctic climate. Together, the nitrogen and hydrogen isotope records signify regime shifts in the oceanography, marine ecosystem, and atmospheric circulation of the northern North Atlantic that are related to variations in the strength of the subpolar gyre.

Regime shifts in the Arctic North Atlantic during the Neoglacial revealed by seabirds and precipitation isotopes on Bjørnøya, Svalbard

NASA Astrophysics Data System (ADS)

D'Andrea, William J.; Hormes, Anne; Bakke, Jostein; Nicolaisen, Line

2016-04-01

The northeastern North Atlantic Ocean, and the Norwegian and Greenland Seas are subject to large hydrographic changes. These variations can influence oceanic heat transport to the Arctic, meridional overturning circulation, and atmospheric circulation patterns and thereby impact global climate patterns. Marine records suggest that numerous large-scale changes in the hydrography of the northern North Atlantic took place during the middle to late Holocene. We report a record of nitrogen and hydrogen isotope measurements from a lake sediment core from Bjørnøya, Svalbard (74.38°N, 19.02°E) that documents major regime shifts in the climate of the northern North Atlantic during the past 6,000 years. Bjørnøya is the nesting ground for one of the largest seabird populations in the North Atlantic. As top predators in the marine ecosystem, seabirds (and their guano) are enriched in 15N; during spring and summer months they deliver isotopically enriched nitrogen to nesting areas. We developed a record of seabird population changes on Bjørnøya based on the nitrogen isotope composition of sediments in a core collected from lake Ellasjøen. The record reveals multiple multicentennial scale changes in δ15N values (varying between ~8-12‰) that track past changes in the size of seabird populations. From the same sediment core, we also developed a record of δD of precipitation, using δD values of sedimentary n-alkanes. Past intervals with the largest inferred bird populations correspond with the most enriched δD of precipitation, which we interpret to represent a more Atlantic climate. Periods with reduced seabird populations correspond with intervals with more negative δD of precipitation and representing a more Arctic climate. Together, the nitrogen and hydrogen isotope records signify regime shifts in the oceanography, marine ecosystem, and atmospheric circulation of the northern North Atlantic that are related to variations in the strength of the subpolar gyre.

Stable water isotope behavior during the last glacial maximum: A general circulation model analysis

NASA Technical Reports Server (NTRS)

Jouzel, Jean; Koster, Randal D.; Suozzo, Robert J.; Russell, Gary L.

1994-01-01

Global water isotope geochemisty during the last glacial maximum (LGM) is simulated with an 8 deg x 10 deg atmospheric general circulation model (GCM). The simulation results suggest that the spatial delta O-18/temperature relationships observed for the present day and LGM climates are very similar. Furthermore, the temporal delta O-18/temperature relationship is similar to the present-day spatial relationship in regions for which the LGM/present-day temperature change is significant. This helps justify the standard practice of applying the latter to the interpretation of paleodata, despite the possible influence of other factors, such as changes in the evaportive sources of precipitation or in the seasonality of precipitation. The model suggests, for example, that temperature shifts inferred from ice core data may differ from the true shifts by only about 30%.

Breath carbon stable isotope ratios identify changes in energy balance and substrate utilization in humans.

PubMed

Whigham, L D; Butz, D E; Johnson, L K; Schoeller, D A; Abbott, D H; Porter, W P; Cook, M E

2014-09-01

Rapid detection of shifts in substrate utilization and energy balance would provide a compelling biofeedback tool for individuals attempting weight loss. As a proof of concept, we tested whether the natural abundance of exhaled carbon stable isotope ratios (breath δ(13)C) reflects shifts between negative and positive energy balance. Volunteers (n=5) consumed a 40% energy-restricted diet for 6 days followed by 50% excess on day 7. Breath was sampled immediately before and 1 h and 2 h after breakfast, lunch and dinner. Exhaled breath δ(13)C values were measured by cavity ring-down spectroscopy. Using repeated measures analysis of variance (ANOVA) followed by Dunnett's contrasts, pre-breakfast breath values on days 2-6 were compared with day 1, and postprandial day 7 time points were compared with pre-breakfast day 7. Energy restriction diminished pre-breakfast breath δ(13)C by day 3 (P<0.05). On day 7, increased energy intake was first detected immediately before dinner (-23.8±0.6 vs -21.9±0.7‰, P=0.002 (means±s.d.)), and breath δ(13)C remained elevated at least 2 h post dinner. In conclusion, when shifting between negative and positive energy balance, breath δ(13)C showed anticipated isotopic changes. Although additional research is needed to determine specificity and repeatability, this method may provide a biomarker for marked increases in caloric intake.

A biomarker stable isotope record of late Quaternary climate and organic matter export in Southwestern Taiwan

NASA Astrophysics Data System (ADS)

Chang, Q.; Hren, M. T.; Lin, A. T.; Eley, Y.; Yu, S. W.; Harris, G.

2017-12-01

We present new leaf wax n-alkane hydrogen (δD) and carbon (δ13C) isotopic data from a 36-m-long core from off-shore southwestern Taiwan to evaluate late Quaternary changes in climate and the source of organic matter exported from the landscape. The core (MD178-3291) is located on the flank of the Gaoping Submarine Canyon that connects with the Gaoping river catchment in southwestern Taiwan. The sediment deposition in this core spans the last 26 kyr, providing a unique record of glacial-interglacial changes in organic matter export from the Taiwan orogen. The δD and δ13C both show a shift in isotopic compositions at 15 kyr, that coincides with the shift in planktonic foraminifera δ18O record from the same core as well as the global sea level. We therefore interpret this dominant shift as affected by the global glacial to interglacial transition. Following by this transition and through the interglacial period, both biomarker δD and δ13C data record fluctuations that we suggest result from short timescale changes in the distribution of organic inputs to the offshore site. This change in source is most likely caused by increases in storm and landslide frequency or intensity during warmer intervals. This interpretation is supported by terrestrial records that show an increase in landslides in the Gaoping catchment and evidence for enhanced rainfall intensity and a corresponding increase in the frequency of turbidity currents.

Low temperature FTIR spectra and hydrogen bonds in polycrystalline cytidine.

PubMed

Rozenberg, M; Jung, C; Shoham, G

2004-08-01

FTIR spectra of polycrystalline samples of cytidine, pure and containing a small quantity of N(O)H or N(O)D groups (<20%), were measured in KBr pellets from 4000 to 400 cm(-1) at temperatures from 300 to 20K. For the first time the bands of the narrow isotopically decoupled proton stretching vibration mode (nu(1)) of OH- and NH- groups were found; their number corresponds to the number of H-bonds in crystal according to structural data. The FTIR spectra at low temperature in the out-of-plane bending nu(4) proton mode range (lower than 1000 cm(-1)) of N(O)H groups revealed narrow bands, which correspond to nu(1) bands together with several "extra" bands, which are influenced by the isotopic exchange and (or) cooling. All of them have their counterparts in the N(O)D-substance spectrum with an isotopic frequency ratio of 1.30-1.40. The "extra" bands are assigned to the H-bound OH and NH protons, which are disordered and cannot be seen with X-ray crystal structure analysis. The peak positions of both mode bands (expressed as the red shift of nu(1) or blue shift of nu(4) modes relatively free molecules) were used for the estimation of the energy of different H-bonds using previously established empirical correlations between spectral and thermodynamic parameters of hydrogen bonds. The correlation of the red shift and H-bond length is also confirmed for all five H-bonds of cytidine.

Hyperfine structure and isotope shift analysis of singly ionized titanium

NASA Astrophysics Data System (ADS)

Bouazza, Safa

2013-04-01

The even-parity low configuration system of Ti II has been considered on the basis of the experimental data found in the literature, and its fine structure has been reanalyzed by simultaneous parameterization of one- and two-body interactions for the model space (3d + 4s)3. Furthermore, the main one-electron hyperfine structure parameters for these configurations have been evaluated. For instance, for 3d24s1, a_{3{\\rm{d}}}^{01} = - {\\rm{63}}.{\\rm{2}}\\left( {{\\rm{3}}.{\\rm{1}}} \\right)\\,{\\rm{MHz}} and a_{4{\\rm{s}}}^{10} = - {\\rm{984}}.{\\rm{1}}\\left( {{\\rm{7}}.{\\rm{1}}} \\right)\\,{\\rm{MHz}} . Field shifts (FS) and specific mass shifts (SMS) of the main Ti II configurations are deduced by means of ab initio estimates combined with a small quantity of experimental isotope shift data available in the literature: FS(3d3) = -63.3 MHz, FS(3d24p1) = -49.7 MHz, FS(3d14s2) = 98.2 MHz, FS(4s24P1) = 163.4 MHz and SMS(3d3) = 1453.3 MHz, SMS(3d14s2) = -2179.7 MHz, …, referred to 3d24s1 for the pair Ti46-Ti48.

Shape Evolution in Neutron-Rich Krypton Isotopes Beyond N =60 : First Spectroscopy of Kr,10098

NASA Astrophysics Data System (ADS)

Flavigny, F.; Doornenbal, P.; Obertelli, A.; Delaroche, J.-P.; Girod, M.; Libert, J.; Rodriguez, T. R.; Authelet, G.; Baba, H.; Calvet, D.; Château, F.; Chen, S.; Corsi, A.; Delbart, A.; Gheller, J.-M.; Giganon, A.; Gillibert, A.; Lapoux, V.; Motobayashi, T.; Niikura, M.; Paul, N.; Roussé, J.-Y.; Sakurai, H.; Santamaria, C.; Steppenbeck, D.; Taniuchi, R.; Uesaka, T.; Ando, T.; Arici, T.; Blazhev, A.; Browne, F.; Bruce, A.; Carroll, R.; Chung, L. X.; Cortés, M. L.; Dewald, M.; Ding, B.; Franchoo, S.; Górska, M.; Gottardo, A.; Jungclaus, A.; Lee, J.; Lettmann, M.; Linh, B. D.; Liu, J.; Liu, Z.; Lizarazo, C.; Momiyama, S.; Moschner, K.; Nagamine, S.; Nakatsuka, N.; Nita, C.; Nobs, C. R.; Olivier, L.; Orlandi, R.; Patel, Z.; Podolyák, Zs.; Rudigier, M.; Saito, T.; Shand, C.; Söderström, P. A.; Stefan, I.; Vaquero, V.; Werner, V.; Wimmer, K.; Xu, Z.

2017-06-01

We report on the first γ -ray spectroscopy of low-lying states in neutron-rich Kr,10098 isotopes obtained from Rb,10199(p ,2 p ) reactions at ˜220 MeV /nucleon . A reduction of the 21+ state energies beyond N =60 demonstrates a significant increase of deformation, shifted in neutron number compared to the sharper transition observed in strontium and zirconium isotopes. State-of-the-art beyond-mean-field calculations using the Gogny D1S interaction predict level energies in good agreement with experimental results. The identification of a low-lying (02+, 22+) state in Kr 98 provides the first experimental evidence of a competing configuration at low energy in neutron-rich krypton isotopes consistent with the oblate-prolate shape coexistence picture suggested by theory.

Observation of narrow isotopic optical magnetic resonances in individual emission spectral lines of neon

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

Saprykin, E G; Sorokin, V A; Shalagin, A M

Narrow resonances are observed in the course of recording the individual emission lines of the glow discharge in the mixture of isotopes {sup 20}Ne and {sup 22}Ne, depending on the strength of the longitudinal magnetic field. The position of resonances in the magnetic scale corresponds to the compensation of the isotopic shift for certain spectral lines due to the Zeeman effect. It is found that the contrast of the resonances is higher for the transitions between the highly excited energy levels, and the resonances themselves are formed in the zone of longitudinal spatial nonuniformity of the magnetic field. (laser applicationsmore » and other topics in quantum electronics)« less

Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

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

Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joël

2014-06-28

Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [“Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry,” J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results frommore » studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ{sup 15}N, δ{sup 18}O, and Δ{sup 17}O). From these measurements an average photolytic isotopic fractionation of {sup 15}ε = (−15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of {sup 15}ε = (−47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from −40 to −74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of {sup 14}NO{sub 3}{sup −} and {sup 15}NO{sub 3}{sup −} in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying this model under the experimental temperature as well as considering the shift in width and center well reproduced the values obtained in the laboratory study. These cross sections can be used in isotopic models to reproduce the stable isotopic composition of nitrate found in Antarctic snow profiles.« less

Sedimentary organic molecules: Origins and information content

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Freeman, K. H.

1991-01-01

To progress in the study of organic geochemistry, we must dissect the processes controlling the composition of sedimentary organic matter. Structurally, this has proven difficult. Individual biomarkers can often be recognized, but their contribution to total organic materials is small, and their presence does not imply that their biochemical cell mates have survived. We are finding, however, that a combination of structural and isotopic lines of evidence provides new information. A starting point is provided by the isotopic compositions of primary products (degradation products of chlorophylls, alkenones derived from coccoliths). We find strong evidence that the isotopic difference between primary carbonate and algal organic material can be interpreted in terms of the concentration of dissolved CO2. Moreover, the isotopic difference between primary and total organic carbon can be interpreted in terms of characteristic isotopic shifts imposed by secondary processes (responsive, for example, to O2 levels in the depositional environment. In favorable cases, isotopic compositions of a variety of secondary products can be interpreted in terms of flows of carbon, and, therefore, in terms of specific processes and environmental conditions within the depositional environment.

Compound-specific stable isotopes of organic compounds from lake sediments track recent environmental changes in an alpine ecosystem, Rocky Mountain National Park, Colorado

USGS Publications Warehouse

Enders, S.K.; Pagani, M.; Pantoja, S.; Baron, Jill S.; Wolfe, A.P.; Pedentchouk, N.; Nunez, L.

2008-01-01

Compound-specific nitrogen, carbon, and hydrogen isotope records from sediments of Sky Pond, an alpine lake in Rocky Mountain National Park (Colorado, United States of America), were used to evaluate factors contributing to changes in diatom assemblages and bulk organic nitrogen isotope records identified in lake sediments across Colorado, Wyoming, and southern Montana. Nitrogen isotopic records of purified algal chlorins indicate a substantial shift in nitrogen cycling in the region over the past ???60 yr. Temporal changes in the growth characteristics of algae, captured in carbon isotope records in and around Sky Pond, as well as a -60??? excursion in the hydrogen isotope composition of algal-derived palmitic acid, are coincident with changes in nitrogen cycling. The confluence of these trends is attributed to an increase in biologically available nitrogenous compounds caused by an expansion of anthropogenic influences and temporal changes in catchment hydrology and nutrient delivery associated with meltwater dynamics. ?? 2008, by the American Society of Limnology and Oceanography, Inc.

Evolving Pb isotope signatures of London airborne particulate matter (PM 10)-constraints from on-filter and solution-mode MC-ICP-MS.

PubMed

Noble, Stephen R; Horstwood, Matthew S A; Davy, Pamela; Pashley, Vanessa; Spiro, Baruch; Smith, Steve

2008-07-01

Pb isotope compositions of biologically significant PM(10) atmospheric particulates from a busy roadside location in London UK were measured using solution- and laser ablation-mode MC-ICP-MS. The solution-mode data for PM(10) sampled between 1998-2001 document a dramatic shift to increasingly radiogenic compositions as leaded petrol was phased out. LA-MC-ICP-MS isotope analysis, piloted on a subset of the available samples, is shown to be a potential reconnaissance analytical technique. PM(10) particles trapped on quartz filters were liberated from the filter surface, without ablating the filter substrate, using a 266 nm UV laser and a dynamic, large diameter, low-fluence ablation protocol. The Pb isotope evolution noted in the London data set obtained by both analytical protocols is similar to that observed elsewhere in Western Europe following leaded petrol elimination. The data therefore provide important baseline isotope composition information useful for continued UK atmospheric monitoring through the early 21(st) century.

Systematics of nuclear ground state properties in 78-100Sr by laser spectroscopy

NASA Astrophysics Data System (ADS)

Buchinger, F.; Ramsay, E. B.; Arnold, E.; Neu, W.; Neugart, R.; Wendt, K.; Silverans, R. E.; Lievens, P.; Vermeeren, L.; Berdichevsky, D.; Fleming, R.; Sprung, D. W. L.; Ulm, G.

1990-06-01

Hyperfine structures and isotope shifts of strontium isotopes with A=78 to A=98 and A=100 were measured by collinear fast beam laser spectroscopy. Nuclear spins, moments and changes in mean square charge radii are extracted from the data. The spins and moments of most of the odd isotopes are explained in the framework of the single particle model. The changes in mean square charge radii are compared with predictions of the droplet model and of Hartree-Fock-plus-BCS calculations. For the isotopes in the transitional regions below and above the N=50 shell closure, the inclusion of quadrupole zero point motion in the Droplet model describes part of the observed shell effect. An additional change in the surface region of the charge distribution at spherical shape is suggested by the microscopic model. Furthermore, we propose that the isotopes 78Sr and 80Sr may show an unusual shape-sharing structure, with different mean deformations in the ground and 2+1 excited states.

Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

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

Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is important for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament- uranium interaction points. The resulting uranium oxide emission exhibitsmore » a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. Lastly, the results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity.« less

Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

PubMed Central

Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

2017-01-01

The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is impor-tant for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament-uranium interaction points. The resulting uranium oxide emis-sion exhibits a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. The results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity. PMID:28272450

Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

DOE PAGES

Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

2017-03-08

The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is important for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament- uranium interaction points. The resulting uranium oxide emission exhibitsmore » a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. Lastly, the results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity.« less

Standoff Detection of Uranium and its Isotopes by Femtosecond Filament Laser Ablation Molecular Isotopic Spectrometry

NASA Astrophysics Data System (ADS)

Hartig, Kyle C.; Ghebregziabher, Isaac; Jovanovic, Igor

2017-03-01

The ability to perform not only elementally but also isotopically sensitive detection and analysis at standoff distances is impor-tant for remote sensing applications in diverse ares, such as nuclear nonproliferation, environmental monitoring, geophysics, and planetary science. We demonstrate isotopically sensitive real-time standoff detection of uranium by the use of femtosecond filament-induced laser ablation molecular isotopic spectrometry. A uranium oxide molecular emission isotope shift of 0.05 ± 0.007 nm is reported at 593.6 nm. We implement both spectroscopic and acoustic diagnostics to characterize the properties of uranium plasma generated at different filament-uranium interaction points. The resulting uranium oxide emis-sion exhibits a nearly constant signal-to-background ratio over the length of the filament, unlike the uranium atomic and ionic emission, for which the signal-to-background ratio varies significantly along the filament propagation. This is explained by the different rates of increase of plasma density and uranium oxide density along the filament length resulting from spectral and temporal evolution of the filament along its propagation. The results provide a basis for the optimal use of filaments for standoff detection and analysis of uranium isotopes and indicate the potential of the technique for a wider range of remote sensing applications that require isotopic sensitivity.

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.

Intrapopulation variability in the timing of ontogenetic habitat shifts in sea turtles revealed using δ15 N values from bone growth rings.

PubMed

Turner Tomaszewicz, Calandra N; Seminoff, Jeffrey A; Peckham, S Hoyt; Avens, Larisa; Kurle, Carolyn M

2017-05-01

Determining location and timing of ontogenetic shifts in the habitat use of highly migratory species, along with possible intrapopulation variation in these shifts, is essential for understanding mechanisms driving alternate life histories and assessing overall population trends. Measuring variations in multi-year habitat-use patterns is especially difficult for remote oceanic species. To investigate the potential for differential habitat use among migratory marine vertebrates, we measured the naturally occurring stable nitrogen isotope (δ 15 N) patterns that differentiate distinct ocean regions to create a 'regional isotope characterization', analysed the δ 15 N values from annual bone growth layer rings from dead-stranded animals, and then combined the bone and regional isotope data to track individual animal movement patterns over multiple years. We used humeri from juvenile North Pacific loggerhead turtles (Caretta caretta), animals that undergo long migrations across the North Pacific Ocean (NPO), using multiple discrete regions as they develop to adulthood. Typical of many migratory marine species, ontogenetic changes in habitat use throughout their decades-long juvenile stage is poorly understood, but each potential habitat has unique foraging opportunities and spatially explicit natural and anthropogenic threats that could affect key life-history parameters. We found a bimodal size/age distribution in the timing that juveniles underwent an ontogenetic habitat shift from the oceanic central North Pacific (CNP) to the neritic east Pacific region near the Baja California Peninsula (BCP) (42·7 ± 7·2 vs. 68·3 ± 3·4 cm carapace length, 7·5 ± 2·7 vs. 15·6 ± 1·7 years). Important to the survival of this population, these disparate habitats differ considerably in their food availability, energy requirements and threats, and these differences can influence life-history parameters such as growth, survival and future fecundity. This is the first evidence of alternative ontogenetic shifts and habitat-use patterns for juveniles foraging in the eastern NPO. We combine two techniques, skeletochronology and stable isotope analysis, to reconstruct multi-year habitat-use patterns of a remote migratory species, linked to estimated ages and body sizes of individuals, to reveal variable ontogeny during the juvenile life stage that could drive alternate life histories and that has the potential to illuminate the migration patterns for other species with accretionary tissues. © 2016 The Authors. Journal of Animal Ecology © 2016 British Ecological Society.

Retrospective characterization of ontogenetic shifts in killer whale diets via δ13C and δ15N analysis of teeth

USGS Publications Warehouse

Newsome, Seth D.; Etnier, Michael A.; Monson, Daniel H.; Fogel, Marilyn L.

2009-01-01

Metabolically inert, accretionary structures such as the dentin growth layers in teeth provide a life history record of individual diet with near-annual resolution. We constructed ontogenetic ??13C and ??15N profiles by analyzing tooth dentin growth layers from 13 individual killer whales Orcinus orca collected in the eastern northeast Pacific Ocean between 1961 and 2003. The individuals sampled were 6 to 52 yr old, representing 2 ecotypes-resident and transient - collected across ???25?? of latitude. The average isotopic values of transient individuals (n = 10) are consistent with a reliance on mammalian prey, while the average isotopic values of residents (n = 3) are consistent with piscivory. Regardless of ecotype, most individuals show a decrease in ??15N values of ???2.5% through the first 3 yr of life, roughly equivalent to a decrease of one trophic level. We interpret this as evidence of gradual weaning, after which, ontogenetic shifts in isotopic values are highly variable. A few individuals (n = 2) maintained relatively stable ??15N and ??13C values throughout the remainder of their lives, whereas ??15N values of most (n = 11) increased by ???1.5%, suggestive of an ontogenetic increase in trophic level. Significant differences in mean ??13C and ??15N values among transients collected off California suggest that individuality in prey preferences may be prevalent within this ecotype. Our approach provides retrospective individual life history and dietary information that cannot be obtained through traditional field observations of free-ranging and elusive species such as killer whales, including unique historic ecological information that pre-dates modern studies. By providing insights into individual diet composition, stable isotope analysis of teeth and/or bones may be the only means of evaluating a number of hypothesized historical dietary shifts in killer whales of the northeast Pacific Ocean. ?? Inter-Research 2009.

Retrospective characterization of ontogenetic shifts in killer whale diets via δ13C and δ15N analysis of teeth

USGS Publications Warehouse

Newsome, Seth D.; Etnier, Michael A.; Monson, Daniel H.; Fogel, Marilyn L.

2009-01-01

Metabolically inert, accretionary structures such as the dentin growth layers in teeth provide a life history record of individual diet with near-annual resolution. We constructed ontogenetic δ13C and δ15N profiles by analyzing tooth dentin growth layers from 13 individual killer whales Orcinus orca collected in the eastern northeast Pacific Ocean between 1961 and 2003. The individuals sampled were 6 to 52 yr old, representing 2 ecotypes—resident and transient—collected across ~25° of latitude. The average isotopic values of transient individuals (n = 10) are consistent with a reliance on mammalian prey, while the average isotopic values of residents (n = 3) are consistent with piscivory. Regardless of ecotype, most individuals show a decrease in δ15N values of ~2.5‰ through the first 3 yr of life, roughly equivalent to a decrease of one trophic level. We interpret this as evidence of gradual weaning, after which, ontogenetic shifts in isotopic values are highly variable. A few individuals (n = 2) maintained relatively stable δ15N and δ13C values throughout the remainder of their lives, whereas δ15N values of most (n = 11) increased by ~1.5‰, suggestive of an ontogenetic increase in trophic level. Significant differences in mean δ13C and δ15N values among transients collected off California suggest that individuality in prey preferences may be prevalent within this ecotype. Our approach provides retrospective individual life history and dietary information that cannot be obtained through traditional field observations of free-ranging and elusive species such as killer whales, including unique historic ecological information that pre-dates modern studies. By providing insights into individual diet composition, stable isotope analysis of teeth and/or bones may be the only means of evaluating a number of hypothesized historical dietary shifts in killer whales of the northeast Pacific Ocean

The OAE1a in Cuchía (Early Aptian, Spain): C and O geochemistry and global correlation

NASA Astrophysics Data System (ADS)

García-Mondéjar, Joaquín; Fernández-Mendiola, Pedro A.; Owen, Hugh G.

2015-12-01

C-isotopes, TOC and O geochemical data from the lower Aptian Cuchía section in the western Basque-Cantabrian basin (BCB) allow an accurate delimitation of the OAE1a-equivalent and its geochemical Menegattís segments, a detailed δ13Ccarb correlation with regional and interregional sections, and a high-resolution construction of TOC and bulk-rock δ18Ocarb curves and their interpretation. The δ13Ccarb values range from -2‰ and +4‰ (VPDB). They agree with previous data from the eastern BCB sections (Aralar) confirming the ammonite age of the OAE1a in the Basque-Cantabrian basin: Deshayesites forbesi, Deshayesites deshayesi, and Deshayesites deshayesi-Dufrenoyia furcata transition Zones. Interregional δ13Ccarb correlation with pelagic (Cismon, Italy, and Mid-Pacific Mountains, DSDP Site 463) and neritic (Roquefort-La Bédoule, France) core sections, reveals a common profile of a wide negative excursion characteristic of the OAE1a. It consists of a double trough separated by a flat relative maximum, with two negative spikes in the upper trough of neritic sections. TOC absolute values range from 0.12% to 1.37%. Segments of the TOC curve with persistent low values closely correspond with descending segments of the δ13Ccarb curve, and are attributed to lesser organic productivity in the BCB. Detailed bulk-rock δ18Ocarb data (-5.71‰ to -1.05 ‰ PDB) and variation curve show two main positive O-isotope shifts and three minor positive inflections, within a general negative trend characteristic of the OAE1a. The two major positive shifts correspond to both shallowing upwards sequences and the lowermost can be related to a eustatic sea level fall. Independent interregional correlation of the O-isotope shifts with C-isotopes supports their interpretation as punctuating colder events within a general warming trend.

Not all jellyfish are equal: isotopic evidence for inter- and intraspecific variation in jellyfish trophic ecology.

PubMed

Fleming, Nicholas E C; Harrod, Chris; Newton, Jason; Houghton, Jonathan D R

2015-01-01

Jellyfish are highly topical within studies of pelagic food-webs and there is a growing realisation that their role is more complex than once thought. Efforts being made to include jellyfish within fisheries and ecosystem models are an important step forward, but our present understanding of their underlying trophic ecology can lead to their oversimplification in these models. Gelatinous zooplankton represent a polyphyletic assemblage spanning >2,000 species that inhabit coastal seas to the deep-ocean and employ a wide variety of foraging strategies. Despite this diversity, many contemporary modelling approaches include jellyfish as a single functional group feeding at one or two trophic levels at most. Recent reviews have drawn attention to this issue and highlighted the need for improved communication between biologists and theoreticians if this problem is to be overcome. We used stable isotopes to investigate the trophic ecology of three co-occurring scyphozoan jellyfish species (Aurelia aurita, Cyanea lamarckii and C. capillata) within a temperate, coastal food-web in the NE Atlantic. Using information on individual size, time of year and δ (13)C and δ (15)N stable isotope values, we examined: (1) whether all jellyfish could be considered as a single functional group, or showed distinct inter-specific differences in trophic ecology; (2) Were size-based shifts in trophic position, found previously in A. aurita, a common trait across species?; (3) When considered collectively, did the trophic position of three sympatric species remain constant over time? Differences in δ (15)N (trophic position) were evident between all three species, with size-based and temporal shifts in δ (15)N apparent in A. aurita and C. capillata. The isotopic niche width for all species combined increased throughout the season, reflecting temporal shifts in trophic position and seasonal succession in these gelatinous species. Taken together, these findings support previous assertions that jellyfish require more robust inclusion in marine fisheries or ecosystem models.

Not all jellyfish are equal: isotopic evidence for inter- and intraspecific variation in jellyfish trophic ecology

PubMed Central

Fleming, Nicholas E.C.; Newton, Jason; Houghton, Jonathan D.R.

2015-01-01

Jellyfish are highly topical within studies of pelagic food-webs and there is a growing realisation that their role is more complex than once thought. Efforts being made to include jellyfish within fisheries and ecosystem models are an important step forward, but our present understanding of their underlying trophic ecology can lead to their oversimplification in these models. Gelatinous zooplankton represent a polyphyletic assemblage spanning >2,000 species that inhabit coastal seas to the deep-ocean and employ a wide variety of foraging strategies. Despite this diversity, many contemporary modelling approaches include jellyfish as a single functional group feeding at one or two trophic levels at most. Recent reviews have drawn attention to this issue and highlighted the need for improved communication between biologists and theoreticians if this problem is to be overcome. We used stable isotopes to investigate the trophic ecology of three co-occurring scyphozoan jellyfish species (Aurelia aurita, Cyanea lamarckii and C. capillata) within a temperate, coastal food-web in the NE Atlantic. Using information on individual size, time of year and δ13C and δ15N stable isotope values, we examined: (1) whether all jellyfish could be considered as a single functional group, or showed distinct inter-specific differences in trophic ecology; (2) Were size-based shifts in trophic position, found previously in A. aurita, a common trait across species?; (3) When considered collectively, did the trophic position of three sympatric species remain constant over time? Differences in δ15N (trophic position) were evident between all three species, with size-based and temporal shifts in δ15N apparent in A. aurita and C. capillata. The isotopic niche width for all species combined increased throughout the season, reflecting temporal shifts in trophic position and seasonal succession in these gelatinous species. Taken together, these findings support previous assertions that jellyfish require more robust inclusion in marine fisheries or ecosystem models. PMID:26244116

A Carbon Source Apportionment Shift in Mexico City Atmospheric Particles During 2003-2004 as Determined with Stable Carbon Isotopes

NASA Astrophysics Data System (ADS)

Lopez-Veneroni, D. G.; Vega, E.

2013-05-01

The stable carbon isotope composition of atmospheric particles (PM2.5) was measured at La Merced (MER), a commercial site in the eastern sector, and at Xalostoc (XAL) an industrial site in the NE sector of Mexico City, during three sampling periods in autumn 2003, and spring and autumn 2004. At each site and sampling campaign particle samples were collected daily with minivol samplers during two week periods. Ancillary data included organic and elemental carbon, trace elements and ionic species. This data base was complement with air quality data from the RAMA (Automatic Atmospheric Monitoring Network). In general, particle concentrations, ionic species and some air quality species showed higher concentrations in autumn and lowest values in spring. Moreover, the concentrations of these chemical species were highest at XAL compared to MER. The stable carbon isotope composition of PM2.5 during autumn 2003 and spring 2004 had and average value of -26.04 (± 1.54) ‰ vs. PDB. Differences in the isotopic composition between the two sites were non significant. The average δ13C during these seasons were 1 ‰ lighter relative to data collected previously at these sites during 2000 and 2001, and is consistent with a predominant source of hydrocarbon combustion. In autumn 2004, however, average δ13C at XAL and MER increased to -22.8 (± 0.9) and -20.6 (± 3.1) ‰, respectively. Organic carbon concentrations during this period increased concomitantly at these sites. The shift in the isotopic composition in ambient particles suggests a predominance of soil-derived carbon during this period. The possible causes and implications of this are discussed.

Using Tidal Fluctuation-Induced Dynamics of Radium Isotopes (224Ra, 223Ra, and 228Ra) to Trace the Hydrodynamics and Geochemical Reactions in a Coastal Groundwater Mixing Zone

NASA Astrophysics Data System (ADS)

Liu, Yi; Jiao, Jiu Jimmy; Liang, Wenzhao; Luo, Xin

2018-04-01

The reactive transport of radium isotopes (224Ra, 223Ra, and 228Ra) in coastal groundwater mixing zones (CGMZs) is sensitive to shifts of redox conditions and geochemical reactions induced by tidal fluctuation. This study presents a spatial distribution and temporal variation of radium isotopes in the CGMZ for the first time. Results show that the activity of radium isotopes in the upper saline plume (USP) is comparatively low due to a short residence time and mixing loss induced by the infiltration of low radium seawater whereas the activity of radium isotopes in the salt wedge (SW) is comparatively high due to a long residence time in the aquifer. The spatial distribution of radium isotopes is determined by the partitioning of radium isotopes, groundwater residence time, and relative ingrowth rates of radium isotopes. In addition, the variation of radium isotopes in the USP lags slightly (˜0 h) whereas the fluctuation of radium isotopes in the SW lags significantly (˜12 h) behind sea level oscillation. Tidal fluctuation affects the partitioning of radium isotopes through controlling seawater infiltration and subsequently influences the dynamics of radium isotopes in the USP. Concurrently, seawater infiltration significantly affects geochemical processes such as the production of nutrients and total alkalinity. Therefore, radium dynamics in the USP have implications for these geochemical processes. The variation of radium isotopes in the USP also has potential implications for transformation of trace metals such as iron and manganese because of the close affinity of radium isotopes to manganese and iron oxides.

The shift of harmonics with different initial vibrational states in the H{}_{2}^{+} molecular ion

NASA Astrophysics Data System (ADS)

Zhang, Jun; Pan, Xue-Fei; Xu, Tong-Tong; Liu, Xue-Shen

2017-05-01

Molecular high-order harmonic generation of H{}2+ and its isotopes is investigated by numerical simulations of the non-Born-Oppenheimer time-dependent Schrödinger equations. The general characteristic of the typical high-order harmonic generation (HHG) spectra for the H{}2+ molecule indicates that only the odd harmonics can be generated. Here we show that how the initial vibrational states and nuclear dynamics break down this standard characteristic, i.e. a redshift or blueshift of the harmonics appears. We investigate the effect of the initial vibrational states on the redshift or blueshift of the HHG spectrum under trapezoidal laser pulses. The ionization probability and time-frequency analysis are used to illustrate the physical mechanism of the shift of the harmonics. We also show the HHG spectra from the different isotopes of H2+ molecule with different initial vibrational states.

Application of non-traditional stable isotopes in analytical ecogeochemistry assessed by MC ICP-MS--A critical review.

PubMed

Irrgeher, Johanna; Prohaska, Thomas

2016-01-01

Analytical ecogeochemistry is an evolving scientific field dedicated to the development of analytical methods and tools and their application to ecological questions. Traditional stable isotopic systems have been widely explored and have undergone continuous development during the last century. The variations of the isotopic composition of light elements (H, O, N, C, and S) have provided the foundation of stable isotope analysis followed by the analysis of traditional geochemical isotope tracers (e.g., Pb, Sr, Nd, Hf). Questions in a considerable diversity of scientific fields have been addressed, many of which can be assigned to the field of ecogeochemistry. Over the past 15 years, other stable isotopes (e.g., Li, Zn, Cu, Cl) have emerged gradually as novel tools for the investigation of scientific topics that arise in ecosystem research and have enabled novel discoveries and explorations. These systems are often referred to as non-traditional isotopes. The small isotopic differences of interest that are increasingly being addressed for a growing number of isotopic systems represent a challenge to the analytical scientist and push the limits of today's instruments constantly. This underlines the importance of a metrologically sound concept of analytical protocols and procedures and a solid foundation of data processing strategies and uncertainty considerations before these small isotopic variations can be interpreted in the context of applied ecosystem research. This review focuses on the development of isotope research in ecogeochemistry, the requirements for successful detection of small isotopic shifts, and highlights the most recent and innovative applications in the field.

Determining Prehistoric Mining Practices in Southeastern Europe Using Copper Isotopes

NASA Astrophysics Data System (ADS)

Powell, Wayne; Mathur, Ryan; Bankoff, H. Arthur; Bulatović, Aleksandar; Filipović, Vojislav

2017-04-01

Copper was first smelted from malachite at 5000 BCE in Serbia. There the Eneolithic (Copper Age) began with the production of small jewelry pieces and progressed to the casting of massive copper tools near its end, approximately 2000 years later. However, copper metallurgy in southeastern Europe ceased or significantly decreased in the later third millennium, several centuries before the Bronze Age began. Whether this metallurgical hiatus was the result a cultural shift or depletion of natural resources remains an ongoing subject of debate. It has been speculated that the marked reduction in metal production at the Eneolithic-Bronze Age transition was due to the exhaustion of surficial weathered oxide ores and the technical inability to smelt the underlying sulfide minerals. The behavior of copper isotopes in near-surface environments allows us to differentiate highly weathered oxide ores that occur at Earth's surface from non-weathered sulfide ores that occur at greater depth. The oxidation of copper generates fluids and associated minerals that are enriched in the 65Cu isotope. Thus, oxidative weathering of sulfide ores leads to the development of three stratified isotopic reservoirs for copper: 1) oxides above the water table that are enriched in 65Cu; 2) residual weathered sulfides minerals at the water table that are depleted in 65Cu; and 3) non-fractionated, non-weathered sulfide ore below the water table. And so, the transformative shift to sulfide-based metallurgy will be delineated by a significant decrease in δ65Cu in copper artifacts corresponding to the first use of 65Cu-depleted residual ore. The degree of variability of primary ore composition from numerable ore deposits would likely result in the overlap of copper isotope composition between populations of artifacts. Therefore, shifts in the mean copper isotope values and associated standard deviations would best reflect changes in ores use. A baseline value of -0.2‰ ±0.5 (1) was determined from an average of 164 published measurements from chalcopyrite and bornite from 8 epithermal and massive sulfide deposits. Twenty-two (88%) of Eneolithic artifacts (n=25) have values greater than this, whereas eight (73%) of the Early Bronze age artifacts (n=11) yield compositions less than -0.2‰. The mean of Middle Bronze Age, Late Bronze Age and Early Iron Age (n=86) cluster near -0.2‰. This pattern is consistent with a progression to the mining of ore assemblages from increasing depths through prehistory. The shift from 65Cu-enriched to 65Cu-depleted copper in artifacts across the Eneolithic-Bronze Age boundary at 2500 BCE indicates that accessible near-surface oxide ore reserves were depleted after approximately two millennia of mining, and that the beginning of the Bronze Age in the Balkans corresponded to the acquisition of pyrotechnology which allowed for the extraction of metals from sulfide minerals and the resumption of copper mining activity in the region.

Late Holocene dinosterol hydrogen isotope variability in Lac Lalolalo and Lac Lanutavake on Wallis Island

NASA Astrophysics Data System (ADS)

Maloney, A. E.; Hing, S. N.; Richey, J. N.; Nelson, D. B.; Sachs, J. P.

2017-12-01

The South Pacific Convergence Zone (SPCZ) is the Southern Hemisphere's largest precipitation feature, yet little is known about the region's rainfall prior to the instrumental record. In the tropics, hydrogen isotopes of precipitation are controlled by the "amount effect" where higher mean annual rainfall rates result in 2H-depleted rain. In turn, hydrogen isotopes in tropical lakes are influenced by both rain water isotopes and evaporative enrichment. Molecular fossils preserved in lake sediments offer a promising tool for improving our understanding of the past SPCZ by tracking changes in lake water isotopes. Hydrogen isotope compositions (δ2H) of the algal lipid biomarker dinosterol were measured in duplicate sediment cores from lakes 2.75km apart on Wallis Island. The modern lakes differ in physical and chemical conditions but are both freshwater in the photic zone and experience identical climate conditions. They are an ideal setting to investigate the fidelity to which δ2Hdinosterol records climate. Duplicate records from Lac Lanutavake are in excellent agreement and reveal little change in during the past 1700 years with minor δ2Hdinosterol fluctuations between -280‰ and -290‰. Duplicate records from Lac Lalolalo also agree extremely well during the past 2,000 years. However, contrary to its neighbor, Lac Lalolalo has a highly variable δ2Hdinosterol history with 2H-depleted values of -300‰ during the youngest part of the record climbing to 2H-enriched values of -230‰ around 1000-2000 years ago. The large shift in Lac Lalolalo δ2Hdinosterol may be due to changes in lake biogeochemistry that impact growth conditions or shifts in dinoflagellate species composition. Alternatively, if the Lac Lalolalo record actually reflects changes in hydrology, large limnological changes must have occurred in Lac Lanutavke to mute the climate signal. This work emphasizes the importance of redundancy and duplication when investigating changes in past climate using molecular tools that are also sensitive to environmental parameters.

Drought Sensitivity of the Carbon Isotope Composition of Leaf Dark-Respired CO2 in C3 (Leymus chinensis) and C4 (Chloris virgata and Hemarthria altissima) Grasses in Northeast China.

PubMed

Zhong, Shangzhi; Chai, Hua; Xu, Yueqiao; Li, Yan; Ma, Jian-Ying; Sun, Wei

2017-01-01

Whether photosynthetic pathway differences exist in the amplitude of nighttime variations in the carbon isotope composition of leaf dark-respired CO 2 (δ 13 C l ) and respiratory apparent isotope fractionation relative to biomass (Δ R,biomass ) in response to drought stress is unclear. These differences, if present, would be important for the partitioning of C 3 -C 4 mixed ecosystem C fluxes. We measured δ 13 C l , the δ 13 C of biomass and of potential respiratory substrates and leaf gas exchange in one C 3 ( Leymus chinensis ) and two C 4 ( Chloris virgata and Hemarthria altissima ) grasses during a manipulated drought period. For all studied grasses, δ 13 C l decreased from 21:00 to 03:00 h. The magnitude of the nighttime shift in δ 13 C l decreased with increasing drought stress. The δ 13 C l values were correlated with the δ 13 C of respiratory substrates, whereas the magnitude of the nighttime shift in δ 13 C l strongly depended on the daytime carbon assimilation rate and the range of nighttime variations in the respiratory substrate content. The Δ R,biomass in the C 3 and C 4 grasses varied in opposite directions with the intensification of the drought stress. The contribution of C 4 plant-associated carbon flux is likely to be overestimated if carbon isotope signatures are used for the partitioning of ecosystem carbon exchange and the δ 13 C of biomass is used as a substitute for leaf dark-respired CO 2 . The detected drought sensitivities in δ 13 C l and differences in respiratory apparent isotope fractionation between C 3 and C 4 grasses have marked implications for isotope partitioning studies at the ecosystem level.

Tellurium Stable Isotopes as a Paleoredox Proxy

NASA Astrophysics Data System (ADS)

Wasserman, N.; Johnson, T. M.

2017-12-01

Despite arguments for variably-oxygenated shallow waters and anoxic deep marine waters, which delayed animal development until the Neoproterozoic Oxidation Event, the magnitude of atmospheric oxygen during the Proterozoic is still uncertain [1]. The evidence for low pO2 (<0.1-1% PAL) is based on geochemical and isotopic proxies, which track the mobilization of Fe and Mn on the continents. For example, large chromium isotope shifts occur at the Neoproterozoic Oxidation Event due to the initiation of Cr redox cycling, but this proxy is insensitive to fluctuations in the lower-pO2 conditions at other times during the Proterozoic. Tellurium, a metalloid with a lower threshold to oxidation, may be sensitive to pO2 shifts in a lower range. In the reduced forms, Te(-II) and Te(0), the element is insoluble and immobile. However, in the more oxidized phases, Te(IV) and Te(VI), Te can form soluble oxyanions (though it tends to adsorb to Fe-oxyhydroxides and clays) [2]. Te stable isotopes have been shown to fractionate during abiotic or biologic reduction of Te(VI) or Te(IV) to elemental Te(0) [3, 4]. Utilizing hydride generation MC-ICP-MS, we are able to obtain high precision (2σ 0.04‰) measurements of δ128Te/125Te for natural samples containing < 10 ng of Te. A suite of Phanerozoic and Proterozoic ironstones show significant variation in δ128Te/125Te (<0.5‰), suggesting that the Te redox cycle was active during the Proterozoic. Future directions will include Te isotope measurements of Precambrian paleosols to determine natural isotope variation before the Great Oxidation Event and experiments to determine fractionation during adsorption to Fe-oxyhydroxides. [1] Planavsky et al. (2014) Science 346 (6209), pp. 635-638 [2] Qin et al. (2017) Environmental Science and Technology 51 (11), pp 6027-6035 [3] Baesman et al. (2007) Applied Environmental Microbiology 73 (7), pp 2135-2143 [4] Smithers and Krause (1968) Canadian Journal of Chemistry 46(4): pp 583-591

Late-Quaternary Molecular Isotopic Paleohydrology of Lake Junin, Peru

NASA Astrophysics Data System (ADS)

Polissar, P. J.; Liu, C.; Rodbell, D. T.; Abbott, M. B.

2013-12-01

There is great potential for reconstructing past changes in the hydrologic cycle using the hydrogen isotopic composition of plant-wax biomarkers. At present, empirical relationships relating plant-wax hydrogen isotope compositions (δDwax) to source water are almost exclusively based upon modern plants, soils and sediments. Relatively little is known about how plant-wax hydrogen isotopes track source water through time. Here we take advantage of existing paleoisotopic information from Lake Junin in the central Peruvian Andes to evaluate the temporal fidelity of δDwax to source water δD. In Lake Junin and the nearby region, oxygen isotopic records from lacustrine carbonates, speleothems and ice-cores provide robust constraints on the isotopic composition of lake water and precipitation in the past. Combined with new measurements of δDwax in Lake Junin sediments, these data allow us to evaluate the isotopic, climatic and vegetation influences on δDwax over the past 20,000 years. The n-alkanoic acid δDwax values exhibit trends through time that are similar to those for precipitation and lakewater δD. Highly negative δDwax values during the Last Glacial Maximum mirror depleted lakewater and precipitation δD values, more positive δDwax values at the beginning of the Holocene correspond to more enriched water δD values, and decreasing δDwax values over the past 10,000 years parallel the decreasing δD of lakewater and precipitation. However, the magnitude of the δDwax shifts are much larger than can be explained by changing δD water values. For example, the enrichment of δDwax values at the beginning of the Holocene is +30‰ and +80‰ larger than those of lakewater or precipitation δD, respectively. These differences could reflect changes in vegetation type, shifting proportions of aquatic and terrestrial plant sources, or environmental factors such as aridity. Vegetation type is an unlikely explanation as pollen abundances indicate only minor fluctuations, at least during the Holocene. Changing proportions of aquatic plant-wax sources may have had some influence as shorter-chain acids from aquatic macrophytes are more abundant in the early Holocene. However, aridity likely had a major role through greater evaporative isotopic enrichment of leaf and/or soil water. Early Holocene lake waters were significantly more highly evaporated indicating overall more arid conditions when leaf-wax δD values are most positive. Comparison of Lake Junin plant-wax and water δD values over the past 20,000 years indicate that although δDwax reflects trends in water δD, there are potentially large influences from evapotranspiration and shifting proportions of aquatic sources. While these factors have been previously identified in spatial calibration studies, our temporal calibration results emphasize the need to critically evaluate these influences on molecular δD at a single location through time.

Shifts in stable-isotope signatures confirm parasitic relationship of freshwater mussel glochidia attached to host fish

USGS Publications Warehouse

Fritts, Mark W.; Fritts, Andrea K.; Carleton, Scott A.; Bringolf, Robert B.

2013-01-01

The parasitic nature of the association between glochidia of unionoidean bivalves and their host fish (i.e. the role of fish hosts in providing nutritional resources to the developing glochidia) is still uncertain. While previous work has provided descriptions of development of glochidia on fish hosts, earlier studies have not explicitly documented the flow of nutrition from the host fish to the juvenile mussel. Therefore, our objective was to use stable isotope analysis to quantitatively document nutrient flow between fish and glochidia. Glochidia were collected from nine adult Lampsilis cardium and used to inoculate Micropterus salmoides(n = 27; three fish per maternal mussel) that produced juvenile mussels for the experiment. Adult mussel tissue samples, glochidia, transformed juvenile mussels and fish gill tissues were analysed for δ15N and δ13C isotope ratios. We used a linear mixing model to estimate the fraction of juvenile mussel tissue derived from the host fish's tissue during attachment. Our analyses indicate a distinct shift in both C and N isotopic ratios from the glochidial stage to the juvenile stage during mussel attachment and development. Linear mixing model analysis indicated that 57.4% of the δ15N in juvenile tissues were obtained from the host fish. This work provides novel evidence that larval unionoideans are true parasites that derive nutrition from host fish during their metamorphosis into the juvenile stage.

Water Source and Isotope changes through the Deglaciation and Holocene

NASA Astrophysics Data System (ADS)

LeGrande, A. N.; Carlson, A. E.; Ullman, D. J.; Nusbaumer, J. M.

2017-12-01

The deglacial period saw radical shifts in climate across the globe. Water isotopologues provide some of the most wide-spread proxy archives of these climate changes. Here we present new analyses on a suite of 12 water isotope-enabled coupled atmosphere-ocean GCM simulations from GISS ModelE-R that span 24kya to the pre-industrial period. We show how millennial scale co-variability in water isotopes and climate (temperature, precipitation, humidity, and moist-static energy) is distinct from regional scale spatial slopes, consistent with proxy archives (e.g., Cuffey et al 1995). We supplement this set of simulations with a new ensemble of deglacial simulations that contain a complementary suite of tracers that determine moisture provenance changes through the deglaciation. We diagnose regions that have had significant changes in moisture provenance and compare this information against simulated changes in the water isotope changes.

Improved repetition rate mixed isotope CO2 TEA laser

NASA Astrophysics Data System (ADS)

Cohn, D. B.

2014-09-01

A compact CO2 TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the 12C16O2 isotope. With mixed 12C16O2 plus 13C16O2 isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Related work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.

Authentication and traceability of Italian extra-virgin olive oils by means of stable isotopes techniques.

PubMed

Portarena, S; Gavrichkova, O; Lauteri, M; Brugnoli, E

2014-12-01

Authentication of food origin is relevant to avoid food fraud. This work aimed to explore the variation of isotopic compositions (δ(13)C, δ(18)O) of extra-virgin olive oils from Italy growing in different environmental conditions. A total of 387 oil samples from nine different regions (from North to South), produced on 2009, 2010 and 2011, were analysed. Statistical analysis showed correlations among oil isotope compositions and latitude, mean annual temperature, mean annual precipitation and xerothermic index. No correlation was found comparing isotope compositions with elevation and longitude. An observed shift of the oil δ(18)O per centigrade degree of the mean annual temperature is congruent with literature. The year effect was significant for both δ(18)O and δ(13)C. Samples from Sicilia and Sardegna were higher in (13)C and (18)O than oils from northern regions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Nuclear quantum shape-phase transitions in odd-mass systems

NASA Astrophysics Data System (ADS)

Quan, S.; Li, Z. P.; Vretenar, D.; Meng, J.

2018-03-01

Microscopic signatures of nuclear ground-state shape-phase transitions in odd-mass Eu isotopes are explored starting from excitation spectra and collective wave functions obtained by diagonalization of a core-quasiparticle coupling Hamiltonian based on energy density functionals. As functions of the physical control parameter—the number of nucleons—theoretical low-energy spectra, two-neutron separation energies, charge isotope shifts, spectroscopic quadrupole moments, and E 2 reduced transition matrix elements accurately reproduce available data and exhibit more-pronounced discontinuities at neutron number N =90 compared with the adjacent even-even Sm and Gd isotopes. The enhancement of the first-order quantum phase transition in odd-mass systems can be attributed to a shape polarization effect of the unpaired proton which, at the critical neutron number, starts predominantly coupling to Gd core nuclei that are characterized by larger quadrupole deformation and weaker proton pairing correlations compared with the corresponding Sm isotopes.

High-Resolution Triple Resonance Autoionization of Uranium Isotopes

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

Schumann, Philipp G.; Wendt, K; Bushaw, Bruce A.

2005-11-01

The near-threshold autoionization (AI) spectrum of uranium has been investigated by triple-resonance excitation with single-mode continuous lasers. Spectra were recorded over the first {approx}30 cm-1 above the first ionization limit at a resolution of 3x10-4 cm 1 using intermediate states with different J values (6, 7, 8) to assign AI level total angular momentum JAI = 5 to 9. Resonances with widths ranging from 8 MHz to 30 GHz were observed; the strongest ones have JAI = 9 and widths of {approx} 60 MHz. Hyperfine structures for 235U and isotope shifts for 234,235U have been measured in the two intermediatemore » levels and in the final AI level for the most favorable excitation path. These measurements were performed using aqueous samples containing sub-milligram quantities of uranium at natural isotopic abundances, indicating the potential of this approach for trace isotope ratio determinations.« less

Multi-proxy reconstructions of hydrologic change during the Eocene-Oligocene transition in the North American Interior

NASA Astrophysics Data System (ADS)

Eley, Y.; Hren, M. T.

2016-12-01

The dramatic shift from a 'greenhouse' to an 'icehouse' world that occurred during the Eocene-Oligocene transition (EOT, 34-33.5 Ma) is associated with changes in atmospheric and oceanic circulation patterns, extinction events in both marine and terrestrial ecosystems, and the establishment of a continental-scale ice sheet on Antarctica. Terrestrial records of the EOT, however, show limited consensus regarding the intensity and impact of this transition, complicating our understanding of how terrestrial hydrology responds to climatic change of this magnitude. Stable isotopes of fossil bones and teeth from the White River Group (WRG) in Nebraska have been interpreted to show an 8 °C decrease in mean annual temperatures across the EOT, with an increase in seasonality, however these studies find no evidence for accompanying changes in aridity. Conversely, other studies have inferred increased aridity in the early Oligocene based on changes in the δ18O and δ13C values of mammalian tooth enamel sampled from the same location. Some of this ambiguity is likely to stem from the difficulty in separating the influence of factors such as temperature, water availability and atmospheric circulation patterns on the δ18O composition of ungulate tooth enamel. We present paired leaf wax biomarker and clay hydrogen isotope data from the WRG to produce a new multi-proxy record of hydrological change and accompanying ecosystem shifts through the EOT in the North American interior. Hydrogen isotopes of clay minerals show a negative shift of <15‰ from the late Eocene through early Oligocene, while in contrast leaf wax n-alkanes record a negative shift in excess of 50‰, in tandem with a positive change in average chain length. We infer an increase in aridity from these data, with an associated potential shift in vegetation cover towards more savannah-style plant species as the climate became drier during the transition into the Oligocene. These data provide new constraints on the impact of the EOT in North America, and highlight the potential role of increasing aridity, in addition to declining temperatures, in shaping the hydrology of the region during this interval.

Large variations in the hydrology for the Paratethys-Mediterranean system during latest Miocene - insights from the hydrogen isotopes on biomarkers

NASA Astrophysics Data System (ADS)

Vasiliev, I.; Reichart, G. J.

2016-12-01

Paratethys - Mediterranean domain, occupying southern Eurasia and northern Africa, was a sea system characterized by recurrently restricted connections to the Open Ocean. To determine the nature of changes in the hydrological budget of the Paratethys - Mediterranean domain occurring during the latest Miocene we use compound-specific hydrogen isotope ratios on terrestrial and aquatic biomarkers extracted at four different locations: 1) the land based sedimentary succession located on Taman Peninsula in Russia, 2) the deep sea succession recovered in 1975 from the Black Sea, 3) the succession of Northern Apennines and Sicily from Italy and 4) the sedimentary infill of the Carpathians Foredeep from the Dacian Basin of Romania. The hydrogen isotopic compositions of n-alkanes (produced predominantly by higher plants) as well as alkenones (produced by haptophyte algae) indicate large environmental changes in the Paratethys-Mediterranean. The hydrogen isotopes of alkenones, showing an enrichment of more than 80‰ at the end of the Miocene, imply a major shift in basin hydrology, possibly resulting in severely increased salinity. These changes in hydrogen isotopic composition of the alkenones concur both with sharp shifts in reconstructed sea surface temperatures and mean annual temperatures. An interval with negative water budget was identified in all sections, most likely caused by enhanced evaporation during the Messinian salinity crisis (5.97 - 5.33 Ma). Additionally, the 60‰ amplitude of changes measured on long chain n-alkanes, produced predominantly by higher plants, can be principally explained by significant changes in the hydrogen isotopic composition of the precipitation reaching the Paratethys-Mediterranean system during the Messinian salinity crisis. These cumulated hydrogen isotopic compositions results indicate that the hydrological regime in Paratethys - Mediterranean domain has significantly varied, with heaviest δD values being recorded from a time-interval corresponding to the exceptionally dry Messinian salinity crisis of the Mediterranean. This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0050 and a Veni grant of the Dutch Science Foundation both awarded to IV.

Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

NASA Astrophysics Data System (ADS)

Stachel, T.; Harris, J. W.; Aulbach, S.; Deines, P.

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions (δ13C: peridotitic -5.4 to -2.2‰ eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side (δ13C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (>=1,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.

Kankan diamonds (Guinea) III: δ13C and nitrogen characteristics of deep diamonds

NASA Astrophysics Data System (ADS)

Stachel, T.; Harris, J. W.; Aulbach, S.; Deines, P.

2001-08-01

Diamonds from the Kankan area in Guinea formed over a large depth profile beginning within the cratonic mantle lithosphere and extending through the asthenosphere and transition zone into the lower mantle. The carbon isotopic composition, the concentration of nitrogen impurities and the nitrogen aggregation level of diamonds representing this entire depth range have been determined. Peridotitic and eclogitic diamonds of lithospheric origin from Kankan have carbon isotopic compositions (δ13C: peridotitic -5.4 to -2.2‰ eclogitic -19.7 to -0.7‰) and nitrogen characteristics (N: peridotitic 17-648 atomic ppm; eclogitic 0-1,313 atomic ppm; aggregation from IaA to IaB) which are generally typical for diamonds of these two suites worldwide. Geothermobarometry of peridotitic and eclogitic inclusion parageneses (worldwide sources) indicates that both suites formed under very similar conditions within the cratonic lithosphere, which is not consistent with a derivation of diamonds with light carbon isotopic composition from subducted organic matter within subducting oceanic slabs. Diamonds containing majorite garnet inclusions fall to the isotopically heavy side (δ13C: -3.1‰ to +0.9‰) of the worldwide diamond population. Nitrogen contents are low (0-126 atomic ppm) and one of the two nitrogen-bearing diamonds shows such a low level of nitrogen aggregation (30% B-centre) that it cannot have been exposed to ambient temperatures of the transition zone (>=1,400 °C) for more than 0.2 Ma. This suggests rapid upward transport and formation of some Kankan diamonds pene-contemporaneous to Cretaceous kimberlite activity. Similar to these diamonds from the asthenosphere and the transition zone, lower mantle diamonds show a small shift towards isotopic heavy compositions (-6.6 to -0.5‰, mode at -3.5‰). As already observed for other mines, the nitrogen contents of lower mantle diamonds were below detection (using FTIRS). The mutual shift of sublithospheric diamonds towards isotopic heavier compositions suggests a common carbon source, which may have inherited an isotopic heavy composition from a component consisting of subducted carbonates.

Isotopic studies of authigenic sulfides, silicates and carbonates, and calcite and pyrite veinlets in the Creede Formation, San Juan Mountains, Southwest Colorado

USGS Publications Warehouse

Bethke, Philip M.; Rye, Robert O.; Finkelstein, David B.

2000-01-01

Sulfur isotope analysis of authigenic pyrite in the Creede Formation documents its precipitation by the reaction between iron in the volcaniclastic sediments and H2S formed through bacteriogenic reduction of sulfate added to the lake during and immediately following repeated volcanic eruptions during sedimentation. Pyrite veinlets in the underlying Snowshoe Mountain Tuff were formed by the percolation of H2S-bearing pore waters into fractures in the tuff. Conventional analyses of bulk samples of authigenic pyrite range from -20.4% to 34.5% essentially equivalent to the range of -30% to 40% determined using SHRIMP microprobe techniques. Conventional analyses of bulk samples of pyrite from veinlets in the Snowshow Mountain Tiff range from -3.5% to 17.6% much more limited than the ranges of -23% to 111% and -15.6% to 67.0% determined by SHRIMP and laser ablation microbeam techniques, respectively. The extreme range of δ34S for the veinlets is interpreted to be the result of continued fractionation of the already 34S-depleted pore water. Oxygen isotope analysis of authigenic smectite, kaolinite, and K-feldspar together with fluid-inclusion temperatures and oxygen isotope analysis of calcite coexisting with kaolinite indicate that the smectites formed early during burial diagenesis, in accord with petrographic observations. The 40Ar/39Ar dating of K-feldspar, concorfance of K-feldspar, kaolinite, and calcite δ18O values, and fluid-inclusion temperatures in calcite, indicate that the sediments at core hole CCM-1 were subjected to a hydrothermal event at 17.6 Ma. The minerals formed oxygen-shifted meteoric waters with δ18O values of ~-9% Smecities at CCM-1 at least partially exchanged with these waters. Carbon and oxygen isotope analysis of authigenic calcites in the Creede Formation show that they formed over a wide range of temperatures from fluids having a wide range of isotopic composition, presumably over an extended period time. Some of the cements apparently formed very late from unexchanged meteoric water. Concretions and possibly some cements at CCM-1 appear to have exchanged with the 17.6 Ma oxygen-shifted hydrothermal fluids. Such exchange is consistent with evidence that lacustrine carbonates at CCM-1 exchanged with low 18O waters, whereas those at CCM-2 underwent little, if any, exchange. The δ13C-δ18O values for calcite veinlets in the Creede Formation are similar to those for authegenic calcites. Fluid-inclusion temperatures and δ18O indicate that some were deposited during the 17.6 Ma hydrothermal event and others from unexchanged meteoric water at a later date. The isotope studies confirm that part of the model of Rye et al., proposing that the barites in the southern end of the Creede Mining District were formed by mixing of the Creede hydrotermal system with Lake Creede pore of lake waters. The silicate and carbonate isotope data indicate that the pores of the Creede Formation were occupied by at least three isotopically distinct water since the time of deposition. The original pore fluids were probably shifted to lower δ18O values during burial diagensis as a result of the hydrolysis of the volcanic glass to for smectites and other hydrous silicates. During or prior to a 17.6 Ma hydrothermal event in the vicinity of CCM-1, the Creede Formation was flushed with oxygen-shifted meteoric water, possibly related to the breaching of the east side of the caldera wall sometime between 20 and 22 Ma. Later, the Creede Formation was again flushed, this time with unexchanged meteoric water with δD-δ18O values of present-day waters, possibly during the incision of the Rio Grande drainage during uplifting of the southern Rocky Mountains beginning about 5 Ma.

Isotope shift constant and nuclear charge model

NASA Astrophysics Data System (ADS)

Fang, Z.; Redi, O.; Stroke, H. H.

1992-04-01

We use the method of Zimmermann [Z. Phys. A 321 (1985) 23-30], which he used to calculate the isotope shift constant for a uniform nuclear charge distribution, to obtain it for a diffuse nuclear charge model. The two models give results that differ slightly on the level of precision of current experiments. The same parameters are used to calculate the model sensitivity of the contributions to the isotope shifts of higher moments of the nuclear charge distribution as formulated by Seltzer [Phys. Rev. 188 (1969) 1916-1919]. These are found to be essentially model independent. Tables are given of the numerical calculations. Nous employons la méthode de Zimmermann [Z. Phys. A 321 (1985) 23-30], qu'il avait utilisé dans un calcul de la constante du déplacement isotopique pour une distribution de charge uniforme, pour l'obtenir avec un modèle de charge nucléaire avec forme quasi-trapézoïdale. Les deux modèles donnent des résultats dont la difference excède de peu la précision des mesures actuelles. Les mêmes paramètres sont utilisés pour comparer la dépendance aux deux modèles de la contribution au déplacement isotopique des moments plus élevés de la distribution de la charge nucléaire dans la formulation de Seltzer [Phys. Rev. 188 (1969) 1916-1919]. On trouve que ces contributions sont essentiellement indépendantes du modèle. Des tables de calculs numériques sont présentées.

Subsequent biotic crises delayed marine recovery following the late Permian mass extinction event in northern Italy

PubMed Central

Danise, Silvia; Price, Gregory D.; Twitchett, Richard J.

2017-01-01

The late Permian mass extinction event was the largest biotic crisis of the Phanerozoic and has the longest recovery interval of any extinction event. It has been hypothesised that subsequent carbon isotope perturbations during the Early Triassic are associated with biotic crises that impeded benthic recovery. We test this hypothesis by undertaking the highest-resolution study yet made of the rock and fossil records of the entire Werfen Formation, Italy. Here, we show that elevated extinction rates were recorded not only in the Dienerian, as previously recognised, but also around the Smithian/Spathian boundary. Functional richness increases across the Smithian/Spathian boundary associated with elevated origination rates in the lower Spathian. The taxonomic and functional composition of benthic faunas only recorded two significant changes: (1) reduced heterogeneity in the Dienerian, and (2) and a faunal turnover across the Smithian/Spathian boundary. The elevated extinctions and compositional shifts in the Dienerian and across the Smithian/Spathian boundary are associated with a negative and positive isotope excursion, respectively, which supports the hypothesis that subsequent biotic crises are associated with carbon isotope shifts. The Spathian fauna represents a more advanced ecological state, not recognised in the previous members of the Werfen Formation, with increased habitat differentiation, a shift in the dominant modes of life, appearance of stenohaline taxa and the occupation of the erect and infaunal tiers. In addition to subsequent biotic crises delaying the recovery, therefore, persistent environmental stress limited the ecological complexity of benthic recovery prior to the Spathian. PMID:28296886

A high resolution paleo-record of export production using deep-sea coral stable isotope values from a unique HNLC zone on the California Margin

NASA Astrophysics Data System (ADS)

Wright, Z.

2015-12-01

The Sur Ridge, located ~30 km off the Big Sur coast of central California, represents a unique system within the highly productive California Current ecosystem. Its unique high nutrient, but low chlorophyll characteristics are not fully understood. Time series of bulk stable carbon (δ13C) and stable nitrogen (δ15N) isotopes can help us better understand past changes in nutrient dynamics and phytoplankton community baselines for this region in order to better predict future changes. Deep-sea proteinaceous corals are particularly powerful paleoarchives of past ocean conditions. These organisms serve as "living sediment traps," incorporating the stable isotope values of exported particulate organic material (POM) from the surface into their growth layers. The longevity of bamboo corals (Isidella, up to 400 years) makes them excellent resources for creating high resolution, centennial time series of δ13C and δ15N dynamics. Bamboo corals used in this study were harvested during summer of 2014 from 1220 to 1300 m depths. Two corals were milled in sub-millimeter intervals to generate a 200 year time series at approximately three year temporal resolution. Over the past 200 years, deep-sea coral δ13C values ranged from -15.7 to -19.0‰ and δ15N values ranged from 14.4 to 15.9‰, consistent with earlier data from the CA margin. The δ13C records were characterized by long periods of remarkable stability, contrasted with several large shifts (~1900 and ~1960) in δ13C of approximately 1‰. We hypothesize that these shifts likely reflect changes in plankton composition or production associated with regional climate shifts. The δ15N data were more dynamic, including several large shifts (1940 - 1960), as well as periods of apparent decadal scale oscillation (1825 - 1925 and 1965 - present). These shifts may reflect changes in the source or utilization of nitrogen at the base of the food web. Together, these data give us a first look at baseline stability of biogeochemical systems in this unique region, and will be crucial in connecting potential future system changes in climate and upwelling to possible shifts in nutrient dynamics and phytoplankton species composition. 

Penetration of Atlantic Walker Circulation Into East Africa During Early to mid-Holocene: Hydrogen Isotope Evidence From Sacred Lake, Mt. Kenya

NASA Astrophysics Data System (ADS)

Hou, J.; Russell, J. M.; Huang, Y.

2007-12-01

The tropics play a very important role in global climate variability, yet the mechanisms behind the tropical climate variation remain poorly understood. Here, we present a high-resolution, well-dated record from Sacred Lake, Kenya, East Africa. We measured D/H ratios of botryococcenes, a class of highly specific biomarkers produced by freshwater algae ( Botrycoccus braunii) in a sediment core obtained from this open lake. Our main goal is to examine changes in East African rainfall amount and moisture source during the past 18kyr BP. During the late Pleistocene and late Holocene, the hydrogen isotope records track local hydrological variations inferred from numerous lake level and pollen records from the region. However, during the early to mid-Holocene (10-5ka cal yr BP), the D/H values from Sacred Lake were as much as 90 per mil heavier than during the late Pleistocene and late Holocene. If the "amount effect" is the main control on the isotopic compositions of rainfall during the early to mid Holocene, Our data would suggest drier conditions, which is inconsistent with the "African Humid Period" inferred by numerous records of the mid-Holocene. We propose that the high isotopic ratios in precipitation in East Africa during the early to mid-Holocene is due to an eastward shift in the large-scale atmospheric circulation of the tropics. In East Africa, this shift involves a major increase in moisture source from the Atlantic Ocean relative to Indian Ocean. Heavier isotope ratios of precipitation originated from Atlantic Ocean result from the intensive convection and recycling of water vapor over the Congo Basin, as opposed to Indian moisture that traverses dry land masses and losses moisture rapidly. In comparison to the late Holocene, the early to mid-Holocene is characterized by relatively northerly positioning of the ITCZ and intense monsoon systems as well as weak ENSO. These factors combine to shift the walker circulation eastward, allowing the Atlantic moisture to penetrate farther into eastern Africa. Our theory is supported by climate model results, paleoclimate records from the Kilimanjaro ice core and Cariaco Basin, and other records from the Indian and Pacific Oceans. For example, the ice core in Kilimanjaro, East Africa suggest that the oxygen isotope ratios of precipitation were ~ 8 per mil higher during early to mid-Holocene than the late Holocene, which is consistent with our results.

Short-term climate changes in the Holsteinian Interglacial - EGU2012-132

NASA Astrophysics Data System (ADS)

Nitychoruk, J.; Bińka, K.; Ruppert, H.; Tudryn, A.

2012-04-01

Oxygen and carbon stable isotopes from fossil lake sediments of the Holsteinian age (eastern Poland) give evidence for the abrupt climate shifts in this interglacial that coincide with the changes in vegetation inferred from palaeobotanical data. Especially changes of the stable isotope ratios as well as decrease in the carbonate content in the deposits and increase in silicate redeposited from the area around the lake are synchronous with the short-term climatic deteriorations within the interglacial pollen flora. Two distinct climate shifts are recorded in the Holsteinian. The first one is marked by the very characteristic pine-birch cold phase after the yew (Taxus) domination that is reported from numerous pollen diagrams from Central Europe. This distinct cooling resembles a phenomenon known as 8.2 ka event in the Holocene, when waters of the Agassiz Lake in North America drained into the Atlantic Ocean (Koutsodendris et al. 2010). Enormous volumes of freshwater from melting of the Laurentian ice-sheet caused disturbances in the Gulf Stream and as a result some decrease in regional temperatures. The second distinct cooling of a lower rank took place within the younger part of the climatic optimum of the Holsteinian. It is relatively less known, because most often pollen records lack sufficient temporal resolution needed to identify this event. A well documented cooling in the Holsteinian deposits from Dethlingen, northern Germany (Koutsodendris et al. 2010) and from the Ossówka, eastern Poland (Nitychoruk et al. 2005) are exceptional. In the sequence from Dethlingen, a distinct increase in the percentage of pioneer trees is accompanied by a lower content of temperate taxa. At Ossówka, the shift of climate is noted as the rise of ratio of oxygen and carbon isotopes. According to Nitychoruk (2000) the cold event is coincident with volcanic eruptions evidenced by volcanic ash found in the lake deposits at that time. Literature Koutsodendris, A., Müller, U.C., Pross, J., Brauer, A., Kotthoff, U., Lotter, A.F. 2010. Vegetation dynamics and climate variability during the Holsteinian interglacial based on a pollen record from Dethlingen (northern Germany). Quaternary Science Reviews, 29, 3298-3307. Nitychoruk, J. 2000. Climate reconstruction from stable-isotope composition of the Mazovian Interglacial (Holsteinian) lake sediments in eastern Poland. Acta Geologica Polonica, 50, 247-294. Nitychoruk, J., Bińka, K., Hoefs, J., Ruppert, H. & Schneider, J. 2005. Climate reconstruction for the Holsteinian Interglacial in Eastern Poland and its comparison with isotopic data from Marine Isotope Stage 11. Quaternary Science Reviews, 24, 631-644.

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 Landforms 40 (9), 1158-1170. Breecker et al. (2012), Geochimica et Cosmochimica Acta 96 (1), 230-246. Schubert and Jahren (2012), Geochimica et Cosmochimica Acta 96, 29-43.

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.

Effects of vacuum exposure on stress and spectral shift of high reflective coatings

NASA Astrophysics Data System (ADS)

Stolz, C. J.; Taylor, J. R.; Eickelberg, W. K.; Lindh, J. D.

1992-06-01

The Atomic Vapor Laser Isotope Laser Separation (AVLIS) program operates the world's largest average power dye laser; the dye laser beams are combined, formatted, and transported in vacuum. The optical system is aligned at atmosphere, while the system must meet requirements in vacuum. Therefore, coating performance must be characterized in both atmosphere and vacuum. Changes in stress and spectral shift in ambient and vacuum environments are reported for conventional and dense multilayer dielectric coatings.

Extreme 13Ccarb enrichment in ca. 2.0 Ga magnesite-stromatolite-dolomite-`red beds' association in a global context: a case for the world-wide signal enhanced by a local environment

NASA Astrophysics Data System (ADS)

Melezhik, Victor A.; Fallick, Anthony E.; Medvedev, Pavel V.; Makarikhin, Vladimir V.

1999-12-01

The Palaeoproterozoic positive excursion of δ 13Ccarb is now considered as three positive shifts of δ 13Ccarb separated by returns to 0‰, which all occurred between 2.40 and 2.06 Ma. This isotopic event is unique in terms of both duration (>300 Ma) and 13C enrichment (up to +18‰). The mechanism responsible for one of the most significant carbon isotopic shifts in Earth history remains highly debatable. To date, δ 13C of +10‰ to +15‰ cannot be balanced by organic carbon burial ( forg) as there is no geological evidence for an enhanced C org accumulation prior to or synchronous with the excursion. Instead, termination of these excursions is followed by formation of a vast reservoir of 13C-depleted organic material (-45‰ at Shunga) and by one of the earliest known oil-generation episodes at 2.0 Ga. None of the three positive excursions of δ 13Ccarb is followed by a negative isotopic shift significantly below 0‰, as has always been observed in younger isotopic events, reflecting an overturn of a major marine carbon reservoirs. This may indicate that forg was constant: implying that the mechanism involved in the production of C org was different. Onset of intensive methane cycling resulting in Δc change is another possibility. The majority of sampled 13Ccarb-rich localities represents shallow-water stromatolitic dolostones, `red beds' and evaporites formed in restricted intracratonic basins, and may not reflect global δ 13Ccarb values. Closely spaced drill core samples ( n=73) of stromatolitic dolostones from the >1980±27 Ma Tulomozerskaya Formation in the Onega palaeobasin, Russian Karelia, have been analysed for δ 13Ccarb and δ 18Ocarb in order to demonstrate that different processes were involved in the formation of 13Ccarb-rich carbonates. The 800 m-thick magnesite-stromatolite-dolomite-`red beds' succession formed in a complex combination of environments on the Karelian craton: peritidal shallow marine, low-energy protected bights, barred basins, evaporative ephemeral ponds, coastal sabkhas and playa lakes. The carbonate rocks exhibit extreme 13C enrichment with δ 13C values ranging from +5.7 to +17.2‰ vs. V-PDB (mean+9.9±2.3‰) and δ 18O from 18.6 to 26.0‰ vs. V-SMOW (mean 22.0±1.6‰). The Tulomozerskaya isotopic excursion is characteristic of the global 2.4-2.06 Ga positive shifts of carbonate 13C/ 12C, although it reveals the greatest enrichment in 13C known from this interval. An external basin(s) is considered to have provided an enhanced C org burial and global seawater enrichment in 13C: the global background value for the isotopic shift at Tulomozero time (ca. 2.0 Ga) is roughly estimated at around +5‰. An explosion of stromatolite-forming microbial communities in shallow-water basins, evaporative and partly restricted environments, high bioproductivity, enhanced uptake of 12C, and pene-contemporaneous recycling of organic material in cyanobacterial mats with the production and consequent loss of CO 2 (and CH 4?) are believed to be additional local factors which may have enhanced δ 13C from +5‰ up to +17‰. Such factors should be taken into account when interpreting carbon isotopic data and attempting to discriminate between the local enrichment in 13C and globally enhanced δ 13C values. We propose that many previously reported δ 13C values from other localities, where environmental interpretations are not available or have not been taken into account may not represent the global δ 13C values.

Exploring the Potential of Laser Ablation Carbon Isotope Analysis for Examining Ecology during the Ontogeny of Middle Pleistocene Hominins from Sima de los Huesos (Northern Spain).

PubMed

Garcia, Nuria; Feranec, Robert S; Passey, Benjamin H; Cerling, Thure E; Arsuaga, Juan Luis

2015-01-01

Laser ablation of tooth enamel was used to analyze stable carbon isotope compositions of teeth of hominins, red deer, and bears from middle Pleistocene sites in the Sierra de Atapuerca in northern Spain, to investigate the possibility that this technique could be used as an additional tool to identify periods of physiological change that are not detectable as changes in tooth morphology. Most of the specimens were found to have minimal intra-tooth variation in carbon isotopes (< 2.3‰), suggesting isotopically uniform diets through time and revealing no obvious periods of physiological change. However, one of the two sampled hominin teeth displayed a temporal carbon isotope shift (3.2‰) that was significantly greater than observed for co-occurring specimens. The δ13C value of this individual averaged about -16‰ early in life, and -13‰ later in life. This isotopic change occurred on the canine crown about 4.2 mm from the root, which corresponds to an approximate age of two to four years old in modern humans. Our dataset is perforce small owing to the precious nature of hominid teeth, but it demonstrates the potential utility of the intra-tooth isotope profile method for extracting ontogenetic histories of human ancestors.

Isotope Tracing of Long-Term Cadmium Fluxes in an Agricultural Soil.

PubMed

Salmanzadeh, Mahdiyeh; Hartland, Adam; Stirling, Claudine H; Balks, Megan R; Schipper, Louis A; Joshi, Chaitanya; George, Ejin

2017-07-05

Globally widespread phosphate fertilizer applications have resulted in long-term increases in the concentration of cadmium (Cd) in soils. The accumulation of this biotoxic, and bioaccumulative metal presents problems for the management of soil-plant-animal systems, because the magnitude and direction of removal fluxes (e.g., crop uptake, leaching) have been difficult to estimate. Here, Cd isotopic compositions (δ 114/110 Cd) of archived fertilizer and soil samples from a 66 year-long agricultural field trial in Winchmore, New Zealand, were used to constrain the Cd soil mass balance between 1959 and 2015 AD, informing future soil Cd accumulation trajectories. The isotopic partitioning of soil Cd sources in this system was aided by a change in phosphate source rocks in 1998 AD, and a corresponding shift in fertilizer isotope composition. The dominant influence of mixing between isotopically distinct Cd end-members was confirmed by a Bayesian modeling approach. Furthermore, isotope mass balance modeling revealed that Cd removal processes most likely increased in magnitude substantially between 2000 and 2015 AD, implying an increase in Cd bioaccumulation and/or leaching over that interval. Natural-abundance stable isotopes are introduced here as a powerful tool for tracing the fate of Cd in agricultural soils, and potentially the wider environment.

Structure and luminescence properties of 10-BN sheets

NASA Astrophysics Data System (ADS)

Han, Wei-Qiang; Liu, Lijia; Sham, T. K.; Liu, Zhenxian

2012-10-01

Isotopic 10BN sheets were first prepared using graphene sheets as templates to react with 10B2O3. The edge-areas of BN sheets have much higher oxygen-doping ratios compared to other areas. The emission peak of X-ray excited optical luminescence spectra of the 10BN-sheets is broader and red-shifted because of the isotopic effect. A broad violet-blue emission at a wavelength centered at ~400 nm is assigned to the defect emission due to oxygen-doping and defects in the BN network.

Absolute vibrational numbering from isotope shifts in fragmentary spectroscopic data

NASA Astrophysics Data System (ADS)

Pashov, A.; Kowalczyk, P.; Jastrzebski, W.

2018-05-01

We discuss application of the isotope effect to establish the absolute vibrational numbering in electronic states of diatomic molecules. This is illustrated by examples of states with potential energy curves of both regular and irregular shape, with one or two potential minima. The minimum number of spectroscopic data (either term values or spectral line positions) necessary to provide a unique numbering is considered. We show that at favourable conditions just four term energies (or spectral lines) in one isotopologue and one term energy in the other suffice.

Proton Conductivity in Phosphoric Acid: The Role of Quantum Effects

DOE PAGES

Heres, M.; Wang, Y.; Griffin, P. J.; ...

2016-10-07

Phosphoric acid has one of the highest intrinsic proton conductivities of any known liquids, and the mechanism of this exceptional conductivity remains a puzzle. In our detailed experimental studies we discovered a strong isotope effect in the conductivity of phosphoric acids caused by (i) a strong isotope shift of the glass transition temperature and (ii) a significant reduction of the energy barrier by zero-point quantum fluctuations. Our results suggest that the high conductivity in phosphoric acids is caused by a very efficient proton transfer mechanism, which is strongly assisted by quantum effects.

A solvent-isotope-effect study of proton transfer during catalysis by Escherichia coli (lacZ) beta-galactosidase.

PubMed Central

Selwood, T; Sinnott, M L

1990-01-01

1. Michaelis-Menten parameters for the hydrolysis of 4-nitrophenyl beta-D-galactopyranoside and 3,4-dinitrophenyl beta-D-galactopyranoside Escherichia coli (lacZ) beta-galactosidase were measured as a function of pH or pD (pL) in both 1H2O and 2H2O. 2. For hydrolysis of 4-nitrophenyl beta-D-galactopyranoside by Mg2(+)-free enzyme, V is pL-independent below pL 9, but the V/Km-pL profile is sigmoid, the pK values shifting from 7.6 +/- 0.1 in 1H2O to 8.2 +/- 0.1 in 2H2O, and solvent kinetic isotope effects are negligible, in accord with the proposal [Sinnott, Withers & Viratelle (1978) Biochem. J. 175, 539-546] that glycone-aglycone fission without acid catalysis governs both V and V/Km. 3. V for hydrolysis of 4-nitrophenyl beta-D-galactopyranoside by Mg2(+)-enzyme varies sigmoidally with pL, the pK value shifting from 9.19 +/- 0.09 to 9.70 +/- 0.07; V/Km shows both a low-pL fall, probably due to competition between Mg2+ and protons [Tenu, Viratelle, Garnier & Yon (1971) Eur. J. Biochem. 20, 363-370], and a high-pL fall, governed by a pK that shifts from 8.33 +/- 0.08 to 8.83 +/- 0.08. There is a negligible solvent kinetic isotope effect on V/Km, but one of 1.7 on V, which a linear proton inventory shows to arise from one transferred proton. 4. The variation of V and V/Km with pL is sigmoid for hydrolysis of 3,4-dinitrophenyl beta-D-galactopyranoside by Mg2(+)-enzyme, with pK values showing small shifts, from 8.78 +/- 0.09 to 8.65 +/- 0.08 and from 8.7 +/- 0.1 to 8.9 +/- 0.1 respectively. There is no solvent isotope effect on V or V/Km for 3,4-dinitrophenyl beta-D-galactopyranoside, despite hydrolysis of the galactosyl-enzyme intermediate governing V. 5. Identification of the 'conformation change' in the hydrolysis of aryl galactosides proposed by Sinnott & Souchard [(1973) Biochem. J. 133, 89-98] with the protolysis of the magnesium phenoxide arising from the action of enzyme-bound Mg2+ as an electrophilic catalyst rationalizes these data and also resolves the conflict between the proposals and the 18O kinetic-isotope-effect data reported by Rosenberg & Kirsch [(1981) Biochemistry 20, 3189-3196]. It should be noted that the actual Km values were determined to higher precision than can be estimated from the Figures in this paper.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:2114090

A solvent-isotope-effect study of proton transfer during catalysis by Escherichia coli (lacZ) beta-galactosidase.

PubMed

Selwood, T; Sinnott, M L

1990-06-01

1. Michaelis-Menten parameters for the hydrolysis of 4-nitrophenyl beta-D-galactopyranoside and 3,4-dinitrophenyl beta-D-galactopyranoside Escherichia coli (lacZ) beta-galactosidase were measured as a function of pH or pD (pL) in both 1H2O and 2H2O. 2. For hydrolysis of 4-nitrophenyl beta-D-galactopyranoside by Mg2(+)-free enzyme, V is pL-independent below pL 9, but the V/Km-pL profile is sigmoid, the pK values shifting from 7.6 +/- 0.1 in 1H2O to 8.2 +/- 0.1 in 2H2O, and solvent kinetic isotope effects are negligible, in accord with the proposal [Sinnott, Withers & Viratelle (1978) Biochem. J. 175, 539-546] that glycone-aglycone fission without acid catalysis governs both V and V/Km. 3. V for hydrolysis of 4-nitrophenyl beta-D-galactopyranoside by Mg2(+)-enzyme varies sigmoidally with pL, the pK value shifting from 9.19 +/- 0.09 to 9.70 +/- 0.07; V/Km shows both a low-pL fall, probably due to competition between Mg2+ and protons [Tenu, Viratelle, Garnier & Yon (1971) Eur. J. Biochem. 20, 363-370], and a high-pL fall, governed by a pK that shifts from 8.33 +/- 0.08 to 8.83 +/- 0.08. There is a negligible solvent kinetic isotope effect on V/Km, but one of 1.7 on V, which a linear proton inventory shows to arise from one transferred proton. 4. The variation of V and V/Km with pL is sigmoid for hydrolysis of 3,4-dinitrophenyl beta-D-galactopyranoside by Mg2(+)-enzyme, with pK values showing small shifts, from 8.78 +/- 0.09 to 8.65 +/- 0.08 and from 8.7 +/- 0.1 to 8.9 +/- 0.1 respectively. There is no solvent isotope effect on V or V/Km for 3,4-dinitrophenyl beta-D-galactopyranoside, despite hydrolysis of the galactosyl-enzyme intermediate governing V. 5. Identification of the 'conformation change' in the hydrolysis of aryl galactosides proposed by Sinnott & Souchard [(1973) Biochem. J. 133, 89-98] with the protolysis of the magnesium phenoxide arising from the action of enzyme-bound Mg2+ as an electrophilic catalyst rationalizes these data and also resolves the conflict between the proposals and the 18O kinetic-isotope-effect data reported by Rosenberg & Kirsch [(1981) Biochemistry 20, 3189-3196]. It should be noted that the actual Km values were determined to higher precision than can be estimated from the Figures in this paper.(ABSTRACT TRUNCATED AT 400 WORDS)

Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

USGS Publications Warehouse

Miller, L.G.; Kalin, Robert M.; McCauley, S.E.; Hamilton, John T.G.; Harper, D.B.; Millet, D.B.; Oremland, R.S.; Goldstein, Allen H.

2001-01-01

The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as ???70???) shifts in ??13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70???) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole Cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.

Stable isotope fractionation of selenium by natural microbial consortia

USGS Publications Warehouse

Ellis, A.S.; Johnson, T.M.; Herbel, M.J.; Bullen, T.D.

2003-01-01

The mobility and bioavailability of Se depend on its redox state, and reduction of Se oxyanions to less mobile, reduced species controls transport of this potentially toxic element in the environment. Stable isotope fractionation of Se is currently being developed as an indicator of Se immobilization through reduction. In this study, Se isotope fractionation resulting from reduction of Se(VI) and Se(IV) oxyanions by natural microbial consortia was measured in sediment slurry experiments under nearly natural conditions, with no substrate added. Experiments were conducted with a wide range of initial Se concentrations and with sediment and water from three locations with contrasting environmental settings. The products of Se(VI) and Se(IV) reduction were enriched in the lighter isotopes relative to the reactants. Shifts of -2.60/00 to -3.10/00 and -5.50/00 to -5.70/00, respectively, were observed in the 80Se/76Se ratio. These isotopic fractionations did not depend significantly on initial Se concentrations, which were varied from 22 μg/l to 8 mg/l, or on geochemical differences among the sediments. These results provide estimates of Se isotope fractionation in organic-rich wetland environments but may not be appropriate for substrate-poor aquifers and marine sediments.

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.

Nocturnal and seasonal patterns of carbon isotope composition of leaf dark-respired carbon dioxide differ among dominant species in a semiarid savanna.

PubMed

Sun, Wei; Resco, Víctor; Williams, David G

2010-10-01

The C isotope composition of leaf dark-respired CO(2) (δ(13)C(l)) integrates short-term metabolic responses to environmental change and is potentially recorded in the isotopic signature of ecosystem-level respiration. Species differences in photosynthetic pathway, resource acquisition and allocation patterns, and associated isotopic fractionations at metabolic branch points can influence δ(13)C(l), and differences are likely to be modified by seasonal variation in drought intensity. We measured δ(13)C(l) in two deep-rooted C(3) trees (Prosopis velutina and Celtis reticulata), and two relatively shallow-rooted perennial herbs (a C(3) dicot Viguiera dentata and a C(4) grass Sporobolus wrightii) in a floodplain savanna ecosystem in southeastern Arizona, USA during the dry pre-monsoon and wet monsoon seasons. δ(13)C(l) decreased during the nighttime and reached minimum values at pre-dawn in all species. The magnitude of nocturnal shift in δ(13)C(l) differed among species and between pre-monsoon and monsoon seasons. During the pre-monsoon season, the magnitude of the nocturnal shift in δ(13)C(l) in the deep-rooted C(3) trees P. velutina (2.8 ± 0.4‰) and C. reticulata (2.9 ± 0.2‰) was greater than in the C(3) herb V. dentata (1.8 ± 0.4‰) and C(4) grass S. wrightii (2.2 ± 0.4‰). The nocturnal shift in δ(13)C(l) in V. dentata and S. wrightii increased to 3.2 ± 0.1‰ and 4.6 ± 0.6‰, respectively, during the monsoon season, but in C(3) trees did not change significantly from pre-monsoon values. Cumulative daytime net CO(2) uptake was positively correlated with the magnitude of the nocturnal decline in δ(13)C(l) across all species, suggesting that nocturnal δ(13)C(l) may be controlled by (13)C/(12)C fractionations associated with C substrate availability and C metabolite partitioning. Nocturnal patterns of δ(13)C(l) in dominant plant species in the semiarid savanna apparently have predictable responses to seasonal changes in water availability, which is important for interpreting and modeling the C isotope signature of ecosystem-respired CO(2).

Trace metal cycling and 238U/235U in New Zealand's fjords: Implications for reconstructing global paleoredox conditions in organic-rich sediments

NASA Astrophysics Data System (ADS)

Hinojosa, Jessica L.; Stirling, Claudine H.; Reid, Malcolm R.; Moy, Christopher M.; Wilson, Gary S.

2016-04-01

Reconstructing the history of ocean oxygenation provides insight into links between ocean anoxia, biogeochemical cycles, and climate. Certain redox-sensitive elements respond to changes in marine oxygen content through phase shifts and concomitant isotopic fractionation, providing new diagnostic proxies of past ocean hypoxia. Here we explore the behavior and inter-dependence of a suite of commonly utilized redox-sensitive trace metals (U, Mo, Fe, and Mn) and the emerging ;stable; isotope system of U (238U/235U, or δ238U) in New Zealand fjords. These semi-restricted basins have chemical conditions spanning the complete redox spectrum from fully oxygenated to suboxic to intermittently anoxic/euxinic. In the anoxic water column, U and Mo concentrations decrease, while Fe and Mn concentrations increase. Similarly, signals of past euxinic conditions can be found by U, Mo, Fe, and Mn enrichment in the underlying sediments. The expected U isotopic shift toward a lower δ238U in the anoxic water column due to U(VI)-U(IV) reduction is not observed; instead, water column δ238U profiles are consistent in fjords of all oxygen content, falling within previously reported ranges for open ocean seawater (δ238U = -0.42 ± 0.07‰). Additionally, surface sediment δ238U results show evidence for competing U isotope fractionation processes. One site indicates increased export of 238U from seawater to the underlying sediments (fractionation between aqueous seawater U and particulate sediment U, or ΔU(aq)-U(solid) = -0.25‰), consistent with redox-driven fractionation. Another site suggests potential U(VI) adsorption-driven fractionation, reflecting increased export of 235U from seawater to sediments (ΔU(aq)-U(solid) = 0.25‰). We discuss several potential factors that could alter δ238U in waters and sediments beyond redox-driven shifts, including adsorption to organic matter in waters of high primary productivity, reaction rates for competing processes of U adsorption and release, and isotopic constraints of U coming into the system from terrestrial environments. These potential complications should be understood and constrained through observations, experiments, and models before future application of δ238U as a global paleoredox tracer can achieve its full potential.

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

Murdock, Justin N.

Algal species vary in carbon (C) need and uptake rates. Understanding differences in C uptake and cellular allocation among species from natural communities will bring new insight into many ecosystem process questions including how species changes will alter energy availability and C sequestration in aquatic ecosystems. A major limitation of current methods that measure algal C incorporation is the inability to separate the response of individual species from mixed-species assemblages. I used Fourier-transform infrared microspectroscopy to qualitatively measure inorganic 13C isotope incorporation into individual algal cells in single species, two species, and natural phytoplankton assemblages. Lateral shifts in spectral peaksmore » from 13C treatments were observed in all species. Comparison of peaks associated with carbohydrates, proteins, and lipids allowed for the detection of which individuals took in C, and which macromolecules the C was used to make. For example, shifts in Spirogyra spectral peaks showed substantial C incorporation in carbohydrates. Further, shifts in peaks at 1160 cm -1, 1108 cm -1, 1080 cm -1, 1048 cm -1, and 1030 cm -1 suggested C was being allocated into cellulose. The natural phytoplankton assemblage demonstrated how C could be tracked into co-occurring species. A diatom had large shifts in protein and carbohydrate peaks, while a green alga and euglenoid had only a few shifts in protein related peaks. Fourier-transform infrared microspectroscopy is an established, label free method for measuring the chemical composition of algal cells. However, adding a label such as 13C isotope can greatly expand the technique's capabilities by qualitatively tracking C movement between inorganic and organic states within single cells.« less

C and N isotope fractionation during biodegradation of the pesticide metabolite 2,6-dichlorobenzamide (BAM): potential for environmental assessments.

PubMed

Reinnicke, Sandra; Simonsen, Allan; Sørensen, Sebastian R; Aamand, Jens; Elsner, Martin

2012-02-07

2,6-Dichlorobenzamide (BAM) is a metabolite of the herbicide 2,6-dichlorobenzonitrile (dichlobenil), and a prominent groundwater contaminant. Observable compound-specific isotope fractionation during BAM formation-through transformation of dichlobenil by Rhodococcus erythropolis DSM 9685-was small. In contrast, isotope fractionation during BAM degradation-with Aminobacter sp. MSH1 and ASI1, the only known bacterial strains capable of mineralizing BAM-was large, with pronounced carbon (ε(C) = -7.5‰ to -7.8‰) and nitrogen (ε(N) = -10.7‰ to -13.5‰) isotopic enrichment factors. BAM isotope values in natural samples are therefore expected to be dominated by the effects of its degradation rather than formation. Dual isotope slopes Δ (=Δδ(15)N/Δδ(13)C ≈ ε(N)/ε(C)) showed only small differences for MSH1 (1.75 ± 0.03) and ASI1 (1.45 ± 0.03) suggesting similar transformation mechanisms of BAM hydrolysis. Observations are in agreement with either a tetrahedral intermediate promoted by OH(-) or H(3)O(+) catalysis, or a concerted reaction mechanism. Therefore, owing to consistent carbon isotopic fractionation, isotope shifts of BAM can be linked to BAM biodegradation, and may even be used to quantify degradation of this persistent metabolite. In contrast, nitrogen isotope values may be rather indicative of different sources. Our results delineate a new approach to assessing the fate of BAM in the environment.

Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Lazarov, Marina; Horn, Ingo

2015-09-01

Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ65Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as (32S33S)+ and (32S-16O17O)+ do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn-H or doubly-charged Sn2 + that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ65Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm2 for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm2 which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible to measure Cu isotopic ratios in native copper and Cu-bearing sulfides, carbonates and oxides in situ with a precision of better than 0.1‰ (2SD) without using a matrix-matched standard during laser ablation analyses. Thus, this is a suitable tool to resolve Cu isotopic zoning larger than 0.1‰ in Cu-sulfides, carbonates and oxides.

Long-Term Geochemical and Geodynamic Segmentation of the Paleo-Pacific Margin of Gondwana: Insight From the Antarctic and Adjacent Sectors

NASA Astrophysics Data System (ADS)

Nelson, D. A.; Cottle, J. M.

2017-12-01

Combined zircon geochemistry and geochronology of Mesozoic volcaniclastic sediments of the central Transantarctic Mountains, Antarctica, yield a comprehensive record of both the timing and geochemical evolution of the magmatic arc along the Antarctic sector of the paleo-Pacific margin of Gondwana. Zircon age populations at 266-183 Ma, 367-328 Ma, and 550-490 Ma correspond to episodic arc activity from the Ediacaran to the Jurassic. Zircon trace element geochemistry indicates a temporal shift from granitoid-dominated source(s) during Ediacaran to Early Ordovician times to mafic sources in the Devonian through Early Jurassic. Zircon initial ɛHf shifts to more radiogenic Hf isotope compositions following the Ross Orogeny and is inferred to reflect juvenile crustal growth within an extensional arc system during progressive slab rollback. These new ages and Hf isotopic record are similar to those from the Australian sector, indicating that these regions constituted an 3,000 km laterally continuous extensional arc from at least the Carboniferous to the Permian. Conversely, the South American sector records enriched zircon Hf isotopic compositions and compressional/advancing arc tectonics during the same time period. Our new data constrain the location of this profound along-arc geochemical and geodynamic "switch" to the vicinity of the Thurston Island block of West Antarctica.

Stable isotope analysis of energy dynamics in aquatic ecosystems suggests trophic shifts following severe wildfire

NASA Astrophysics Data System (ADS)

Martens, A. M.; Silins, U.; Bladon, K. D.; Williams, C.; Wagner, M. J.; Luchkow, E.

2015-12-01

Wildfire alters landscapes and can have significant impacts on stream ecosystems. The 2003 Lost Creek wildfire was one of the most severe on Alberta's eastern rocky mountain slopes, resulting in elevated sediment production and nutrient (phosphorus, nitrogen, and carbon) export in impacted streams. These resulted in increased algal productivity and macroinvertebrate abundance and diversity, and as a result, fish in watersheds draining wildfire affected catchments were larger than those in the same age class from reference (unburned) watersheds. In the present investigation, stable isotope analysis of C and N was utilized to evaluate ecosystem energy dynamics and describe trophic relationships in those watersheds. Aquatic invertebrates from burned catchments showed enrichment in δ13C and δ15N relative to algae suggesting a reliance on algae (autochthony) as a primary source of energy. Invertebrates from unburned systems were depleted in δ13C relative to algae indicating reliance on allochthonous or terrestrial primary energy sources. Preliminary analysis of δ15N in macroinvertebrates showed slight enrichment in burned catchments suggesting a trophic shift. More comprehensive macroinvertebrate sampling and identification has been conducted; isotopic analysis will provide greater resolution of how specific families within feeding guilds have been affected by wildfire. This will provide more robust insights into how wildfires may impact stream ecology in mountain environments.

Mass Independent Fractionation of Cadmium Isotopes During Thermal Ionization

NASA Astrophysics Data System (ADS)

Abouchami, W.; Galer, S. J.; Feldmann, H.; Schmitt, A. D.

2008-12-01

We have previously reported that Cd isotopes exhibit anomalous, non-mass dependent fractionation of odd versus even isotopes when measured by TIMS using silica gel-phosphoric acid activator. The deviation from mass dependent fractionation (MDF) on the odd masses 111 and 113 varies by fractions of a per-cent between runs. The effects cannot be explained by isobaric interferences, but seem, instead, to reflect mass independent fractionation (MIF) of Cd isotopes, much like that recently documented for Hg isotopes in natural systems (Bergquist and Blum, 2007). The absence of comparable Cd isotope anomalies in the ICP torch, and during extreme in-vacuo volatilization of Cd metal (Wombacher et al., 2004) conclusively implicates the silica gel activator in the process. So far, MIF has been documented for Cd, Zn and Pb isotopes when measured using the silica gel technique (Thirlwall, 2000; Schmitt et al., 2006; Manhes and Göpel, 2007). These MIF effects on Cd isotopes might perhaps be related to the non-mass dependence of nuclear volume with mass number, as described by Bigeleisen (1996) - also known as the "nuclear field shift". The MIF caused by the nuclear field shift results is a departure from MDF broadly characterized by a odd-even staggering with mass number. These effects have been quantified by Schauble (2007) who showed that the magnitude of the non-mass dependence for Hg and Tl isotopes lies in the ppm range for some simple reactions. Such MIF effects would appear, overall, far too small to account for our data, which require MIF offsets on the odd masses 111 and 113 approaching a per-cent. Moreover, an in-depth examination along the lines of Fujii et al. (2006) predicts tell-tale offsets for the even-even isotope pairs 114Cd/112Cd and 116Cd/112Cd as well, based upon the theory and the respective nuclear radii, but such accompanying offsets are unequivocally absent in our data. The odd-even isotope effects seen in our runs using silica gel activator are better explained by appealing to the nuclear spin (and magnetic moment) of odd nuclei alone. The "magnetic isotope effect" is a consequence of hyperfine coupling, in which an electron interacts with a nucleus of non-zero magnetic moment - i.e. one that has an odd number of nucleons (Turro, 1983; Buchachenko, 1995, 2001). This is purely a kinetic phenomenon in which the life-time, and thus the outcome, of reaction transition states is altered by the hyperfine splitting present in atoms with odd nuclei. The mechanism by which silica gel activator enhances the thermal ionization of elements such as Cd, Pb and Zn has been outlined by Kessinger and Delmore (2002). The first step involves the in-situ reduction of Cd2+ ions to Cd metal in the molten silica gel-phosphoric acid glass. It is most likely in this step - whereby two electrons are added - that a suitably long-lived transition state exists, during which the magnetic isotope effect enhances (or inhibits) reduction of masses 111 and 113 to metal species compared to those of even isotopes of Cd. The resulting "odd" and "even" populations of Cd-metal in the molten silica gel then cannot be related simply in terms of MDF. Overall, the magnetic isotope effect provides the best explanation of the MIF effects observed for Pb, Cd and Zn during thermal ionization with silica gel activator, and, probably, why the measured fractionation is always biased towards light isotopes.

Stable isotope tracing of anaerobic methane oxidation in the gassy sediments of Eckernfoerde Bay, German Baltic Sea

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

Martens, C.S.; Albert, D.B.; Alperin, M.J.

Methane concentrations in the pore waters of Eckernfoerde Bay in the German Baltic Sea generally reach gas bubble saturation values within the upper meter of the sediment column. The depth at which saturation occurs is controlled by a balance between rates of methane production, consumption (oxidation), and transport. The relative importance of anaerobic methane oxidation (AMO) in controlling dissolved and gas bubble methane distributions in the bay's sediments is indirectly revealed through methane concentration versus depth profiles, depth variations in the stable C and H isotope composition of methane, and the C isotope composition of total dissolved inorganic carbon ({Sigma}CO{submore » 2}). Direct radiotracer measurements indicate that AMO rates of over 15 mM/yr are focused at the base of the sulfate reduction zone. Diagenetic equations that describe the depth destructions of the {delta}{sup 13}C and {delta}D values of methane reproduce isotopic shifts observed throughout the methane oxidation zone and are best fit with kinetic isotope fractionation factors of 1.012 {+-} 0.001 and 1.120 {plus{underscore}minus} 0.020 respectively.« less

A test of the significance of intermolecular vibrational coupling in isotopic fractionation

DOE PAGES

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.; ...

2017-07-15

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

Evaluation of uranium transitions for isotopically-selective laser induced fluorescence with diode lasers (technical report for ST064)

NASA Astrophysics Data System (ADS)

Cannon, B. D.

1993-10-01

Isotopically-selective excitation of uranium atoms by diode lasers can be the basis for a portable instrument to perform uranium isotopic assays in the field. Such an instrument would improve the ability of on-site inspections to detect and deter nuclear proliferation. Published and unpublished spectroscopic data on atomic uranium were examined to identify candidate transitions for isotopically-selective laser excitation with diode lasers. Eleven candidate transitions were identified and evaluated for their potential usefulness for a portable uranium assay instrument. Eight of these transitions are suitable for laser induced fluorescence using different excitation and detection wavelengths, which will improve sensitivity and elemental selectivity. Data sheets on the 25 uranium transitions in the wavelength range 629 nm to 1,000 nm that originate in the ground or first excited states of neutral atomic uranium are included. Each data sheet provides the wavelength, upper and lower energy levels, angular momentum quantum numbers, U-235 isotope shift (relative to U-238, and high-resolution spectra of weapons-grade uranium (93% U-235 and 7% U-238).

Paleoclimate and Amerindians: Evidence from stable isotopes and atmospheric circulation

USGS Publications Warehouse

Lovvorn, M.B.; Frison, G.C.; Tieszen, L.L.

2001-01-01

Two Amerindian demographic shifts are attributed to climate change in the northwest plains of North America: at ???11,000 calendar years before present (yr BP), Amerindian culture apparently split into foothills-mountains vs. plains biomes; and from 8,000-5,000 yr BP, scarce archaeological sites on the open plains suggest emigration during xeric "Altithermal" conditions. We reconstructed paleoclimates from stable isotopes in prehistoric bison bone and relations between weather and fractions of C4 plants in forage. Further, we developed a climate-change model that synthesized stable isotope, existing qualitative evidence (e.g., palynological, erosional), and global climate mechanisms affecting this midlatitude region. Our isotope data indicate significant warming from ???12,400 to 11,900 yr BP, supporting climate-driven cultural separation. However, isotope evidence of apparently wet, warm conditions at 7,300 yr BP refutes emigration to avoid xeric conditions. Scarcity of archaeological sites is best explained by rapid climate fluctuations after catastrophic draining of the Laurentide Lakes, which disrupted North Atlantic Deep Water production and subsequently altered monsoonal inputs to the open plains.

Isotopic coherence of refractory inclusions from CV and CK meteorites: Evidence from multiple isotope systems

NASA Astrophysics Data System (ADS)

Shollenberger, Quinn R.; Borg, Lars E.; Render, Jan; Ebert, Samuel; Bischoff, Addi; Russell, Sara S.; Brennecka, Gregory A.

2018-05-01

Calcium-aluminum-rich inclusions (CAIs) are the oldest dated materials in the Solar System and numerous previous studies have revealed nucleosynthetic anomalies relative to terrestrial rock standards in many isotopic systems. However, most of the isotopic data from CAIs has been limited to the Allende meteorite and a handful of other CV3 chondrites. To better constrain the isotopic composition of the CAI-forming region, we report the first Sr, Mo, Ba, Nd, and Sm isotopic compositions of two CAIs hosted in the CK3 desert meteorites NWA 4964 and NWA 6254 along with two CAIs from the CV3 desert meteorites NWA 6619 and NWA 6991. After consideration of neutron capture processes and the effects of hot-desert weathering, the Sr, Mo, Ba, Nd, and Sm stable isotopic compositions of the samples show clearly resolvable nucleosynthetic anomalies that are in agreement with previous results from Allende and other CV meteorites. The extent of neutron capture, as manifested by shifts in the observed 149Sm-150Sm isotopic composition of the CAIs is used to estimate the neutron fluence experienced by some of these samples and ranges from 8.40 × 1013 to 2.11 × 1015 n/cm2. Overall, regardless of CAI type or host meteorite, CAIs from CV and CK chondrites have similar nucleosynthetic anomalies within analytical uncertainty. We suggest the region that CV and CK CAIs formed was largely uniform with respect to Sr, Mo, Ba, Nd, and Sm isotopes when CAIs condensed and that CAIs hosted in CV and CK meteorites are derived from the same isotopic reservoir.

Stable Isotopes of Precipitation During Tropical Sumatra Squalls in Singapore

NASA Astrophysics Data System (ADS)

He, Shaoneng; Goodkin, Nathalie F.; Kurita, Naoyuki; Wang, Xianfeng; Rubin, Charles Martin

2018-04-01

Sumatra Squalls, organized bands of thunderstorms, are the dominant mesoscale convective systems during the intermonsoon and southwest monsoon seasons in Singapore. To understand how they affect precipitation isotopes, we monitored the δ value of precipitation daily and continuously (every second and integrated over 30 s) during all squalls in 2015. We found that precipitation δ18O values mainly exhibit a "V"-shape pattern and less commonly a "W"-shape pattern. Variation in δ18O values during a single event is about 1 to 6‰ with the lowest values mostly observed in the stratiform zone, which agrees with previous observations and modeling simulations. Reevaporation can significantly affect δ values, especially in the last stage of the stratiform zone. Daily precipitation is characterized by periodic negative shifts in δ value, largely associated with the squalls rather than moisture source change. The shifts can be more than 10‰, larger than intraevent variation. Initial δ18O values of events are highly variable, and those with the lowest values also have the lowest initial values. Therefore, past convective activities in the upwind area can significantly affect the δ18O, and convection at the sampling site has limited contribution to isotopic variability. A significant correlation between precipitation δ18O value and regional outgoing longwave radiation and rainfall in the Asian monsoon region and western Pacific suggests that regional organized convection probably drives stable isotopic compositions of precipitation. A drop in the frequency of the squalls in 2015 is related to weak organized convection in the region caused by El Niño.

Vanadium isotope heterogeneity of the early solar system

NASA Astrophysics Data System (ADS)

Nielsen, S.; Auro, M. E. E.; Magna, T.; Davis, D. M.; Mezger, K.; Sarafian, A. R.

2017-12-01

Vanadium (V) has two isotopes with masses 50 and 51 that have 51V/50V ratio of 410. This ratio can be modified by production of 50V through cosmic irradiation, heterogeneous distribution of anomalous nucleosynthetic material and stable isotope fractionation. Due to the existence of only two V isotopes in nature, these latter processes cannot directly be distinguished from irradiation processes. Previous data has suggested that Earth is characterized by 51V/50V that is significantly different to that of meteorites. These data are difficult to reconcile with a singular process that caused the V isotope variation in the early Solar System. Here we present new V isotope data for a large range of meteorites in order to investigate the ultimate origin of V isotope variation in the early Solar System. We find limited and non-systematic 51V/50V variation of 0.3‰ for 25 martian meteorites (depleted/intermediate/enriched shergottites, nakhlites, and chassignite and orthopyroxenite ALH 84001), which suggests that igneous processes on Mars did not induce significant V isotope shifts. Our best estimate for V isotope composition of the bulk silicate Mars can thus be approximated by the mean value of the entire Martian meteorite suite. This value is significantly lighter ( 0.4‰) than that measured for pristine terrestrial rocks. In contrast, meteorites from the HED parent body reveal significant 51V/50V variation that may be linked to magmatic processes such as fractional crystallization of Vestan magma ocean. The two data sets illustrate that several processes are likely to explain the V isotope variation found in meteorites. We will also present new V isotope data for carbonaceous and ordinary chondrites and put them in the context of the values found for Earth, Mars and the HED parent body.

Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology

NASA Astrophysics Data System (ADS)

Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis

2013-06-01

Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

NASA Astrophysics Data System (ADS)

Blum, P.; Sültenfuß, J.; Martus, P.

2014-12-01

Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

Persistence of El Niño effects on stable isotope ratios in cellulose of Coast Redwood tree-rings

NASA Astrophysics Data System (ADS)

Johnstone, J. A.

2005-12-01

An anomalously wet El Niño winter in 1998 in Sonoma County, California, USA produced sharp changes in the oxygen and carbon isotope ratios of tree-ring cellulose of Coast Redwood ( Sequoia sempervirens (D.Don) Endl.) which persisted for several years thereafter. High-resolution cellulose sampling reveals a negative shift in both δ18O and δ13C, consistent with greater reliance on winter rain water supplies (rather than summer fog) as well as reduced drought stress due to the anomalous precipitation. The annual cycle of these isotopic ratios is also muted for several years following the 1998 winter. These observations suggest a disproportionate and persistent influence of extreme years in the interannual variability of Coast Redwood hydrology and physiology.

[Review on the feeding ecology and migration patterns of sharks using stable isotopes].

PubMed

Li, Yun-Kai

2014-09-01

With the rapidly increasing use of stable isotope analysis (SIA) in ecology, it becomes a powerful tool and complement to traditional methods for investigating the trophic ecology of animals. Sharks play a keystone role in marine food webs as the apex predators and are recently becoming the frontier topic of food web studies and marine conservation because of their unique characteristics of evolution. Recently, SIA has recently been applied to trophic ecology studies of shark species. Here, we reviewed the current applications of SIA in shark species, focusing on available tissues for analyzing, standardized analytical approaches, diet-tissue discrimination factors, diet shift investigation, migration patterns predictions and niche-width analyses, with the aim of getting better understanding of stable-isotope dynamics in shark biology and ecology research.

Increasing subtropical North Pacific Ocean nitrogen fixation since the Little Ice Age.

PubMed

Sherwood, Owen A; Guilderson, Thomas P; Batista, Fabian C; Schiff, John T; McCarthy, Matthew D

2014-01-02

The North Pacific subtropical gyre (NPSG) plays a major part in the export of carbon and other nutrients to the deep ocean. Primary production in the NPSG has increased in recent decades despite a reduction in nutrient supply to surface waters. It is thought that this apparent paradox can be explained by a shift in plankton community structure from mostly eukaryotes to mostly nitrogen-fixing prokaryotes. It remains uncertain, however, whether the plankton community domain shift can be linked to cyclical climate variability or a long-term global warming trend. Here we analyse records of bulk and amino-acid-specific (15)N/(14)N isotopic ratios (δ(15)N) preserved in the skeletons of long-lived deep-sea proteinaceous corals collected from the Hawaiian archipelago; these isotopic records serve as a proxy for the source of nitrogen-supported export production through time. We find that the recent increase in nitrogen fixation is the continuation of a much larger, centennial-scale trend. After a millennium of relatively minor fluctuation, δ(15)N decreases between 1850 and the present. The total shift in δ(15)N of -2 per mil over this period is comparable to the total change in global mean sedimentary δ(15)N across the Pleistocene-Holocene transition, but it is happening an order of magnitude faster. We use a steady-state model and find that the isotopic mass balance between nitrate and nitrogen fixation implies a 17 to 27 per cent increase in nitrogen fixation over this time period. A comparison with independent records suggests that the increase in nitrogen fixation might be linked to Northern Hemisphere climate change since the end of the Little Ice Age.

An 8,600 year lacustrine record of summer monsoon variability from Yunnan, China

NASA Astrophysics Data System (ADS)

Hillman, Aubrey L.; Abbott, Mark B.; Finkenbinder, Matthew S.; Yu, JunQing

2017-10-01

Interactions between the Indian Summer Monsoon (ISM) and East Asian Summer Monsoon (EASM) are complex, yet needed to provide a long-term perspective of precipitation patterns in southeast Asia. Here we present an 8600-year sediment record from Xingyun Lake in Yunnan, China, a transitional zone that receives inputs of precipitation from both the ISM and EASM. Analysis of stable oxygen isotopes (δ18O) from authigenic calcite yields a semi-quantitative estimate of the timing and magnitude of lake level change that reflects changes in effective moisture from monsoon variability. Between 8600 and 6900 years BP, δ18O values are stable and low, indicating high lake levels and overflowing conditions resulting from a strong ISM. After 6900 years BP, δ18O values shift to higher values, which we suggest reflects a weakening of the ISM caused by declining summer insolation. The most substantial positive shift in isotopes occurs from 5000 to 4300 years BP and is coincident with aridity in India and the Tibetan Plateau. Other proxy records indicate increased ENSO variability and a southward shift in the ITCZ, which has an effect on the strength and onset of the ISM and may account for this change in hydrologic balance. After 4300 years BP, δ18O values continue to increase reflecting a gradual drying trend, but increases are smaller than prior periods, in part due to lake bathymetry that limits the potential for isotopic enrichment driven by evaporation. The relative influence of the ISM and EASM in the Yunnan Province of China during the Holocene remains a topic for future study, but our results suggest the predominance of the ISM and a possible connection to ENSO patterns on centennial to millennial timescales.

Comparative isotope ecology of African great apes.

PubMed

Oelze, Vicky M; Fahy, Geraldine; Hohmann, Gottfried; Robbins, Martha M; Leinert, Vera; Lee, Kevin; Eshuis, Henk; Seiler, Nicole; Wessling, Erin G; Head, Josephine; Boesch, Christophe; Kühl, Hjalmar S

2016-12-01

The isotope ecology of great apes is a useful reference for palaeodietary reconstructions in fossil hominins. As extant apes live in C 3 -dominated habitats, variation in isotope signatures is assumed to be low compared to hominoids exploiting C 4 -plant resources. However, isotopic differences between sites and between and within individuals are poorly understood due to the lack of vegetation baseline data. In this comparative study, we included all species of free-ranging African great apes (Pan troglodytes, Pan paniscus, Gorilla sp.). First, we explore differences in isotope baselines across different habitats and whether isotopic signatures in apes can be related to feeding niches (faunivory and folivory). Secondly, we illustrate how stable isotopic variations within African ape populations compare to other extant and extinct primates and discuss possible implications for dietary flexibility. Using 701 carbon and nitrogen isotope data points resulting from 148 sectioned hair samples and an additional collection of 189 fruit samples, we compare six different great ape sites. We investigate the relationship between vegetation baselines and climatic variables, and subsequently correct great ape isotope data to a standardized plant baseline from the respective sites. We obtained temporal isotopic profiles of individual animals by sectioning hair along its growth trajectory. Isotopic signatures of great apes differed between sites, mainly as vegetation isotope baselines were correlated with site-specific climatic conditions. We show that controlling for plant isotopic characteristics at a given site is essential for faunal data interpretation. While accounting for plant baseline effects, we found distinct isotopic profiles for each great ape population. Based on evidence from habituated groups and sympatric great ape species, these differences could possibly be related to faunivory and folivory. Dietary flexibility in apes varied, but temporal variation was overall lower than in fossil hominins and extant baboons, shifting from C 3 to C 4 -resources, providing new perspectives on comparisons between extinct and extant primates. Copyright © 2016 Elsevier Ltd. All rights reserved.

Depth gradients in food web processes linking large lake habitats

EPA Science Inventory

In large lakes around the world, shifts in ecological communities are often associated with water depth. This suggests that there may be concomitant changes in patterns of resource allocation. Using Lake Superior as an example, we explored this idea through stable isotope analyse...

Assignment for the Infrared Spectrum of Solid Sodium Propionate from Low-Temperature Measurements in Combination with 13C Isotopic Shifts

NASA Astrophysics Data System (ADS)

Kakihana, Masato; Nagumo, Tadashi

1987-05-01

The infrared spectra of CH3CH2COONa and its 13C-labeled modifications (1-13C, 2-13C, and 3-13C) suspended in KBr disks were measured in the region 4000 -200 cm-1 at room temperature and liquid nitrogen temperature. Overlapping complex band contours appeared in some regions of the room temperature spectrum, most notably in the region 1500 -1350 cm-1, where 5 fundamentals having contributions from the methyl deformation, methylene bending, and carboxylate stretching modes should occur. In contrast to this, excellent resolution was reached at the low temperature, from which all 22 fundamentals expected in the whole spectral region investigated were detected. A complete assignment of the fundamentals is proposed mainly on the basis of the characteristic isotopic shifts of the three 13C substituted sodium propionate species. A fair number of the fundamentals were found to feature coupled modes having contributions from several group vibrations.

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.

Nuclear quantum effects of light and heavy water studied by all-electron first principles path integral simulations

NASA Astrophysics Data System (ADS)

Machida, Masahiko; Kato, Koichiro; Shiga, Motoyuki

2018-03-01

The isotopologs of liquid water, H2O, D2O, and T2O, are studied systematically by first principles PIMD simulations, in which the whole entity of the electrons and nuclei are treated quantum mechanically. The simulation results are in reasonable agreement with available experimental data on isotope effects, in particular, on the peak shift in the radial distributions of H2O and D2O and the shift in the evaporation energies. It is found that, due to differences in nuclear quantum effects, the H atoms in the OH bonds more easily access the dissociative region up to the hydrogen bond center than the D (T) atoms in the OD (OT) bonds. The accuracy and limitation in the use of the current density-functional-theory-based first principles PIMD simulations are also discussed. It is argued that the inclusion of the dispersion correction or relevant improvements in the density functionals are required for the quantitative estimation of isotope effects.

Mediation of donor–acceptor distance in an enzymatic methyl transfer reaction

PubMed Central

Zhang, Jianyu; Kulik, Heather J.; Martinez, Todd J.; Klinman, Judith P.

2015-01-01

Enzymatic methyl transfer, catalyzed by catechol-O-methyltransferase (COMT), is investigated using binding isotope effects (BIEs), time-resolved fluorescence lifetimes, Stokes shifts, and extended graphics processing unit (GPU)-based quantum mechanics/molecular mechanics (QM/MM) approaches. The WT enzyme is compared with mutants at Tyr68, a conserved residue that is located behind the reactive sulfur of cofactor. Small (>1) BIEs are observed for an S-adenosylmethionine (AdoMet)-binary and abortive ternary complex containing 8-hydroxyquinoline, and contrast with previously reported inverse (<1) kinetic isotope effects (KIEs). Extended GPU-based computational studies of a ternary complex containing catecholate show a clear trend in ground state structures, from noncanonical bond lengths for WT toward solution values with mutants. Structural and dynamical differences that are sensitive to Tyr68 have also been detected using time-resolved Stokes shift measurements and molecular dynamics. These experimental and computational results are discussed in the context of active site compaction that requires an ionization of substrate within the enzyme ternary complex. PMID:26080432

Symbiodinium Clade Affects Coral Skeletal Isotopic Ratio

NASA Astrophysics Data System (ADS)

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

2011-12-01

The influence of different physiologies of Symbiodinium dinoflagellate symbiont clades on the skeletal chemistry of associated coral hosts has not previously been investigated. This is an important issue because coral skeletons are routinely used for tropical paleoclimatic reconstructions. We analyzed coral skeletal samples collected simultaneously from neighboring colonies off Belize and found that those harboring different clades of Symbiodinium displayed significantly different skeletal oxygen isotopic compositions. We also found evidence for mean shifts in skeletal oxygen isotopic composition after coral bleaching (the loss and potential exchange of symbionts) in two of four longer coral cores from the Mesoamerican Reef, though all experienced similar climatic conditions. Thus, we suggest that symbiont clade identity leaves a signature in the coral skeletal archive and that this influence must be considered for quantitative environmental reconstruction. In addition, we suggest that the skeletal isotopic signature may be used to identify changes in the dominant symbiont clade that have occurred in the past, to identify how common and widespread this phenomenon is--a potential adaptation to climate change.

Barium and neodymium isotopic anomalies in the Allende meteorite

NASA Technical Reports Server (NTRS)

Mcculloch, M. T.; Wasserburg, G. J.

1978-01-01

The discovery of Ba and Nd isotopic anomalies in two inclusions from the Allende meteorite is reported. The inclusions are Ca-Al-rich objects typical of the type considered as high-temperature condensation products in the solar nebula and contain distinctive Mg and O isotopic anomalies of the FUN (mass Fractionation, Unknown Nuclear processes) type. Mass-spectrometry results are discussed which show that inclusion C1 has anomalies in Ba at masses 134 and 136, while inclusion EK1-4-1 exhibits large marked negative anomalies at 130, 132, 134, and 136, as well as a positive anomaly at 137. It is also found that inclusion EK1-4-1 shows marked negative anomalies in Nd at masses 142, 146, 148, and 150, in addition to a positive anomaly at 145. These isotopic shifts are attributed to addition of r-process nuclei rather than mass fractionation. It is suggested that an onion-shell supernova explosion followed by injection into the solar nebula is the most likely generic model that may explain the observations.

Improved repetition rate mixed isotope CO{sub 2} TEA laser

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

Cohn, D. B., E-mail: dbctechnology@earthlink.net

2014-09-15

A compact CO{sub 2} TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the {sup 12}C{sup 16}O{sub 2} isotope. With mixed {sup 12}C{sup 16}O{sub 2} plus {sup 13}C{sup 16}O{sub 2} isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Relatedmore » work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.« less

Weight loss and isotopic shifts for water drops frozen on a liquid nitrogen surface.

PubMed

Eguchi, Keiko; Abe, Osamu; Hiyama, Tetsuya

2008-10-01

A liquid nitrogen freezing method was used to collect raindrops for the determination of isotope-size distribution. Water drops that fall onto a surface of liquid nitrogen stay suspended for 10 to 20 s, until their temperature reaches the Leidenfrost point (126 K). As their temperature falls to the freezing point, they release their heat by thermal conduction. At the freezing point, latent heat of fusion is released, along with a significant loss of water. After freezing completely, the ice droplets stay suspended, cooling by thermal conduction until they reach the Leidenfrost point. They then lose buoyancy and start sinking. Consistent isotopic changes of 1.5 +/- 0.4 and 0.33 +/- 0.05 per thousand for hydrogen and oxygen, respectively, were found for droplets with radii between 1.0 and 1.5 mm. Isotope fractionation appeared to occur at the same time as water loss, as the droplets were freezing, in what was probably a kinetic effect.

New perspective on Aptian carbon isotope stratigraphy: Data from δ13C records of terrestrial organic matter

NASA Astrophysics Data System (ADS)

Ando, Atsushi; Kakegawa, Takeshi; Takashima, Reishi; Saito, Tsunemasa

2002-03-01

Carbon isotope analyses were performed on detrital woody materials in Aptian (mid- Cretaceous) marine sediments of central Hokkaido, northern Japan. A positive δ13Cwood excursion (from -25.4‰ to -21.8‰) following a remarkable negative isotope shift is recognized in the early Aptian, and a small positive anomaly is also found in the latest Aptian. This δ13Cwood profile is exactly in phase with the δ13Ccarbonate curve from a Pacific guyot when the age of the guyot carbonates is revised using published Sr isotope stratigraphies. The highly conformable δ13C profiles of Pacific and Hokkaido sections suggest that δ13C compositions of Aptian marine and terrestrial carbon reservoirs changed simultaneously by the same amplitude within the ocean-atmosphere-biosphere system. Fluctuation patterns of Tethyan δ13Ccarbonate curves are slightly different from those of Pacific and Hokkaido sections. Such differences in δ13C profiles may be attributed to the local paleoceanographic setting of the Aptian Mediterranean Tethys.

Pan-derived isotopic composition of atmospheric vapour in a Mediterranean wetland (Rhône River Delta, France).

PubMed

Vallet-Coulomb, Christine; Cartapanis, Olivier; Radakovitch, Olivier; Sonzogni, Corinne; Pichaud, Marc

2010-03-01

A continuous record of atmospheric vapour isotopic composition (delta(A)) can be derived from the isotope mass balance of a water body submitted to natural evaporation. In this paper, we present preliminary results of the application of this method to a drying evaporation pan, located in a Mediterranean wetland, during a two-month summer period. Results seem consistent with few atmospheric vapour data based on the assumption of isotopic equilibrium with precipitation, but we observed a shift between pan-derived delta(A) and the composition of vapour samples collected by cold trapping. These results suggest that further investigations are necessary to evaluate the effect of diurnal variations of atmospheric conditions on the applicability of the pan-evaporation method, and on the representative of grab atmospheric samples. We also propose a sensitivity analysis for evaluating the impact of the different measured components on delta(A) calculation, and show an improvement in the method efficiency as the pan is drying.

RIS3: A program for relativistic isotope shift calculations

NASA Astrophysics Data System (ADS)

Nazé, C.; Gaidamauskas, E.; Gaigalas, G.; Godefroid, M.; Jönsson, P.

2013-09-01

An atomic spectral line is characteristic of the element producing the spectrum. The line also depends on the isotope. The program RIS3 (Relativistic Isotope Shift) calculates the electron density at the origin and the normal and specific mass shift parameters. Combining these electronic quantities with available nuclear data, isotope-dependent energy level shifts are determined. Program summaryProgram title:RIS3 Catalogue identifier: ADEK_v2_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADEK_v2_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 5147 No. of bytes in distributed program, including test data, etc.: 32869 Distribution format: tar.gz Programming language: Fortran 77. Computer: HP ProLiant BL465c G7 CTO. Operating system: Centos 5.5, which is a Linux distribution compatible with Red Hat Enterprise Advanced Server. Classification: 2.1. Catalogue identifier of previous version: ADEK_v1_0 Journal reference of previous version: Comput. Phys. Comm. 100 (1997) 81 Subprograms used: Cat Id Title Reference ADZL_v1_1 GRASP2K VERSION 1_1 to be published. Does the new version supersede the previous version?: Yes Nature of problem: Prediction of level and transition isotope shifts in atoms using four-component relativistic wave functions. Solution method: The nuclear motion and volume effects are treated in first order perturbation theory. Taking the zero-order wave function in terms of a configuration state expansion |Ψ>=∑μcμ|Φ(γμPJMj)>, where P, J and MJ are, respectively, the parity and angular quantum numbers, the electron density at the nucleus and the normal and specific mass shift parameters may generally be expressed as ∑cμcν<γμPJMj|V|γνPJMj> where V is the relevant operator. The matrix elements, in turn, can be expressed as sums over radial integrals multiplied by angular coefficients. All the angular coefficients are calculated using routines from the GRASP2K version 1_1 package [1]. Reasons for new version: This new version takes the nuclear recoil corrections into account within the (m2/M approximation [2] and also allows storage of the angular coefficients for a series of calculations within a given isoelectronic sequence. Furthermore, the program JJ2LSJ, a module of the GRASP2K version 1_1 toolkit that allows a transformation of ASFs from a jj-coupled CSF basis into an LSJ-coupled CSF basis, has been especially adapted to present RIS3 results using LSJ labels of the states. This additional tool is called RIS3_LSJ. Summary of revisions: This version is compatible with the new angular approach of the GRASP2K version 1_1 package [1] and can store necessary angular coefficients. According to the formalism of the relativistic nuclear recoil, the "uncorrected" expression of the normal mass shift has been fundamentally modified compared with its expression in [3]. Restrictions: The complexity of the cases that can be handled is entirely determined by the GRASP2K package [1] used for the generation of the electronic wave functions. Unusual features: Angular data is stored on disk and can be reused. LSJ labels are used for the states. Running time: As an example, we evaluated the isotope shift parameters and the electron density at the origin using the wave functions of Be-like system. We used the MCDHF wave function built on a complete active space (CAS) with n=8 (296 626 CSFs-62 orbitals) that contains 3 non-interacting blocks of given parity and J values involving 6 different eigenvalues in total. Calculations take around 10 h on one AMD Opteron 6100 @ 2.3 GHz CPU with 8 cores (64 GB DDR3 RAM 1.333 GHz). If angular files are available the time is reduced to 20 min. The storage of the angular data takes 139 MB and 7.2 GB for the one-body and the two-body elements, respectively. References: [1] P. Jönsson, G. Gaigalas, J. Bieroń, C. Froese Fischer, I.P. Grant, New version: GRASP2K relativistic atomic structure package, Comput. Phys. Commun. 184 (9) (2013) 2197-2203. [2] E. Gaidamauskas, C. Nazé, P. Rynkun, G. Gaigalas, P. Jönsson, M. Godefroid, J. Phys. B: At. Mol. Opt. Phys. 44 (17) (2011) 175003. [3] P. Jönsson, C. Froese Fischer, Comput. Phys. Commun. 100 (1997) 81-92.

Lessons from the past: isotopes of an endangered rail as indicators of underlying change to tidal marsh habitats

USGS Publications Warehouse

Merritt, Angela M.; Casazza, Michael L.; Overton, Cory T.; Takekawa, John Y.; Hahn, Thomas P.; Hull, Joshua M.

2017-01-01

Introduction: Tidal marsh systems along the Pacific coast of the United States have experienced substantial stress and loss of area and ecosystem function, which we examined by using the endangered California Ridgway’s Rail, Rallus obsoletus obsoletus (‘rail’) as an indicator of its tidal marsh habitat in the San Francisco Estuary. We organized a collection of historical (1885-1940) and modern (2005-2014) rail feathers and analyzed the feather isotope means for delta carbon (δ13C), sulfur (δ34S), and nitrogen (δ15N) by region and time period.Outcomes: Feather isotopes represented the primary foraging habitat during historical then modern time periods. Neither individual nor regional rail feather isotopes suggested freshwater or terrestrial foraging by the rail. Three regions with both historic and modern feather isotopes revealed non-uniform spatial shifts in isotope levels consistent with a marine based food web and significant δ15N enrichment.Discussion: Our results supported the rail’s status as a generalist forager and obligate tidal marsh species throughout the historic record. The variable isoscape trends generated from feather isotope means illustrated a modern loss of the isotopic homogeneity between regions of historical tidal marsh, which correlated with spatially-explicit habitat alterations such as increasing biological invasions and sewage effluent over time.Conclusion: These findings have reinforced the importance of tidal marsh conservation in the face of ongoing underlying changes to these important ecosystems.

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.

Exploring the Potential of Laser Ablation Carbon Isotope Analysis for Examining Ecology during the Ontogeny of Middle Pleistocene Hominins from Sima de los Huesos (Northern Spain)

PubMed Central

Garcia, Nuria; Feranec, Robert S.; Passey, Benjamin H.; Cerling, Thure E.; Arsuaga, Juan Luis

2015-01-01

Laser ablation of tooth enamel was used to analyze stable carbon isotope compositions of teeth of hominins, red deer, and bears from middle Pleistocene sites in the Sierra de Atapuerca in northern Spain, to investigate the possibility that this technique could be used as an additional tool to identify periods of physiological change that are not detectable as changes in tooth morphology. Most of the specimens were found to have minimal intra-tooth variation in carbon isotopes (< 2.3‰), suggesting isotopically uniform diets through time and revealing no obvious periods of physiological change. However, one of the two sampled hominin teeth displayed a temporal carbon isotope shift (3.2‰) that was significantly greater than observed for co-occurring specimens. The δ13C value of this individual averaged about -16‰ early in life, and -13‰ later in life. This isotopic change occurred on the canine crown about 4.2 mm from the root, which corresponds to an approximate age of two to four years old in modern humans. Our dataset is perforce small owing to the precious nature of hominid teeth, but it demonstrates the potential utility of the intra-tooth isotope profile method for extracting ontogenetic histories of human ancestors. PMID:26673156

Seasonal Cyclicity in Trace Elements and Stable Isotopes of Modern Horse Enamel.

PubMed

de Winter, Niels J; Snoeck, Christophe; Claeys, Philippe

2016-01-01

The study of stable isotopes in fossil bioapatite has yielded useful results and has shown that bioapatites are able to faithfully record paleo-environmental and paleo-climatic parameters from archeological to geological timescales. In an effort to establish new proxies for the study of bioapatites, intra-tooth records of enamel carbonate stable isotope ratios from a modern horse are compared with trace element profiles measured using laboratory micro X-Ray Fluorescence scanning. Using known patterns of tooth eruption and the relationship between stable oxygen isotopes and local temperature seasonality, an age model is constructed that links records from six cheek upper right teeth from the second premolar to the third molar. When plotted on this age model, the trace element ratios from horse tooth enamel show a seasonal pattern with a small shift in phase compared to stable oxygen isotope ratios. While stable oxygen and carbon isotopes in tooth enamel are forced respectively by the state of the hydrological cycle and the animal's diet, we argue that the seasonal signal in trace elements reflects seasonal changes in dust intake and diet of the animal. The latter explanation is in agreement with seasonal changes observed in carbon isotopes of the same teeth. This external forcing of trace element composition in mammal tooth enamel implies that trace element ratios may be used as proxies for seasonal changes in paleo-environment and paleo-diet.

Seasonal Cyclicity in Trace Elements and Stable Isotopes of Modern Horse Enamel

PubMed Central

Snoeck, Christophe; Claeys, Philippe

2016-01-01

The study of stable isotopes in fossil bioapatite has yielded useful results and has shown that bioapatites are able to faithfully record paleo-environmental and paleo-climatic parameters from archeological to geological timescales. In an effort to establish new proxies for the study of bioapatites, intra-tooth records of enamel carbonate stable isotope ratios from a modern horse are compared with trace element profiles measured using laboratory micro X-Ray Fluorescence scanning. Using known patterns of tooth eruption and the relationship between stable oxygen isotopes and local temperature seasonality, an age model is constructed that links records from six cheek upper right teeth from the second premolar to the third molar. When plotted on this age model, the trace element ratios from horse tooth enamel show a seasonal pattern with a small shift in phase compared to stable oxygen isotope ratios. While stable oxygen and carbon isotopes in tooth enamel are forced respectively by the state of the hydrological cycle and the animal’s diet, we argue that the seasonal signal in trace elements reflects seasonal changes in dust intake and diet of the animal. The latter explanation is in agreement with seasonal changes observed in carbon isotopes of the same teeth. This external forcing of trace element composition in mammal tooth enamel implies that trace element ratios may be used as proxies for seasonal changes in paleo-environment and paleo-diet. PMID:27875538

Signal or noise? Separating grain size-dependent Nd isotope variability from provenance shifts in Indus delta sediments, Pakistan

NASA Astrophysics Data System (ADS)

Jonell, T. N.; Li, Y.; Blusztajn, J.; Giosan, L.; Clift, P. D.

2017-12-01

Rare earth element (REE) radioisotope systems, such as neodymium (Nd), have been traditionally used as powerful tracers of source provenance, chemical weathering intensity, and sedimentary processes over geologic timescales. More recently, the effects of physical fractionation (hydraulic sorting) of sediments during transport have called into question the utility of Nd isotopes as a provenance tool. Is source terrane Nd provenance resolvable if sediment transport strongly induces noise? Can grain-size sorting effects be quantified? This study works to address such questions by utilizing grain size analysis, trace element geochemistry, and Nd isotope geochemistry of bulk and grain-size fractions (<63μm, 63-125 μm, 125-250 μm) from the Indus delta of Pakistan. Here we evaluate how grain size effects drive Nd isotope variability and further resolve the total uncertainties associated with Nd isotope compositions of bulk sediments. Results from the Indus delta indicate bulk sediment ɛNd compositions are most similar to the <63 µm fraction as a result of strong mineralogical control on bulk compositions by silt- to clay-sized monazite and/or allanite. Replicate analyses determine that the best reproducibility (± 0.15 ɛNd points) is observed in the 125-250 µm fraction. The bulk and finest fractions display the worst reproducibility (±0.3 ɛNd points). Standard deviations (2σ) indicate that bulk sediment uncertainties are no more than ±1.0 ɛNd points. This argues that excursions of ≥1.0 ɛNd points in any bulk Indus delta sediments must in part reflect an external shift in provenance irrespective of sample composition, grain size, and grain size distribution. Sample standard deviations (2s) estimate that any terrigenous bulk sediment composition should vary no greater than ±1.1 ɛNd points if provenance remains constant. Findings from this study indicate that although there are grain-size dependent Nd isotope effects, they are minimal in the Indus delta such that resolvable provenance-driven trends can be identified in bulk sediment ɛNd compositions over the last 20 k.y., and that overall provenance trends remain consistent with previous findings.

Zn isotope fractionation in the komatiitic and tholeiitic lava flows of Fred's flow and Theo's flow (Ontario, Canada)

NASA Astrophysics Data System (ADS)

Mattielli, N. D.; Haenecour, P.; Debaille, V.

2010-12-01

Komatiites are subvolcanic or volcanic ultramafic rocks characterized by a high MgO content (>18 wt%) usually but not systematically associated to a spinifex texture. Komatiites are nearly exclusively Archean in age and essentially found in the greenstone belts of the oldest cratons, although some rare Proterozoic and Cretaceous examples are also known. Komatiitic flows are commonly associated with tholeiitic lavas, which have many petrological, textural and geochemical similarities with komatiites. We present new high-precision MC-ICPMS Zinc isotopic data for the komatiitic lavas of Fred’s flow and the associated tholeiitic lavas of Theo’s flow from Munro Township in the 2.7 Ga Abitibi greenstone belt (Ontario, Canada). Zinc isotopes show a significant shift between Fred’s flow (mean δ66Zn = +0.30±0.04‰ (2SD)) and Theo’s flow samples (mean δ66Zn = +0.39±0.03‰ (1)). In addition, the two flows show a systematic shift in δ66Zn between the ultrabasic level at the bottom of the sequence (= +0.51± 0.04‰ and +0.47±0.04‰ for Fred’s Flow and Theo’s Flow, respectively) and the rest of the pile (Δ = 0.21±0.01‰). According to the literature, processes of secondary alteration may cause Zn isotope fractionation. However, petrographic data indicate a slight alteration fingerprint while the geochemical study (whole rock and in-situ) shows no remobilization of HFSE and REE by secondary alteration (low-grade metamorphism and/or hydrothermal alteration). In addition, if similar levels of alteration affected the two lava flows, the alteration process cannot explain the difference of δ66Zn between Fred’s and Theo’s flows. Alternatively, this isotopic difference can be interpreted as reflecting either source effects or mineral fractionation related to spinel crystallization. The correlation between the δ66Zn values and the Cr bulk concentrations may suggest fractionation effects of Zn isotopes by the crystallization of spinel minerals. However, the conditions and the processes implying Zn isotopic fractionation during the crystallization of spinel minerals are still not much studied. Isotopic fractionation related to source effects cannot also be excluded. This latter hypothesis implies that Fred’s flow and Theo’s flow formed from two geochemical or mineralogical different mantle sources. While the geochemical data do not support or invalidate this second hypothesis, two different sources may explain the difference between the two lava flows; however, it cannot account for the isotopic variations observed at the ultrabasic levels. In conclusion, the role of mineralogy either at the origin or during the crystallization evolution should be investigated for a better understanding of Zn isotope fractionation in the mantle. (1): To validate the quality of isotopic analyses, reference materials BCR-1(basalt) (δ66Zn = +0.33±0.03‰) and HRM-27(gabbro) (+0.17±0.01‰) (n=3) have been measured.

Modeling of isotope fractionation at the catchment scale: How promising is compound specific isotope analysis (CSIA) as a tool for analyzing diffuse pollution by agrochemicals?

NASA Astrophysics Data System (ADS)

Lutz, S. R.; van Meerveld, H. J.; Waterloo, M. J.; Broers, H. P.; van Breukelen, B. M.

2012-04-01

Concentration measurements are indispensable for the assessment of subsurface and surface water pollution by agrochemicals such as pesticides. However, monitoring data is often ambiguous and easily misinterpreted as a decrease in concentration could be caused by transformation, dilution or changes in the application of the pesticide. In this context, compound specific isotope analysis (CSIA) has recently emerged as a complementary monitoring technique. It is based on the measurement of the isotopic composition (e.g. δ13C and δ2H) of the contaminant. Since transformation processes are likely accompanied by isotope fractionation, thus a change in this composition, CSIA offers the opportunity to gain additional knowledge about transport and degradation processes as well as to track pollutants back to their sources. Isotopic techniques have not yet been applied in a comprehensive way in the analysis of catchment-wide organic pollution. We therefore incorporated fractionation processes associated with the fate of pesticides into the numerical flow and solute transport model HydroGeoSphere in order to assess the feasibility of CSIA within the context of catchment monitoring. The model was set up for a hypothetical hillslope transect which drains into a river. Reactive solute transport was driven by two pesticides applications within one year and actual data for rainfall and potential evapotranspiration from a meteorological station in the Netherlands. Degradation of the pesticide was assumed to take place at a higher rate under the prevailing oxic conditions in the topsoil than in deeper, anoxic subsurface layers. In terms of CSIA, these two degradation pathways were associated with different strengths of isotope fractionation for both hydrogen and carbon atoms. By simulating changes in δ13C and δ2H, the share of the oxic and the anoxic reaction on the overall degradation could be assessed. Model results suggest that CSIA is suitable for assessing degradation of diffuse agrochemical pollutants in a relatively simple hydrological system. The simulated shifts in isotopic signals are within a range that could be detected with current isotope analytics. Concentrations in the stream vary significantly only for a short period during and after intense rainfall events. In contrast, CSIA values reveal longer response times such that isotopic shifts are likely to be detected in samples with a coarser temporal resolution. Rainfall events which result in fast lateral subsurface transport from the pollution source to the stream can be separated from those that lead to pollution migration through deeper subsurface zones with much longer travel times. Two-dimensional CSIA highlights an increasing importance of the oxic reaction in the topsoil during the wetter period of the year. In order to examine to which extent CSIA is applicable for more complex hydrological systems, it is projected to simulate isotope fractionation in a 3-dimensional catchment featuring additional processes such as migration from several pollution sources or in-stream degradation.

Using Natural Stable Calcium Isotopes to Rapidly Assess Changes in Bone Mineral Balance Using a Bed Rest Model to Induce Bone Loss

NASA Technical Reports Server (NTRS)

Morgan, J. L. L.; Skulan, J. L.; Gordon, G. E.; Smith, Scott M.; Romaniello, S. J.; Anbar, A. D.

2012-01-01

Metabolic bone diseases like osteoporosis result from the disruption of normal bone mineral balance (BMB) resulting in bone loss. During spaceflight astronauts lose substantial bone. Bed rest provides an analog to simulate some of the effects of spaceflight; including bone and calcium loss and provides the opportunity to evaluate new methods to monitor BMB in healthy individuals undergoing environmentally induced-bone loss. Previous research showed that natural variations in the Ca isotope ratio occur because bone formation depletes soft tissue of light Ca isotopes while bone resorption releases that isotopically light Ca back into soft tissue (Skulan et al, 2007). Using a bed rest model, we demonstrate that the Ca isotope ratio of urine shifts in a direction consistent with bone loss after just 7 days of bed rest, long before detectable changes in bone mineral density (BMD) occur. The Ca isotope variations tracks changes observed in urinary N-teleopeptide, a bone resorption biomarker. Bone specific alkaline phosphatase, a bone formation biomarker, is unchanged. The established relationship between Ca isotopes and BMB can be used to quantitatively translate the changes in the Ca isotope ratio to changes in BMD using a simple mathematical model. This model predicts that subjects lost 0.25 0.07% ( SD) of their bone mass from day 7 to day 30 of bed rest. Given the rapid signal observed using Ca isotope measurements and the potential to quantitatively assess bone loss; this technique is well suited to study the short-term dynamics of bone metabolism.

Changes in hydrogen isotope ratios in sequential plumage stages: an implication for the creation of isotope-base maps for tracking migratory birds.

PubMed

Duxbury, J M; Holroyd, G L; Muehlenbachs, K

2003-09-01

Accurate reference maps are important in the use of stable-isotopes to track the movements of migratory birds. Reference maps created by the analysis of samples collected from young at the nest site are more accurate than simply referring to naturally occurring patterns of hydrogen isotope ratios created by precipitation cycles. Ratios of hydrogen isotopes in the nutrients incorporated early in the development of young birds can be derived from endogenous, maternal sources. Base-maps should be created with the analysis of tissue samples from hatchlings after local the isotopic signature of exogenous nutrients is dominant. Migratory species such as Peregrine Falcons are known to use endogenous sources in the creation of their eggs, therefore knowledge of what plumage stage best represents the local hydrogen ratios would assist in the planning of nest visits. We conducted diet manipulation experiments involving Japanese Quail and Peregrine Falcons to determine the plumage stage when hydrogen isotope ratios were indicative of a switch in their food source. The natal down of both the quail and falcons reflected the diet of breeding adult females. The hydrogen isotope ratios of a new food source were dominant in the juvenile down of the young falcons, although a further shift was detected in the final juvenile plumage. The juvenile plumage is grown during weeks 3-4 after hatch on Peregrine Falcons. Nest visits for the purpose of collecting feathers for isotope-base-map creation should be made around 4 weeks after the presumed hatch of the young falcons.

Tracing metal-silicate segregation and late veneer in the Earth and the ureilite parent body with palladium stable isotopes

NASA Astrophysics Data System (ADS)

Creech, J. B.; Moynier, F.; Bizzarro, M.

2017-11-01

Stable isotope studies of highly siderophile elements (HSE) have the potential to yield valuable insights into a range of geological processes. In particular, the strong partitioning of these elements into metal over silicates may lead to stable isotope fractionation during metal-silicate segregation, making them sensitive tracers of planetary differentiation processes. We present the first techniques for the precise determination of palladium stable isotopes by MC-ICPMS using a 106Pd-110Pd double-spike to correct for instrumental mass fractionation. Results are expressed as the per mil (‰) difference in the 106Pd/105Pd ratio (δ106Pd) relative to an in-house solution standard (Pd_IPGP) in the absence of a certified Pd isotopic standard. Repeated analyses of the Pd isotopic composition of the chondrite Allende demonstrate the external reproducibility of the technique of ±0.032‰ on δ106Pd. Using these techniques, we have analysed Pd stable isotopes from a range of terrestrial and extraterrestrial samples. We find that chondrites define a mean δ106Pdchondrite = -0.19 ± 0.05‰. Ureilites reveal a weak trend towards heavier δ106Pd with decreasing Pd content, similar to recent findings based on Pt stable isotopes (Creech et al., 2017), although fractionation of Pd isotopes is significantly less than for Pt, possibly related to its weaker metal-silicate partitioning behaviour and the limited field shift effect. Terrestrial mantle samples have a mean δ106Pdmantle = -0.182 ± 0.130‰, which is consistent with a late-veneer of chondritic material after core formation.

Autotrophic fixation of geogenic CO2 by microorganisms contributes to soil organic matter formation and alters isotope signatures in a wetland mofette

NASA Astrophysics Data System (ADS)

Nowak, M. E.; Beulig, F.; von Fischer, J.; Muhr, J.; Küsel, K.; Trumbore, S. E.

2015-12-01

To quantify the contribution of autotrophic microorganisms to organic matter (OM) formation in soils, we investigated natural CO2 vents (mofettes) situated in a wetland in northwest Bohemia (Czech Republic). Mofette soils had higher soil organic matter (SOM) concentrations than reference soils due to restricted decomposition under high CO2 levels. We used radiocarbon (Δ14C) and stable carbon (δ13C) isotope ratios to characterize SOM and its sources in two mofettes and compared it with respective reference soils, which were not influenced by geogenic CO2. The geogenic CO2 emitted at these sites is free of radiocarbon and enriched in 13C compared to atmospheric CO2. Together, these isotopic signals allow us to distinguish C fixed by plants from C fixed by autotrophic microorganisms using their differences in 13C discrimination. We can then estimate that up to 27 % of soil organic matter in the 0-10 cm layer of these soils was derived from microbially assimilated CO2. Isotope values of bulk SOM were shifted towards more positive δ13C and more negative Δ14C values in mofettes compared to reference soils, suggesting that geogenic CO2 emitted from the soil atmosphere is incorporated into SOM. To distinguish whether geogenic CO2 was fixed by plants or by CO2 assimilating microorganisms, we first used the proportional differences in radiocarbon and δ13C values to indicate the magnitude of discrimination of the stable isotopes in living plants. Deviation from this relationship was taken to indicate the presence of microbial CO2 fixation, as microbial discrimination should differ from that of plants. 13CO2-labelling experiments confirmed high activity of CO2 assimilating microbes in the top 10 cm, where δ13C values of SOM were shifted up to 2 ‰ towards more negative values. Uptake rates of microbial CO2 fixation ranged up to 1.59 ± 0.16 μg gdw-1 d-1. We inferred that the negative δ13C shift was caused by the activity of autotrophic microorganisms using the Calvin-Benson-Bassham (CBB) cycle, as indicated from quantification of cbbL/cbbM marker genes encoding for RubisCO by quantitative polymerase chain reaction (qPCR) and by acetogenic and methanogenic microorganisms, shown present in the mofettes by previous studies. Combined Δ14C and δ13C isotope mass balances indicated that microbially derived carbon accounted for 8-27 % of bulk SOM in this soil layer. The findings imply that autotrophic microorganisms can recycle significant amounts of carbon in wetland soils and might contribute to observed radiocarbon reservoir effects influencing Δ14C signatures in peat deposits.

Autotrophic fixation of geogenic CO2 by microorganisms contributes to soil organic matter formation and alters isotope signatures in a wetland mofette

NASA Astrophysics Data System (ADS)

Nowak, M. E.; Beulig, F.; von Fischer, J.; Muhr, J.; Küsel, K.; Trumbore, S. E.

2015-09-01

To quantify the contribution of autotrophic microorganisms to organic matter formation (OM) in soils, we investigated natural CO2 vents (mofettes) situated in a wetland in NW Bohemia (Czech Republic). Mofette soils had higher SOM concentrations than reference soils due to restricted decomposition under high CO2 levels. We used radiocarbon (Δ14C) and stable carbon isotope ratios (δ13C) to characterize SOM and its sources in two moffetes and compared it with respective reference soils, which were not influenced by geogenic CO2. The geogenic CO2 emitted at these sites is free of radiocarbon and enriched in δ13C compared to atmospheric CO2. Together, these isotopic signals allow us to distinguish C fixed by plants from C fixed by autotrophic microorganisms using their differences in δ13C discrimination. We can then estimate that up to 27 % of soil organic matter in the 0-10 cm layer of these soils was derived from microbially assimilated CO2. Isotope values of bulk SOM were shifted towards more positive δ13C and more negative Δ14C values in mofettes compared to reference soils, suggesting that geogenic CO2 emitted from the soil atmosphere is incorporated into SOM. To distinguish whether geogenic CO2 was fixed by plants or by CO2 assimilating microorganisms, we first used the proportional differences in radiocarbon and δ13C values to indicate the magnitude of discrimination of the stable isotopes in living plants. Deviation from this relationship was taken to indicate the presence of microbial CO2 fixation, as microbial discrimination should differ from that of plants. 13CO2-labelling experiments confirmed high activity of CO2 assimilating microbes in the top 10 cm, where δ13C values of SOM were shifted up to 2 ‰ towards more negative values. Uptake rates of microbial CO2 fixation ranged up to 1.59 ± 0.16 μg gdw-1 d-1. We inferred that the negative δ13C shift was caused by the activity of chemo-lithoautotrophic microorganisms, as indicated from quantification of cbbL/cbbM marker genes encoding for RubisCO by quantitative polymerase chain reaction (qPCR) and by acetogenic and methanogenic microorganisms, shown present in the moffettes by previous studies. Combined Δ14C and δ13C isotope mass balances indicated that microbially derived carbon accounted for 8 to 27 % of bulk SOM in this soil layer. The findings imply that autotrophic organisms can recycle significant amounts of carbon in wetland soils and might contribute to observed reservoir effects influencing radiocarbon signatures in peat deposits.

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 δ18O record provides insight into the response of surficially closed, throughflow lakes to changes in hydroclimatic conditions and suggests that centennial to millennial changes in Holocene precipitation-evaporation balance forced by synoptic Pacific Ocean dynamics were coherently expressed across the greater Pacific Northwest region.

Fatty acids and stable isotopes of a marine ecosystem: Study on the Japanese anchovy ( Engraulis japonicus) food web in the Yellow Sea

NASA Astrophysics Data System (ADS)

Wan, Ruijing; Wu, Ying; Huang, Liang; Zhang, Jing; Gao, Lei; Wang, Na

2010-06-01

In recent years, the decline of the fish resource in the Yellow Sea has been dramatic. The fish community structure is changing. We determined the stable isotope and fatty acids composition in the Japanese anchovy ( Engraulis japonicus) (dominant species) food web in the Yellow Sea, China, to study the ecological variation especially in the shifting trophic level. The major fatty acids found in the species were 14:0, 16:0, 16:1 n-7, 18:0, 18:1 n-7, 18:1 n-9, 20:5 n-3, and 22:6 n-3, which made up 60-80% of the total fatty acids (FA). Scomberomorus niphonius and Conger myriaster were richer in 18:1 n-9. A higher percentage of saturated FA and lower percentage of polyunsaturated FA were found in Pseudosciaena polyactis, Chelidonichthys kumu, and Priacanthus macracanthus. A special feature of the grassfish was the high level of 20:4 n-6. An enrichment of stable carbon and nitrogen isotopes was observed from phytoplankton and zooplankton to fishes; the stable nitrogen isotope varied in the range 2.9-13.9‰ and the mean values of stable carbon isotopes of fishes tended to vary within a limited range (-19.4 to -17.9‰). Both δ 15N and specific fatty acids (such as 18:1 n-9, DHA, EPA) showed a good relationship with trophic level. A distinct change in the fatty acids signature and stable isotopes was observed for the Japanese anchovy with the increase in body length, which was independent of the variety of geographic locations. Egg and postlarva samples were richer in 16:1 n-7, 18:1 n-9, and C22:6 n-3. The major fatty acids were 16:0 and 18:1 n-9, followed by 20:5 n-3, 22:6 n-3, and 20:4 n-6, in young and adult Japanese anchovy. The shift in diet between the different life stages could be the explanation for this observation. Variations in trophic levels can be proven using stable isotope and fatty acids compositions, but this should be done with caution, such as with the application of principal components analysis in this study.

Paleo-environmental gateways in the eastern Canadian arctic - Recent isotope hydrology and diatom oxygen isotopes from Nettilling Lake, Baffin Island, Canada

NASA Astrophysics Data System (ADS)

Chapligin, B.; Narancic, B.; Meyer, H.; Pienitz, R.

2016-09-01

Nettilling Lake is located on Baffin Island, Nunavut, Canada between the areas of past warming (Canadian High Arctic to the North) and climatic stability (Northern Quebec and Labrador region to the South). Despite being the largest lake in the Nunavut region with a postglacial marine to lacustrine transition history only a few paleo-environmental investigations were completed in this area. The oxygen isotope composition of diatoms (δ18Odiatom) can provide valuable insights into paleo-environmental conditions. Here, the recent (isotope) hydrology and hydrochemical data from the lake are presented to facilitate the interpretation of a δ18Odiatom record from an 82 cm sediment core (Ni-2B). The well-mixed lake (δ18Owater = -17.4‰) is influenced by a heavier (less negative) isotope composition (-18.80‰) from Amadjuak River draining Amadjuak Lake to the South and water of lighter (more negative) isotopic composition (-16.4‰) from the Isurtuq River originating from Penny Ice Cap in the North-East. From the δ18Owater and δ18Odiatom of the topmost sample of core Ni-2B a Δ18Osilica-water of 1000 ln α(silica-water) = 40.2‰ for sub-recent diatoms of Nettilling Lake was calculated matching the known water-silica fractionation for fossil sediments well and thereby showing the general applicability of this proxy for paleo-reconstructions in this region. Extremely large δ18Odiatom variations in the core of more than 13‰ are mainly induced by changes in the isotopic composition of the lake water due to a shift from glaciomarine (δ18Odiatom = +34.6‰) through brackish (+23.4 to +27.2‰) towards lacustrine (+21.5‰) conditions (transition zones glaciomarine to brackish at 69 cm/7300 yr cal. BP and brackish to lacustrine at 35 cm/6000 yr cal. BP) associated with a shift in the degree of salinity. Our study provides the first evidence that paleo-salinity can be reconstructed by δ18Odiatom. Additionally, for the lacustrine section it could be demonstrated that δ18Odiatom may serve as a proxy for past air temperature within the same core recording a late Holocene cooling of about 4 °C being consistent with other published values for the greater Baffin region.

Isotopic signatures, foraging habitats and trophic relationships between fish and seasnakes on the coral reefs of New Caledonia

NASA Astrophysics Data System (ADS)

Brischoux, F.; Bonnet, X.; Cherel, Y.; Shine, R.

2011-03-01

A predator's species, sex and body size can influence the types of prey that it consumes, but why? Do such dietary divergences result from differences in foraging habitats, or reflect differential ability to locate, capture or ingest different types of prey? That question is difficult to answer if foraging occurs in places that preclude direct observation. In New Caledonia, amphibious sea kraits ( Laticauda laticaudata and L. saintgironsi) mostly eat eels—but the species consumed differ between snake species and vary with snake body size and sex. Because the snakes capture eels within crevices on the sea floor, it is not possible to observe snake foraging on any quantitative basis. We used stable isotopes to investigate habitat-divergence and ontogenetic shifts in feeding habits of sympatric species of sea kraits. Similarities in δ15 N (~10.5‰) values suggest that the two snake species occupy similar trophic levels in the coral-reef foodweb. However, δ13C values differed among the eight eel species consumed by snakes, as well as between the two snake species, and were linked to habitat types. Specifically, δ13C differed between soft- vs. hard-substrate eel species, and consistently differed between the soft-bottom forager L. laticaudata (~ -14.7‰) and the hard-bottom forager L. saintgironsi (~ -12.5‰). Differences in isotopic signatures within and between the two sea krait species and their prey were consistent with the hypothesis of habitat-based dietary divergence. Isotopic composition varied with body size within each of the snake species and varied with body size within some eel species, reflecting ontogenetic shifts in feeding habits of both the sea kraits and their prey. Our results support the findings of previous studies based on snake stomach contents, indicating that further studies could usefully expand these isotopic analyses to a broader range of trophic levels, fish species and spatial scales.

Carbon isotopic fractionation in lipids from methanotrophic bacteria: relevance for interpretation of the geochemical record of biomarkers

NASA Technical Reports Server (NTRS)

Summons, R. E.; Jahnke, L. L.; Roksandic, Z.

1994-01-01

Experiments with cultured aerobic methane oxidising bacteria confirm that their biomarker lipids will be significantly depleted in 13C compared to the substrate. The methanotrophic bacteria Methylococcus capsulatus and Methylomonas methanica, grown on methane and using the RuMP cycle for carbon assimilation, show maximum 13C fractionation of approximately 30% in the resultant biomass. In M. capsulatus, the maximum fractionation is observed in the earliest part of the exponential growth stage and decreases to approximately 16% as cells approach stationary phase. This change may be associated with a shift from the particulate form to the soluble form of the methane monooxygenase enzyme. Less than maximum fractionation is observed when cells are grown with reduced methane availability. Biomass of M. capsulatus grown on methanol was depleted by 9% compared to the substrate. Additional strong 13C fractionation takes place during polyisoprenoid biosynthesis in methanotrophs. The delta 13C values of individual hopanoid and steroid biomarkers produced by these organisms were as much as l0% more negative than total biomass. In individual cultures, squalene was 13C-enriched by as much as 14% compared to the triterpane skeleton of bacteriohopaneaminopentol. Much of the isotopic dispersion in lipid metabolites could be attributed to shifts in their relative abundances, combined with an overall reduction in fractionation during the growth cycle. In cells grown on methanol, where there was no apparent effect of growth stage on overall fractionation there were still significant isotopic differences between closely related lipids including a 5.3% difference between the hopane and 3 beta-methylhopane skeletons. Hopane and sterane polyisoprenoids were also 13C-depleted compared to fatty acids. These observations have significant implications for the interpretation of specific compound isotopic signatures now being measured for hydrocarbons and other lipids present in sediments and petroleum. In particular, biomarker lipids produced by a single organism do not necessarily have the same carbon isotopic composition.

Organic carbon isotope constraints on the dissolved organic carbon (DOC) reservoir at the Cryogenian-Ediacaran transition

NASA Astrophysics Data System (ADS)

Jiang, Ganqing; Wang, Xinqiang; Shi, Xiaoying; Zhang, Shihong; Xiao, Shuhai; Dong, Jin

2010-10-01

Prominent negative carbonate carbon isotope (δ 13C carb) anomalies from some Ediacaran successions are accompanied by invariant or decoupled organic carbon isotope (δ 13C org) values and have been interpreted as resulting from the remineralization of a large dissolved organic carbon (DOC) reservoir capable of buffering carbon isotopes of organic matter. This inferred oceanic DOC reservoir was thought to have initiated with the onset of Cryogenian glaciations (ca. 720 Ma) and lasted for millions of years until the late Ediacaran Period (< 560 Ma). Carbon isotope analyses of the basal Doushantuo Formation (ca. 635 Ma) in south China reveal that (1) the cap carbonate has δ 13C org around -26‰ (VPDB) and relatively low Δδ 13C (22 ± 2‰) and (2) the overlying organic-rich black shale and shaly dolostone have more negative δ 13C org (-28‰ to -35‰) and higher Δδ 13C (28‰-30‰). Both δ 13C carb and δ 13C org show a + 6‰ shift within a 4-m-thick interval overlying the Doushantuo cap carbonate. The δ 13C org values of the cap carbonate are associated with low TOC (mostly < 0.1%); their paleoceanographic significance requires further tests in other Ediacaran basins. The co-varying positive shift in δ 13C carb and δ 13C org following cap carbonate deposition is best interpreted as resulting from a rapid increase in organic carbon burial, which may have resulted in the rise of oxygen and heralded the first appearance of animals a few meters above the Doushantuo cap carbonate. The data suggest that a large oceanic DOC reservoir did not exist in the early Ediacaran ocean. Excess oceanic DOC required to explain the Ediacaran Shuram and upper Doushantuo δ 13C excursions, if it existed, had to be developed during the Ediacaran Period after cap carbonate deposition.

Palynological evidence for a southward shift of the North Atlantic Current at 2.6 Ma during the intensification of late Cenozoic Northern Hemisphere glaciation

NASA Astrophysics Data System (ADS)

Hennissen, Jan A. I.; Head, Martin J.; De Schepper, Stijn; Groeneveld, Jeroen

2014-06-01

The position of the North Atlantic Current (NAC) during the intensification of Northern Hemisphere glaciation (iNHG) has been evaluated using dinoflagellate cyst assemblages and foraminiferal geochemistry from a 260 kyr interval straddling the base of the Quaternary System from two sites: eastern North Atlantic Deep Sea Drilling Project Site 610 in the path of the present NAC and central North Atlantic Integrated Ocean Drilling Program Site U1313 in the subtropical gyre. Stable isotope and foraminiferal Mg/Ca analyses confirm cooling near the marine isotope stage (MIS) G7-G6 transition (2.74 Ma). However, a continued dominance of the dinoflagellate cyst Operculodinium centrocarpum sensu Wall and Dale (1966) indicates an active NAC in the eastern North Atlantic for a further 140 kyr. At MIS 104 ( 2.60 Ma), a profound dinoflagellate cyst assemblage turnover indicates NAC shutdown in the eastern North Atlantic, implying elevated atmospheric pressure over the Arctic and a resulting shift in the westerlies that would have driven the NAC. These findings challenge recent suggestions that there was no significant southward shift of the NAC or the Arctic Front during iNHG, and reveal a fundamental climatic reorganization near the base of the Quaternary.

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

NASA Technical Reports Server (NTRS)

Shemesh, Aldo; Peteet, Dorothy

1997-01-01

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

New developments of the in-source spectroscopy method at RILIS/ISOLDE

NASA Astrophysics Data System (ADS)

Marsh, B. A.; Andel, B.; Andreyev, A. N.; Antalic, S.; Atanasov, D.; Barzakh, A. E.; Bastin, B.; Borgmann, Ch.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Dehairs, M.; Derkx, X.; De Witte, H.; Fedorov, D. V.; Fedosseev, V. N.; Focker, G. J.; Fink, D. A.; Flanagan, K. T.; Franchoo, S.; Ghys, L.; Huyse, M.; Imai, N.; Kalaninova, Z.; Köster, U.; Kreim, S.; Kesteloot, N.; Kudryavtsev, Yu.; Lane, J.; Lecesne, N.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Molkanov, P. L.; Nicol, T.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Schweikhard, L.; Seliverstov, M. D.; Sels, S.; Sjödin, A. M.; Truesdale, V.; Van Beveren, C.; Van Duppen, P.; Wendt, K.; Wienholtz, F.; Wolf, R. N.; Zemlyanoy, S. G.

2013-12-01

At the CERN ISOLDE facility, long isotope chains of many elements are produced by proton-induced reactions in target materials such as uranium carbide. The Resonance Ionization Laser Ion Source (RILIS) is an efficient and selective means of ionizing the reaction products to produce an ion beam of a chosen isotope. Coupling the RILIS with modern ion detection techniques enables highly sensitive studies of nuclear properties (spins, electromagnetic moments and charge radii) along an isotope chain, provided that the isotope shifts and hyperfine structure splitting of the atomic transitions can be resolved. At ISOLDE the campaign to measure the systematics of isotopes in the lead region (Pb, Bi, Tl and Po) has been extended to include the gold and astatine isotope chains. Several developments were specifically required for the feasibility of the most recent measurements: new ionization schemes (Po, At); a remote controlled narrow line-width mode of operation for the RILIS Ti:sapphire laser (At, Au, Po); isobar free ionization using the Laser Ion Source Trap, LIST (Po); isobar selective particle identification using the multi-reflection time-of-flight mass separator (MR-ToF MS) of ISOLTRAP (Au, At). These are summarized as part of an overview of the current status of the in-source resonance ionization spectroscopy setup at ISOLDE.

Exploring the Middle Pleistocene Lake Suguta Sr-isotope Stratigraphic record

NASA Astrophysics Data System (ADS)

Vonhof, Hubert; Junginger, Annett; Agmon, Nadav; Trauth, Martin

2017-04-01

Several studies into the Quaternary stratigraphic record of the Sr-isotope composition of paleolake Turkana in the East African Rift System (EARS) show how variation of climate left a signal of changing lacustrine Sr isotope values. This Sr isotope signal was captured in the lacustrine fossil record of the Turkana Basin, and can be a useful chemostratigraphic tool (e.g. Joordens et al., 2011; van der Lubbe et al., submitted). Such lacustrine Sr-isotope changes are believed to be paced by orbital-forced insolation cyclicity, and interpreted to be the result of changing contribution of run-off from different sub-catchments of lake Turkana, as climate change shifted regional rainfall patterns. Here, we present a first set of data from a middle Pleistocene stratigraphical sequence in the Suguta Valley, South of the Turkana Basin in the EARS. This sequence spans a couple of sedimentological cycles that potentially represent precession-forced lake level variation. In this setting, the Sr-isotope data do not vary in phase with these sedimentological cycles, but demonstrate a long trend of Sr isotope change. This may suggest that the catchment configuration of the Suguta Valley in the Mid Pleistocene was less suitable to record precession-forced hydroclimate change in Lacustrine Sr isotope ratios. This may have implications for the Turkana Basin Sr isotope record as well, because the two basins are believed to have been hydrologically connected in the Middle Pleistocene. references: 1)Joordens, J.C.A. et al., 2011. An astronomically-tuned climate framework for hominins in the Turkana Basin. Earth and Planetary Science Letters 307, 1-8. 2)van der Lubbe et al., submitted. Gradual or abrupt? Changes in water source of Lake Turkana (Kenya) during the African Humid Period inferred from Sr isotope ratios

Reassessing the stable isotope composition assigned to methane flux from natural wetlands in isotope-constrained budgets

NASA Astrophysics Data System (ADS)

Hornibrook, Edward; Maxfield, Peter; Gauci, Vincent; Stott, Andrew

2013-04-01

Stable isotope ratios in CH4 preserve information about its origin and history, and are commonly used to constrain global CH4 budgets. Wetlands are key contributors to the atmospheric burden of CH4 and typically are assigned a stable carbon isotope composition of ~-60 permil in isotope-weighted stable isotope models despite the considerable range of δ13C(CH4) values (~ -100 to -40 permil) known to occur in these diverse ecosystems. Kinetic isotope effects (KIEs) associated with the metabolism of CH4-producing microorganisms generate much of the natural variation but highly negative and positive δ13C(CH4) values generally result from secondary processes (e.g., diffusive transport or oxidation by soil methanotrophs). Despite these complexities, consistent patterns exist in the isotope composition of wetland CH4 that can be linked conclusively to trophic status and consequently, natural succession or human perturbations that impact nutrient levels. Another challenge for accurate representation of wetlands in carbon cycle models is parameterisation of sporadic CH4 emission events. Abrupt release of large volumes of CH4-rich bubbles in short periods of time can account for a significant proportion of the annual CH4 flux from a wetland but such events are difficult to detect using conventional methods. New infrared spectroscopy techniques capable of high temporal resolution measurements of CH4 concentration and stable isotope composition can readily quantify short-lived CH4 pulses. Moreover, the isotope data can be used conclusively to determine shifts in the mode of CH4 transport and provide the potential to link initiation of abrupt emission events to forcing by internal or external factors.

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

Conroy, Jessica L; Cobb, Kim M; Noone, David

The objective of this field campaign was to investigate climatic controls on the stable isotopic composition of water vapor, precipitation, and seawater in the western tropical Pacific. Simultaneous measurements of the stable isotopic composition of vapor and precipitation from April 28 to May 8, 2013, at the Manus Tropical Western Pacific Atmospheric Radiation Measurement site, provided several key insights into the nature of the climate signal archived in precipitation and vapor isotope ratios. We observed a large shift from lower to higher isotopic values in vapor and precipitation because of the passage of a mesoscale convective system west of themore » site and a transition from a regional stormy period into a more quiescent period. During the quiescent period, the stable isotopic composition of vapor and precipitation indicated the predominance of oceanic evaporation in determining the isotopic composition of boundary-layer vapor and local precipitation. There was not a consistent relationship between intra-event precipitation amount at the site and the stable isotopic composition of precipitation, thus challenging simplified assumptions about the isotopic “amount effect” in the tropics on the time scale of individual storms. However, some storms did show an amount effect, and deuterium excess values in precipitation had a significant relationship with several meteorological variables, including precipitation, temperature, relative humidity, and cloud base height across all measured storms. The direction of these relationships points to condensation controls on precipitation deuterium excess values on intra-event time scales. The relationship between simultaneous measurements of vapor and precipitation isotope ratios during precipitation events indicates the ratio of precipitation-to-vapor isotope ratios can diagnose precipitation originating from a vapor source unique from boundary-layer vapor and rain re-evaporation.« less

Assessing connectivity of estuarine fishes based on stable isotope ratio analysis

NASA Astrophysics Data System (ADS)

Herzka, Sharon Z.

2005-07-01

Assessing connectivity is fundamental to understanding the population dynamics of fishes. I propose that isotopic analyses can greatly contribute to studies of connectivity in estuarine fishes due to the high diversity of isotopic signatures found among estuarine habitats and the fact that variations in isotopic composition at the base of a food web are reflected in the tissues of consumers. Isotopic analysis can be used for identifying nursery habitats and estimating their contribution to adult populations. If movement to a new habitat is accompanied by a shift to foods of distinct isotopic composition, recent immigrants and residents can be distinguished based on their isotopic ratios. Movement patterns thus can be reconstructed based on information obtained from individuals. A key consideration is the rate of isotopic turnover, which determines the length of time that an immigrant to a given habitat will be distinguishable from a longtime resident. A literature survey indicated that few studies have measured turnover rates in fishes and that these have focused on larvae and juveniles. These studies reveal that biomass gain is the primary process driving turnover rates, while metabolic turnover is either minimal or undetectable. Using a simple dilution model and biomass-specific growth rates, I estimated that young fishes with fast growth rates will reflect the isotopic composition of a new diet within days or weeks. Older or slower-growing individuals may take years or never fully equilibrate. Future studies should evaluate the factors that influence turnover rates in fishes during various stages of the life cycle and in different tissues, as well as explore the potential for combining stable isotope and otolith microstructure analyses to examine the relationship between demographic parameters, movement and connectivity.

Stable Isotope Analyses of Ancient Penguin Tissues Support the Krill Surplus Hypothesis in Antarctica

NASA Astrophysics Data System (ADS)

Emslie, S. D.; Polito, M. J.; Patterson, W. P.

2010-12-01

The krill surplus hypothesis in Antarctica is based on the premise that historic depletion of krill-eating whales and seals in the 18-20th centuries provided a surplus of krill in the southern ocean that benefited penguins. Previous study of δ13C and δ15N stable isotopes in ancient and modern tissues of Adélie Penguin (Pygoscelis adeliae) from dozens of active and abandoned colonies in Antarctica have provided the first test in support of this hypothesis (Emslie and Patterson 2007). Specifically, there is a significant decrease in both δ13C and δ15N isotope values in modern versus ancient Adélie Penguin tissues from an apparent dietary shift from fish to krill associated with the timing of the purported krill surplus. Here, we present new data on similar analyses of Gentoo Penguin (P. papua) tissues from active and abandoned colonies at two locations in the Antarctic Peninsula to determine if this species recorded a similar shift in its diet in association with the krill surplus. Our results demonstrate a significant decrease (1.5-2.0 ‰) in δ13C in modern versus fossil eggshells (two-tailed t-test of modern versus fossil mean values, t = 1.98, p < 0.0001) in accordance with this hypothesis. δ15N values are more variable among modern localities and probably were so in the past as well. Although we found a weak but significant decrease in δ15N (0.3 ‰) in modern versus fossil eggshell values, we do not consider this to be an adequate signal for a dietary shift. Our data also indicate that the decrease in δ13C values in Gentoo Penguins is not as large as that previously observed in Adélie Penguins (a 4-6 ‰ decrease in δ13C values). This weaker signal for the dietary shift in Gentoo Penguins probably results from a greater and more consistent reliance on fish, past and present, in this species compared to the Adélie Penguin. Emslie, S. D. and W. P. Patterson. 2007. Abrupt recent shift in δ13C and δ15N values in Adélie Penguin eggshell in Antarctica. Proceedings of the National Academy of Sciences 104: 11666-11669. A pair of Adélie Penguins with their well-fed chick.

Depth gradients in food web processes linking large lake habitats -presentation

EPA Science Inventory

In large lakes around the world, shifts in ecological communities are often associated with water depth. This suggests that there may be concomitant changes in patterns of resource allocation. Using Lake Superior as an example, we explored this idea through stable isotope analyse...

Terrestrial Plant Biomarkers Preserved in Cariaco Basin Sediments: Records of Abrupt Tropical Vegetation Response to Rapid Climate Changes

NASA Astrophysics Data System (ADS)

Hughen, K. A.; Eglinton, T. I.; Makou, M.; Xu, L.; Sylva, S.

2004-12-01

Organic-rich sediments from the anoxic Cariaco Basin, Venezuela, preserve high concentrations of biomarkers for reconstruction of terrestrial environmental conditions. Molecular-level investigations of organic compounds provide a valuable tool for extracting terrestrial signals from these annually laminated marine sediments. Differences in hydrogen isotopic fractionation between C16-18 and C24-30 n-alkanoic acids suggest a marine source for the shorter chain lengths and a terrestrial source for the longer chains. Records of carbon and hydrogen isotopes, as well as average carbon chain length (ACL), from long-chain n-alkanoic acids parallel millennial-scale changes in vegetation and climate between the late Glacial and Preboreal periods, 15,000 to 10,000 years ago. Data from all terrestrial chain lengths were combined to produce single δ D and δ 13C indices through deglaciation, exhibiting enrichment during the late Glacial and Younger Dryas and depletion during the Bolling-Allerod and Preboreal periods. δ D reflects the hydrogen isotopic composition of environmental water used for plant growth, combined with evaporative enrichment within leaf spaces, and as such may act as a proxy for local aridity. Leaf wax δ 13C, which is a proxy for C3 versus C4 metabolic pathways, indicates that C3 plants predominated in the Cariaco watershed during warm/wet Bolling-Allerod and Holocene periods, and C4 plant biomass proliferated during cool/dry Glacial and Younger Dryas intervals. Coupled carbon and hydrogen isotopic measurements together clearly distinguish deglacial climatic periods as wetter with C3 vegetation versus drier with C4 vegetation. High resolution biomarker records reveal the rapidity of vegetation changes in northern South America during the last deglaciation. The leaf wax data reveal that local vegetation biomass, although not necessarily entire assemblages, shifted between arid grassland and wetter forest taxa on timescales of decades. Comparison of ACL versus δ 13C for Cariaco Basin and NW African leaf waxes indicate that biomarkers reflect real changes in local South American vegetation and not contamination from long-distance transport during cold windy climates. The precise temporal relationship between tropical vegetation shifts and climate changes is measured by direct comparison of terrestrial vegetation and climate proxies from the same core. Abrupt deglacial climate shifts in tropical and high-latitude North Atlantic regions were synchronous, whereas changes in tropical vegetation consistently lagged climate shifts by several decades.

Early Onset of Ground State Deformation in Neutron Deficient Polonium Isotopes

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

Cocolios, T. E.; Van de Walle, J.; ISOLDE, CERN, CH-1211 Geneva 23

2011-02-04

In-source resonant ionization laser spectroscopy of the even-A polonium isotopes {sup 192-210,216,218}Po has been performed using the 6p{sup 3}7s {sup 5}S{sub 2} to 6p{sup 3}7p {sup 5}P{sub 2} ({lambda}=843.38 nm) transition in the polonium atom (Po-I) at the CERN ISOLDE facility. The comparison of the measured isotope shifts in {sup 200-210}Po with a previous data set allows us to test for the first time recent large-scale atomic calculations that are essential to extract the changes in the mean-square charge radius of the atomic nucleus. When going to lighter masses, a surprisingly large and early departure from sphericity is observed, whichmore » is only partly reproduced by beyond mean field calculations.« less

Optical magnetic resonances induced by the interference of reactive components in the near radiation-field zone of atoms in a glow discharge of a mixture of even neon isotopes

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

Saprykin, E. G., E-mail: Saprykin@gorodok.net

2016-02-15

Four types of anomalous optical magnetic resonances shifted with respect to the zero magnetic field and with different shapes are found in radiation of a glow discharge in a mixture of even neon isotopes placed in a swept longitudinal magnetic field. This testifies to the manifestation of collective processes of synchronous light emission by oscillators belonging to isotopically different spatially separated atoms in discharge plasma. The origin of resonances is associated with nonstationary interference of reactive fields in the near radiation-field zones of emission of atoms, averaged over the lifetime of the fields (interference), while different types of resonances aremore » associated with different methods of synchronization of the phases of the fields.« less

Climatic and Oceanographic Changes Across the Eocene-Oligocene Boundary: Results From South Atlantic ODP Site 1090

NASA Astrophysics Data System (ADS)

Pusz, A. E.; Thunell, R. C.; Scher, H. D.; Barbeau, D. L.; Miller, K. G.; Wright, J. D.

2008-12-01

The Eocene-Oligocene (E-O) boundary is marked by one of the largest climate transitions of the past 50 Ma. The Oi-1 event is characterized by a 1.0‰ increase in benthic foraminiferal δ 18O that occurred at ca. 33.5 Ma. This δ 18O shift has mainly been attributed to large-scale Antarctic ice- sheet growth, whereas deep-water temperature change during Oi-1 remains unresolved. However, recent studies have suggested that this event and its precursor (EOT-1) require the presence of significant ice sheets in Antarctica and the Northern Hemisphere, a eustatic lowering of ~150 meters, and ice-volume storage that is ~2.0 to 2.5 times that of modern ice sheets. We examined the δ 18O and δ 13C of the benthic foraminifera Cibicidoides from South Atlantic ODP site 1090 during Oi-1 at a 10 ka resolution. The benthic δ 18O record from site 1090 shows an overall ~1.5‰ step-wise increase composed primarily of a 0.5‰ shift at ca. 33.8 Ma followed by an even larger 1.0‰ shift at ca. 33.5 Ma, similar to the punctuated shift across the E-O transition documented at sites 1218, 522, and St. Stephens Quarry. Our benthic foraminiferal δ 13C record for site 1090 displays a 1.0‰ increase associated with Oi-1 that is coeval with the δ 18O change. In addition, we analyzed planktonic foraminiferal δ 18O and δ 13C (Subbotina) across this interval. Our planktonic δ 18O data show a transient (<200 kyr) increase of 1.5‰ at 34.0 Ma that we attribute to a change in the structure of the thermocline. A planktonic foraminiferal δ 13C decrease at ca. 34.1 Ma supports the interpretation of a stronger thermocline with a coeval drop in the vertical carbon isotope gradient between the thermocline-dwelling planktonic and deep-dwelling benthic foraminifera. Additional planktonic and benthic foraminiferal stable isotope data from South Atlantic ODP site 1265 across the E-O interval should help determine the cause of the planktonic foraminiferal δ 18O and δ 13C changes. We also investigated changes in deep water circulation patterns during Oi-1 at site 1090 using Nd isotope ratios from fossil fish teeth, which display a trend towards less radiogenic values during the E-O transition, culminating at Oi-1 (~33.5 Ma). Lower 143Nd/144Nd isotopic ratios in seawater are consistent with Nd from an ancient continental source. Thus, these results may reflect a change in the Southern Ocean endmember 143Nd/144Nd value in response to the exhumation and erosion of ancient east Antarctic craton(s) during ice sheet growth. The Nd isotope results from ODP Site 1090 corroborate findings from Kerguelan Plateau and Maud Rise sediment cores.

High regional climate sensitivity over continental China constrained by glacial-recent changes in temperature and the hydrological cycle.

PubMed

Eagle, Robert A; Risi, Camille; Mitchell, Jonathan L; Eiler, John M; Seibt, Ulrike; Neelin, J David; Li, Gaojun; Tripati, Aradhna K

2013-05-28

The East Asian monsoon is one of Earth's most significant climatic phenomena, and numerous paleoclimate archives have revealed that it exhibits variations on orbital and suborbital time scales. Quantitative constraints on the climate changes associated with these past variations are limited, yet are needed to constrain sensitivity of the region to changes in greenhouse gas levels. Here, we show central China is a region that experienced a much larger temperature change since the Last Glacial Maximum than typically simulated by climate models. We applied clumped isotope thermometry to carbonates from the central Chinese Loess Plateau to reconstruct temperature and water isotope shifts from the Last Glacial Maximum to present. We find a summertime temperature change of 6-7 °C that is reproduced by climate model simulations presented here. Proxy data reveal evidence for a shift to lighter isotopic composition of meteoric waters in glacial times, which is also captured by our model. Analysis of model outputs suggests that glacial cooling over continental China is significantly amplified by the influence of stationary waves, which, in turn, are enhanced by continental ice sheets. These results not only support high regional climate sensitivity in Central China but highlight the fundamental role of planetary-scale atmospheric dynamics in the sensitivity of regional climates to continental glaciation, changing greenhouse gas levels, and insolation.

Qualitative Distinction of Autotrophic and Heterotrophic Processes at the Leaf Level by Means of Triple Stable Isotope (C–O–H) Patterns

PubMed Central

Kimak, Adam; Kern, Zoltan; Leuenberger, Markus

2015-01-01

Foliar samples were harvested from two oaks, a beech, and a yew at the same site in order to trace the development of the leaves over an entire vegetation season. Cellulose yield and stable isotopic compositions (δ13C, δ18O, and δD) were analyzed on leaf cellulose. All parameters unequivocally define a juvenile and a mature period in the foliar expansion of each species. The accompanying shifts of the δ13C-values are in agreement with the transition from remobilized carbohydrates (juvenile period), to current photosynthates (mature phase). While the opponent seasonal trends of δ18O of blade and vein cellulose are in perfect agreement with the state-of-art mechanistic understanding, the lack of this discrepancy for δD, documented for the first time, is unexpected. For example, the offset range of 18 permil (oak veins) to 57 permil (oak blades) in δD may represent a process driven shift from autotrophic to heterotrophic processes. The shared pattern between blade and vein found for both oak and beech suggests an overwhelming metabolic isotope effect on δD that might be accompanied by proton transfer linked to the Calvin-cycle. These results provide strong evidence that hydrogen and oxygen are under different biochemical controls even at the leaf level. PMID:26635835

Qualitative Distinction of Autotrophic and Heterotrophic Processes at the Leaf Level by Means of Triple Stable Isotope (C-O-H) Patterns.

PubMed

Kimak, Adam; Kern, Zoltan; Leuenberger, Markus

2015-01-01

Foliar samples were harvested from two oaks, a beech, and a yew at the same site in order to trace the development of the leaves over an entire vegetation season. Cellulose yield and stable isotopic compositions (δ(13)C, δ(18)O, and δD) were analyzed on leaf cellulose. All parameters unequivocally define a juvenile and a mature period in the foliar expansion of each species. The accompanying shifts of the δ(13)C-values are in agreement with the transition from remobilized carbohydrates (juvenile period), to current photosynthates (mature phase). While the opponent seasonal trends of δ(18)O of blade and vein cellulose are in perfect agreement with the state-of-art mechanistic understanding, the lack of this discrepancy for δD, documented for the first time, is unexpected. For example, the offset range of 18 permil (oak veins) to 57 permil (oak blades) in δD may represent a process driven shift from autotrophic to heterotrophic processes. The shared pattern between blade and vein found for both oak and beech suggests an overwhelming metabolic isotope effect on δD that might be accompanied by proton transfer linked to the Calvin-cycle. These results provide strong evidence that hydrogen and oxygen are under different biochemical controls even at the leaf level.

Late Holocene moisture balance variability in the southwest Yukon Territory, Canada

NASA Astrophysics Data System (ADS)

Anderson, Lesleigh; Abbott, Mark B.; Finney, Bruce P.; Burns, Stephen J.

2007-01-01

Analyses of sediment cores from Marcella Lake, a small, hydrologically closed lake in the semi-arid southwest Yukon, provides effective moisture information for the last ˜4500 years at century-scale resolution. Water chemistry and oxygen isotope analyses from lakes and precipitation in the region indicate that Marcella Lake is currently enriched in 18O by summer evaporation. Past lake water values are inferred from oxygen isotope analyses of sedimentary endogenic carbonate in the form of algal Charophyte stem encrustations. A record of the δ18O composition of mean annual precipitation at Jellybean Lake, a nearby evaporation-insensitive system, provides data of simultaneous δ18O variations related to decade-to-century scale shifts in Aleutian Low intensity/position. The difference between the two isotope records, Δδ, represents 18O-enrichment in Marcella Lake water caused by summer effective moisture conditions. Results indicate increased effective moisture between ˜3000 and 1200 cal BP and two marked shifts toward increased aridity at ˜1200 and between 300 and 200 cal BP. These prominent late Holocene changes in effective moisture occurred simultaneously with changes in Aleutian Low circulation patterns over the Gulf of Alaska indicated by Jellybean Lake. The reconstructed climate patterns are consistent with the topographically controlled climatic heterogeneity observed in the coastal mountains and interior valleys of the region today.

Latitudinal change in precipitation and water vapor isotopes over Southern ocean

NASA Astrophysics Data System (ADS)

Rahul, P.

2015-12-01

The evaporation process over ocean is primary source of water vapor in the hydrological cycle. The Global Network of Isotopes in Precipitation (GNIP) dataset of rainwater and water vapor isotopes are predominantly based on continental observations, with very limited observation available from the oceanic area. Stable isotope ratios in precipitation provide valuable means to understand the process of evaporation and transport of water vapor. This is further extended in the study of past changes in climate from the isotopic composition of ice core. In this study we present latitudinal variability of water vapor and rainwater isotopic composition and compared it with factors like physical condition of sea surface water from near equator (1°S) to the polar front (56°S) during the summer time expedition of the year 2013. The water vapor and rainwater isotopes showed a sharp depletion in isotopes while progressively move southward from the tropical regions (i.e. >30°S), which follows the pattern recorded in the surface ocean water isotopic composition. From the tropics to the southern latitudes, the water vapor d18O varied between -11.8‰ to -14.7‰ while dD variation ranges between -77.7‰ to -122.2‰. Using the data we estimated the expected water vapor isotopic composition under kinetic as well as equilibrium process. Our observation suggests that the water vapor isotopic compositions are in equilibrium with the sea water in majority of cases. At one point of observation, where trajectory of air parcel originated from the continental region, we observed a large deviation from the existing trend of latitudinal variability. The deduced rainwater composition adopting equilibrium model showed a consistent pattern with observed values at the tropical region, while role of kinetic process become dominant on progressive shift towards the southern latitudes. We will draw comparison of our observation with other data available in the literature together with isotope model data during the presentation.

Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin.

PubMed

Shen, Xiaoli; Xu, Zemin; Zhang, Xichang; Yang, Fangxing

2015-11-01

In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from -29.0‰ to -26.5‰ in soil spiked with 2mg/kg lambda-cyhalothrin, and to -27.5‰ with 10mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as -2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. Copyright © 2015 Elsevier B.V. All rights reserved.

Quantum path integral simulation of isotope effects in the melting temperature of ice Ih.

PubMed

Ramírez, R; Herrero, C P

2010-10-14

The isotope effect in the melting temperature of ice Ih has been studied by free energy calculations within the path integral formulation of statistical mechanics. Free energy differences between isotopes are related to the dependence of their kinetic energy on the isotope mass. The water simulations were performed by using the q-TIP4P/F model, a point charge empirical potential that includes molecular flexibility and anharmonicity in the OH stretch of the water molecule. The reported melting temperature at ambient pressure of this model (T=251 K) increases by 6.5±0.5 and 8.2±0.5 K upon isotopic substitution of hydrogen by deuterium and tritium, respectively. These temperature shifts are larger than the experimental ones (3.8 and 4.5 K, respectively). In the classical limit, the melting temperature is nearly the same as that for tritiated ice. This unexpected behavior is rationalized by the coupling between intermolecular interactions and molecular flexibility. This coupling makes the kinetic energy of the OH stretching modes larger in the liquid than in the solid phase. However, the opposite behavior is found for intramolecular modes, which display larger kinetic energy in ice than in liquid water.

Late Eocene to present isotopic (Sr-Nd-Pb) and geochemical evolution of sediments from the Lomonosov Ridge, Arctic Ocean: Implications for continental sources and linkage with the North Atlantic Ocean

NASA Astrophysics Data System (ADS)

Stevenson, Ross; Poirier, André; Véron, Alain; Carignan, Jean; Hillaire-Marcel, Claude

2015-09-01

New geochemical and isotopic (Sr, Nd, Pb) data are presented for a composite sedimentary record encompassing the past 50 Ma of history of sedimentation on the Lomonosov Ridge in the Arctic Ocean. The sampled sediments encompass the transition of the Arctic basin from an enclosed anoxic basin to an open and ventilated oxidized ocean basin. The transition from anoxic basin to open ventilated ocean is accompanied by at least three geochemical and isotopic shifts and an increase in elements (e.g., K/Al) controlled by detrital minerals highlighting significant changes in sediment types and sources. The isotopic compositions of the sediments prior to ventilation are more variable but indicate a predominance of older crustal contributions consistent with sources from the Canadian Shield. Following ventilation, the isotopic compositions are more stable and indicate an increased contribution from younger material consistent with Eurasian and Pan-African crustal sources. The waxing and waning of these sources in conjunction with the passage of water through Fram Strait underlines the importance of the exchange of water mass between the Arctic and North Atlantic Oceans.

All-diode-laser cooling of Sr+ isotope ions for analytical applications

NASA Astrophysics Data System (ADS)

Jung, Kyunghun; Yamamoto, Kazuhiro; Yamamoto, Yuta; Miyabe, Masabumi; Wakaida, Ikuo; Hasegawa, Shuichi

2017-06-01

Trapping and cooling of Sr+ isotope ions by an all-diode-laser system has been demonstrated in order to develop a novel mass spectrometric technique in combination with ion trap-laser cooling. First, we constructed external cavity diode lasers and associated stabilization apparatus for laser cooling of Sr+ ions. The transition frequencies confirmed by optogalvanic spectroscopy enabled successful cooling of 88Sr+ ions. An image of two trapped ions has been captured by CCD camera. Minor isotopes, 84Sr+ and 86Sr+, were also cooled and trapped. From an analysis of the observed spectra of a string crystal of each isotope, the isotope shifts of the cooling transition (5s 2S1/2 → 5p 2P1/2) of Sr+ ions were determined to be +371(8) MHz for Δν84-88 and +169(8) MHz for Δν86-88. In the case of the repumping transition (4d 2D3/2 → 5p 2P1/2), Δν84-88 and Δν86-88 were measured to be -833(6) and -400(5) MHz, respectively. These values are in good agreement with previously reported values.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

Moisture source history and changes in atmospheric circulation are the most important attributes for portraying past climate changes and for estimating possible future trends. However, few climate records reflecting these attributes are available from the marginal zones of the Asian summer monsoon. Here, we present a record of the oxygen isotopic composition of authigenic carbonates (δ18Ocarb) of sequential sediments from Genggahai Lake in the northeastern Qinghai-Tibetan Plateau (QTP). Isotopic analyses were performed on the fine-grained carbonate fraction (<38 μm), mollusc shells, and stem encrustations from submerged plants. The stratigraphic variations of the δ18O record from the different carbonate components exhibit a remarkably similar pattern, probably reflecting the fact that δ18Ocarb variability was controlled primarily by changes in the oxygen isotopic composition of the lake water (δ18OLW). Disequilibrium effects and water temperature are precluded as major factors affecting the δ18Ocarb variations. Genggahai Lake is hydrologically open and characterized by a rapid discharge rate, as indicated by analysis of the hydrological setting of the lake system and by the observed significant positive correlation between δ18OLW and the oxygen isotopic composition of the inflowing water (δ18OI). Under such hydrological conditions, we argue that the isotopic signals of different moisture sources should be reflected in the carbonate isotopic composition. Furthermore, placing the δ18Ocarb record in the context of regional palaeoclimate archives, we found that the isotopic signals, particularly the negative shifts from the average values, cannot be interpreted consistently, despite a process of evaporative enrichment at the lake surface. During the early- to mid-Holocene, low δ18Ocarb values during 10.6-9.4 and 7.4-6.3 ka were associated with higher lake levels, and thus the record may have been significantly affected by a strengthened Asian summer monsoon at those times and hence by a positive moisture balance. Isotopic depletions with similar magnitudes occurred at 15-14.5, 13.8-13.3, 12.5-11.4, 5.3-4.8, 3.7-3.4, 2.8-2.3, 1.7, 1.3, and 0.6 ka, i.e., within the Lateglacial and the late Holocene. These negative shifts in δ18Ocarb corresponded to lower lake-level phases, and most likely were a response to intensification of the mid-latitude westerly circulation that may have transported significantly more 18O-depleted moisture to the region, compared to that from the Asian summer monsoon. Overall, our results suggest that the alternating influence of the Asian summer monsoon and the westerlies played a significant role in determining the pattern of atmospheric circulation on the northeastern QTP.

Sulfur and Carbon Isotope Systematics in Middle-Upper Cambrian Port au Port Group From Western Newfoundland, Canada: Implications for Seawater Sulfate Concentrations

NASA Astrophysics Data System (ADS)

Hurtgen, M. T.; Pruss, S.; Knoll, A. H.

2006-12-01

The biogeochemical cycles of carbon and sulfur are intimately linked through a variety of feedbacks that operate on timescales of days to millions of years. For example, under anaerobic conditions, some bacteria respire organic matter by sulfate reduction, reducing sulfate to sulfide, which then reacts with iron to form iron sulfide (preserved as pyrite). On much longer timescales, increases in the fraction of total carbon buried as organic carbon can drive increases in atmospheric oxygen concentrations which then facilitate an increase in the extent to which sulfides on land are oxidatively weathered and ultimately delivered to the oceans as sulfate via rivers. Interestingly, these two processes impose very different isotope relationships between the C isotope composition of marine dissolved inorganic carbon (DIC) and the S isotope composition of seawater sulfate. The former leads to a positive correlation between δ13Ccarbonate and δ34Ssulfate whereas the latter prescribes a long-term negative correlation. Of course, the recognition of either a positive or negative correlation between δ13Ccarbonate and δ34Ssulfate depends strongly on the relative sizes of the DIC and seawater sulfate reservoirs-- neither of which is well constrained for the Cambrian Period. Here, we present a high-resolution δ34S (sulfate and pyrite) and δ13Ccarbonate record from the mixed carbonate-siliciclastic Middle-Upper Cambrian Port au Port Group in western Newfoundland, Canada. The δ34Ssulfate profile displays systematic shifts of >15‰ over relatively short stratigraphic distances (10 m, likely to represent < 1 Myr). C isotope values shift sympathetically throughout much of the composite section; however, important deviations from this relationship exist. First, in the Middle Cambrian March Point Formation, a 15‰- δ34Ssulfate decrease precedes a 3‰-δ13Ccarbonate fall suggesting that the sulfur cycle recorded the perturbation to the system before the carbon cycle did. Secondly, further up in the section, the Upper Cambrian Man O' War Member exhibits a ~6‰ positive C isotope excursion (SPICE Event) with almost no change in S isotope values. In combination, these data suggest that seawater sulfate concentrations were much lower than modern values, at least in this basin, resulting in a sulfate reservoir that was more susceptible to isotopic variation. Moreover, differences in the relationship between C and S isotopes indicate that the relative sizes of the marine DIC and sulfate reservoir changed through this interval and/or that the various perturbations recorded in the lower and upper parts of this succession affected the carbon and sulfur cycles in different ways.

Glucose metabolism during rotational shift-work in healthcare workers.

PubMed

Sharma, Anu; Laurenti, Marcello C; Dalla Man, Chiara; Varghese, Ron T; Cobelli, Claudio; Rizza, Robert A; Matveyenko, Aleksey; Vella, Adrian

2017-08-01

Shift-work is associated with circadian rhythm disruption and an increased risk of obesity and type 2 diabetes. We sought to determine the effect of rotational shift-work on glucose metabolism in humans. We studied 12 otherwise healthy nurses performing rotational shift-work using a randomised crossover study design. On each occasion, participants underwent an isotope-labelled mixed meal test during a simulated day shift and a simulated night shift, enabling simultaneous measurement of glucose flux and beta cell function using the oral minimal model. We sought to determine differences in fasting and postprandial glucose metabolism during the day shift vs the night shift. Postprandial glycaemic excursion was higher during the night shift (381±33 vs 580±48 mmol/l per 5 h, p<0.01). The time to peak insulin and C-peptide and nadir glucagon suppression in response to meal ingestion was also delayed during the night shift. While insulin action did not differ between study days, the beta cell responsivity to glucose (59±5 vs 44±4 × 10 -9  min -1 ; p<0.001) and disposition index were decreased during the night shift. Impaired beta cell function during the night shift may result from normal circadian variation, the effect of rotational shift-work or a combination of both. As a consequence, higher postprandial glucose concentrations are observed during the night shift.

Amino acid stable isotope applications to deep-sea corals: A molecular geochemistry approach to reconstructing past ocean conditions

NASA Astrophysics Data System (ADS)

McMahon, K.; McCarthy, M. D.; Guilderson, T. P.; Sherwood, O.; Williams, B.; Larsen, T.; Glynn, D. S.

2017-12-01

Future climate change is predicted to alter ocean productivity, food web dynamics, biogeochemical cycling, and the efficacy of the biological pump. Proteinaceous deep-sea corals act as "living sediment traps," providing long-term, high-resolution records of exported surface ocean production and a window into past changes in ocean condition as a historical context for potential future changes. Here, we present recent work developing the application of compound-specific stable isotope analysis of individual amino acids to proteinaceous deep-sea corals to reconstruct past changes in phytoplankton community composition and biogeochemical cycling. We present new calibrations for molecular isotope comparisons between metabolically active coral polyp tissue and bioarchival proteinaceous skeleton. We then applied these techniques to deep-sea corals from the North Pacific Subtropical Gyre (NPSG) to reconstruct centennial to millennial time scale changes in phytoplankton community composition and biogeochemical cycling as a function of regional climate change. This work suggests that the NPSG has undergone multiple major phytoplankton regime shifts over the last millennium between prokaryotic and eukaryotic phytoplankton communities and associated sources of nitrogen fueling production. The most recent regime, which started around the end of the Little Ice Age and the onset of the Industrial era, is unprecedented in the last 1000 years and resulted in a 30-50% increase in diazotrophic cyanobacteria contribution to export production and an associated 17-27% increase in N2-fixation in the NPSG over last century. By offering the first direct phylogenetic context for long-term shifts in isotopic records of exported particulate organic matter, our data represent a major step forward in understanding the evolution of marine plankton community dynamics, food web architecture, biogeochemical cycling, and the climate feedback loops through the biological pump.

Feeding strategies and resource partitioning among elasmobranchs and cephalopods in Mediterranean deep-sea ecosystems

NASA Astrophysics Data System (ADS)

Valls, Maria; Rueda, Lucía; Quetglas, Antoni

2017-10-01

Cephalopods and elasmobranchs are important components of marine ecosystems, whereby knowing the ecological role they play in the structure and dynamics of trophic networks is paramount. With this aim, stomach contents and stable isotopes of the most abundant elasmobranch and cephalopod species (5 and 18 species, respectively) inhabiting deep-sea ecosystems from the western Mediterranean were analyzed. The predators investigated encompassed different taxonomic groups, such as rays and sharks within elasmobranchs, and squids, octopuses and cuttlefishes within cephalopods. Specifically, we investigated ontogenetic shifts in diet, feeding strategies and prey consumption, trophic structure and potential dietary overlap between and within both taxonomical groups. Stable isotope analysis revealed ontogenetic shifts in diet in three elasmobranch (rays and sharks) and two cephalopod (octopuses and squids) species. Isotopic data showed a contrasting food source gradient (δ13C), from pelagic (squids and cuttlefishes) to benthic (octopuses and elasmobranchs). Stomach data highlighted a great variety of trophic guilds which could be further aggregated into three broad categories: benthic, benthopelagic and pelagic feeders. The combination of both stomach content and stable isotope analyses revealed a clear food partitioning among species. Mesopelagic prey were found to be an important food resource for deep-sea elasmobranchs and cephalopods, which could be related to the strong oligotrophic conditions in the area. The observed differences in feeding strategies within cephalopods and elasmobranchs should be taken into account when defining functional groups in trophodynamic models from the western Mediterranean. Our results also revealed that cephalopods play a key role for the benthopelagic coupling, whereas demersal elasmobranchs contribute primarily to a one-way flux accumulating energy resources into deep-sea ecosystems.

Cerenkov Radiation Energy Transfer (CRET) Imaging: A Novel Method for Optical Imaging of PET Isotopes in Biological Systems

PubMed Central

Dothager, Robin S.; Goiffon, Reece J.; Jackson, Erin; Harpstrite, Scott; Piwnica-Worms, David

2010-01-01

Background Positron emission tomography (PET) allows sensitive, non-invasive analysis of the distribution of radiopharmaceutical tracers labeled with positron (β+)-emitting radionuclides in small animals and humans. Upon β+ decay, the initial velocity of high-energy β+ particles can momentarily exceed the speed of light in tissue, producing Cerenkov radiation that is detectable by optical imaging, but is highly absorbed in living organisms. Principal Findings To improve optical imaging of Cerenkov radiation in biological systems, we demonstrate that Cerenkov radiation from decay of the PET isotopes 64Cu and 18F can be spectrally coupled by energy transfer to high Stokes-shift quantum nanoparticles (Qtracker705) to produce highly red-shifted photonic emissions. Efficient energy transfer was not detected with 99mTc, a predominantly γ-emitting isotope. Similar to bioluminescence resonance energy transfer (BRET) and fluorescence resonance energy transfer (FRET), herein we define the Cerenkov radiation energy transfer (CRET) ratio as the normalized quotient of light detected within a spectral window centered on the fluorophore emission divided by light detected within a spectral window of the Cerenkov radiation emission to quantify imaging signals. Optical images of solutions containing Qtracker705 nanoparticles and [18F]FDG showed CRET ratios in vitro as high as 8.8±1.1, while images of mice with subcutaneous pseudotumors impregnated with Qtracker705 following intravenous injection of [18F]FDG showed CRET ratios in vivo as high as 3.5±0.3. Conclusions Quantitative CRET imaging may afford a variety of novel optical imaging applications and activation strategies for PET radiopharmaceuticals and other isotopes in biomaterials, tissues and live animals. PMID:20949021

Cerenkov radiation energy transfer (CRET) imaging: a novel method for optical imaging of PET isotopes in biological systems.

PubMed

Dothager, Robin S; Goiffon, Reece J; Jackson, Erin; Harpstrite, Scott; Piwnica-Worms, David

2010-10-11

Positron emission tomography (PET) allows sensitive, non-invasive analysis of the distribution of radiopharmaceutical tracers labeled with positron (β(+))-emitting radionuclides in small animals and humans. Upon β(+) decay, the initial velocity of high-energy β(+) particles can momentarily exceed the speed of light in tissue, producing Cerenkov radiation that is detectable by optical imaging, but is highly absorbed in living organisms. To improve optical imaging of Cerenkov radiation in biological systems, we demonstrate that Cerenkov radiation from decay of the PET isotopes (64)Cu and (18)F can be spectrally coupled by energy transfer to high Stokes-shift quantum nanoparticles (Qtracker705) to produce highly red-shifted photonic emissions. Efficient energy transfer was not detected with (99m)Tc, a predominantly γ-emitting isotope. Similar to bioluminescence resonance energy transfer (BRET) and fluorescence resonance energy transfer (FRET), herein we define the Cerenkov radiation energy transfer (CRET) ratio as the normalized quotient of light detected within a spectral window centered on the fluorophore emission divided by light detected within a spectral window of the Cerenkov radiation emission to quantify imaging signals. Optical images of solutions containing Qtracker705 nanoparticles and [(18)F]FDG showed CRET ratios in vitro as high as 8.8±1.1, while images of mice with subcutaneous pseudotumors impregnated with Qtracker705 following intravenous injection of [(18)F]FDG showed CRET ratios in vivo as high as 3.5±0.3. Quantitative CRET imaging may afford a variety of novel optical imaging applications and activation strategies for PET radiopharmaceuticals and other isotopes in biomaterials, tissues and live animals.

Rates for neutron-capture reactions on tungsten isotopes in iron meteorites. [Abstract only

NASA Technical Reports Server (NTRS)

Masarik, J.; Reedy, R. C.

1994-01-01

High-precision W isotopic analyses by Harper and Jacobsen indicate the W-182/W-183 ratio in the Toluca iron meteorite is shifted by -(3.0 +/- 0.9) x 10(exp -4) relative to a terrestrial standard. Possible causes of this shift are neutron-capture reactions on W during Toluca's approximately 600-Ma exposure to cosmic ray particles or radiogenic growth of W-182 from 9-Ma Hf-182 in the silicate portion of the Earth after removal of W to the Earth's core. Calculations for the rates of neutron-capture reactions on W isotopes were done to study the first possibility. The LAHET Code System (LCS) which consists of the Los Alamos High Energy Transport (LAHET) code and the Monte Carlo N-Particle(MCNP) transport code was used to numerically simulate the irradiation of the Toluca iron meteorite by galactic-cosmic-ray (GCR) particles and to calculate the rates of W(n, gamma) reactions. Toluca was modeled as a 3.9-m-radius sphere with the composition of a typical IA iron meteorite. The incident GCR protons and their interactions were modeled with LAHET, which also handled the interactions of neutrons with energies above 20 MeV. The rates for the capture of neutrons by W-182, W-183, and W-186 were calculated using the detailed library of (n, gamma) cross sections in MCNP. For this study of the possible effect of W(n, gamma) reactions on W isotope systematics, we consider the peak rates. The calculated maximum change in the normalized W-182/W-183 ratio due to neutron-capture reactions cannot account for more than 25% of the mass 182 deficit observed in Toluca W.

Long-term feeding ecology and habitat use in harbour porpoises Phocoena phocoena from Scandinavian waters inferred from trace elements and stable isotopes.

PubMed

Fontaine, Michaël C; Tolley, Krystal A; Siebert, Ursula; Gobert, Sylvie; Lepoint, Gilles; Bouquegneau, Jean-Marie; Das, Krishna

2007-01-17

We investigated the feeding ecology and habitat use of 32 harbour porpoises by-caught in 4 localities along the Scandinavian coast from the North Sea to the Barents Sea using time-integrative markers: stable isotopes (delta13C, delta15N) and trace elements (Zn, Cu, Fe, Se, total Hg and Cd), in relation to habitat characteristics (bathymetry) and geographic position (latitude). Among the trace elements analysed, only Cd, with an oceanic specific food origin, was found to be useful as an ecological tracer. All other trace elements studied were not useful, most likely because of physiological regulation and/or few specific sources in the food web. The delta13C, delta15N signatures and Cd levels were highly correlated with each other, as well as with local bathymetry and geographic position (latitude). Variation in the isotopic ratios indicated a shift in harbour porpoise's feeding habits from pelagic prey species in deep northern waters to more coastal and/or demersal prey in the relatively shallow North Sea and Skagerrak waters. This result is consistent with stomach content analyses found in the literature. This shift was associated with a northward Cd-enrichment which provides further support to the Cd 'anomaly' previously reported in polar waters and suggests that porpoises in deep northern waters include Cd-contaminated prey in their diet, such as oceanic cephalopods. As stable isotopes and Cd provide information in the medium and the long term respectively, the spatial variation found, shows that harbour porpoises experience different ecological regimes during the year along the Scandinavian coasts, adapting their feeding habits to local oceanographic conditions, without performing extensive migration.

A late Pleistocene refugium in Mediterranean North Africa? Palaeoenvironmental reconstruction from stable isotope analyses of land snail shells (Haua Fteah, Libya)

NASA Astrophysics Data System (ADS)

Prendergast, A. L.; Stevens, R. E.; O'Connell, T. C.; Hill, E. A.; Hunt, C. O.; Barker, G. W.

2016-05-01

The late Pleistocene to Holocene archaeological record of North Africa is key to understanding the emergence of anatomically modern humans into West Asia and Europe, and the broadening of subsistence strategies in the shift from hunter-gatherer to pastoral-agricultural lifeways. Some contend that these developments were modulated by major shifts in climate and environment. Evaluation of this hypothesis requires the pairing of local and regional climate records with well-dated archaeological sequences. The Haua Fteah archaeological site in the Gebel Akhdar region of Libya provides a key site to test this hypothesis as the cave contains one of the longest and most complete sequences of human occupation in North Africa as well as abundant material for palaeoenvironmental reconstruction. This study uses stable isotope analyses (δ18O and δ13C) of the terrestrial mollusc Helix melanostoma to construct a palaeoenvironmental framework for interpreting North African human-environment interactions from the Upper Palaeolithic to the Neolithic (∼30,000 to 5000 years ago). The land snail stable isotope records from Haua Fteah suggests that cool arid conditions in the cave peaked during marine isotope stage (MIS) 2. This stage was, however, only marginally drier than previous and subsequent stages and coincided with an increase in occupation density in the cave. This suggests that the Gebel Akhdar may have served as an environmental refugium from the more extreme aridity in the surrounding Sahara and arid coastal plains for Late Stone Age (LSA) populations in North Africa. Conditions became progressively wetter towards the Holocene. However, generally wetter conditions were interrupted by two arid episodes at c. 8.0 ka and 7.3 ka that appear to coincide with regional changes reflected elsewhere in the Mediterranean basin.

Isotope effects in liquid water probed by transmission mode x-ray absorption spectroscopy at the oxygen K-edge.

PubMed

Schreck, Simon; Wernet, Philippe

2016-09-14

The effects of isotope substitution in liquid water are probed by x-ray absorption spectroscopy at the O K-edge as measured in transmission mode. Confirming earlier x-ray Raman scattering experiments, the D2O spectrum is found to be blue shifted with respect to H2O, and the D2O spectrum to be less broadened. Following the earlier interpretations of UV and x-ray Raman spectra, the shift is related to the difference in ground-state zero-point energies between D2O and H2O, while the difference in broadening is related to the difference in ground-state vibrational zero-point distributions. We demonstrate that the transmission-mode measurements allow for determining the spectral shapes with unprecedented accuracy. Owing in addition to the increased spectral resolution and signal to noise ratio compared to the earlier measurements, the new data enable the stringent determination of blue shift and broadening in the O K-edge x-ray absorption spectrum of liquid water upon isotope substitution. The results are compared to UV absorption data, and it is discussed to which extent they reflect the differences in zero-point energies and vibrational zero-point distributions in the ground-states of the liquids. The influence of the shape of the final-state potential, inclusion of the Franck-Condon structure, and differences between liquid H2O and D2O resulting from different hydrogen-bond environments in the liquids are addressed. The differences between the O K-edge absorption spectra of water from our transmission-mode measurements and from the state-of-the-art x-ray Raman scattering experiments are discussed in addition. The experimentally extracted values of blue shift and broadening are proposed to serve as a test for calculations of ground-state zero-point energies and vibrational zero-point distributions in liquid H2O and D2O. This clearly motivates the need for new calculations of the O K-edge x-ray absorption spectrum of liquid water.

Quantifying seasonal shifts in nitrogen sources to Oregon estuaries using a transport model combined with stable isotopes

EPA Science Inventory

Identifying the sources of dissolved inorganic nitrogen (DIN) in estuaries is complicated by the multiple sources, temporal variability in inputs, and variations in transport. We used a hydrodynamic model to simulate the transport and uptake of three sources of DIN (oceanic, riv...

Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

USGS Publications Warehouse

Schimmelmann, A.; Mastalerz, Maria; Gao, L.; Sauer, P.E.; Topalov, K.

2009-01-01

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., 2H/1H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., {single bond}OH, {single bond}COOH, {single bond}NH2). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ???2.5 to ???3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong ??13Ckerogen vs. ??15Nkerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate ??13CVPDB and ??18OVSMOW values are consistent with thermal generation of 13C-depleted and 18O-enriched CO2 from decarboxylation and pyrolysis of organic matter. Lower background concentrations of 13C-enriched carbonate in thermally unaffected coal may be linked to 13C-enrichment in residual CO2 in the process of CO2 reduction via microbial methanogenesis. Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic ??D values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) ??13C and ??15N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen. ?? 2009 Elsevier Ltd. All rights reserved.

Stable Isotopic signatures of Adélie penguin remains provide long-term paleodietary records in Northern Victoria Land (Ross Sea, Antarctica)

NASA Astrophysics Data System (ADS)

Lorenzini, Sandra; Baroni, Carlo; Fallick, Anthony Edward; Baneschi, Ilaria; Salvatore, Maria Cristina; Zanchetta, Giovanni; Dallai, Luigi

2010-05-01

The stable isotopes geochemistry of carbon and nitrogen provides a powerful tools for investigating in animal dietary patterns and shifts during the past. The signature of C and N isotopes provide direct information about the diet of an individual and its dietary patterns, especially when the dietary sources consist of prey from different trophic levels (i.e. different C and N isotopic composition) (DeNiro and Epstein 1978, Minawaga and Wada 1984, Koch et al. 1994, Hobson 1995). By analyzing the isotopic composition of penguin remains, we present a new detailed Adélie penguin (Pygoscelis adeliae) paleodietary record for the area of Terra Nova Bay (Victoria Land, Ross Sea). Adélie penguins primarily feed on fish (mainly the silverfish Pleuragramma antarcticum) and krill (Euphausia superba, Euphausia cristallorophias) (Ainley 2002, Lorenzini et al. 2009) that belonging to two different trophic levels. Consequently, they are characterized by different isotopic signatures. Specifically, we analyzed 13C/12C and 15N/14N ratios of more than one thousand of modern and fossil Adélie penguin eggshell and guano samples collected from ornithogenic soils (penguin guano-formed) dated back to ≈7,200 years BP (Baroni and Orombelli 1994, Lambert et al. 2002, Baroni and Hall 2004, Hall et al. 2006). The expanded database of stable isotope values obtained from Adélie penguin remains define a detailed paleodietary record with an excellent temporal continuity over all the investigated time period. Our data indicate a significant dietary shift between fish and krill, with a gradual decrease from past to present time in the proportion of fish compared to krill in Adélie penguin diet. From 7200 yrs BP to 2000 yrs BP, δ13C and δ15N values indicate fish as the most eaten prey. The dietary contribution of lower-trophic prey in penguin diet started becoming evident not earlier than 2000 yrs BP, when the δ13C values reveal a mixed diet based on fish and krill consumption. Modern eggshell and guano δ15N values document a major dietary contribution of krill but not a krill-dominated diet, since δ13C values remain much too high if krill prevail in the diet. According to the Holocene environmental background attested for Victoria Land, Adélie penguin dietary shifts between fish and krill seem to reflect penguin paleoecological responses to different paleoenvironmental setting with different conditions of sea-ice extension and persistence. References Baroni C, Hall BL (2004) A new Holocene relative sea-level curve for Terra Nova Bay, Victoria Land, Antarctica. J Quaternary Sci 19:377-396. Baroni C, Orombelli G (1994) Abandoned penguin rookeries as Holocene paleoclimatic indicators in Antarctica. Geology 22:23-26. DeNiro MJ, Epstein S (1978) Influences of diet on the distribution of carbon isotopes in animals. Geochim Cosmochim Ac 42(5):495-506. Hall BL, Hoelzel AR, Baroni C, Denton GH, Le Boeuf BJ, Overturf B, Töpf AL (2006) Holocene elephant seal distribution implies warmer-than-present climate in the Ross Sea. P Natl Acad Sci Usa 103:10213-10217. Hobson KA (1995) Reconstructing avian diets using stable-carbon and nitrogen isotope analysis of egg components: patterns of isotopic fractionation and turnover. The Condor 97:752-762. Koch PL, Fogel ML, Tuross N (1994) Tracing the diet of fossil animals using stable isotopes. Pages 63-92 in K. Lajtha and R. H. Michener, editors. Stable isotopes in ecology and environmental science. Blackwell Scientific Publications, USA. Lambert DM, Ritchie PA, Millar CD, Holland B, Drummond AJ, Baroni C (2002) Rates of evolution in Ancient DNA from Adélie Penguins. Science 295:2270-2273. Lorenzini S, Olmastroni S, Pezzo F, Salvatore MC, Baroni C (2009) Holocene Adélie penguin diet in Victoria Land, Antarctica. Polar Biol 32:1077-1086. Minagawa M, Wada E (1984) Stepwise enrichment of δ15N along food chains: further evidence and the relation between δ15N and animal age. Geochim Cosmochim Ac 48:1135-1140.

Seabird satellite tracking validates the use of latitudinal isoscapes to depict predators' foraging areas in the Southern Ocean.

PubMed

Jaeger, Audrey; Lecomte, Vincent J; Weimerskirch, Henri; Richard, Pierre; Cherel, Yves

2010-12-15

Stable isotopes are increasingly being used to trace wildlife movements. A fundamental prerequisite of animal isotopic tracking is a good knowledge of spatial isotopic variations in the environment. Few accessible reference maps of the isotopic landscape ("isoscapes") are available for marine predators. Here, we validate for the first time an isotopic gradient for higher trophic levels by using a unique combination of a large number of satellite-tracks and subsequent blood plasma isotopic signatures from a wide-ranging oceanic predator. The plasma δ(13)C and δ(15)N values of wandering albatrosses (n = 45) were highly and positively correlated to the Southern Ocean latitudes at which the satellite-tracked individuals foraged. The well-defined latitudinal baseline carbon isoscapes in the Southern Ocean is thus reflected in the tissue of consumers, but with a positive shift due to the cumulative effect of a slight (13)C-enrichment at each trophic level. The data allowed us to estimate the carbon isotopic position of the main oceanic fronts in the area, and thus to delineate robust isoscapes of the main foraging zones for top predators. The plasma δ(13)C and δ(15)N values were positively and linearly correlated, thus suggesting that latitudinal isoscapes also occur for δ(15)N at the base of the food web in oceanic waters of the Southern Ocean. The combination of device deployments with sampling of relevant tissues for isotopic analysis appears to be a powerful tool for investigating consumers' isoscapes at various spatio-temporal scales. Copyright © 2010 John Wiley & Sons, Ltd.

Coordinated Isotopic and Mineral Characterization of Highly Fractionated 18O-Rich Silicates in the Queen Alexandra Range 99177 CR3 Chondrite

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Keller, L. P.; Messenger, S.; Rahman, Z.

2016-01-01

Carbonaceous chondrites contain a mixture of solar system condensates, pre-solar grains, and primitive organic matter. Each of these materials record conditions and processes in different regions of the solar nebula, on the meteorite parent body, and beyond the solar system. Oxygen isotopic studies of meteorite components can trace interactions of distinct oxygen isotopic reservoirs in the early solar system and secondary alteration processes. The O isotopic compositions of the earliest solar system condensates fall along a carbonaceous chondrite anhydrous mineral (CCAM) line of slope approximately 1 in a plot of delta 17O against delta 18O. This trend is attributed to mixing of material from 16O-poor and 16O-rich reservoirs. Secondary processing can induce mass-dependent fractionation of the O isotopes, shifting these compositions along a line of slope approximately 0.52. Substantial mass-dependent fractionation of O isotopes has been observed in secondary minerals in CAIs, calcite, and FUN inclusions. These fractionations were caused by significant thermal or aqueous alteration. We recently reported the identification of four silicate grains with extremely fractionated O isotopic ratios (delta 18O equals 37 - 55 per mille) in the minimally altered CR3 chondrite QUE 99177. TEM analysis of one grain indicates it is a nebular condensate that did not experience substantial alteration. The history of these grains is thus distinct from those of the aforementioned fractionated materials. To constrain the origin of the silicate grains, we conducted further Mg and Fe isotopic studies and TEM analyses of two grains.

Neutron capture on Pt isotopes in iron meteorites and the Hf-W chronology of core formation in planetesimals

NASA Astrophysics Data System (ADS)

Kruijer, Thomas S.; Fischer-Gödde, Mario; Kleine, Thorsten; Sprung, Peter; Leya, Ingo; Wieler, Rainer

2013-01-01

The short-lived 182Hf-182W isotope system can provide powerful constraints on the timescales of planetary core formation, but its application to iron meteorites is hampered by neutron capture reactions on W isotopes resulting from exposure to galactic cosmic rays. Here we show that Pt isotopes in magmatic iron meteorites are also affected by capture of (epi)thermal neutrons and that the Pt isotope variations are correlated with variations in 182W/184W. This makes Pt isotopes a sensitive neutron dosimeter for correcting cosmic ray-induced W isotope shifts. The pre-exposure 182W/184W derived from the Pt-W isotope correlations of the IID, IVA and IVB iron meteorites are higher than most previous estimates and are more radiogenic than the initial 182W/184W of Ca-Al-rich inclusions (CAI). The Hf-W model ages for core formation range from +1.6±1.0 million years (Ma; for the IVA irons) to +2.7±1.3 Ma after CAI formation (for the IID irons), indicating that there was a time gap of at least ˜1 Ma between CAI formation and metal segregation in the parent bodies of some iron meteorites. From the Hf-W ages a time limit of <1.5-2 Ma after CAI formation can be inferred for the accretion of the IID, IVA and IVB iron meteorite parent bodies, consistent with earlier conclusions that the accretion of differentiated planetesimals predated that of most chondrite parent bodies.

Using the Abitibi Greenstone Belt to Understand Martian Hydrothermal Systems and the Potential for Biosignature Preservation in High Temperature Aqueous Environments

NASA Technical Reports Server (NTRS)

Hurowitz, J.; Abelson, J.; Allwood, A.; Anderson, R.; Atkinson, B.; Beaty, D.; Bristow, T.; Ehlmann, B.; Eigenbrode, J.; Grotzinger, J.;

Stable isotope turnover and half-life in animal tissues: a literature synthesis.

PubMed

Vander Zanden, M Jake; Clayton, Murray K; Moody, Eric K; Solomon, Christopher T; Weidel, Brian C

2015-01-01

Stable isotopes of carbon, nitrogen, and sulfur are used as ecological tracers for a variety of applications, such as studies of animal migrations, energy sources, and food web pathways. Yet uncertainty relating to the time period integrated by isotopic measurement of animal tissues can confound the interpretation of isotopic data. There have been a large number of experimental isotopic diet shift studies aimed at quantifying animal tissue isotopic turnover rate λ (%·day(-1), often expressed as isotopic half-life, ln(2)/λ, days). Yet no studies have evaluated or summarized the many individual half-life estimates in an effort to both seek broad-scale patterns and characterize the degree of variability. Here, we collect previously published half-life estimates, examine how half-life is related to body size, and test for tissue- and taxa-varying allometric relationships. Half-life generally increases with animal body mass, and is longer in muscle and blood compared to plasma and internal organs. Half-life was longest in ecotherms, followed by mammals, and finally birds. For ectotherms, different taxa-tissue combinations had similar allometric slopes that generally matched predictions of metabolic theory. Half-life for ectotherms can be approximated as: ln (half-life) = 0.22*ln (body mass) + group-specific intercept; n = 261, p<0.0001, r2 = 0.63. For endothermic groups, relationships with body mass were weak and model slopes and intercepts were heterogeneous. While isotopic half-life can be approximated using simple allometric relationships for some taxa and tissue types, there is also a high degree of unexplained variation in our models. Our study highlights several strong and general patterns, though accurate prediction of isotopic half-life from readily available variables such as animal body mass remains elusive.

Ca, Sr, O and D isotope approach to defining the chemical evolution of hydrothermal fluids: example from Long Valley, CA, USA

USGS Publications Warehouse

Brown, Shaun T.; Kennedy, B. Mack; DePaolo, Donald J.; Hurwitz, Shaul; Evans, William C.

2013-01-01

We present chemical and isotopic data for fluids, minerals and rocks from the Long Valley meteoric-hydrothermal system. The samples encompass the presumed hydrothermal upwelling zone in the west moat of the caldera, the Casa Diablo geothermal field, and a series of wells defining a nearly linear, ∼16 km long, west-to-east trend along the likely fluid flow path. Fluid samples were analyzed for the isotopes of water, Sr, and Ca, the concentrations of major cations and anions, alkalinity, and total CO2. Water isotope data conform to trends documented in earlier studies, interpreted as indicating a single hydrothermal fluid mixing with local groundwater. Sr isotopes show subtle changes along the flow path, which requires rapid fluid flow and minimal reaction between the channelized fluids and the wallrocks. Sr and O isotopes are used to calculate fracture spacing using a dual porosity model. Calculated fracture spacing and temperature data for hydrothermal fluids indicate the system is (approximately) at steady-state. Correlated variations among total CO2, and the concentration and isotopic composition of Ca suggest progressive fluid degassing (loss of CO2), which drives calcite precipitation as the fluid flows west-to-east and cools. The shifts in Ca isotopes require that calcite precipitated at temperatures of 150–180 °C is fractionated by ca. −0.3‰ to −0.5‰ relative to aqueous species. Our data are the first evidence that Ca isotopes undergo kinetic fractionation at high temperatures (>100 °C) and can be used to trace calcite precipitation along hydrothermal fluid flow paths.

Selenium stable isotope ratios in California agricultural drainage water management systems

USGS Publications Warehouse

Herbel, M.J.; Johnson, T.M.; Tanji, K.K.; Gao, S.; Bullen, T.D.

2002-01-01

Selenium stable isotope ratios are known to shift in predictable ways during various microbial, chemical, and biological processes, and can be used to better understand Se cycling in contaminated environments. In this study we used Se stable isotopes to discern the mechanisms controlling the transformation of oxidized, aqueous forms of Se to reduced, insoluble forms in sediments of Se-affected environments. We measured 80Se/76Se in surface waters, shallow ground waters, evaporites, digested plants and sediments, and sequential extracts from several sites where agricultural drainage water is processed in the San Joaquin Valley of California. Selenium isotope analyses of samples obtained from the Tulare Lake Drainage District flow-through wetland reveal small isotopic contrasts (mean difference 0.7%o) between surface water and reduced Se species in the underlying sediments. Selenium in aquatic macrophytes was very similar isotopically to the NaOH and Na2SO3 sediment extracts designed to recover soluble organic Se and Se(O), respectively. For the integrated on-farm drainage management sites, evaporite salts were slightly (approximately 0.6%o) enriched in the heavier isotope relative to the inferred parent waters, whereas surface soils were slightly (approximately 1.4%o) depleted. Bacterial or chemical reduction of Se(VI) or Se(IV) may be occurring at these sites, but the small isotopic contrasts suggest that other, less isotopically fractionating mechanisms are responsible for accumulation of reduced forms in the sediments. These findings provide evidence that Se assimilation by plants and algae followed by deposition and mineralization is the dominant transformation pathway responsible for accumulation of reduced forms of Se in the wetland sediments.

Stable isotopes document resource partitioning and effects of forest disturbance on sympatric cheirogaleid lemurs

NASA Astrophysics Data System (ADS)

Crowley, B. E.; Blanco, M. B.; Arrigo-Nelson, S. J.; Irwin, M. T.

2013-10-01

The future of Madagascar’s forests and their resident lemurs is precarious. Determining how species respond to forest fragmentation is essential for management efforts. We use stable isotope biogeochemistry to investigate how disturbance affects resource partitioning between two genera of cheirogaleid lemurs ( Cheirogaleus and Microcebus) from three humid forest sites: continuous and fragmented forest at Tsinjoarivo, and selectively logged forest at Ranomafana. We test three hypotheses: (H1) cheirogaleids are unaffected by forest fragmentation, (H2) species respond individually to disturbance and may exploit novel resources in fragmented habitat, and (H3) species alter their behavior to rely on the same key resource in disturbed forest. We find significant isotopic differences among species and localities. Carbon data suggest that Microcebus feed lower in the canopy than Cheirogaleus at all three localities and that sympatric Cheirogaleus crossleyi and C. sibreei feed at different canopy heights in the fragmented forest. Microcbus have higher nitrogen isotope values than Cheirogaleus at all localities, indicating more faunivory. After accounting for baseline isotope values in plants, our results provide the most support for H3. We find similar isotopic variations among localities for both genera. Small differences in carbon among localities may reflect shifts in diet or habitat use. Elevated nitrogen values for cheirogaleid lemurs in fragments may reflect increased arthropod consumption or nutritional stress. These results suggest that cheirogaleids are affected by forest disturbance in Eastern Madagascar and stress the importance of accounting for baseline isotopic differences in plants in any work comparing localities.

North Pacific Atmospheric Circulation Change and Effective Moisture Variability in the Yukon Territory, Canada

NASA Astrophysics Data System (ADS)

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

2005-12-01

Analyses of sediment cores from Marcella Lake, a small, hydrologically-closed lake in the semi-arid interior southwest Yukon Territory, provide evaporation information for the last 4500 years at century-scale resolution. Water chemistry and oxygen isotope data from lakes and precipitation in the region indicate that oxygen isotope ratios from Marcella Lake are currently affected by summer evaporation. Past lake water changes were reconstructed from oxygen isotope analyses of sedimentary endogenic calcite. An oxygen isotope record of mean-annual precipitation from Jellybean Lake, a nearby open evaporation-insensitive system, provides simultaneous oxygen isotope ratio variations related to atmospheric circulation and ambient temperature. The difference between the two isotope records represents oxygen-18-enrichment in Marcella Lake water caused by summer evaporation. The oxygen isotope results indicate a prolonged period of lower evaporation between 3000 and 1500 cal BP, a finding that is consistent with independent evidence for higher lake levels during this period (i.e. increased effective moisture). The data indicate that since 1500 cal BP evaporation has increased and that during the last 200 years it has been greater than during the previous ~4000 years. Two prominent increases in evaporation occurred at 1200 and 200 cal BP. These shifts correspond with increases in aridity observed in other records of effective moisture variability in the interior southwest Yukon and with prominent changes in North Pacific atmospheric circulation patterns over the Gulf of Alaska.

Transgenerational isotopic marking of carp Cyprinus carpio, L. using a 86Sr /84Sr double spike

NASA Astrophysics Data System (ADS)

Zitek, Andreas; Cervicek, Magdalena; Irrgeher, Johanna; Horsky, Monika; Kletzl, Manfred; Weismann, Thomas; Prohaska, Thomas

2013-04-01

Transgenerational isotopic marking has been recognized recently as an effective tool for mass marking and tracking of individual fish to their original source. Compared to other conventional marking techniques, transgenerational marking offers several advantages. Most importantly, it is possible to mark all offspring of one individual female without the necessity of handling eggs or larval fish. Furthermore it is possible to vary the concentrations of individual isotopes to obtain specific marks for individual female fish. An enriched isotopic spike solution is usually applied to gravid female spawners by injection into the body cavity for transgenerational marking. The isotope is then incorporated into the central otolith region of the offspring which is known to be built up by maternally derived material. Within this study transgenerational marking of a typical cyprinid fish species, Cyprinus carpio, L., was tested using a 86Sr /84Sr double spike. Buffered solutions with different isotopic composition and concentrations were administered to 4 female individuals by intraperitoneal injection 5 days before spawning, while one female was injected a blank solution. After spawning, otoliths (Lapilli) from juvenile fish were sampled at the age of about 5 months at fish sizes between 3 and 4 cm and analyzed for their isotopic composition by LA-ICPMS applying cross sectional line scans. Central otolith regions of the progeny showed a shift in the natural isotope ratios for the administered isotopes. Deconvolution of the blank corrected measurement data of the Sr isotopes was done to trace back the original spike ratio. The different spike ratios could be well distinguished reflecting the original composition of the spike solution. This study proved that it is possible to create batch-specific unique transgenerational marks in otolith cores by varying the concentrations of two naturally occurring Sr isotopes. This method has high potential to reduce the marking effort for any application in aquaculture and ecological research and management where the tracking of high numbers of offspring is needed.

Effects of geothermal activity and primary production on molybdenum isotopes: Lake Mývatn, Iceland

NASA Astrophysics Data System (ADS)

Neely, R.; Gíslason, S. R.; Ólafsson, M.; Pearce, C. R.; Torssander, P.; Eiríksdóttir, E. S.; Burton, K. W.

2016-12-01

Molybdenum (Mo) is highly sensitive to oxidation state and its isotopes are used as a proxy for redox conditions in the palaeoenvironent, particularly in the oceans. Geothermal systems play an important role in element cycles, comprising 10% of the Mo flux to the oceans and the dominant mechanism for Mo ore formation in porphyry deposits. Currently, little is known about Mo isotopes in either geothermal or groundwaters or how these systems may affect global mass balance. This study takes the Lake Mývatn area as a natural laboratory to study both geothermally affected and unaffected groundwaters, along with seasonal variations in a lacustrine environment. We present a comprehensive elemental and Mo isotope study of two groundwater systems from a basaltic terrain in North Iceland. The waters are of meteoric origin, range in sampling temperature from 2-93°C and in Mo isotope composition (δ98MoNIST) from -0.40 to 1.81‰. The Mo isotopic signature of the waters is largely controlled by mixing between cold groundwaters (isotopically light) and a geothermal end member (isotopically heavy). One of these groundwater systems forms the only input into Lake Mývatn: one of the most productive lakes in the northern hemisphere. Here we also present a time series from the Laxá River, which is the only outflow from the lake. Whilst seasonal variations in Mo isotopes are small (from δ98MoNIST 0.1 to 0.3‰) they positively correlate (R2 = 0.8) with variations in δ34S (from δ43S 1.7 to 4.6‰) with a shift to a heavier isotope peaks in late summer (September). This increase in δ98Mo coincides with a documented cyanobacteria bloom in late July to early September, known to preferentially use light isotopes.

Hydrogen and Oxygen Stable Isotope Fractionation in Body Fluid Compartments of Dairy Cattle According to Season, Farm, Breed, and Reproductive Stage

PubMed Central

Abeni, Fabio; Petrera, Francesca; Capelletti, Maurizio; Dal Prà, Aldo; Bontempo, Luana; Tonon, Agostino; Camin, Federica

2015-01-01

Environmental temperature affects water turnover and isotope fractionation by causing water evaporation from the body in mammals. This may lead to rearrangement of the water stable isotope equilibrium in body fluids. We propose an approach to detect possible variations in the isotope ratio in different body fluids on the basis of different homoeothermic adaptations in varying reproductive stages. Three different reproductive stages (pregnant heifer, primiparous lactating cow, and pluriparous lactating cow) of two dairy cattle breeds (Italian Friesian and Modenese) were studied in winter and summer. Blood plasma, urine, faecal water, and milk were sampled and the isotope ratios of H (2H/1H) and O (18O/16O) were determined. Deuterium excess and isotope-fractionation factors were calculated for each passage from plasma to faeces, urine and milk. The effects of the season, reproductive stages and breed on δ 2H and δ 18O were significant in all the fluids, with few exceptions. Deuterium excess was affected by season in all the analysed fluids. The correlations between water isotope measurements in bovine body fluids ranged between 0.6936 (urine-milk) and 0.7848 (urine-plasma) for δ 2H, and between 0.8705 (urine-milk) and 0.9602 (plasma-milk) for δ 18O. The increase in both isotopic δ values in all body fluids during summer is representative of a condition in which fractionation took place as a consequence of a different ratio between ingested and excreted water, which leads to an increased presence of the heavy isotopes. The different body water turnover between adult lactating cattle and non-lactating heifers was confirmed by the higher isotopic δ for the latter, with a shift in the isotopic equilibrium towards values more distant from those of drinking water. PMID:25996911

Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0-70 °C

NASA Astrophysics Data System (ADS)

Deng, Yuying; Li, Yingzhou; Li, Long

2018-04-01

Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH- (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)-NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)-NH3(aq) = 14.6 - 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

CONTROL SYSTEM FOR ISOTOPE SEPARATING APPARATUS

DOEpatents

Barnes, S.W.

1960-01-26

A method is described for controlling the position of the ion beams in a calutron used for isotope separation. The U/sup 238/ beams is centered over the U/sup 235/ receiving pocket, the operator monitoring the beam until a maximum reading is achieved on the meter connected to that pocket. Then both beams are simultaneously shifted by a preselected amount to move the U/sup 235/ beam over the U/sup 235/ pocket. A slotted door is placed over the entrance to that pocket during the U/sup 238/ beam centering to reduce the contamination to the pocket, while allowing enough beam to pass for monitoring purposes.

Optical phonon modes in rhombohedral boron monosulfide under high pressure

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

Cherednichenko, Kirill A.; IMPMC, UPMC Sorbonne Universités, CNRS UMR 7590, 75005 Paris; LSPM–CNRS, Université Paris Nord, 93430 Villetaneuse

2015-05-14

Raman spectra of rhombohedral boron monosulfide (r-BS) were measured under pressures up to 34 GPa at room temperature. No pressure-induced structural phase transition was observed, while strong pressure shift of Raman bands towards higher wavenumbers has been revealed. IR spectroscopy as a complementary technique has been used in order to completely describe the phonon modes of r-BS. All experimentally observed bands have been compared with theoretically calculated ones and modes assignment has been performed. r-BS enriched by {sup 10}B isotope was synthesized, and the effect of boron isotopic substitution on Raman spectra was observed and analyzed.

Laser-spectroscopy studies of the nuclear structure of neutron-rich radium

NASA Astrophysics Data System (ADS)

Lynch, K. M.; Wilkins, S. G.; Billowes, J.; Binnersley, C. L.; Bissell, M. L.; Chrysalidis, K.; Cocolios, T. E.; Goodacre, T. Day; de Groote, R. P.; Farooq-Smith, G. J.; Fedorov, D. V.; Fedosseev, V. N.; Flanagan, K. T.; Franchoo, S.; Garcia Ruiz, R. F.; Gins, W.; Heinke, R.; Koszorús, Á.; Marsh, B. A.; Molkanov, P. L.; Naubereit, P.; Neyens, G.; Ricketts, C. M.; Rothe, S.; Seiffert, C.; Seliverstov, M. D.; Stroke, H. H.; Studer, D.; Vernon, A. R.; Wendt, K. D. A.; Yang, X. F.

2018-02-01

The neutron-rich radium isotopes, Ra-233222, were measured with Collinear Resonance Ionization Spectroscopy (CRIS) at the ISOLDE facility, CERN. The hyperfine structure of the 7 s2S10→7 s 7 p P31 transition was probed, allowing measurement of the magnetic moments, quadrupole moments, and changes in mean-square charge radii. These results are compared to existing literature values, and the new moments and change in mean-square charge radii of 231Ra are presented. Low-resolution laser spectroscopy of the very neutron-rich 233Ra has allowed the isotope shift and relative charge radius to be determined for the first time.

Cr isotope fractionation factors for Cr(VI) reduction by a metabolically diverse group of bacteria

NASA Astrophysics Data System (ADS)

Basu, Anirban; Johnson, Thomas M.; Sanford, Robert A.

2014-10-01

Reduction of Cr(VI) is an important process that determines the geochemical behavior, mobility and bioavailability of Cr in both terrestrial and marine environments. Many metabolically diverse microorganisms possess Cr(VI) reduction capacity. Cr(VI) reduction fractionates Cr isotopes and thus 53Cr/52Cr ratios can be used to monitor Cr(VI) reduction and redox conditions. The magnitude of isotopic fractionation (ε) for a variety of microbial reduction mechanisms must be known for accurate interpretation of observed shifts in 53Cr/52Cr ratios. We determined isotopic fractionation factors for Cr(VI) reduction by metal reducers Geobacter sulfurreducens and Shewanella sp. strain NR, a denitrifying soil bacterium Pseudomonas stutzeri DCP-Ps1, and a sulfate reducer Desulfovibrio vulgaris. All bacteria investigated in this study produced significant Cr isotope fractionation. The fractionation (ε) for G. sulfurreducens, Shewanella sp. (NR), P. stutzeri DCP-Ps1, and D. vulgaris were -3.03‰ ± 0.12‰, -2.17‰ ± 0.22‰, -3.14‰ ± 0.13‰, and -3.01‰ ± 0.11‰, respectively. Despite differences in microbial strains in this study, the ε did not vary significantly except for Shewanella sp. (NR). Our results suggest that strong isotopic fractionation is induced during Cr(VI) reduction under electron donor poor (∼300 μM) conditions.

Absence of fractionation of mercury isotopes during trophic transfer of methylmercury to freshwater fish in captivity

USGS Publications Warehouse

Kwon, Sae Yun; Blum, Joel D.; Carvan, Michael J.; Basu, Niladri; Head, Jessica A.; Madenjian, Charles P.; David, Solomon R.

2012-01-01

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on unamended food pellets (0.1 μg/g MeHg) or was switched to food pellets with 1.0 μg/g or 4.0 μg/g of added MeHg, for a period of 2 months. The difference in δ202Hg (MDF) and Δ199Hg (MIF) between fish tissues and food pellets with added MeHg was within the analytical uncertainty (δ202Hg, 0.07 ‰; Δ199Hg, 0.06 ‰), indicating no isotope fractionation. In experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ202Hg and Δ199Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting reequilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems.

Isotopic evolution of the idaho batholith and Challis intrusive province, Northern US Cordillera

USGS Publications Warehouse

Gaschnig, Richard M.; Vervoort, J.D.; Lewis, R.S.; Tikoff, B.

2011-01-01

The Idaho batholith and spatially overlapping Challis intrusive province in the North American Cordillera have a history of magmatism spanning some 55 Myr. New isotopic data from the ???98 Ma to 54 Ma Idaho batholith and ???51 Ma to 43 Ma Challis intrusions, coupled with recent geochronological work, provide insights into the evolution of magmatism in the Idaho segment of the Cordillera. Nd and Hf isotopes show clear shifts towards more evolved compositions through the batholith's history and Pb isotopes define distinct fields correlative with the different age and compositionally defined suites of the batholith, whereas the Sr isotopic compositions of the various suites largely overlap. The subsequent Challis magmatism shows the full range of isotopic compositions seen in the batholith. These data suggest that the early suites of metaluminous magmatism (98-87 Ma) represent crust-mantle hybrids. Subsequent voluminous Atlanta peraluminous suite magmatism (83-67 Ma) results primarily from melting of different crustal components. This can be attributed to crustal thickening, resulting from either subduction processes or an outboard terrane collision. A later, smaller crustal melting episode, in the northern Idaho batholith, resulted in the Bitterroot peraluminous suite (66-54 Ma) and tapped different crustal sources. Subsequent Challis magmatism was derived from both crust and mantle sources and corresponds to extensional collapse of the over-thickened crust. ?? The Author 2011. Published by Oxford University Press. All rights reserved.

Absence of fractionation of mercury isotopes during trophic transfer of methylmercury to freshwater fish in captivity

PubMed Central

Kwon, Sae Yun; Blum, Joel D; Carvan, Michael J; Basu, Niladri; Head, Jessica A; Madenjian, Charles P; David, Solomon R

2015-01-01

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In Experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on un-amended food pellets (0.1 µg/g MeHg), or was switched to food pellets with 1.0 µg/g or 4.0 µg/g of added MeHg, for a period of 2 months. The difference in δ202Hg (MDF) and Δ199Hg (MIF) between fish tissues and food pellets with added MeHg were within the analytical uncertainty (δ202Hg; 0.07 ‰, Δ199Hg; 0.06 ‰) indicating no isotope fractionation. In Experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets, and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ202Hg and Δ199Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting re-equilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems. PMID:22681311

Enhanced collectivity along the N = Z line: Lifetime measurements in 44Ti, 48Cr, and 52Fe

NASA Astrophysics Data System (ADS)

Arnswald, K.; Braunroth, T.; Seidlitz, M.; Coraggio, L.; Reiter, P.; Birkenbach, B.; Blazhev, A.; Dewald, A.; Fransen, C.; Fu, B.; Gargano, A.; Hess, H.; Hirsch, R.; Itaco, N.; Lenzi, S. M.; Lewandowski, L.; Litzinger, J.; Müller-Gatermann, C.; Queiser, M.; Rosiak, D.; Schneiders, D.; Siebeck, B.; Steinbach, T.; Vogt, A.; Wolf, K.; Zell, K. O.

2017-09-01

Lifetimes of the 21+ states in 44Ti, 48,50Cr, and 52Fe were determined with high accuracy exploiting the recoil distance Doppler-shift method. The reduced E2 transition strengths of 44Ti and 52Fe differ considerably from previously known values. A systematic increase in collectivity is found for the N = Z nuclei compared to neighboring isotopes. The B (E2) values along the Ti, Cr, and Fe isotopic chains are compared to shell-model calculations employing established interactions for the 0 f 1 p shell, as well as a novel effective shell-model Hamiltonian starting from a realistic nucleon-nucleon potential. The theoretical approaches underestimate the B (E2) values for the lower-mass Ti isotopes. Strong indication is found for particle-hole cross-shell configurations, recently corroborated by similar results for the neighboring isotone 42Ca.

Isotope effect in quasi-two-dimensional metal-organic antiferromagnets

NASA Astrophysics Data System (ADS)

Goddard, P. A.; Singleton, J.; Maitland, C.; Blundell, S. J.; Lancaster, T.; Baker, P. J.; McDonald, R. D.; Cox, S.; Sengupta, P.; Manson, J. L.; Funk, K. A.; Schlueter, J. A.

2008-08-01

Although the isotope effect in superconducting materials is well documented, changes in the magnetic properties of antiferromagnets due to isotopic substitution are seldom discussed and remain poorly understood. This is perhaps surprising given the possible link between the quasi-two-dimensional (Q2D) antiferromagnetic and superconducting phases of the layered cuprates. Here we report the experimental observation of shifts in the Néel temperature and critical magnetic fields (ΔTN/TN≈4%;ΔBc/Bc≈4%) in a Q2D organic molecular antiferromagnet on substitution of hydrogen for deuterium. These compounds are characterized by strong hydrogen bonds through which the dominant superexchange is mediated. We evaluate how the in-plane and interplane exchange energies evolve as the atoms of hydrogen on different ligands are substituted, and suggest a possible mechanism for this effect in terms of the relative exchange efficiency of hydrogen and deuterium bonds.

Proposed in situ secondary ion mass spectrometry on Mars.

PubMed

Inglebert, R L; Klossa, B; Lorin, J C; Thomas, R

1995-01-01

Secondary ion mass spectrometry is a powerful analytical tool, which has the potentiality, through molecular ion emission, of detecting minor phases, as well as the unique capability of directly measuring isotope abundances in mineral or organic phases without any prior physical, chemical or thermal processing. Applied to the in situ analysis of the Martian regolith, it can provide evidence of the presence of carbonates and, by inference (if carbonates constitute significant deposits), of past liquid water--a necessary condition for the development of life. In addition, oxygen isotopic composition of carbonates preserves a record of the temperature at which this phase precipitated and may therefore help decipher the past climatology of Mars. Detection of a carbon isotopic composition shift between carbonates and organic matter (on Earth, the result of a kinetic fractionation effect during photosynthesis) would provide a definite clue regarding the existence of a past biochemical activity on Mars.

Deuterium isotope effects in polymerization of benzene under pressure

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

Cai, Weizhao; Dunuwille, Mihindra; He, Jiangang

The enormous versatility in the properties of carbon materials depends on the content of the sp 2 and sp 3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C 6H 6 and C 6D 6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures showmore » the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C 6D 6 shed light on the mechanism of polymerization of benzene. Lastly, we find that C 6D 6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp 3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C 6D 6 is observed.« less

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

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

Deuterium isotope effects in polymerization of benzene under pressure

DOE PAGES

Cai, Weizhao; Dunuwille, Mihindra; He, Jiangang; ...

2017-04-10

The enormous versatility in the properties of carbon materials depends on the content of the sp 2 and sp 3 covalent bonds. Under compression, if intermolecular distances cross a critical threshold, then unsaturated hydrocarbons gradually transform to saturated carbon polymers. However, the mechanism of polymerization, even for benzene, the simplest aromatic hydrocarbon, is still not understood. We used high-pressure synchrotron X-ray, neutron diffraction, and micro-Raman spectroscopy together with density functional calculations to investigate the isotope effects in benzene isotopologues C 6H 6 and C 6D 6 up to 46.0 GPa. Raman spectra of polymeric products recovered from comparable pressures showmore » the progression of polymerization exhibiting a pronounced kinetic isotope effect. Kinetically retarded reactions in C 6D 6 shed light on the mechanism of polymerization of benzene. Lastly, we find that C 6D 6-derived products recovered from P < 35 GPa actively react with moisture, forming polymers with higher sp 3 hydrogen contents. Significant isotopic shift (≥7 GPa) in persistence of Bragg reflections of C 6D 6 is observed.« less

Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

Response of carbon isotopic compositions of Early-Middle Permian coals in North China to palaeo-climate change

NASA Astrophysics Data System (ADS)

Ding, Dianshi; Liu, Guijian; Sun, Xiaohui; Sun, Ruoyu

2018-01-01

To investigate the magnitude to which the carbon isotopic ratio (δ13C) varies in coals in response to their contemporary terrestrial environment, the Early-Middle Permian Huainan coals (including coals from the Shanxi Formation, Lower Shihezi Formation and Upper Shihezi Formation) in North China were systematically sampled. A 2.5‰ variation range of δ13C values (-25.15‰ to -22.65‰) was observed in Huainan coals, with an average value of -24.06‰. As coal diagenesis exerts little influence on carbon isotope fractionation, δ13C values in coals were mainly imparted by those of coal-forming flora assemblages which were linked to the contemporary climate. The δ13C values in coals from the Shanxi and Lower Shihezi Formations are variable, reflecting unstable climatic oscillations. Heavy carbon isotope is enriched in coals of the Capitanian Upper Shihezi Formation, implying a shift to high positive δ13C values of coeval atmospheric CO2. Notably, our study provides evidence of the Kamura event in the terrestrial environment for the first time.

Assessment of Hg Pollution Released from a WWII Submarine Wreck (U-864) by Hg Isotopic Analysis of Sediments and Cancer pagurus Tissues.

PubMed

Rua-Ibarz, Ana; Bolea-Fernandez, Eduardo; Maage, Amund; Frantzen, Sylvia; Valdersnes, Stig; Vanhaecke, Frank

2016-10-04

Hg pollution released from the U-864 submarine sunk during WWII and potential introduction of that Hg into the marine food chain have been studied by a combination of quantitative Hg and MeHg determination and Hg isotopic analysis via cold vapor generation multicollector inductively coupled plasma-mass spectrometry (CVG-MC-ICP-MS) in sediment and Cancer pagurus samples. The sediment pollution could be unequivocally linked with the metallic Hg present in the wreck. Crabs were collected at the wreck location and 4 nmi north and south, and their brown and claw meat were analyzed separately. For brown meat, the δ 202 Hg values of the individuals from the wreck location were shifted toward the isotopic signature of the sediment and, thus, the submarine Hg. Such differences were not found for claw meat. The isotope ratio results suggest direct ingestion of metallic Hg by C. pagurus but do not offer any proof for any other introduction of the submarine Hg into the marine food chain.

Aquatic Habits of Cetacean Ancestors: Integrating Bone Microanatomy and Stable Isotopes.

PubMed

Cooper, Lisa Noelle; Clementz, Mark T; Usip, Sharon; Bajpai, Sunil; Hussain, S Taseer; Hieronymus, Tobin L

2016-12-01

The earliest cetaceans were interpreted as semi-aquatic based on the presence of thickened bones and stable oxygen isotopes in tooth enamel. However, the origin of aquatic behaviors in cetacean relatives (e.g., raoellids, anthracotheres) remains unclear. This study reconstructs the origins of aquatic behaviors based on long bone microanatomy and stable oxygen isotopes of tooth enamel in modern and extinct cetartiodactylans. Our findings are congruent with published accounts that microanatomy can be a reliable indicator of aquatic behaviors in taxa that are obligatorily aquatic, and also highlight that some "semi-aquatic" behaviors (fleeing into the water to escape predation) may have a stronger relationship to bone microanatomy than others (herbivory in near-shore aquatic settings). Bone microanatomy is best considered with other lines of information in the land-to-sea transition of cetaceans, such as stable isotopes. This study extends our understanding of the progression of skeletal phenotypes associated with habitat shifts in the relatives of cetaceans. © The Author 2016. Published by Oxford University Press on behalf of the Society for Integrative and Comparative Biology. All rights reserved. For permissions please email: journals.permissions@oup.com.

Isotopic Shift of Atom-Dimer Efimov Resonances in K-Rb Mixtures: Critical Effect of Multichannel Feshbach Physics.

PubMed

Kato, K; Wang, Yujun; Kobayashi, J; Julienne, P S; Inouye, S

2017-04-21

Multichannel Efimov physics is investigated in ultracold heteronuclear admixtures of K and Rb atoms. We observe a shift in the scattering length where the first atom-dimer resonance appears in the ^{41}K-^{87}Rb system relative to the position of the previously observed atom-dimer resonance in the ^{40}K-^{87}Rb system. This shift is well explained by our calculations with a three-body model including van der Waals interactions, and, more importantly, multichannel spinor physics. With only minor differences in the atomic masses of the admixtures, the shift in the atom-dimer resonance positions can be cleanly ascribed to the isolated and overlapping Feshbach resonances in the ^{40}K-^{87}Rb and ^{41}K-^{87}Rb systems, respectively. Our study demonstrates the role of multichannel Feshbach physics in determining Efimov resonances in heteronuclear three-body systems.

Re-assessing the Molybdenum Isotope Composition of Pre-GOE Seawater: Evidence for Dynamic Ocean Redox

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Kendall, B.; Roy, M.; Romaniello, S. J.; Nunn, S. J.; Gordon, G. W.; Olson, S. L.; Lyons, T. W.; Zheng, W.; Anbar, A. D.

2016-12-01

Molybdenum (Mo) isotope compositions of Archean shales can provide important insights into ocean and atmosphere redox dynamics prior to the Great Oxidation Event (GOE). Unfortunately, the relatively limited Mo isotope database and small number of sample sets for Archean shales do not allow for in-depth reconstructions and specifically make it difficult to differentiate global from local effects. To accurately estimate the Mo isotope composition of Archean seawater and better investigate the systematics of local and global redox, more complete sample sets are needed. We carried out a Mo isotope analysis of the euxinic 2.65 Ga Roy Hill Shale sampled in two stratigraphically correlated cores, and revisited the well-studied euxinic 2.5 Ga Mt. McRae Shale in higher resolution. Our data show contrasting Mo isotope values in the 2.65 Ga Roy Hill Shale between near- and offshore depositional environments, with systematically heavier isotope values in the near-shore environment. High-resolution analysis of the Mt. McRae Shale yields oscillating Mo concentrations and isotope values at the cm- to dm-scale during the well-characterized "whiff of O2" interval, with the heaviest isotope values measured during euxinic deposition. Variations in the measured isotope values within each section are primarily associated with redox changes in the local depositional environment and amount of detrital content. Both non-quantitative removal of Mo associated with incorporation into non-euxinic sediments and large detrital Mo contributions shift some measured isotopic compositions toward lighter values. This is readily apparent in the near-shore Roy Hill Shale section and the Mt. McRae Shale, but may not fully explain variations observed in the offshore Roy Hill Shale deposit. Here, euxinic deposition is not accompanied by Mo enrichments or isotopic compositions as heavy as the near-shore equivalent, even after detrital correction. This disparity between the near- and offshore environment could signify spatial variation in the Mo isotope composition of 2.65 Ga seawater and highlights the need for multi-site and high-resolution studies in order to best assess paleoenvironmental conditions.

Long-term data set analysis of stable isotopic composition in German rivers

NASA Astrophysics Data System (ADS)

Reckerth, Anne; Stichler, Willibald; Schmidt, Axel; Stumpp, Christine

2017-09-01

Stable isotopes oxygen-18 (18O) and deuterium (2H) are commonly used to investigate hydrological processes in catchments. However, only a few isotope studies have been conducted on a large scale and rarely over long time periods. The objective of this study was to identify the spatial and seasonal variability of isotopic composition in river water and how it is affected by geographical and hydrological factors. The stable isotopic composition of river water has been measured in nine large river catchments in Germany for a time period of 12 years or 26 years. We conducted time series and correlation analyses to identify spatial and temporal patterns of the isotopic composition in the rivers. Further, we compared it to isotopic composition in local precipitation and catchments characteristics. In the majority of the rivers, the spatial and temporal patterns of precipitation were directly reflected in river water. The isotopic signals of the river water were time shifted and show attenuated amplitudes. Further deviations from isotopic compositions in local precipitation were observed in catchments with complex flow systems. These deviations were attributed to catchment processes and influences like evaporation, damming and storage. The seasonality of the isotopic composition was mainly determined by the discharge regimes of the rivers. We found correlations between isotopic long-term averages and catchment altitude as well as latitude and longitude, resulting in a northwest-southeast gradient. Furthermore, it was shown that long-term averages of d-excess were inversely related to flow length and catchment size, which indicates that evaporation enrichment has an impact on the isotopic composition even in catchments of humid climates. This study showed that isotopic composition in rivers can serve as a proxy for the local precipitation and can be utilized as an indicator for hydrological processes even in large river basins. In future, such long time series will help to also understand the impact of changes in the hydrological cycle on the larger scales. They can also be used for calibration and validation of flow and transport models at catchment and sub-catchment scale.

Disequilibrium δ18O values in microbial carbonates as a tracer of metabolic production of dissolved inorganic carbon

NASA Astrophysics Data System (ADS)

Thaler, Caroline; Millo, Christian; Ader, Magali; Chaduteau, Carine; Guyot, François; Ménez, Bénédicte

2017-02-01

Carbon and oxygen stable isotope compositions of carbonates are widely used to retrieve paleoenvironmental information. However, bias may exist in such reconstructions as carbonate precipitation is often associated with biological activity. Several skeleton-forming eukaryotes have been shown to precipitate carbonates with significant offsets from isotopic equilibrium with water. Although poorly understood, the origin of these biologically-induced isotopic shifts in biogenic carbonates, commonly referred to as "vital effects", could be related to metabolic effects that may not be restricted to mineralizing eukaryotes. The aim of our study was to determine whether microbially-mediated carbonate precipitation can also produce offsets from equilibrium for oxygen isotopes. We present here δ18O values of calcium carbonates formed by the activity of Sporosarcina pasteurii, a carbonatogenic bacterium whose ureolytic activity produces ammonia (thus increasing pH) and dissolved inorganic carbon (DIC) that precipitates as solid carbonates in the presence of Ca2+. We show that the 1000 lnαCaCO3-H2O values for these bacterially-precipitated carbonates are up to 24.7‰ smaller than those expected for precipitation at isotopic equilibrium. A similar experiment run in the presence of carbonic anhydrase (an enzyme able to accelerate oxygen isotope equilibration between DIC and water) resulted in δ18O values of microbial carbonates in line with values expected at isotopic equilibrium with water. These results demonstrate for the first time that bacteria can induce calcium carbonate precipitation in strong oxygen isotope disequilibrium with water, similarly to what is observed for eukaryotes. This disequilibrium effect can be unambiguously ascribed to oxygen isotope disequilibrium between DIC and water inherited from the oxygen isotope composition of the ureolytically produced CO2, probably combined with a kinetic isotope effect during CO2 hydration/hydroxylation. The fact that both disequilibrium effects are triggered by the metabolic production of CO2, which is common in many microbially-mediated carbonation processes, leads us to propose that metabolically-induced offsets from isotopic equilibrium in microbial carbonates may be more common than previously considered. Therefore, precaution should be taken when using the oxygen isotope signature of microbial carbonates for diagenetic and paleoenvironmental reconstructions.

Zircon (U-Th)/He Thermochronometric Constraints on Himalayan Thrust Belt Exhumation, Bedrock Weathering, and Cenozoic Seawater Chemistry

NASA Astrophysics Data System (ADS)

Colleps, Cody L.; McKenzie, N. Ryan; Stockli, Daniel F.; Hughes, Nigel C.; Singh, Birendra P.; Webb, A. Alexander G.; Myrow, Paul M.; Planavsky, Noah J.; Horton, Brian K.

2018-01-01

Shifts in global seawater 187Os/188Os and 87Sr/86Sr are often utilized as proxies to track global weathering processes responsible for CO2 fluctuations in Earth history, particularly climatic cooling during the Cenozoic. It has been proposed, however, that these isotopic records instead reflect the weathering of chemically distinctive Himalayan lithologies exposed at the surface. We present new zircon (U-Th)/He thermochronometric and detrital zircon U-Pb geochronologic evidence from the Himalaya of northwest India to explore these contrasting interpretations concerning the driving mechanisms responsible for these seawater records. Our data demonstrate in-sequence southward thrust propagation with rapid exhumation of Lesser Himalayan strata enriched in labile 187Os and relatively less in radiogenic 87Sr at ˜16 Ma, which directly corresponds with coeval shifts in seawater 187Os/188Os and 87Sr/86Sr. Results presented here provide substantial evidence that the onset of exhumation of 187Os-enriched Lesser Himalayan strata could have significantly impacted the marine 187Os/188Os record at 16 Ma. These results support the hypothesis that regional weathering of isotopically unique source rocks can drive seawater records independently from shifts in global-scale weathering rates, hindering the utility of these records as reliable proxies to track global weathering processes and climate in deep geologic time.

Functional Single-Cell Approach to Probing Nitrogen-Fixing Bacteria in Soil Communities by Resonance Raman Spectroscopy with 15N2 Labeling.

PubMed

Cui, Li; Yang, Kai; Li, Hong-Zhe; Zhang, Han; Su, Jian-Qiang; Paraskevaidi, Maria; Martin, Francis L; Ren, Bin; Zhu, Yong-Guan

2018-04-17

Nitrogen (N) fixation is the conversion of inert nitrogen gas (N 2 ) to bioavailable N essential for all forms of life. N 2 -fixing microorganisms (diazotrophs), which play a key role in global N cycling, remain largely obscure because a large majority are uncultured. Direct probing of active diazotrophs in the environment is still a major challenge. Herein, a novel culture-independent single-cell approach combining resonance Raman (RR) spectroscopy with 15 N 2 stable isotope probing (SIP) was developed to discern N 2 -fixing bacteria in a complex soil community. Strong RR signals of cytochrome c (Cyt c, frequently present in diverse N 2 -fixing bacteria), along with a marked 15 N 2 -induced Cyt c band shift, generated a highly distinguishable biomarker for N 2 fixation. 15 N 2 -induced shift was consistent well with 15 N abundance in cell determined by isotope ratio mass spectroscopy. By applying this biomarker and Raman imaging, N 2 -fixing bacteria in both artificial and complex soil communities were discerned and imaged at the single-cell level. The linear band shift of Cyt c versus 15 N 2 percentage allowed quantification of N 2 fixation extent of diverse soil bacteria. This single-cell approach will advance the exploration of hitherto uncultured diazotrophs in diverse ecosystems.

Henry Taube and Coordination Chemistry

Science.gov Websites

Shifts Caused by Cr++ in Aqueous Solutions, DOE Technical Report, 1962 Reactions of Solvated Ions Final Report, DOE Technical Report, 1962 Isotopic Discrimination of Some Solutes in Liquid Ammonia, DOE Technical Report, 1966 Final Technical Report of Research, DOE Technical Report, 1972 Top Additional Web

Herbivore-induced shifts in carbon and nitrogen allocation in red oak seedlings

Treesearch

Christopher J. Frost; Mark D. Hunter

2008-01-01

A dual-isotope, microcosm experiment was conducted with Quercus rubra (red oak) seedlings to test the hypothesis that foliar herbivory would increase belowground carbon allocation (BCA), carbon (C) rhizodeposition and nitrogen (N) uptake. Plant BCA links soil ecosystems to aboveground processes and can be affected by insect herbivores, though the...

Decoupling of monsoon activity across the northern and southern Indo-Pacific during the Late Glacial

NASA Astrophysics Data System (ADS)

Denniston, R. F.; Asmerom, Y.; Polyak, V. J.; Wanamaker, A. D.; Ummenhofer, C. C.; Humphreys, W. F.; Cugley, J.; Woods, D.; Lucker, S.

2017-11-01

Recent studies of stalagmites from the Southern Hemisphere tropics of Indonesia reveal two shifts in monsoon activity not apparent in records from the Northern Hemisphere sectors of the Austral-Asian monsoon system: an interval of enhanced rainfall at ∼19 ka, immediately prior to Heinrich Stadial 1, and a sharp increase in precipitation at ∼9 ka. Determining whether these events are site-specific or regional is important for understanding the full range of sensitivities of the Austral-Asian monsoon. We present a discontinuous 40 kyr carbon isotope record of stalagmites from two caves in the Kimberley region of the north-central Australian tropics. Heinrich stadials are represented by pronounced negative carbon isotopic anomalies, indicative of enhanced rainfall associated with a southward shift of the intertropical convergence zone and consistent with hydroclimatic changes observed across Asia and the Indo-Pacific. Between 20 and 8 ka, however, the Kimberley stalagmites, like the Indonesian record, reveal decoupling of monsoon behavior from Southeast Asia, including the early deglacial wet period (which we term the Late Glacial Pluvial) and the abrupt strengthening of early Holocene monsoon rainfall.

N zooming into the Mediterranean outflow fossil moat during the 1.2-1.8 million years period (Early-Pleistocene) - An approach by radiogenic and stable isotopes

NASA Astrophysics Data System (ADS)

Lebreiro, Susana M.; Antón, Laura; Reguera, M. Isabel; Fernández, Marta; Conde, Estefanía; Barrado, Ana I.; Yllera, Abel

2015-12-01

The fossil Alvarez Cabral erosive Moat contains hemipelagite, contourite and turbidite facies where oceanography changes in the Mediterranean outflow are archived over the 1.2-1.8 Myr time period. Here we used Pb and Sr radiogenic isotopes to trace water masses and sediment source changes, for the first time in twenty glacial-interglacial (G-I) cycles of the Early-Pleistocene interval, and the last Glacial Maximum through Holocene cycle (including the Younger Dryas and Heinrich Stadial-1). A mixing line of Pb isotopes gives reliable low radiogenic 208Pb/204Pb, 206Pb/204Pb, and 206Pb/207Pb typical of Mediterranean Outflow Water (MOW) in one end-member and the signature of high radiogenic isotopes of Atlantic Waters (AW) towards the second end-member. The 87Sr/86Sr isotopes also display two end-members of the mixing line between eolian transport/dust source (0.71) and fluvial transport/weathering source (0.73) previously proposed in the Gulf of Cadiz. Combination of Pb and Sr radiogenic isotopes with O and C stable isotopes of planktonic and benthic foraminifera, and the response of foraminifera benthos over the Early-Pleistocene interval, reveals a direct link between water masses circulation and shifts in G-I. We found a persistent cyclic pattern of MOW circulation and fluvial deposition during glaciations and AW and aeolian influence during interglaciations. On site U1386B/C, the upper-MOW was less ventilated but productive and with high flux of organic flux matter during glacials, while Atlantic Waters were better ventilated, enriched in O, but less productive during interglacials. We infer that shifts in ocean and atmospheric processes in the Gulf of Cadiz were strongly controlled by Earth's obliquity (41 kyr-cycle) and 35°NH insolation during the Early-Pleistocene. We propose a correlation in changes in phase-relationship between precession and obliquity. In general terms, physical properties of fine sediments (glacials) show lower NGR, low reflectance and high magnetic susceptibility. These curves measured in a 20 cm sampling interval, on board ship, present a number of gaps due to non-recovery of sediment. To overcome this problem and obtain a complete lithological record the point-sensor curves of physical properties were correlated with down-hole logs of HSGR (standard total Gamma-ray in gAPI units) (Suppl. Fig. 1) and HROM (high resolution corrected bulk density in g/cm3) (IODP Expedition 339 by the Scientific Party, Logging Summaries).

Paradox of the peak-PCIM (Paleocene Carbon Isotope Maxima; ~57.8Ma) and Abrupt Global Warming

NASA Astrophysics Data System (ADS)

Harper, D. T.; Hoenisch, B.; Zachos, J. C.

2015-12-01

The Paleocene Carbon Isotope Maxima (PCIM; ~57.8Ma) represents a major transition in global δ13C during the late Paleocene, when the long-term positive trend in δ13C reversed from positive to negative. The peak-PCIM (~57.7Ma) has been tightly resolved in new high-resolution, astronomically-tuned benthic isotope records from IODP Sites 1209 (Pacific) and 1262 (Atlantic), which show the final phase of δ13C enrichment as abrupt (~1‰ in <100kyrs) and coinciding with a 0.5‰ decline in benthic δ18O indicative of 2-3ºC of bottom water warming, effectively marking the onset of a gradual 8Myr long warming trend [Littler et al., EPSL 2014]. Typically, during the Paleogene on orbital time scales, warming is observed during intervals of δ13C depletion, consistent with release of isotopically light carbon to the atmosphere. This event, which has the appearance of a bifurcation in the long-term coupling of climate system and the carbon cycle, poses an interesting paradox as any rapid carbon release to the atmosphere should, in theory, create a negative excursion because all of the major carbon sources are isotopically light, whether volcanic outgassing, weathering/oxidation of organic carbon, or methane release [Dunkley-Jones et al., Phil. Trans. R. Soc. A 2010]. If global, there are several testable mechanisms that may explain the shift including increase in burial flux of light carbon, a reduction in heavy carbon burial flux, or a large-scale circulation change perhaps associated with the transition of a major oceanic gateway. Using trace metal (B/Ca and Mg/Ca) and stable isotope (δ11B, δ18O, and δ13C) geochemistry, here we establish the nature of the peak-PCIM at sites from 3 different ocean basins (IODP Sites 690, 1209, and 1262) and begin to test several of the possible mechanisms for change. Mg/Ca in mixed-layer planktonic foraminifera show 2-3°C of sea surface warming coinciding with, and abrupt as, the benthic carbon isotope enrichment at all sites. Bottom water Δ[CO32-], as indicated by B/Ca in benthic foraminifera, abruptly increases by 30-40µmol/kgsw. While this may indicate a change in bottom water circulation, surface B-based proxies also respond with a positive shift during the peak-PCIM indicating a slight increase in surface pH and highlighting the global nature of the event.

Last Deglaciation Events (16.1-11.4 cal-Ka) Recorded in a Speleothem from DeSoto Caverns, Alabama, U.S.A.

NASA Astrophysics Data System (ADS)

Lambert, W. J.; Aharon, P.; Hellstrom, J.

2007-12-01

Whereas the rapid climate swings that occurred during the last deglaciation have been well documented in the Greenland ice cores, their cause/s continue to be a subject of heated debate. Clearly, more geographically dispersed records are required in order to provide better insight into the history of deglaciation, and by extension into the cause/s of the abrupt climate shifts. Particularly scarce are continental deglaciation records from the southeast North America whose atmospheric conditions were controlled by the retreating Laurentide Ice Sheet to the north and the Gulf of Mexico warm waters to the south. In order to remedy the absence of deglaciation records in the Southeast USA in general, and the Gulf Coast in particular, we have initiated a study of a 55-cm long stalagmite (DSSG-2) from the DeSoto Caverns in Childersburg, Alabama (33° 18'N, 86° 17'W). Seven radiocarbon AMS and eighteen U/Th TIMS dates reveal that the continuously layered stalagmite covers the time interval 31 to 11.4 cal-Ka at growth rates varying from 61 μm/decade at the start of deglaciation and up to 2700 μm/decade close to its termination. The combination of unusually high growth rates, pristine aragonite mineralogy and tight sampling (n=602) afforded generation of high fidelity δ13C and δ18O records from about 16.1 to 11.4 cal-Ka whose high resolution is comparable with the contemporaneous Greenland ice core records. The stalagmite δ18O record shows excellent agreement in relative amplitude shifts and timing of abrupt and brief cold reversals (Oldest Dryas, Older Dryas, Inter-Allerød Cold Period) that punctuated the overall trend of deglaciation warming (Bølling/Allerød period). The succeeding Younger Dryas is depicted in the stalagmite by rapid positive shifts in δ18O and δ13C of 1.3‰ and 2.3‰ (V-PDB) relative to the baseline mean value and its start and termination (12.7-11.8 Ka) are concordant within error with the dates reported from GISP2 ice core (12.82-11.60 Ka). We interpret the negative isotope shifts during the warm B/A interval and the positive shifts during the cold ODs and YD intervals as being primarily an expression of rapid shifts in rainfall amount alternating between excessive floods and severe droughts. The excellent correspondence observed between the DeSoto stalagmite and the GISP2 isotope records further suggests that disturbances in thermohaline circulation caused by repeated fresh water discharge episodes into the North Atlantic from the retreating American and European ice sheets were the principal governing factors controlling the documented isotope shifts in the Southeastern USA and Greenland.

Environmental Implications of Ediacaran C-isotopic Shifts

NASA Astrophysics Data System (ADS)

Kelly, A. E.; Rothman, D. H.; Love, G. D.; Grosjean, E.; Fike, D. A.; Zumberge, J. E.; Summons, R. E.

2008-12-01

Compound-specific carbon isotope analyses of biomarkers show a widespread reversal in isotopic patterns in the Ediacaran. We analyzed oils and/or rocks from Eastern Siberia, Oman and Australia and confirmed that, in sediments and oils older than ~550 Ma, n-alkanes are enriched in 13C relative to the acyclic isoprenoids pristane and phytane. In younger sediments, the n-alkanes are depleted compared to these isoprenoids with the possible exception of those deposited during Phanerozoic oceanic anoxic events.1 Pristane and phytane are considered to be derived from photosynthetic primary inputs and, based on established biosynthetic relationships of organisms that dominate the modern ocean, should be 13C- enriched relative to n-alkanes from the same source. Therefore, the presence of n-alkanes with anomalously enriched isotopic compositions before 550 Ma may signify a high relative abundance of bacterial heterotrophs that extensively recycled organic matter (Corg) in the water column.2 The switch from anomalous isotopic ordering to isoprenoid: n-alkyl biosynthetic relationships characteristic of the Phanerozoic is observed to take place in the Ediacaran. In Oman, this coincides with the termination of the Shuram Excursion when marine carbonates show very negative δ13C values with no corresponding shift in the isotopic composition of co-occurring Corg.3 This has been attributed to the oxidation of a large pool of Corg in the deep ocean3 with a corresponding fundamental change in C-cycle dynamics.4 Several hypotheses, many ultimately linked to release of molecular oxygen via enhanced Corg burial, have been proposed to explain these phenomena. They include the evolution of: bilaterian animals with guts that rapidly export organic matter to the ocean floor as fecal pellets, reducing the amount of heterotrophy in the water column,2 biomineralization, providing ballast for organic export,4 and algae with decay-resistant biopolymers.4 Alternatively, tectonism and the rifting of Rodinia may have indirectly increased the burial flux of Corg. Additionally, the success of sponges and other filter-feeding Ediacaran fauna at the time may have been an important factor. References 1. e.g. Grice et al., 2005. Science 307, 706-709. 2. Logan et al., 1995. Nature 376, 53-56. 3. Fike et al., 2006. Nature 444, 744-747. 4. Rothman et al., 2003. PNAS 100, 8124-8129.

Subtropical Climate Variability since the Last Glacial Maximum from Speleothem Precipitation Reconstructions in Florida

NASA Astrophysics Data System (ADS)

Polk, J.; van Beynen, P.; DeLong, K. L.; Asmerom, Y.; Polyak, V. J.

2017-12-01

Teleconnections between the tropical-subtropical regions of the Americas since the Last Glacial Maximum (LGM), particularly the Mid- to Late-Holocene, and high-resolution proxy records refining climate variability over this period continue to receive increasing attention. Here, we present a high-resolution, precisely dated speleothem record spanning multiple periods of time since the LGM ( 30 ka) for the Florida peninsula. The data indicate that the amount effect plays a significant role in determining the isotopic signal of the speleothem calcite. Collectively, the records indicate distinct differences in climate in the region between the LGM, Mid-Holocene, and Late Holocene, including a progressive shift in ocean composition and precipitation isotopic values through the period, suggesting Florida's sensitivity to regional and global climatic shifts. Comparisons between speleothem δ18O values and Gulf of Mexico marine records reveal a strong connection between the Gulf region and the terrestrial subtropical climate in the Late Holocene, while the North Atlantic's influence is clear in the earlier portions of the record. Warmer sea surface temperatures correspond to enhanced evaporation, leading to more intense atmospheric convection in Florida, and thereby modulating the isotopic composition of rainfall above the cave. These regional signals in climate extend from the subtropics to the tropics, with a clear covariance between the speleothem signal and other proxy records from around the region, as well as global agreement during the LGM period with other records. These latter connections appear to be driven by changes in the mean position of the Intertropical Convergence Zone and time series analysis of the δ18O values reveals significant multidecadal periodicities in the record, which are evidenced by agreement with the AMV and other multidecadal influences (NAO and PDO) likely having varying influence throughout the period of record. The climate variability recorded in our record suggests complex responses to major and abrupt shifts during these periods, likely due to Florida's subtropical location and the influence of multiple climate forcing mechanisms in the region.

¹H-MAS-NMR chemical shifts in hydrogen-bonded complexes of chlorophenols (pentachlorophenol, 2,4,6-trichlorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol, and p-chlorophenol) and amine, and H/D isotope effects on ¹H-MAS-NMR spectra.

PubMed

Honda, Hisashi

2013-04-22

Chemical shifts (CS) of the ¹H nucleus in N···H···O type hydrogen bonds (H-bond) were observed in some complexes between chlorophenols [pentachlorophenol (PCP), 2,4,6-tricholorophenol (TCP), 2,6-dichlorophenol (26DCP), 3,5-dichlorophenol (35DCP), and p-chlorophenol (pCP)] and nitrogen-base (N-Base) by solid-state high-resolution ¹H-NMR with the magic-angle-spinning (MAS) method. Employing N-Bases with a wide range of pKa values (0.65-10.75), ¹H-MAS-NMR CS values of bridging H atoms in H-bonds were obtained as a function of the N-Base's pKa. The result showed that the CS values were increased with increasing pKa values in a range of DpKa < 0 [DpKa = pKa(N-Base)-pKa(chlorophenols)] and decreased when DpKa > 2: The maximum CS values was recorded in the PCP (pKa = 5.26)-4-methylpyridine (6.03), TCP (6.59)-imidazole (6.99), 26DCP (7.02)-2-amino-4-methylpyridine (7.38), 35DCP (8.04)-4-dimethylaminopyridine (9.61), and pCP (9.47)-4-dimethylaminopyridine (9.61) complexes. The largest CS value of 18.6 ppm was recorded in TCP-imidazole crystals. In addition, H/D isotope effects on ¹H-MAS-NMR spectra were observed in PCP-2-amino-3-methylpyridine. Based on the results of CS simulation using a B3LYP/6-311+G** function, it can be explained that a little changes of the N-H length in H-bond contribute to the H/D isotope shift of the ¹H-MAS-NMR peaks.

Stable isotope evaluation of population- and individual-level diet variability in a large, oligotrophic lake with non-native lake trout

USGS Publications Warehouse

Ng, Elizabeth L.; Fredericks, Jim P.; Quist, Michael C.

2016-01-01

Non-native piscivores can alter food web dynamics; therefore, evaluating interspecific relationships is vital for conservation and management of ecosystems with introduced fishes. Priest Lake, Idaho, supports a number of introduced species, including lake troutSalvelinus namaycush, brook trout S. fontinalis and opossum shrimp Mysis diluviana. In this study, we used stable isotopes (δ13C and δ15N) to describe the food web structure of Priest Lake and to test hypotheses about apparent patterns in lake trout growth. We found that isotopic niches of species using pelagic-origin carbon did not overlap with those using more littoral-origin carbon. Species using more littoral-origin carbon, such as brook trout and westslope cutthroat trout Oncorhynchus clarki lewisi, exhibited a high degree of isotopic niche overlap and high intrapopulation variability in resource use. Although we hypothesised that lake trout would experience an ontogenetic diet shift, no such patterns were apparent in isotopic signatures. Lake trout growth rates were not associated with patterns in δ15N, indicating that variation in adult body composition may not be related to adult diet. Understanding trophic relationships at both the individual and species levels provides a more complete understanding of food webs altered by non-native species.

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis

PubMed Central

Valentine, Benjamin; Kamenov, George D.; Kenoyer, Jonathan Mark; Shinde, Vasant; Mushrif-Tripathy, Veena; Otarola-Castillo, Erik; Krigbaum, John

2015-01-01

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people’s movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape. PMID:25923705

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

NASA Technical Reports Server (NTRS)

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

1995-01-01

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

Complexities of nitrogen isotope biogeochemistry in plant-soil systems: implications for the study of ancient agricultural and animal management practices

PubMed Central

Szpak, Paul

2014-01-01

Nitrogen isotopic studies have the potential to shed light on the structure of ancient ecosystems, agropastoral regimes, and human-environment interactions. Until relatively recently, however, little attention was paid to the complexities of nitrogen transformations in ancient plant-soil systems and their potential impact on plant and animal tissue nitrogen isotopic compositions. This paper discusses the importance of understanding nitrogen dynamics in ancient contexts, and highlights several key areas of archaeology where a more detailed understanding of these processes may enable us to answer some fundamental questions. This paper explores two larger themes that are prominent in archaeological studies using stable nitrogen isotope analysis: (1) agricultural practices (use of animal fertilizers, burning of vegetation or shifting cultivation, and tillage) and (2) animal domestication and husbandry (grazing intensity/stocking rate and the foddering of domestic animals with cultigens). The paucity of plant material in ancient deposits necessitates that these issues are addressed primarily through the isotopic analysis of skeletal material rather than the plants themselves, but the interpretation of these data hinges on a thorough understanding of the underlying biogeochemical processes in plant-soil systems. Building on studies conducted in modern ecosystems and under controlled conditions, these processes are reviewed, and their relevance discussed for ancient contexts. PMID:25002865

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis.

PubMed

Valentine, Benjamin; Kamenov, George D; Kenoyer, Jonathan Mark; Shinde, Vasant; Mushrif-Tripathy, Veena; Otarola-Castillo, Erik; Krigbaum, John

2015-01-01

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people's movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape.

Carbon isotope equilibration during sulphate-limited anaerobic oxidation of methane

NASA Astrophysics Data System (ADS)

Yoshinaga, Marcos Y.; Holler, Thomas; Goldhammer, Tobias; Wegener, Gunter; Pohlman, John W.; Brunner, Benjamin; Kuypers, Marcel M. M.; Hinrichs, Kai-Uwe; Elvert, Marcus

2014-03-01

Collectively, marine sediments comprise the largest reservoir of methane on Earth. The flux of methane from the sea bed to the overlying water column is mitigated by the sulphate-dependent anaerobic oxidation of methane by marine microbes within a discrete sedimentary horizon termed the sulphate-methane transition zone. According to conventional isotope systematics, the biological consumption of methane leaves a residue of methane enriched in 13C (refs , , ). However, in many instances the methane within sulphate-methane transition zones is depleted in 13C, consistent with the production of methane, and interpreted as evidence for the intertwined anaerobic oxidation and production of methane. Here, we report results from experiments in which we incubated cultures of microbial methane consumers with methane and low levels of sulphate, and monitored the stable isotope composition of the methane and dissolved inorganic carbon pools over time. Residual methane became progressively enriched in 13C at sulphate concentrations above 0.5 mM, and progressively depleted in 13C below this threshold. We attribute the shift to 13C depletion during the anaerobic oxidation of methane at low sulphate concentrations to the microbially mediated carbon isotope equilibration between methane and carbon dioxide. We suggest that this isotopic effect could help to explain the 13C-depletion of methane in subseafloor sulphate-methane transition zones.

Lead isotope ratios in tree bark pockets: an indicator of past air pollution in the Czech Republic.

PubMed

Conkova, M; Kubiznakova, J

2008-10-15

Tree bark pockets were collected at four sites in the Czech Republic with differing levels of lead (Pb) pollution. The samples, spanning 1923-2005, were separated from beech (Fagus sylvatica) and spruce (Picea abies). Elevated Pb content (0.1-42.4 microg g(-1)) reflected air pollution in the city of Prague. The lowest Pb content (0.3-2.6 microg g(-1)) was found at the Kosetice EMEP "background pollution" site. Changes in (206)Pb/(207)Pb and (208)Pb/(206)Pb isotope ratios were in agreement with operation times of the Czech main anthropogenic Pb sources. Shortly after the Second World War, the (206)Pb/(207)Pb isotope ratio in bark pockets decreased from 1.17 to 1.14 and the (208)Pb/(206)Pb isotope ratio increased from 2.12 to 2.16. Two dominant emission sources responsible for these changes, lignite and leaded petrol combustion, contributed to the shifts in Pb isotope ratios. Low-radiogenic petrol Pb ((206)Pb/(207)Pb of 1.11) lead to lower (206)Pb/(207)Pb in bark pockets over time. High-radiogenic lignite-derived Pb ((206)Pb/(207)Pb of 1.18 to 1.19) was detected in areas affected by coal combustion rather than by traffic.

Past leaded gasoline emissions as a nonpoint source tracer in riparian systems: A study of river inputs to San Francisco Bay

USGS Publications Warehouse

Dunlap, C.E.; Bouse, R.; Flegal, A.R.

2000-01-01

Variations in the isotopic composition of lead in 1995-1998 river waters flowing into San Francisco Bay trace the washout of lead deposited in the drainage basin from leaded gasoline combustion. At the confluence of the Sacramento and San Joaquin rivers where they enter the Bay, the isotopic compositions of lead in the waters define a linear trend away from the measured historical compositions of leaded gas in California. The river waters are shifted away from leaded gasoline values and toward an isotopic composition similar to Sierra Nevadan inputs which became the predominant source of sedimentation in San Francisco Bay following the onset of hydraulic gold mining in 1853. Using lead isotopic compositions of hydraulic mine sediments and average leaded gasoline as mixing end members, we calculate that more than 50% of the lead in the present river water originated from leaded gasoline combustion. The strong adsorption of lead (log K(d) > 7.4) to particulates appears to limit the flushing of gasoline lead from the drainage basin, and the removal of that lead from the system may have reached an asymptotic limit. Consequently, gasoline lead isotopes should prove to be a useful nonpoint source tracer of the environmental distribution of particle- reactive anthropogenic metals in freshwater systems.

Stable Isotopes, Quantum Computing and Consciousness

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2000-10-01

Recent proposals of quantum computing/computers (QC) based on nuclear spins suggest that consciousness (CON) activity may be related (assisted) to subset of C13 atoms incorporated randomly, or quasirandomly, in neural structures. Consider two DNA chains. Even if they are completely identical chemically (same sequence of codons), patterns of 12C and 13C isotopes in them are different (possible origin of personal individuality). Perhaps it is subsystem of nuclear spins of 13C "sublattice" which forms dynamical system capable of QC and on which CON is "spanned". Some issues related to this hypothesis are: (1) existence of CON-driven positional correlations among C13 atoms, (2) motion (hopping) of C13 via enhanced neutron tunneling, cf. quantum "anti Zeno-effect", (3) possible optimization of concentration of QC-active C13 atoms above their standard isotopic abundance, (4) characteristic time-scales for operation of C13-based QC (perrhaps, broad range of scales), (5) reflection of QC dynamics of C13 on CON, (6) possibility that C13-based QC operates "above" level of "regular" CON (perhaps, Jungian sub/super-CON), (7) isotopicity as connector to universal Library of Patterns ("Platonic World"), (8) self-stabilization of coherence in C13 (sub)system. Some of this questions are, in principle, experimentally addressable through shifting of isotopic abundances.

Oxygen and carbon isotopes in terrestrial mollusk shells. From modern to fossil values, climatic impact on the mollusk diet.

NASA Astrophysics Data System (ADS)

Metref, S.; Labonne, M.; Rousseau, D.; Rousseau, D.; Bentaleb, I.; Vianey-Liaud, M.

2001-12-01

Stable isotope studies on fossil material as well as on sediment have been very successful these past years indicating such method a very promising Quaternary paleonvironmental index for continental studies. Although most of the studies on fossil material was related to modern material collected near the fossil record, no precise analysis of the impact of the diet and precipitation was carried out in order to justify the previous assumptions. Here we present the results of two sets of analysis from terrestrial mollusk shells, a particularly good climate indicator. On one hand, individuals from hatched eggs of raised Helix aspersa were fed with different plants characteristic of the two main photosynthetic pathways (C3 and C4), and waters of different isotopic values. The shells were analyzed in order to observe the impact of the food diet and of the precipitation on the isotope content of the shell carbonate. On the other hand, the study of fossil shells (Vertigo modesta) from the loess series of the Great Plains, an area where shifts in photosynthetic pathways where detected during the last isotopic stage 2 (24,000-12,000 yr B.P.), is carried out. The interpretation of the results is based on those of the study of modern shells

Stable isotope analysis of CO2 in breath indicates metabolic fuel shifts in torpid arctic ground squirrels.

PubMed

Lee, Trixie N; Richter, Melanie M; Williams, Cory T; Tøien, Øivind; Barnes, Brian M; O'Brien, Diane M; Buck, C Loren

2017-07-01

Stable carbon isotope ratios (δ 13 C) in breath show promise as an indicator of immediate metabolic fuel utilization in animals because tissue lipids have a lower δ 13 C value than carbohydrates and proteins. Metabolic fuel consumption is often estimated using the respiratory exchange ratio (RER), which has lipid and carbohydrate boundaries, but does not differentiate between protein and mixed fuel catabolism at intermediate values. Because lipids have relatively low δ 13 C values, measurements of stable carbon isotopes in breath may help distinguish between catabolism of protein and mixed fuel that includes lipid. We measured breath δ 13 C and RER concurrently in arctic ground squirrels (Urocitellus parryii) during steady-state torpor at ambient temperatures from -2 to -26°C. As predicted, we found a correlation between RER and breath δ 13 C values; however, the range of RER in this study did not reach intermediate levels to allow further resolution of metabolic substrate use with the addition of breath δ 13 C measurements. These data suggest that breath δ 13 C values are 1.1‰ lower than lipid tissue during pure lipid metabolism. From RER, we determined that arctic ground squirrels rely on nonlipid fuel sources for a significant portion of energy during torpor (up to 37%). The shift toward nonlipid fuel sources may be influenced by adiposity of the animals in addition to thermal challenge. Copyright © 2017 Elsevier Inc. All rights reserved.

Evolution of ectomycorrhizas as a driver of diversification and biogeographic patterns in the model mycorrhizal mushroom genus Laccaria.

PubMed

Wilson, Andrew W; Hosaka, Kentaro; Mueller, Gregory M

2017-03-01

A systematic and evolutionary ecology study of the model ectomycorrhizal (ECM) genus Laccaria was performed using herbarium material and field collections from over 30 countries covering its known geographic range. A four-gene (nrITS, 28S, RPB2, EF1α) nucleotide sequence dataset consisting of 232 Laccaria specimens was analyzed phylogenetically. The resulting Global Laccaria dataset was used for molecular dating and estimating diversification rates in the genus. Stable isotope analysis of carbon and nitrogen was used to evaluate the origin of Laccaria's ECM ecology. In all, 116 Laccaria molecular species were identified, resulting in a near 50% increase in its known diversity, including the new species described herein: Laccaria ambigua. Molecular dating indicates that the most recent common ancestor to Laccaria existed in the early Paleocene (56-66 million yr ago), probably in Australasia. At this time, Laccaria split into two lineages: one represented by the new species L. ambigua, and the other reflecting a large shift in diversification that resulted in the remainder of Laccaria. L. ambigua shows a different isotopic profile than all other Laccaria species. Isotopes and diversification results suggest that the evolution of the ECM ecology was a key innovation in the evolution of Laccaria. Diversification shifts associated with Laccaria's dispersal to the northern hemisphere are attributed to adaptations to new ecological niches. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

Trophic Ecology of Atlantic Bluefin Tuna (Thunnusthynnus) Larvae from the Gulf of Mexico and NW Mediterranean Spawning Grounds: A Comparative Stable Isotope Study

PubMed Central

Malca, Estrella; Quintanilla, José María; Muhling, Barbara A.; Alemany, Francisco; Privoznik, Sarah L.; Shiroza, Akihiro; Lamkin, John T.; García, Alberto

2015-01-01

The present study uses stable isotopes of nitrogen and carbon (δ15Nandδ13C) as trophic indicators for Atlantic bluefin tuna larvae (BFT) (6–10 mm standard length) in the highly contrasting environmental conditions of the Gulf of Mexico (GOM) and the Balearic Sea (MED). These regions are differentiated by their temperature regime and relative productivity, with the GOM being significantly warmer and more productive. MED BFT larvae showed the highest δ15N signatures, implying an elevated trophic position above the underlying microzooplankton baseline. Ontogenetic dietary shifts were observed in the BFT larvae from the GOM and MED which indicates early life trophodynamics differences between these spawning habitats. Significant trophic differences between the GOM and MED larvae were observed in relation to δ15N signatures in favour of the MED larvae, which may have important implications in their growth during their early life stages.These low δ15N levels in the zooplankton from the GOM may be an indication of a shifting isotopic baseline in pelagic food webs due to diatrophic inputs by cyanobacteria. Lack of enrichment for δ15N in BFT larvae compared to zooplankton implies an alternative grazing pathway from the traditional food chain of phytoplankton—zooplankton—larval fish. Results provide insight for a comparative characterization of the trophic pathways variability of the two main spawning grounds for BFT larvae. PMID:26225849

Integrated stratigraphy of a shallow marine Paleocene-Eocene boundary section, MCBR cores, Maryland (USA)

NASA Astrophysics Data System (ADS)

Self-Trail, J. M.; Robinson, M. M.; Edwards, L. E.; Powars, D. S.; Wandless, G. A.; Willard, D. A.

2013-12-01

An exceptional Paleocene-Eocene boundary section occurs in a cluster of six short (<15m) coreholes (MCBR 1 through 6) drilled near Mattawoman Creek in western Charles County, Maryland. The sediments consist of glauconite-rich sand of the upper Paleocene Aquia Formation and silty clay of the lower Eocene Marlboro Clay. Sediment samples were analyzed for carbon and oxygen isotopes, percent calcium carbonate, calcareous nannofossils, planktic and benthic foraminifera, dinoflagellates, pollen, and lithology. A well-defined carbon isotope excursion (CIE) documents a gradual negative shift in δ13C values that starts below the lithologic break between the Aquia Formation and the Marlboro Clay. A benthic foraminifer extinction event, reduction of calcareous nannofossil assemblages, and change in core color from gray to alternating gray and pink also occurs within the CIE transition. These alternating changes in color coincide with cyclic peaks in the carbon isotope and percent calcium carbonate curves, where gray color corresponds to a positive shift in carbon isotope values and to a corresponding increase in percent benthic and planktic foraminifera. The upper third of the Marlboro Clay is barren of all calcareous microfossil material, although the presence of foraminiferal molds and linings proves that deposition occurred in a marine environment. Co-occurrence of the dinoflagellates Apectodinium augustum and Phthanoperidinium crenulatum at the top of the Marlboro Clay suggests that the Marlboro Clay at Mattawoman Creek is truncated. This is corroborated by the absence in the Marlboro of specimens of the calcareous nannofossil Rhomboaster-Discoaster assemblage, which is restricted to early Eocene Zone NP9b. Based on planktic/benthic foraminifera ratios, deposition of sediments at Mattawoman Creek occurred predominantly in an inner neritic environment, at water depths between 25-50 m. Occasional deepening to approximately 75m (middle neritic environment) occurred in the early Eocene, as represented by the basal Marlboro Clay. The planktic/benthic ratio, however, could also be affected by surface productivity and/or river runoff. The gradual shift up-section in core color from gray to alternating gray and red, to dark red, coupled with dissolution of calcareous microfossil assemblages, is possibly secondary and may represent lysocline shoaling in a nearshore environment. This would suggest that lysocline shoaling continued after the CIE and well into the early Eocene.

Predicting equilibrium uranium isotope fractionation in crystals and solution

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2015-12-01

Despite the rapidly growing interest in using 238U/235U measurements as a proxy for changes in oxygen abundance in surface and near-surface environments, the present theoretical understanding of uranium isotope fractionation is limited to a few simple gas-phase molecules and analogues of dissolved species (e.g., 1,2,3). Understanding uranium isotope fractionation behavior in more complicated species, such as crystals and adsorption complexes, will help in the design and interpretation of experiments and field studies, and may suggest other uses for 38U/235U measurements. In this study, a recently developed first-principles method for estimating the nuclear volume component of field shift fractionation in crystals and complex molecular species (4) is combined with mass-dependent fractionation theory to predict equilibrium 38U/235U fractionations in aqueous and crystalline uranium compounds, including uraninite (UO2). The nuclear field shift effect, caused by the interaction of electrons with the finite volume of the positive charge distribution in uranium nuclei, is estimated using Density Functional Theory and the Projector Augmented Wave method (DFT-PAW). Tests against relativistic electronic structure calculations and Mössbauer isomer shift data indicate that the DFT-PAW method is reasonably accurate, while being much better suited to models of complex and crystalline species. Initial results confirm previous predictions that the nuclear volume effect overwhelms mass depdendent fractionation in U(VI)-U(IV) exchange reactions, leading to higher 238U/235U in U(IV) species (i.e., for UO2 xtal vs. UO22+aq, ln αNV ≈ +1.8‰ , ln αMD ≈ -0.8‰, ln αTotal ≈ +1.0‰ at 25ºC). UO2 and U(H2O)94+, are within ~0.4‰ of each other, while U(VI) species appear to be more variable. This suggests that speciation is likely to significantly affect natural uranium isotope fractionations, in addition to oxidation state. Tentatively, it appears that uranyl-type (UO22+-bearing) structures will tend to have higher 238U/235U than uranate-type structures that lack strong U=O bonds. References: 1. Bigeleisen (1996) JACS 118:3676; 2. Schauble (2006) Eos 87:V21B-0570; 3. Abe et al. (2008) J Chem Phys 128:144309, 129:164309, & Abe et al. (2010) J Chem Phys 133:044309; 4. Schauble (2013) PNAS 110:17714.

Hydrogen stable isotopic constraints on methane emissions from oil and gas extraction in the Colorado Front Range, USA

NASA Astrophysics Data System (ADS)

Townsend-Small, A.; Botner, E. C.; Jimenez, K.; Blake, N. J.; Schroeder, J.; Meinardi, S.; Barletta, B.; Simpson, I. J.; Blake, D. R.; Flocke, F. M.; Pfister, G.; Bon, D.; Crawford, J. H.

2015-12-01

The climatic implications of a shift from oil and coal to natural gas depend on the magnitude of fugitive emissions of methane from the natural gas supply chain. Attempts to constrain methane emissions from natural gas production regions can be confounded by other sources of methane. Here we demonstrate the utility of stable isotopes, particularly hydrogen isotopes, for source apportionment of methane emissions. The Denver, Colorado area is home to a large oil and gas field with both conventional oil and gas wells and newer hydraulic fracturing wells. The region also has a large metropolitan area with several landfills and a sizable cattle population. As part of the DISCOVER-AQ and FRAPPE field campaigns in summer 2014, we collected three types of canister samples for analysis of stable isotopic composition of methane: 1), samples from methane sources; 2), samples from two stationary ground sites, one in the Denver foothills, and one in an oil and gas field; and 3), from the NCAR C-130 aircraft in samples upwind and downwind of the region. Our results indicate that hydrogen isotope ratios are excellent tracers of sources of methane in the region, as we have shown previously in California and Texas. Use of carbon isotope ratios is complicated by the similarity of natural gas isotope ratios to that of background methane. Our results indicate that, despite the large amount of natural gas production in the region, biological sources such as cattle feedlots and landfills account for at least 50% of total methane emissions in the Front Range. Future work includes comparison of isotopes and alkane ratios as tracers of methane sources, and calculation of total methane fluxes in the region using continuous measurements of methane concentrations during aircraft flights.

Isotopic incorporation rates and discrimination factors in mantis shrimp crustaceans.

PubMed

deVries, Maya S; Del Rio, Carlos Martínez; Tunstall, Tate S; Dawson, Todd E

2015-01-01

Stable isotope analysis has provided insights into the trophic ecology of a wide diversity of animals. Knowledge about isotopic incorporation rates and isotopic discrimination between the consumer and its diet for different tissue types is essential for interpreting stable isotope data, but these parameters remain understudied in many animal taxa and particularly in aquatic invertebrates. We performed a 292-day diet shift experiment on 92 individuals of the predatory mantis shrimp, Neogonodactylus bredini, to quantify carbon and nitrogen incorporation rates and isotope discrimination factors in muscle and hemolymph tissues. Average isotopic discrimination factors between mantis shrimp muscle and the new diet were 3.0 ± 0.6 ‰ and 0.9 ± 0.3 ‰ for carbon and nitrogen, respectively, which is contrary to what is seen in many other animals (e.g. C and N discrimination is generally 0-1 ‰ and 3-4 ‰, respectively). Surprisingly, the average residence time of nitrogen in hemolymph (28.9 ± 8.3 days) was over 8 times longer than that of carbon (3.4 ± 1.4 days). In muscle, the average residence times of carbon and nitrogen were of the same magnitude (89.3 ± 44.4 and 72.8 ± 18.8 days, respectively). We compared the mantis shrimps' incorporation rates, along with rates from four other invertebrate taxa from the literature, to those predicted by an allometric equation relating carbon incorporation rate to body mass that was developed for teleost fishes and sharks. The rate of carbon incorporation into muscle was consistent with rates predicted by this equation. Our findings provide new insight into isotopic discrimination factors and incorporation rates in invertebrates with the former showing a different trend than what is commonly observed in other animals.

Isotopic Incorporation Rates and Discrimination Factors in Mantis Shrimp Crustaceans

PubMed Central

deVries, Maya S.; del Rio, Carlos Martínez; Tunstall, Tate S.; Dawson, Todd E.

2015-01-01

Stable isotope analysis has provided insights into the trophic ecology of a wide diversity of animals. Knowledge about isotopic incorporation rates and isotopic discrimination between the consumer and its diet for different tissue types is essential for interpreting stable isotope data, but these parameters remain understudied in many animal taxa and particularly in aquatic invertebrates. We performed a 292-day diet shift experiment on 92 individuals of the predatory mantis shrimp, Neogonodactylus bredini, to quantify carbon and nitrogen incorporation rates and isotope discrimination factors in muscle and hemolymph tissues. Average isotopic discrimination factors between mantis shrimp muscle and the new diet were 3.0 ± 0.6 ‰ and 0.9 ± 0.3 ‰ for carbon and nitrogen, respectively, which is contrary to what is seen in many other animals (e.g. C and N discrimination is generally 0–1 ‰ and 3–4 ‰, respectively). Surprisingly, the average residence time of nitrogen in hemolymph (28.9 ± 8.3 days) was over 8 times longer than that of carbon (3.4 ± 1.4 days). In muscle, the average residence times of carbon and nitrogen were of the same magnitude (89.3 ± 44.4 and 72.8 ± 18.8 days, respectively). We compared the mantis shrimps’ incorporation rates, along with rates from four other invertebrate taxa from the literature, to those predicted by an allometric equation relating carbon incorporation rate to body mass that was developed for teleost fishes and sharks. The rate of carbon incorporation into muscle was consistent with rates predicted by this equation. Our findings provide new insight into isotopic discrimination factors and incorporation rates in invertebrates with the former showing a different trend than what is commonly observed in other animals. PMID:25835953

Heterogeneity of the Caribbean plateau mantle source: Sr, O and He isotopic compositions of olivine and clinopyroxene from Gorgona Island

NASA Astrophysics Data System (ADS)

Révillon, S.; Chauvel, C.; Arndt, N. T.; Pik, R.; Martineau, F.; Fourcade, S.; Marty, B.

2002-12-01

The composition of the mantle plumes that created large oceanic plateaus such as Ontong Java or the Caribbean is still poorly known. Geochemical and isotopic studies on accreted portions of the Caribbean plateau have shown that the plume source was heterogeneous and contained isotopically depleted and relatively enriched portions. A distinctive feature of samples from the Caribbean plateau is their unusual Sr isotopic compositions, which, at a given Nd isotopic ratio, are far higher than in samples from other oceanic plateaus. Sr, O and He isotopic compositions of whole rocks and magmatic minerals (clinopyroxene or olivine) separated from komatiites, gabbros and peridotites from Gorgona Island in Colombia were determined to investigate the origin of these anomalously radiogenic compositions. Sequentially leached clinopyroxenes have Sr isotopic compositions in the range 87Sr/ 86Sr=0.70271-0.70352, systematically lower than those of leached and unleached whole rocks. Oxygen isotopic ratios of clinopyroxene vary within the range δ 18O=5.18-5.35‰, similar to that recorded in oceanic island basalts. He isotopic ratios are high ( R/ Ra=8-19). The lower 87Sr/ 86Sr ratios of most of the clinopyroxenes shift the field of the Caribbean plateau in Nd-Sr isotope diagrams toward more 'normal' values, i.e. a position closer to the field defined by mid-ocean ridge basalts and oceanic-island basalts. Three clinopyroxenes have slightly higher 87Sr/ 86Sr ratios that cannot be explained by an assimilation model. The high 87Sr/ 86Sr and variations of 143Nd/ 144Nd are interpreted as a source characteristic. Trace-element ratios, however, are controlled mainly by fractionation during partial melting. We combine these isotopic data in a heterogeneous plume source model that accounts for the diversity of isotopic signatures recorded on Gorgona Island and throughout the Caribbean plateau. The heterogeneities are related to old recycled oceanic lithosphere in the plume source; the high 3He/ 4He ratios may indicate that the source material once resided in the lower mantle.

Carbon cycle perturbations recorded by δ13C of bulk organic matter: the Carnian Pluvial Event in the Dolomites, northern Italy

NASA Astrophysics Data System (ADS)

Preto, Nereo; Breda, Anna; Dal Corso, Jacopo; Rigo, Manuel; Roghi, Guido; Spötl, Christoph

2015-04-01

A period of increased rainfall occurred in the Carnian (Late Triassic), known as Carnian Pluvial Event (CPE), which is evidenced by major lithological changes in continental and marine successions at tropical latitudes. Increased continental weathering and erosion led to the supply of large amounts of siliciclastics into the marginal basins of the Tethys. Seawater anoxia is also observed locally in semi-restricted basins. Simultaneously, microbial factories on high-relief carbonate platforms were replaced by metazoan factories, forming low-relief carbonate ramps and mixed low-gradient shelves. This environmental change has been shown to be closely associated with a negative carbon isotope excursion. A negative δ13C shift is recorded by bulk organic matter in the Milieres section (central Dolomites) and parallels a coeval excursion in carbon-isotope records of higher plant and marine algal biomarker, thus testifying a global change in the isotopic composition of carbon dioxide in the atmosphere and of dissolved inorganic carbon (DIC) in the ocean. This isotopic excursion was identified in organic carbon records throughout the western Tethys, but so far could not be reproduced convincingly using carbon isotope records from carbonate. A long carbon isotope record was produced from bulk organic matter of the early to late Carnian Milieres - Dibona section in the Dolomites, northern Italy. Carbon isotope analyses of carbonate (limestone and dolomite) were also obtained. This new carbon isotope record illustrates the structure of this complex carbon cycle perturbation related to the CPE. But while sharp carbon isotope oscillations are evident in the bulk organic carbon record, there is no evidence of a similar pattern in carbonate record. It can be shown that the carbon isotope record of carbonates is influenced by fractionation and diagenetic processes that completely obliterated the original δ13C signal. We conclude that the Carnian carbonates of the Dolomites do not record the δ13C of marine DIC. We suggest that the identification of the Carnian carbon isotope excursion in carbonate records may only be possible if the isotopic analyses are coupled with petrographic screening that prove a minimal diagenetic overprint.

Microbial degradation of the brominated flame retardant TBNPA by groundwater bacteria: laboratory and field study.

PubMed

Balaban, Noa; Bernstein, Anat; Gelman, Faina; Ronen, Zeev

2016-08-01

In the present study, the biodegradation of the brominated flame retardant tribromoneopentylalcohol (TBNPA) by a groundwater enrichment culture was investigated using a dual carbon ((13)C/(12)C)- bromine ((81)Br/(79)Br) stable isotope analysis. An indigenous aerobic bacterial consortium was enriched from the polluted groundwater underlying an industrial site in the northern Negev Desert, Israel, where TBNPA is an abundant pollutant. Aerobic biodegradation was shown to be rapid, with complete debromination within a few days, whereas anaerobic biodegradation was not observed. Biodegradation under aerobic conditions was accompanied by a significant carbon isotope effect with an isotopic enrichment factor of ɛCbulk = -8.8‰ ± 1.5‰, without any detectable bromine isotope fractionation. It was found that molecular oxygen is necessary for biodegradation to occur, suggesting an initial oxidative step. Based on these results, it was proposed that H abstraction from the C-H bond is the first step of TBNPA biodegradation under aerobic conditions, and that the C-H bond cleavage results in the formation of unstable intermediates, which are rapidly debrominated. A preliminary isotopic analysis of TBNPA in the groundwater underlying the industrial area revealed that there are no changes in the carbon and bromine isotope ratio values downstream of the contamination source. Considering that anoxic conditions prevail in the groundwater of the contaminated site, the lack of isotope shifts in TBNPA indicates the lack of TBNPA biodegradation in the groundwater, in accordance with our findings. Copyright © 2016 Elsevier Ltd. All rights reserved.

δ15N values of atmospheric N species simultaneously collected using sector-based samplers distant from sources - Isotopic inheritance and fractionation

NASA Astrophysics Data System (ADS)

Savard, Martine M.; Cole, Amanda; Smirnoff, Anna; Vet, Robert

2017-08-01

The nitrogen isotope ratios (δ15N) of atmospheric N species are commonly suggested as indicators of N emission sources. Therefore, numerous research studies have developed analytical methodologies and characterized primary (gases) and secondary emission products (mostly precipitation and aerosols) from various emitters. These previous studies have generally collected either reduced or oxidized N forms, and sampled them separately prior to determining their δ15N values. Distinctive isotopic signals have been reported for emissions from various sources, and seasonality of the δ15N values has been frequently attributed to shifts in relative contributions from sources with different isotopic signals. However, theoretical concepts suggest that temperature effects on isotopic fractionation may also affect the δ15N values of atmospheric reaction products. Here we use a sector-based multi-stage filter system to simultaneously collect seven reduced and oxidized N species downwind from five different source types in Alberta, Canada. We report δ15N values obtained with a state-of-the-art gold-furnace pre-concentrator online with an isotope ratio mass spectrometer (IRMS) to provide representative results even for oxidized-N forms. We find that equilibrium isotope effects and their temperature dependence play significant roles in determining the δ15N values of the secondary emission products. In the end, seasonal δ15N changes here are mainly caused by temperature effects on fractionation, and the δ15N values of only two N species from one source type can be retained as potential fingerprints of emissions.

Nitrogen and carbon isotopic dynamics of subarctic soils and plants in southern Yukon Territory and its implications for paleoecological and paleodietary studies.

PubMed

Tahmasebi, Farnoush; Longstaffe, Fred J; Zazula, Grant; Bennett, Bruce

2017-01-01

We examine here the carbon and nitrogen isotopic compositions of bulk soils (8 topsoil and 7 subsoils, including two soil profiles) and five different plant parts of 79 C3 plants from two main functional groups: herbs and shrubs/subshrubs, from 18 different locations in grasslands of southern Yukon Territory, Canada (eastern shoreline of Kluane Lake and Whitehorse area). The Kluane Lake region in particular has been identified previously as an analogue for Late Pleistocene eastern Beringia. All topsoils have higher average total nitrogen δ15N and organic carbon δ13C than plants from the same sites with a positive shift occurring with depth in two soil profiles analyzed. All plants analyzed have an average whole plant δ13C of -27.5 ± 1.2 ‰ and foliar δ13C of -28.0 ± 1.3 ‰, and average whole plant δ15N of -0.3 ± 2.2 ‰ and foliar δ15N of -0.6 ± 2.7 ‰. Plants analyzed here showed relatively smaller variability in δ13C than δ15N. Their average δ13C after suitable corrections for the Suess effect should be suitable as baseline for interpreting diets of Late Pleistocene herbivores that lived in eastern Beringia. Water availability, nitrogen availability, spacial differences and intra-plant variability are important controls on δ15N of herbaceous plants in the study area. The wider range of δ15N, the more numerous factors that affect nitrogen isotopic composition and their likely differences in the past, however, limit use of the modern N isotopic baseline for vegetation in paleodietary models for such ecosystems. That said, the positive correlation between foliar δ15N and N content shown for the modern plants could support use of plant δ15N as an index for plant N content and therefore forage quality. The modern N isotopic baseline cannot be applied directly to the past, but it is prerequisite to future efforts to detect shifts in N cycling and forage quality since the Late Pleistocene through comparison with fossil plants from the same region.

[Applications of stable isotope analysis in the trophic ecology studies of cephalopods].

PubMed

Li, Yun-Kai; Gong, Yi; Chen, Xin-Jun

2014-05-01

Cephalopods play an important role in marine food webs, however, knowledge about their complex life history, especially their feeding ecology, remains limited. With the rapidly increasing use of stable isotope analysis (SIA) in ecology, it becomes a powerful tool and complement of traditional methods for investigating the trophic ecology and migration patterns of invertebrates. Here, after summarizing the current methods for trophic ecology investigation of cephalopods, applications of SIA in studying the trophic ecology of cephalopods were reviewed, including the key issues such as standardization of available tissues for SIA analyzing, diet shift and migration patterns of cephalopods, with the aim of advancing its application in the biology of cephalopods in the future.

Photolytic separation of isotopes in cryogenic solution

DOEpatents

Freund, S.M.; Maier, W.B. II; Holland, R.F.; Battie, W.H.

Separation of carbon isotopes by photolysis of CS/sub 2/ in cryogenic solutions of nitrogen, krypton and argon with 206 nm light from an iodine resonance lamp is reported. The spectral distributionn of the ultraviolet absorption depends on solvent. Thus, in liquid nitrogen the photolytic decomposition rate of /sup 13/CS/sub 2/ is greater than that of /sup 12/CS/sub 2/ (because the absorption of 206 nm radiation is greater for /sup 13/CS/sub 2/), whereas in liquid krypton and liquid argon the reverse is true. The shift in ultraviolet spectrum is a general phenomenon readily characterized as a function of solvent polarizability, and exhibits behavior similar to that for vibrational transitions occurring in the infrared.

Photolytic separation of isotopes in cryogenic solution

DOEpatents

Freund, Samuel M.; Maier, II, William B.; Holland, Redus F.; Beattie, Willard H.

1985-01-01

Separation of carbon isotopes by photolysis of CS.sub.2 in cryogenic solutions of nitrogen, krypton and argon with 206 nm light from an iodine resonance lamp is reported. The spectral distribution of the ultraviolet absorption depends on solvent. Thus, in liquid nitrogen the photolytic decomposition rate of .sup.13 CS.sub.2 is greater than that of .sup.12 CS.sub.2 (because the absorption of 206 nm radiation is greater for .sup.13 CS.sub.2), whereas in liquid krypton and liquid argon the reverse is true. The shift in ultraviolet spectrum is a general phenomenon readily characterized as a function of solvent polarizability, and exhibits behavior similar to that for vibrational transitions occurring in the infrared.

Prediction of plant vulnerability to salinity increase in a coastal ecosystem by stable isotopic composition (δ18O) of plant stem water: a model study

USGS Publications Warehouse

Zhai, Lu; Jiang, Jiang; DeAngelis, Donald L.; Sternberg, Leonel d.S.L

2016-01-01

Sea level rise and the subsequent intrusion of saline seawater can result in an increase in soil salinity, and potentially cause coastal salinity-intolerant vegetation (for example, hardwood hammocks or pines) to be replaced by salinity-tolerant vegetation (for example, mangroves or salt marshes). Although the vegetation shifts can be easily monitored by satellite imagery, it is hard to predict a particular area or even a particular tree that is vulnerable to such a shift. To find an appropriate indicator for the potential vegetation shift, we incorporated stable isotope 18O abundance as a tracer in various hydrologic components (for example, vadose zone, water table) in a previously published model describing ecosystem shifts between hammock and mangrove communities in southern Florida. Our simulations showed that (1) there was a linear relationship between salinity and the δ18O value in the water table, whereas this relationship was curvilinear in the vadose zone; (2) hammock trees with higher probability of being replaced by mangroves had higher δ18O values of plant stem water, and this difference could be detected 2 years before the trees reached a tipping point, beyond which future replacement became certain; and (3) individuals that were eventually replaced by mangroves from the hammock tree population with a 50% replacement probability had higher stem water δ18O values 3 years before their replacement became certain compared to those from the same population which were not replaced. Overall, these simulation results suggest that it is promising to track the yearly δ18O values of plant stem water in hammock forests to predict impending salinity stress and mortality.

Isotopic variability of cave bears (δ15N, δ13C) across Europe during MIS 3

NASA Astrophysics Data System (ADS)

Krajcarz, Magdalena; Pacher, Martina; Krajcarz, Maciej T.; Laughlan, Lana; Rabeder, Gernot; Sabol, Martin; Wojtal, Piotr; Bocherens, Hervé

2016-01-01

Collagen, the organic fraction of bone, records the isotopic parameters of consumed food for carbon (δ13C) and nitrogen (δ15N). This relationship of isotopic signature between diet and tissue is an important tool for the study of dietary preferences of modern and fossil animal species. Since the first information on the isotopic signature of cave bear was reported, numerous data from Europe have become available. The goal of this work is to track the geographical variation of cave bear collagen isotopic values in Europe during Marine Isotopic Stage 3 (about 60,000-25,000 yr BP). In this study the results of new δ13C and δ15N isotopic analyses of cave bear collagen from four Central-Eastern European sites are presented, as well as a review of all published isotopic data for cave bears of the same period. The main conclusion is a lack of geographical East-West pattern in the variations of δ13C and δ15N values of cave bear collagen. Moreover, no relationship was found between cave bear taxonomy and isotopic composition. The cave bears from Central-Eastern Europe exhibit δ13C and δ15N values near the average of the range of Central, Western and Southern European cave bears. Despite the fact that most cave bear sites follow an altitudinal gradient, separate groups of sites exhibit shift in absolute values of δ13C, what disturbs an altitude-related isotopic pattern. The most distinct groups are: high Alpine sites situated over 1500 m a.s.l. - in terms of δ13C; and two Romanian sites Peştera cu Oase and Urşilor - in case of δ15N. Although the cave bear isotopic signature is driven by altitude, the altitudinal adjustment of isotopic data is not enough to explain the isotopic dissimilarity of these cave bears. The unusually high δ15N signature of mentioned Romanian sites is an isolated case in Europe. Cave bears from relatively closely situated Central-Eastern European sites and other Romanian sites are more similar to Western European than to Romanian populations in terms of isotopic composition, and probably ecology.

Stable isotope stratigraphy of Latest Miocene sequences in northwest Morocco: The Bou Regreg section

NASA Astrophysics Data System (ADS)

Hodell, David A.; Benson, Richard H.; Kennett, James P.; Rakic-El Bied, Kruna

1989-08-01

Oxygen and carbon isotopic ratios of foraminifers were measured from outcrop and drill core sequences from the Bou Regreg Section, northwest Morocco. This composite section was located at the western end of the Rifian Corridor during the late Miocene and thus potentially contains a record of water exchange between the Atlantic and Mediterranean during the late Tortonian and Messinian stages. Here we correlate isotopic and sedimentologic events in the Bou Regreg Section with Mediterranean and deep-sea sequences during the time leading up to and including the deposition of the Messinian evaporites. The late Miocene chron 6 carbon shift was identified in two Moroccan sequences, providing a valuable 6.3-Ma datum level. In both sections, the carbon shift coincides with the first occurrence of Globorotalia conomiozea and the Tortonian/Messinian boundary. Near this boundary, a major faunal turnover occurred in ostracod, planktonic foraminiferal, and nannofossil assemblages that indicates a cooling of surface and deep water in the Rifian Corridor. At 6.1 Ma, just above the Tortonian/Messinian boundary, mean ∂18O values of benthic foraminifers increased by 0.4-0.5‰ suggesting decreased temperature and/or increased continental ice volume. The faunal and isotopic changes are interpreted as reflecting a reversal in the direction of deep water flow through the Rifian Corridor that occurred between 6.3 and 6.1 Ma. At this time, cold, nutrient-rich waters filled the Mediterranean basins from intermediate depths of the Atlantic, and the production of Mediterranean Outflow Water ceased. The upwelling of nutrient-rich Atlantic intermediate water stimulated productivity in the Mediterranean, which led to the deposition of organic-rich strata such as those found in the Tripoli Formation. At ˜5.5 Ma, coincident with a coiling shift in Neogloboquadrina acostaensis, the variability of the benthic ∂18O signal increased markedly, and strong color variations appeared in the sediments (alternating between red and blue marls). These isotopic and sedimentologic changes at Bou Regreg represented markedly fluctuating oceanographic conditions in the Rifian Corridor between 5.5 and 4.8 Ma. We speculate that these cycles were related to sea level variations that controlled the periodic influx of marine water into the Mediterranean during the time of evaporite deposition. The onset of these cycles occurred at 5.5 Ma and is correlated to a eustatic fall in sea level at the base of the Caliza Tosca Formation in Carmona, Spain, and to the base of the lowermost evaporite unit in the Mediterranean (e.g., Calcare di Base in Sicily). In this proposed scenario, the duration of the Messinian salinity crisis was 700,000 years and lasted between 5.5 and 4.8 Ma.

Seawater calcium isotope ratios across the Eocene-Oligocene transition

USGS Publications Warehouse

Griffith, E.M.; Paytan, A.; Eisenhauer, A.; Bullen, T.D.; Thomas, E.

2011-01-01

During the Eocene-Oligocene transition (EOT, ca. 34 Ma), Earth's climate cooled significantly from a greenhouse to an icehouse climate, while the calcite (CaCO3) compensation depth (CCD) in the Pacific Ocean increased rapidly. Fluctuations in the CCD could result from various processes that create an imbalance between calcium (Ca) sources to, and sinks from, the ocean (e.g., weathering and CaCO3 deposition), with different effects on the isotopic composition of dissolved Ca in the oceans due to differences in the Ca isotopic composition of various inputs and outputs. We used Ca isotope ratios (??44/40Ca) of coeval pelagic marine barite and bulk carbonate to evaluate changes in the marine Ca cycle across the EOT. We show that the permanent deepening of the CCD was not accompanied by a pronounced change in seawater ??44/40Ca, whereas time intervals in the Neogene with smaller carbonate depositional changes are characterized by seawater ??44/40Ca shifts. This suggests that the response of seawater ??44/40Ca to changes in weathering fluxes and to imbalances in the oceanic alkalinity budget depends on the chemical composition of seawater. A minor and transient fluctuation in the Ca isotope ratio of bulk carbonate may reflect a change in isotopic fractionation associated with CaCO3 precipitation from seawater due to a combination of factors, including changes in temperature and/or in the assemblages of calcifying organisms. ?? 2011 Geological Society of America.

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

Bowman, J.R.; Rohrs, D.T.

The isotopic compositions of hydrogen and oxygen have been determined for spring waters and thermal fluids from the Roosevelt Hot Springs and Cove Fort-Sulphurdale thermal areas, for clay mineral separates from shallow alteration of the acid-sulfate type in the Roosevelt Hot Springs area, and for spring and well waters from the Goshen Valley area of central Utah. The water analyses in the Roosevelt Hot Springs thermal area confirm the origin of the thermal fluids from meteoric water in the Mineral Range. The water analyses in the Cove Fort-Sulphurdale thermal area restrict recharge areas for this system to the upper elevationsmore » of the Pavant and/or Tushar Ranges. The low /sup 18/O shift observed in these thermal fluids (+0.7 permil) implies either high water/rock ratios or incomplete isotope exchange or both, and further suggests minimal interaction between the thermal fluid and marble country rock in the system. Hydrogen and oxygen-isotope data for clay mineral separates from shallow alteration zones in the Roosevelt Hot Springs thermal system suggest that the fluids responsible for the shallow acid-sulfate alteration were in part derived from condensed steam produced by boiling of the deep reservoir fluid. The isotope evidence supports the chemical model proposed by Parry et al. (1980) for origin of the acid-sulfate alteration at Roosevelt Hot Springs. The isotope analyses of spring and well waters from the Goshen Valley area indicate only a general correlation of isotope composition, salinity and chemical temperatures.« less

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Viers, J.; Emnova, E. E.; Kompantseva, E. I.; Freydier, R.

2008-04-01

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric ( Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic ( Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine ( Skeletonema costatum) and freshwater ( Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ 65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria ( Rhodobacter sp.), cyanobacteria ( Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria ( P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ 65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ 65Cu (solid-solution) = -1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ 65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively. Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu 2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution. Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.

Distribution of Iridium in Upper Triassic-Lower Jurassic Strata of the Northern Calcareous Alps, Austria

NASA Astrophysics Data System (ADS)

Tanner, L. H.; Kyte, F. T.; Richoz, S.

2014-12-01

Samples from strata spanning the Triassic-Jurassic boundary in the classic sections at Kuhjoch and Kendlbach were studied by NAA to determine Ir levels, and the results compared to previously determined carbon isotope stratigraphy. Ir concentrations in the Kössen Formation are very low (< 10 pg/g), well below average crustal levels until the top of the formation, reaching levels of ~15 pg/g, in the T-bed at the top of the Eiberg Member. The Tiefengraben Member (Kendlbach Formation) is enriched in Ir in general relative to the strata below. The shift to higher levels is abrupt at the base of the member. Concentrations of 60 to 80 pg/g are typical through the entire thickness of the Schattwald Beds and into the gray Tiefengraben, peaking at 145 pg/g. Above 560 cm from the Tiefengraben base, concentrations decline gradually from 50 pg/g to ~30 pg/g. The analyses from the Kendlbach section compare well with those from Kuhjoch, with the same order of magnitude difference in Ir concentration between the Kössen and Kendlbach formations. The same range of Ir values (60 to 80 pg/g) is seen in the lower 200 cm of the Tiefengraben Member, with a significant decline seen above 220 cm. In both sections, the initial increase in Ir corresponds to the initial carbon isotope excursion, considered the peak extinction horizon, but otherwise there is no clear correlation to the C-isotope data. The positive shift to background δ13C values is not accompanied by any noticeable change in Ir, however. There do appear (at least visually) to be smaller parallel shifts in both δ13C and Ir, but the shifts are of smaller magnitude. The difference between the Ir concentration in the Kössen and Kendlbach formations levels has a strong lithologic control; levels are very low carbonate versus elevated levels in siliclastics, but variations within the Kendlbach Formation are independent of lithology. Although there is no obvious evidence of volcanic input in the sections studied, we consider outgassing during eruptions of the Central Atlantic Magmatic Province, which is widely accepted as the driver of Late Triassic extinctions, a viable hypothesis to explain the origin of the slightly elevated Ir levels.

Identifying guanosine self assembly at natural isotopic abundance by high-resolution 1H and 13C solid-state NMR spectroscopy.

PubMed

Webber, Amy L; Masiero, Stefano; Pieraccini, Silvia; Burley, Jonathan C; Tatton, Andrew S; Iuga, Dinu; Pham, Tran N; Spada, Gian Piero; Brown, Steven P

2011-12-14

By means of the (1)H chemical shifts and the proton-proton proximities as identified in (1)H double-quantum (DQ) combined rotation and multiple-pulse spectroscopy (CRAMPS) solid-state NMR correlation spectra, ribbon-like and quartet-like self-assembly can be identified for guanosine derivatives without isotopic labeling for which it was not possible to obtain single crystals suitable for diffraction. Specifically, characteristic spectral fingerprints are observed for dG(C10)(2) and dG(C3)(2) derivatives, for which quartet-like and ribbon-like self-assembly has been unambiguously identified by (15)N refocused INADEQUATE spectra in a previous study of (15)N-labeled derivatives (Pham, T. N.; et al. J. Am. Chem. Soc.2005, 127, 16018). The NH (1)H chemical shift is observed to be higher (13-15 ppm) for ribbon-like self-assembly as compared to 10-11 ppm for a quartet-like arrangement, corresponding to a change from NH···N to NH···O intermolecular hydrogen bonding. The order of the two NH(2)(1)H chemical shifts is also inverted, with the NH(2) proton closest in space to the NH proton having a higher or lower (1)H chemical shift than that of the other NH(2) proton for ribbon-like as opposed to quartet-like self-assembly. For the dG(C3)(2) derivative for which a single-crystal diffraction structure is available, the distinct resonances and DQ peaks are assigned by means of gauge-including projector-augmented wave (GIPAW) chemical shift calculations. In addition, (14)N-(1)H correlation spectra obtained at 850 MHz under fast (60 kHz) magic-angle spinning (MAS) confirm the assignment of the NH and NH(2) chemical shifts for the dG(C3)(2) derivative and allow longer range through-space N···H proximities to be identified, notably to the N7 nitrogens on the opposite hydrogen-bonding face. © 2011 American Chemical Society

Chromium isotope heterogeneity in the mantle

NASA Astrophysics Data System (ADS)

Xia, Jiuxing; Qin, Liping; Shen, Ji; Carlson, Richard W.; Ionov, Dmitri A.; Mock, Timothy D.

2017-04-01

To better constrain the Cr isotopic composition of the silicate Earth and to investigate potential Cr isotopic fractionation during high temperature geological processes, we analyzed the Cr isotopic composition of different types of mantle xenoliths from diverse geologic settings: fertile to refractory off-craton spinel and garnet peridotites, pyroxenite veins, metasomatised spinel lherzolites and associated basalts from central Mongolia, spinel lherzolites and harzburgites from North China, as well as cratonic spinel and garnet peridotites from Siberia and southern Africa. The δ53CrNIST 979 values of the peridotites range from - 0.51 ± 0.04 ‰ (2SD) to + 0.75 ± 0.05 ‰ (2SD). The results show a slight negative correlation between δ53Cr and Al2O3 and CaO contents for most mantle peridotites, which may imply Cr isotopic fractionation during partial melting of mantle peridotites. However, highly variable Cr isotopic compositions measured in Mongolian peridotites cannot be caused by partial melting alone. Instead, the wide range in Cr isotopic composition of these samples most likely reflects kinetic fractionation during melt percolation. Chemical diffusion during melt percolation resulted in light Cr isotopes preferably entering into the melt. Two spinel websterite veins from Mongolia have extremely light δ53Cr values of - 1.36 ± 0.04 ‰ and - 0.77 ± 0.06 ‰, respectively, which are the most negative Cr isotopic compositions yet reported for mantle-derived rocks. These two websterite veins may represent crystallization products from the isotopically light melt that may also metasomatize some peridotites in the area. The δ53Cr values of highly altered garnet peridotites from southern Africa vary from - 0.35 ± 0.04 ‰ (2SD) to + 0.12 ± 0.04 ‰ (2SD) and increase with increasing LOI (Loss on Ignition), reflecting a shift of δ53Cr to more positive values by secondary alteration. The Cr isotopic composition of the pristine, fertile upper mantle is estimated as δ53Cr = - 0.14 ± 0.12 ‰, after corrections for the effects of partial melting and metasomatism. This value is in line with that estimated for the BSE (- 0.12 ± 0.10 ‰) previously.

Developing the Molybdenum Isotopic Proxy in Marine Barite

NASA Astrophysics Data System (ADS)

Erhardt, A. M.; Paytan, A.; Aggarwal, J.

2006-12-01

Molybdenum isotope ratios in seawater fluctuate in response to changing redox conditions and can provide clues into the degree of global ocean anoxia. The isotopic ratio of molybdenum has been shown to be sensitive to the relative proportion of oxic, suboxic, and euxinic environments. Deposition in oxic environments is isotopically light (~ -1.6‰ for δ^{97/95}Mo) relative to an average crustal source (0‰). Conversely, euxinic environments have been shown to be consistently heavier (~1.3‰) than the oxic sink through time, with suboxic sediments falling between these two signals. Shifts in the relative proportion of each sink, relative to a constant source, would alter the isotopic ratio of seawater over long time scales. Previously, this seawater value, and hence the degree of global anoxia, could only be inferred through mass balance calculations. We seek to quantify the isotopic signature of seawater though time using a phase that directly records this ratio. Marine barite precipitates inorganically in the water column directly from seawater, potentially providing a direct record of seawater characteristics. Molybdenum is a trace constituent of barite, with the molybdate ion substituting for sulfate at concentrations of about 1 ppm. To accurately determine the molybdenum isotopic ratio at these low concentrations (<15 ng per sample), modifications to existing measurement techniques are required. We will present the variations made to existing separation and mass-spectrometry techniques and the calibration of these new methods. The modifications were undertaken to reduce molybdenum blank to below 1 ng per analysis, to quantitatively remove interfering zirconium and to measure precise and reproducible isotope values. Preliminary data will be presented to illustrate potential applications for this new paleoredox proxy. This technique will allow for the measurement of molybdenum isotopic ratios at low concentrations, expanding the breath of compounds and signals that potentially record changes in planetary materials.

Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

NASA Astrophysics Data System (ADS)

Fu, Qi; Socki, Richard A.; Niles, Paul B.

2015-04-01

Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic compounds is critical for understanding deep subsurface ecosystems and the origin of organic compounds on Mars and other planets.

Relationships between carbon isotope evolution and variation of microbes during the Permian-Triassic transition at Meishan Section, South China

NASA Astrophysics Data System (ADS)

Luo, Genming; Huang, Junhuang; Xie, Shucheng; Wignall, Paul B.; Tang, Xinyan; Huang, Xianyu; Yin, Hongfu

2010-06-01

This paper investigates kerogen carbon isotopes, the difference between carbonate and kerogen carbon isotopes (Δ13Ccarb-kero = δ 13Ccarb - δ 13Ckero) and the difference between carbonate and n-C19 alkane compound-specific carbon isotopes (Δ13Ccarb- n-C19 = δ 13Ccarb - δ 13C n-C19) during the Permian-Triassic transition at Meishan, South China. The results show that kerogen carbon isotopes underwent both gradual and sharp shifts in beds 23-25 and 26-29, respectively. The differences between carbonate and organic carbon isotopes, both the Δ13Ccarb-kero and Δ13Ccarb- n-C19, which are mainly affected by CO2-fixing enzyme and pCO2, oscillated frequently during the Permian-Triassic transition. Both the variations of Δ13Ccarb- n-C19 and Δ13Ccarb-kero coupled with the alternation between cyanobacteria and green sulfur bacteria indicated by biomarkers. The episodic low values of Δ13Ccarb- n-C19 corresponded to episodic blooms of green sulfur bacteria, while the episodic high values of Δ13Ccarb- n-C19 corresponded to episodic blooms of cyanobacteria. The relationships between the variation of carbon isotopes and biota show that the microbes which flourished after the extinction of macroorganism affected the carbon isotope fractionation greatly. Combining the carbon isotope compositions and the pattern of size variation of the conodont Neogondolella, this paper supposes that anoxia of the photic zone at bed 24 was episodic and it would be caused by the degradation of terrigenous organic matters by sulfate reducing bacteria in the upper water column. Considered together with results from previous research, the high resolution variation of the biogeochemistry presents the sequence of the important geo-events during the Permian-Triassic crisis.

Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotopes in phosphate

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

Jaisi, Deb P.; Kukkadapu, Ravi K.; Stout, Lisa M.

2011-07-06

A key question to address in the development of oxygen isotope ratios in phosphate (18Op) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here we present experimental results aimed at understanding the biotic and abiotic pathway of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of specific sedimentary phosphate phases by Escherichia coli, Vibrio fischeri and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction ofmore » phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 hrs) due to efficient O-isotope exchange between phosphate and water (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate promoted the exchange of intact phosphate radicals (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli and V. fischeri ‘extracted’ loosely sorbed phosphate first while M. aquaeolei preferred iron-oxide bound phosphate. Each bacterium imprinted a biotic isotopic signature on each P phase that it took up and cycled. For example, the 18Op value of the sorbed phosphate phase shifted gradually towards equilibrium isotopic composition and the value of Fe oxide-bound phosphate showed slight changes at first, but when new iron oxides were formed, co-precipitated/occluded phosphate retained 18O values of aqueous phosphate at that time. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of 18Op as a tracer of phosphorus cycling in sediments, soils and aquatic environments and as an indicator of paleo- environmental conditions.« less

Tissue Turnover Rates and Isotopic Trophic Discrimination Factors in the Endothermic Teleost, Pacific Bluefin Tuna (Thunnus orientalis)

PubMed Central

Madigan, Daniel J.; Litvin, Steven Y.; Popp, Brian N.; Carlisle, Aaron B.; Farwell, Charles J.; Block, Barbara A.

2012-01-01

Stable isotope analysis (SIA) of highly migratory marine pelagic animals can improve understanding of their migratory patterns and trophic ecology. However, accurate interpretation of isotopic analyses relies on knowledge of isotope turnover rates and tissue-diet isotope discrimination factors. Laboratory-derived turnover rates and discrimination factors have been difficult to obtain due to the challenges of maintaining these species in captivity. We conducted a study to determine tissue- (white muscle and liver) and isotope- (nitrogen and carbon) specific turnover rates and trophic discrimination factors (TDFs) using archived tissues from captive Pacific bluefin tuna (PBFT), Thunnus orientalis, 1–2914 days after a diet shift in captivity. Half-life values for 15N turnover in white muscle and liver were 167 and 86 days, and for 13C were 255 and 162 days, respectively. TDFs for white muscle and liver were 1.9 and 1.1‰ for δ 15N and 1.8 and 1.2‰ for δ 13C, respectively. Our results demonstrate that turnover of 15N and 13C in bluefin tuna tissues is well described by a single compartment first-order kinetics model. We report variability in turnover rates between tissue types and their isotope dynamics, and hypothesize that metabolic processes play a large role in turnover of nitrogen and carbon in PBFT white muscle and liver tissues. 15N in white muscle tissue showed the most predictable change with diet over time, suggesting that white muscle δ 15N data may provide the most reliable inferences for diet and migration studies using stable isotopes in wild fish. These results allow more accurate interpretation of field data and dramatically improve our ability to use stable isotope data from wild tunas to better understand their migration patterns and trophic ecology. PMID:23145128

Ontogenetic, spatial and temporal variation in trophic level and diet of Chukchi Sea fishes

NASA Astrophysics Data System (ADS)

Marsh, Jennifer M.; Mueter, Franz J.; Iken, Katrin; Danielson, Seth

2017-01-01

Climate warming and increasing development are expected to alter the ecosystem of the Chukchi Sea, including its fish communities. As a component of the Arctic Ecosystem Integrated Survey, we assessed the ontogenetic, spatial and temporal variability of the trophic level and diet of key fish species in the Chukchi Sea using N and C stable isotopes. During August and September of 2012 and 2013, 16 common fish species and two primary, invertebrate consumers were collected from surface, midwater and bottom trawls within the eastern Chukchi Sea. Linear mixed-effects models were used to detect possible variation in the relationship between body length and either δ13C or δ15N values among water masses and years for 13 fish species with an emphasis on Arctic cod (Boreogadus saida). We also examined the fish community isotopic niche space, trophic redundancy, and trophic separation within each water mass as measures of resiliency of the fish food web. Ontogenetic shifts in trophic level and diet were observed for most species and these changes tended to vary by water mass. As they increased in length, most fish species relied more on benthic prey with the exception of three forage fish species (walleye pollock, Gadus chalcogrammus, capelin, Mallotus villosus, and Pacific sandlance, Ammodytes hexapterus). Species that exhibited interannual differences in diet and trophic level were feeding at lower trophic levels and consumed a more pelagic diet in 2012 when zooplankton densities were higher. Fish communities occupied different isotopic niche spaces depending on water mass association. In more northerly Arctic waters, the fish community occupied the smallest isotopic niche space and relied heavily on a limited range of intermediate δ13C prey, whereas in warmer, nutrient-rich Bering Chukchi Summer Water, pelagic prey was important. In the warmest, Pacific-derived coastal water, fish consumed both benthic and pelagic prey. Examining how spatial gradients in trophic position are linked to environmental drivers can provide insight into potential fish community shifts with a changing climate.

Spatial variations in food web structures with alternative stable states: evidence from stable isotope analysis in a large eutrophic lake

NASA Astrophysics Data System (ADS)

Li, Yunkai; Zhang, Yuying; Xu, Jun; Zhang, Shuo

2018-03-01

Food web structures are well known to vary widely among ecosystems. Moreover, many food web studies of lakes have generally attempted to characterize the overall food web structure and have largely ignored internal spatial and environmental variations. In this study, we hypothesize that there is a high degree of spatial heterogeneity within an ecosystem and such heterogeneity may lead to strong variations in environmental conditions and resource availability, in turn resulting in different trophic pathways. Stable carbon and nitrogen isotopes were employed for the whole food web to describe the structure of the food web in different sub-basins within Taihu Lake. This lake is a large eutrophic freshwater lake that has been intensively managed and highly influenced by human activities for more than 50 years. The results show significant isotopic differences between basins with different environmental characteristics. Such differences likely result from isotopic baseline differences combining with a shift in food web structure. Both are related to local spatial heterogeneity in nutrient loading in waters. Such variation should be explicitly considered in future food web studies and ecosystem-based management in this lake ecosystem.

Isotopic and chemical evidence concerning the genesis and contamination of basaltic and rhyolitic magma beneath the Yellowstone Plateau Volcanic Field

USGS Publications Warehouse

Hildreth, W.; Halliday, A.N.; Christiansen, R.L.

1991-01-01

Since 2.2 Ma, the Yellowstone Plateau Volcanic Field has produced ~6000 km3 of rhyolite tuffs and lavas in >60 separate eruptions, as well as ~100 km3 of tholeiitic basalt from >50 vents peripheral to the silicic focus. Intermediate eruptive products are absent. Early postcollapse rhyolites show large shifts in Nd, Sr, Pb, and O isotopic composition caused by assimilation of roof rocks and hydrothermal brines during collapse and resurgence. Younger intracaldera rhyolite lavas record partial isotopic recovery toward precaldera ratios. Thirteen extracaldera rhyolites show none of these effects and have sources independent of the subcaldera magma system. Contributions from the Archaean crust have extreme values and wide ranges of Nd-, Sr, and Pb-isotope ratios, but Yellowstone rhyolites have moderate values and limited ranges. This requires their deep-crustal sources to have been pervasively hybridized by distributed intrusion of Cenozoic basalt, most of which was probably contemporaneous with the Pliocene and Quaternary volcanism. Most Yellowstone basalts had undergone cryptic clinopyroxene fractionation in the lower crust or crust-mantle transition zone and, having also ascended through or adjacent to crustal zones of silicic-magma generation, most underwent some crustal contamination. -from Authors

The response of East Asian monsoon to the precessional cycle

NASA Astrophysics Data System (ADS)

Lee, J. E.

2017-12-01

The oxygen isotopic composition of cave speleothems exhibits a large amplitude change following the insolation, particularly the precessional cycle. Whether speleothem d18O reflects local precipitation amount, however, has been questioned by alternative hypotheses: (1) d18O reflects upstream Indian monsoon precipitation, which influences the isotopic composition of the input vapor to East Asia, and (2) the isotopic composition of pre-monsoon and monsoon exhibits a large difference, and the seasonality of precipitation may have shifted in response to insolation. Motivated the fact that the magnitude of Asian monsoon d18O was not reproduced by most climate models, here I show new results, using the fully coupled GFDL model, that precipitation increases when the northern hemisphere receives more summer insolation, similar to the original claim. I argue that previous models do not produce enough rainfall during the monsoon season, possibly because the westerly jet is located too north in relation to the Tibetan Plateau during the monsoon season. I conclude that Asian monsoon intensity probably increases with increasing insolation there, given a large change in speleothem d18O. My next step will be testing this hypothesis after incorporating isotopes into the GFDL model.

New aragonite 87Sr/86Sr records of Mesozoic ammonoids and approach to the problem of N, O, C and Sr isotope cycles in the evolution of the Earth

NASA Astrophysics Data System (ADS)

Zakharov, Yuri D.; Dril, Sergei I.; Shigeta, Yasunari; Popov, Alexander M.; Baraboshkin, Eugenij Y.; Michailova, Irina A.; Safronov, Peter P.

2018-02-01

New Sr isotope data from well-preserved aragonite ammonoid shell material from the Mesozoic are compared with that from a living Nautilus shell. The prominent negative Sr isotope excursions known from the Middle Permian, Jurassic and Cretaceous probably have their origins in intensive plate tectonic activity, followed by enhanced hydrothermal activity at the mid-ocean ridges (mantle volcanism) which supplied low radiogenic Sr to seawater. The maximum positive (radiogenic) shift in the lower Mesozoic Sr isotope curve (Lower Triassic peak) was likely caused by a significant expansion of dry land surfaces (Dabie-Sulu Triassic orogeny) and their intensive silicate weathering in conditions of extreme warming and aridity in the very end of the Smithian, followed by warm and humid conditions in the late Spathian, which apparently resulted in a significant oceanic input of radiogenic Sr through riverine flux. The comparatively high 87Sr/86Sr ratio obtained from the living Nautilus shell is probably a function of both the Alpine orogeny, which was accompanied by significant continental weathering and input of radiogenic Sr to the oceans, and the weakening of mantle volcanism.

Matrix Effects on Boron Containing Materials due to Laser Ablation Molecular Isotopic Spectrometry (LAMIS)

NASA Astrophysics Data System (ADS)

Brown, Staci R.; Akpovo, Charlemagne A.; Martinez, Jorge; Ford, Alan; Herbert, Kenley; Johnson, Lewis

2014-03-01

Laser Induced Breakdown Spectroscopy (LIBS) is a spectroscopic technique that is used for the qualitative and quantitative analysis of materials in the liquid, solid, or gas phase. LIBS can also be used for the detection of isotopic shifts in atomic and diatomic species via Laser-Ablation Molecular Isotopic Spectroscopy (LAMIS). However, any additional elements that are entrained into the plasma other than the element of interest, can affect the extent of ablation and quality of spectra and hence, potentially obscure or aid in the relative abundance assessment for a given element. To address the importance of matrix effects, the isotopic analysis of boron obtained from boron oxide (BO) emission originating from different boron-containing compounds, such as boron nitride (BN), boric acid (H3BO3) , and borax (Na2B4O710H2O), via LIBS has been performed here. Each of these materials has different physical properties and elemental composition in order to illustrate possible challenges for the LAMIS method. A calibration-free model similar to that for the original LAMIS work is used to determine properties of the plasma as the matrix is changed. DTRA

Isotope production and target preparation for nuclear astrophysics data

NASA Astrophysics Data System (ADS)

Schumann, Dorothea; Dressler, Rugard; Maugeri, Emilio Andrea; Heinitz, Stephan

2017-09-01

Targets are in many cases an indispensable ingredient for successful experiments aimed to produce nuclear data. With the recently observed shift to study nuclear reactions on radioactive targets, this task can become extremely challenging. Concerted actions of a certain number of laboratories able to produce isotopes and manufacture radioactive targets are urgently needed. We present here some examples of successful isotope and target production at PSI, in particular the production of 60Fe samples used for half-life measurements and neutron capture cross section experiments, the chemical processing and fabrication of lanthanide targets for capture cross section experiments at n_TOF (European Organization for Nuclear Research (CERN), Switzerland) as well as the recently performed manufacturing of highly-radioactive 7Be targets for the measurement of the 7Be(n,α)4He cross section in the energy range of interest for the Big-Bang nucleosynthesis contributing to the solving of the cosmological Li-problem. The two future projects: "Determination of the half-life and experiments on neutron capture cross sections of 53Mn" and "32Si - a new chronometer for nuclear dating" are briefly described. Moreover, we propose to work on the establishment of a dedicated network on isotope and target producing laboratories.

Bacterial Production of Site Specific 13C Labeled Phenylalanine and Methodology for High Level Incorporation into Bacterially Expressed Recombinant Proteins

PubMed Central

Ramaraju, Bhargavi; McFeeters, Hana; Vogler, Bernhard; McFeeters, Robert L.

2016-01-01

Nuclear magnetic resonance spectroscopy studies of ever larger systems have benefited from many different forms of isotope labeling, in particular, site specific isotopic labeling. Site specific 13C labeling of methyl groups has become an established means of probing systems not amenable to traditional methodology. However useful, methyl reporter sites can be limited in number and/or location. Therefore, new complementary site specific isotope labeling strategies are valuable. Aromatic amino acids make excellent probes since they are often found at important interaction interfaces and play significant structural roles. Aromatic side chains have many of the same advantages as methyl containing amino acids including distinct 13C chemical shifts and multiple magnetically equivalent 1H positions. Herein we report economical bacterial production and one-step purification of phenylalanine with 13C incorporation at the Cα, Cγ and Cε positions, resulting in two isolated 1H-13C spin systems. We also present methodology to maximize incorporation of phenylalanine into recombinantly overexpressed proteins in bacteria and demonstrate compatibility with ILV-methyl labeling. Inexpensive, site specific isotope labeled phenylalanine adds another dimension to biomolecular NMR, opening new avenues of study. PMID:28028744

What water isotopes tell us about water cycle responses to climate change

NASA Astrophysics Data System (ADS)

Raudzens Bailey, A.; Singh, H. A.; Nusbaumer, J. M.; Dee, S.; Blossey, P. N.; Posmentier, E. S.

2017-12-01

The water cycle is expected to respond strongly to rising global temperatures. Models predict regional imbalances in evaporation and precipitation will intensify, resulting in a slowing of the large-scale circulation. This slowing will extend the moisture length scale by increasing the amount of time water resides in the atmosphere. However, verifying these changes observationally is challenging. Isotope ratios in water vapor and precipitation represent an integrated record of moisture's journey from evaporative source to precipitation sink. Consequently, they provide a unique opportunity to identify changes in moisture length scale associated with shifts in regional hydrologic balance. Leveraging satellite retrievals, box models, climate simulations, and in situ data, this presentation demonstrates how water isotope ratios can be used to estimate water cycle changes over the historical period and into the future. These changes are closely linked to variations in the divergence of atmospheric moisture fluxes, which result from variations in specific humidity, wind direction, and wind speed. This presentation highlights the extent to which isotopic measurements allow us to track changes in the dynamic, or wind-driven, component of moisture transport and to investigate whether remote moisture contributions are becoming increasingly important in augmenting local precipitation.

Isotope analyses to explore diet and mobility in a medieval Muslim population at Tauste (NE Spain)

PubMed Central

Guede, Iranzu; Zuluaga, Maria Cruz; Alonso-Olazabal, Ainhoa; Murelaga, Xabier; Pina, Miriam; Gutierrez, Francisco Javier; Iacumin, Paola

2017-01-01

The Islamic necropolis discovered in Tauste (Zaragoza, Spain) is the only evidence that a large Muslim community lived in the area between the 8th and 10th centuries. A multi-isotope approach has been used to investigate the mobility and diet of this medieval Muslim population living in a shifting frontier region. Thirty-one individuals were analyzed to determine δ15N, δ13C, δ18O and 87Sr/86Sr composition. A combination of strontium and oxygen isotope analysis indicated that most individuals were of local origin although three females and two males were non-local. The non-local males would be from a warmer zone whereas two of the females would be from a more mountainous geographical region and the third from a geologically-different area. The extremely high δ15N baseline at Tauste was due to bedrock composition (gypsum and salt). High individual δ15N values were related to the manuring effect and consumption of fish. Adult males were the most privileged members of society in the medieval Muslim world and, as isotope data reflected, consumed more animal proteins than females and young males. PMID:28472159

Transformation of chlorpyrifos in integrated recirculating constructed wetlands (IRCWs) as revealed by compound-specific stable isotope (CSIA) and microbial community structure analysis.

PubMed

Tang, Xiaoyan; Yang, Yang; Huang, Wenda; McBride, Murray B; Guo, Jingjing; Tao, Ran; Dai, Yunv

2017-06-01

Carbon isotope analysis and 454 pyrosequencing methods were used to investigate in situ biodegradation of chlorpyrifos during its transport through three model integrated recirculating constructed wetlands (IRCWs). Results show that plant and Fe-impregnated biochar promoted degradation of chlorpyrifos and its metabolite 3,5,6-trichloro-2-pyridinol (TCP). Carbon isotope ratios in the IRCWs shifted to -31.24±0.58‰ (IRCW1, plant free), -26.82±0.60‰ (IRCW2, with plant) and -24.76±0.94‰ (IRCW3, with plant and Fe-biochar). The enrichment factors (Ɛ bulk,c ) were determined as -0.69±0.06‰ (IRCW1), -0.91±0.07‰ (IRCW2) and -1.03±0.09‰ (IRCW3). Microbial community analysis showed that IRCW3 was dominated by members of Bacillus, which can utilize and degrade chlorpyrifos. These results reveal that plant and Fe-biochar can induce carbon isotope fractionation and have a positive impact on the chlorpyrifos degradation efficiency by influencing the development of beneficial microbial communities. Copyright © 2017. Published by Elsevier Ltd.

Plant biomarkers in aerosols record isotopic discrimination of terrestrial photosynthesis.

PubMed

Conte, Maureen H; Weber, John C

2002-06-06

Carbon uptake by the oceans and by the terrestrial biosphere can be partitioned using changes in the (12)C/(13)C isotopic ratio (delta(13)C) of atmospheric carbon dioxide, because terrestrial photosynthesis strongly discriminates against (13)CO(2), whereas ocean uptake does not. This approach depends on accurate estimates of the carbon isotopic discrimination of terrestrial photosynthesis (Delta; ref. 5) at large regional scales, yet terrestrial ecosystem heterogeneity makes such estimates problematic. Here we show that ablated plant wax compounds in continental air masses can be used to estimate Delta over large spatial scales and at less than monthly temporal resolution. We measured plant waxes in continental air masses advected to Bermuda, which are mainly of North American origin, and used the wax isotopic composition to estimate Delta simply. Our estimates indicate a large (5 6 per thousand) seasonal variation in Delta of the temperate North American biosphere, with maximum discrimination occurring in late spring, coincident with the onset of production. We suggest that the observed seasonality arises from several factors, including seasonal shifts in the proportions of production by C(3) and C(4) plants, and environmentally controlled adjustments in the photosynthetic discrimination of C(3)-plant-dominated ecosystems.

Molybdenum and zinc stable isotope variation in mining waste rock drainage and waste rock at the Antamina mine, Peru.

PubMed

Skierszkan, E K; Mayer, K U; Weis, D; Beckie, R D

2016-04-15

The stable isotope composition of molybdenum (Mo) and zinc (Zn) in mine wastes at the Antamina Copper-Zn-Mo mine, Peru, was characterized to investigate whether isotopic variation of these elements indicated metal attenuation processes in mine drainage. Waste rock and ore minerals were analyzed to identify the isotopic composition of Mo and Zn sources, namely molybdenites (MoS2) and sphalerites (ZnS). Molybdenum and Zn stable isotope ratios are reported relative to the NIST-SRM-3134 and PCIGR-1 Zn standards, respectively. δ(98)Mo among molybdenites ranged from -0.6 to +0.6‰ (n=9) while sphalerites showed no δ(66)Zn variations (0.11±0.01‰, 2 SD, n=5). Mine drainage samples from field waste rock weathering experiments were also analyzed to examine the extent of isotopic variability in the dissolved phase. Variations spanned 2.2‰ in δ(98)Mo (-0.1 to +2.1‰) and 0.7‰ in δ(66)Zn (-0.4 to +0.3‰) in mine drainage over a wide pH range (pH2.2-8.6). Lighter δ(66)Zn signatures were observed in alkaline pH conditions, which was consistent with Zn adsorption and/or hydrozincite (Zn5(OH)6(CO3)2) formation. However, in acidic mine drainage Zn isotopic compositions reflected the value of sphalerites. In addition, molybdenum isotope compositions in mine drainage were shifted towards heavier values (0.89±1.25‰, 2 SD, n=16), with some overlap, in comparison to molybdenites and waste rock (0.13±0.82‰, 2 SD, n=9). The cause of heavy Mo isotopic signatures in mine drainage was more difficult to resolve due to isotopic heterogeneity among ore minerals and a variety of possible overlapping processes including dissolution, adsorption and secondary mineral precipitation. This study shows that variation in metal isotope ratios are promising indicators of metal attenuation. Future characterization of isotopic fractionation associated to key environmental reactions will improve the power of Mo and Zn isotope ratios to track the fate of these elements in mine drainage. Copyright © 2015 Elsevier B.V. All rights reserved.

Detrital sources and water mass circulation in the tropical North Atlantic during the Late Cretaceous to Paleogene

NASA Astrophysics Data System (ADS)

Martin, E. E.; Pugh, E.; Kamenov, G. D.; MacLeod, K. G.

2014-12-01

Seawater Nd isotopes from fossil fish teeth in Campanian to Paleogene calcareous claystone on Demerara Rise in the tropical North Atlantic record a change from epsilon Nd values of -17 to -11 during the late Maastrichtian. This shift has been identified in three different Ocean Drilling Program (ODP) sites that span from 600 to 1500 m paleodepths (ODP sites 1259, 1260 and 1261) and has been interpreted as a transition from a warm saline intermediate water mass formed on the South American margin, referred to as Demerara Bottom Water, to a source from the North Atlantic. A study of corresponding detrital Sr, Nd and Pb isotopes was undertaken to confirm the isotopic values derived from fish teeth record water mass compositions rather than diagenesis or boundary exchange. Several leaching procedures designed to remove Fe-Mn oxide coatings and the seawater signature they carry from the detrital fractions were tested. Sr isotopic data indicate a 0.02 M hydroxylamine hydrochloride (HH) leach was ineffective at removing the Fe-Mn oxides whereas a 1.0 M HH leach produced detrital Sr isotopic values that were consistent for all three sites and plotted farther from the seawater value. Detrital isotopic results can be divided into three intervals: 1) 73 - 66 Ma, when DBW is present, 2) 66 - 61 Ma, during the transition to North Atlantic sources, and 3) <61 Ma, when North Atlantic sources appear to dominate. During interval 1, detrital Nd isotopes increase gradually, while Sr and Pb isotopic ratios are relatively constant. Leading into interval 2, detrital Nd isotopes are fairly constant while there is a stepwise increase in Sr and Pb isotopes. Leading into interval 3, there is a large increase in Nd and decrease in Sr isotopes and a slight decrease in Pb isotopes. The subtle differences in the timing of changes in fish teeth and detrital Nd isotopes suggest the seawater signal is responding to changes in water mass rather than changes in sediment composition (boundary exchange). The timing of the changes in detrital inputs indicates changes in provenance may correlate with the rearrangement of the currents transporting sediment to the region associated with the transition from a water mass sourced from the tropics to a more northern source.

Metasomatism-induced magnesium isotope fractionation in ultramafic rocks: Evidence from the Franciscan Complex, California

NASA Astrophysics Data System (ADS)

Li, W. Y.; Teng, F. Z.; Xiao, Y.

2016-12-01

To investigate the behaviour of Mg isotopes during metasomatic reactions between peridotites and infiltrating fluids along the slab-mantle interface, we analyzed Mg isotopic compositions of a set of well-characterized samples from the ultramafic blocks in the Franciscan Complex of California [1]. The Group 1 and Group 2 samples that were defined by the initial serpentinization and complete serpentinization of peridotites at temperatures of 450-500 ºC, respectively [1], have δ26Mg values (from -0.26 to -0.14‰) clustered around the mantle value. This suggests that Mg isotope fractionation during serpentinization by slab-derived fluids, if any, is small. By contrast, the Group 3 samples that were defined by the replacement of serpentine by talc [1], are enriched in heavy Mg isotopes (δ26Mg of -0.13 to -0.01‰). This may reflect the loss of light Mg isotopes into fluids during the dehydration reaction that produced talc from serpentine, which is consistent with previous observations that secondary clay minerals preferentially incorporate heavy Mg isotopes during water-rock interactions [2, 3]. The Group 4 samples that were defined by the further replacement of talc by tremolite [1], however, have light Mg isotopic compositions (δ26Mg of -0.50 to -0.41‰). Such a shift towards light Mg isotopic compositions likely results from metasomatism by fluids that derived from isotopically light carbonates, which is supported by the remarkably higher CaO content of Group 4 samples (from 6.9 to 9.2 wt%) than Group 3 ones (from 1.1 to 1.4 wt%). Collectively, significant Mg isotopic variations occur during metasomatism of peridotites in the mantle wedge, which would potentially lead to heterogeneous Mg isotopic compositions in arc lavas [4]. Therefore, Mg isotopes can be used as a powerful tracer of crust-mantle interaction at subduction zones. [1] King et al. (2003) Geol. Soc. Am. Bull. 115, 1097-1109. [2] Teng et al. (2010) Earth Planet. Sci. Lett. 300, 63-71. [3] Wimpenny et al. (2014) Geochim. Cosmochim. Acta 128, 178-194. [4] Teng et al. (2016) Proc. Natl. Acad. Sci. 113, 7082-7087. et al. (2016) Proc. Natl. Acad. Sci. 113, 7082-7087.

Elucidating the trophodynamics of four coral reef fishes of the Solomon Islands using δ15N and δ13C

NASA Astrophysics Data System (ADS)

Greenwood, N. D. W.; Sweeting, C. J.; Polunin, N. V. C.

2010-09-01

Size-related diet shifts are important characteristics of fish trophodynamics. Here, body size-related changes in muscle δ15N and δ13C of four coral reef fishes, Acanthurus nigrofuscus (herbivore), Chaetodon lunulatus (corallivore) , Chromis xanthura (planktivore) and Plectropomus leopardus (piscivore) were investigated at two locations in the Solomon Islands. All four species occupied distinct isotopic niches and the concurrent δ13C' values of C. xanthura and P. leopardus suggested a common planktonic production source. Size-related shifts in δ15N, and thus trophic level, were observed in C. xanthura, C. lunulatus and P. leopardus, and these trends varied between location, indicating spatial differences in trophic ecology. A literature review of tropical fishes revealed that positive δ15N-size trends are common while negative δ15N-size trends are rare. Size-δ15N trends fall into approximately equal groups representing size-based feeding within a food chain, and that associated with a basal resource shift and occurs in conjunction with changes in production source, indicated by δ13C. The review also revealed large scale differences in isotope-size trends and this, combined with small scale location differences noted earlier, highlights a high degree of plasticity in the reef fishes studied. This suggests that trophic size analysis of reef fishes would provide a productive avenue to identify species potentially vulnerable to reef impacts as a result of constrained trophic behaviour.

From wetland specialist to hand-fed generalist: shifts in diet and condition with provisioning for a recently urbanized wading bird.

PubMed

Murray, Maureen H; Kidd, Anjelika D; Curry, Shannon E; Hepinstall-Cymerman, Jeffrey; Yabsley, Michael J; Adams, Henry C; Ellison, Taylor; Welch, Catharine N; Hernandez, Sonia M

2018-05-05

Many wildlife species shift their diets to use novel resources in urban areas. The consequences of these shifts are not well known, and consumption of reliable-but low quality-anthropogenic food may present important trade-offs for wildlife health. This may be especially true for carnivorous species such as the American white ibis ( Eudocimus albus ), a nomadic wading bird which has been increasingly observed in urban parks in South Florida, USA. We tested the effects of anthropogenic provisioning on consumer nutrition (i.e. dietary protein), body condition and ectoparasite burdens along an urban gradient using stable isotope analysis, scaled mass index values and GPS transmitter data. Ibises that assimilated more provisioned food were captured at more urban sites, used more urban habitat, had lower mass-length residuals, lower ectoparasite scores, assimilated less δ 15N and had smaller dietary isotopic ellipses. Our results suggest that ibises in urban areas are heavily provisioned with anthropogenic food, which appears to offer a trade-off by providing low-quality, but easily accessible, calories that may not support high mass but may increase time available for anti-parasite behaviours such as preening. Understanding such trade-offs is important for investigating the effects of provisioning on infection risk and the conservation of wildlife in human-modified habitats.This article is part of the theme issue 'Anthropogenic resource subsidies and host-parasite dynamics in wildlife'. © 2018 The Author(s).

Solvent dependent frequency shift and Raman noncoincidence effect of S=O stretching mode of Dimethyl sulfoxide in liquid binary mixtures.

PubMed

Upadhyay, Ganesh; Devi, Th Gomti; Singh, Ranjan K; Singh, A; Alapati, P R

2013-05-15

The isotropic and anisotropic Raman peak frequencies of S=O stretching mode of Dimethyl sulfoxide (DMSO) have been discussed in different chemical and isotopic solvent molecules using different mechanisms. The shifting of peak frequency in further dilution of DMSO with solvent molecule is observed for all solvents. Transition dipole - transition dipole interaction and hydrogen bonding may play a major role in shifting of peak frequencies. The non-coincidence effect (NCE) of DMSO was determined for all the solvents and compared with four theoretical models such as McHale's model, Mirone's modification of McHale's model, Logan's model and Onsager-Fröhlich dielectric continuum model respectively. Most of the theoretical models are largely consistent with our experimental data. Copyright © 2013. Published by Elsevier B.V.

Decoupling biogeochemical records, extinction, and environmental change during the Cambrian SPICE event

PubMed Central

Schiffbauer, James D.; Huntley, John Warren; Fike, David A.; Jeffrey, Matthew Jarrell; Gregg, Jay M.; Shelton, Kevin L.

2017-01-01

Several positive carbon isotope excursions in Lower Paleozoic rocks, including the prominent Upper Cambrian Steptoean Positive Carbon Isotope Excursion (SPICE), are thought to reflect intermittent perturbations in the hydrosphere-biosphere system. Models explaining these secular changes are abundant, but the synchronicity and regional variation of the isotope signals are not well understood. Examination of cores across a paleodepth gradient in the Upper Cambrian central Missouri intrashelf basin (United States) reveals a time-transgressive, facies-dependent nature of the SPICE. Although the SPICE event may be a global signal, the manner in which it is recorded in rocks should and does vary as a function of facies and carbonate platform geometry. We call for a paradigm shift to better constrain facies, stratigraphic, and biostratigraphic architecture and to apply these observations to the variability in magnitude, stratigraphic extent, and timing of the SPICE signal, as well as other biogeochemical perturbations, to elucidate the complex processes driving the ocean-carbonate system. PMID:28275734

Enhanced collectivity along the N = Z line: lifetime measurements in 44Ti, 48Cr, and 52Fe

NASA Astrophysics Data System (ADS)

Arnswald, K.; Reiter, P.; Coraggio, L.; Birkenbach, B.; Blazhev, A.; Braunroth, T.; Dewald, A.; Fransen, C.; Fu, B.; Gargano, A.; Hess, H.; Hirsch, R.; Itaco, N.; Lenzi, S. M.; Lewandowski, L.; Litzinger, J.; Müller-Gatermann, C.; Queiser, M.; Rosiak, D.; Schneiders, D.; Seidlitz, M.; Siebeck, B.; Steinbach, T.; Vogt, A.; Wolf, K.; Zell, K. O.

2018-02-01

Lifetimes of the {2}1+ states in 44Ti, 48,50Cr, and 52Fe were determined with high accuracy exploiting the recoil distance Doppler-shift method. The reduced E2 transition strengths of 44Ti and 52 Fe differ considerably from previously known values. A systematic increase in collectivity is found for the N = Z nuclei compared to neighboring isotopes. The B(E2) values along the Ti, Cr, and Fe isotopic chains are compared to shell-model calculations employing established interactions for the 0f 1p shell, as well as a novel effective shell-model Hamiltonian starting from a realistic nucleon-nucleon potential. The theoretical approaches underestimate the B(E2) values for the lower-mass Ti isotopes. Strong indication is found for particle-hole cross-shell configurations, recently corroborated by similar results for the neighboring isotone 42 Ca. A detailed manuscript has meanwhile been published in Physics Letters B [1].

Rapid neodymium release to marine waters from lithogenic sediments in the Amazon estuary

PubMed Central

Rousseau, Tristan C. C.; Sonke, Jeroen E.; Chmeleff, Jérôme; van Beek, Pieter; Souhaut, Marc; Boaventura, Geraldo; Seyler, Patrick; Jeandel, Catherine

2015-01-01

Rare earth element (REE) concentrations and neodymium isotopic composition (ɛNd) are tracers for ocean circulation and biogeochemistry. Although models suggest that REE release from lithogenic sediment in river discharge may dominate all other REE inputs to the oceans, the occurrence, mechanisms and magnitude of such a source are still debated. Here we present the first simultaneous observations of dissolved (<0.45 μm), colloidal and particulate REE and ɛNd in the Amazon estuary. A sharp drop in dissolved REE in the low-salinity zone is driven by coagulation of colloidal matter. At mid-salinities, total dissolved REE levels slightly increase, while ɛNd values are shifted from the dissolved Nd river endmember (−8.9) to values typical of river suspended matter (−10.6). Combining a Nd isotope mass balance with apparent radium isotope ages of estuarine waters suggests a rapid (3 weeks) and globally significant Nd release by dissolution of lithogenic suspended sediments. PMID:26158849

No evidence of reduced collectivity in Coulomb-excited Sn isotopes

NASA Astrophysics Data System (ADS)

Kumar, R.; Saxena, M.; Doornenbal, P.; Jhingan, A.; Banerjee, A.; Bhowmik, R. K.; Dutt, S.; Garg, R.; Joshi, C.; Mishra, V.; Napiorkowski, P. J.; Prajapati, S.; Söderström, P.-A.; Kumar, N.; Wollersheim, H.-J.

2017-11-01

In a series of Coulomb excitation experiments the first excited 2+ states in semimagic Sn 112 ,116 ,118 ,120 ,122 ,124 isotopes were excited using a 58Ni beam at safe Coulomb energy. The B (E 2 ; 0+→2+) values were determined with high precision (˜3 %) relative to 58Ni projectile excitation. These results disagree with previously reported B (E 2 ↑) values [A. Jungclaus et al., Phys. Lett. B 695, 110 (2011)., 10.1016/j.physletb.2010.11.012] extracted from Doppler-shift attenuation lifetime measurements, whereas the reported mass dependence of B (E 2 ↑) values is very similar to a recent Coulomb excitation study [J. M. Allmond et al., Phys. Rev. C 92, 041303(R) (2015), 10.1103/PhysRevC.92.041303]. The stable Sn isotopes, key nuclei in nuclear structure, show no evidence of reduced collectivity and we, thus, reconfirm the nonsymmetric behavior of reduced transition probabilities with respect to the midshell A =116 .

Proton Radii of 4,6,8He Isotopes from High-Precision Nucleon-Nucleon Interactions

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

Caurier, E; Navratil, P

2005-11-16

Recently, precision laser spectroscopy on {sup 6}He atoms determined accurately the isotope shift between {sup 4}He and {sup 6}He and, consequently, the charge radius of {sup 6}He. A similar experiment for {sup 8}He is under way. We have performed large-scale ab initio calculations for {sup 4,6,8}He isotopes using high-precision nucleon-nucleon (NN) interactions within the no-core shell model (NCSM) approach. With the CD-Bonn 2000 NN potential we found point-proton root-mean-square (rms) radii of {sup 4}He and {sup 6}He 1.45(1) fm and 1.89(4), respectively, in agreement with experiment and predict the {sup 8}He point proton rms radius to be 1.88(6) fm. Atmore » the same time, our calculations show that the recently developed nonlocal INOY NN potential gives binding energies closer to experiment, but underestimates the charge radii.« less

Electron Scattering from MERCURY-198 and Mercury -204.

NASA Astrophysics Data System (ADS)

Laksanaboonsong, Jarungsaeng

This experiment is the first electron scattering study on mercury isotopes. Electron scattering from ^{198}Hg and ^{204 }Hg has been performed at the NIKHEF-K Medium Energy Accelerator. Measured cross sections cover an effective momentum transfer range from 0.4 to 2.9 fm^ {-1}. Elastic cross sections were determined for scattering from both isotopes. Cross section for inelastic excitations in ^{198}Hg below 3 MeV were also determined. Measured cross sections were fit using DWBA phase shift codes to determine coefficients for Fourier-Bessel expansions of ground state and transition charge densities. Differences between the ground state charge densities of the two isotopes reveal the effect of the polarization of the proton core in response to the addition of neutrons. Spin and parity of several excited states of ^{198}Hg were determined. Extracted transition densities of these states show their predominantly collective nature. Charge densities for members of the ground state rotational band were compared with axially symmetric Hartree-Fock and geometrical model predictions.

Tracing sources of nitrate in snowmelt runoff using a high-resolution isotopic technique

NASA Astrophysics Data System (ADS)

Ohte, N.; Sebestyen, S. D.; Shanley, J. B.; Doctor, D. H.; Kendall, C.; Wankel, S. D.; Boyer, E. W.

2004-11-01

The denitrifier method to determine the dual isotopic composition (δ15N and δ18O) of nitrate is well suited for studies of nitrogen contributions to streams during runoff events. This method requires only 70 nmol of NO3- and enables high throughput of samples. We studied nitrate sources to a headwater stream during snowmelt by generating a high-temporal resolution dataset at the Sleepers River Research Watershed in Vermont, USA. In the earliest phase of runoff, stream NO3- concentrations were highest and stream discharge, NO3- concentrations, and δ18O of NO3- generally tracked one another during diurnal melting. The isotopic composition of stream NO3- varied in-between atmospheric and groundwater NO3- end members indicating a direct contribution of atmospherically-derived NO3- from the snow pack to the stream. During the middle to late phases of snowmelt, the source shifted toward soil NO3- entering the stream via shallow subsurface flow paths.

Evidence for tunneling in base-catalyzed isomerization of glyceraldehyde to dihydroxyacetone by hydride shift under formose conditions.

PubMed

Cheng, Liang; Doubleday, Charles; Breslow, Ronald

2015-04-07

Hydrogen atom transfer reactions between the aldose and ketose are key mechanistic features in formose chemistry by which formaldehyde is converted to higher sugars under credible prebiotic conditions. For one of these transformations, we have investigated whether hydrogen tunneling makes a significant contribution to the mechanism by examining the deuterium kinetic isotope effect associated with the hydrogen transfer during the isomerization of glyceraldehyde to the corresponding dihydroxyacetone. To do this, we developed a quantitative HPLC assay that allowed us to measure the apparent large intrinsic kinetic isotope effect. From the Arrhenius plot of the kinetic isotope effect, the ratio of the preexponential factors AH/AD was 0.28 and the difference in activation energies Ea(D) - Ea(H) was 9.1 kJ·mol(-1). All these results imply a significant quantum-mechanical tunneling component in the isomerization mechanism. This is supported by multidimensional tunneling calculations using POLYRATE with small curvature tunneling.

Doublet-spacing enhancement caused by {Lambda}N-{Sigma}N coupling in {sub {Lambda}L}i hypernuclear isotopes

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

Umeya, Atsushi; Harada, Toru; Research Center for Physics and Mathematics, Osaka Electro-Communication University, Neyagawa, Osaka 572-8530

2011-03-15

We theoretically investigate energy spacings of doublets in {sub {Lambda}L}i hypernuclear isotopes with A=7-10 in shell-model calculations with a {Lambda}N-{Sigma}N coupling effect. The calculated results show that the energy shifts are {Delta}{epsilon}=0.09-0.28 MeV and the {Sigma}-mixing probabilities are P{sub {Sigma}}=0.10%-0.34% in {Lambda} ground states for the isotopes because of the {Lambda}N-{Sigma}N coupling in the first-order perturbation. It is found that the energy spacing of the doublet is enhanced as a neutron number N increases; the contribution of the {Lambda}N-{Sigma}N coupling interaction is comparable to that of the {Lambda}N interaction in the neutron-rich {Lambda} hypernuclei. The coherent mechanism of this doublet-spacingmore » enhancement is also discussed in terms of Fermi-type and Gamow-Teller-type {Lambda}N-{Sigma}N couplings.« less

Differing source water inputs, moderated by evaporative enrichment, determine the contrasting δ18OCELLULOSE signals in maritime Antarctic moss peat banks

NASA Astrophysics Data System (ADS)

Royles, Jessica; Sime, Louise C.; Hodgson, Dominic A.; Convey, Peter; Griffiths, Howard

2013-03-01

Oxygen isotope palaeoclimate records, preserved in moss tissue cellulose, are complicated by environmental influences on the relationships between source water inputs and evaporative conditions. We carried out stable isotope analyses of precipitation collected from the maritime Antarctic and cellulose extracted from co-located Chorisodontium aciphyllum dominated moss peat bank deposits accumulated since 1870 A.D. Analyses of stable oxygen and hydrogen isotope composition of summer precipitation on Signy Island (60.7°S, 45.6°W) established a local meteoric water line (LMWL) similar to both the global MWL and other LMWLs, and almost identical to the HadAM3 isotope-enabled global circulation model output. The oxygen isotopic composition of cellulose (δ18OC) revealed little temporal variation between four moss peat banks on Signy Island since 1870. However, δ18OC followed two patterns with Sites A and D consistently 3‰ enriched relative to δ18OC values from Sites B and C. The growing moss surfaces at Sites A and D are likely to have been hydrated by isotopically heavier summer precipitation, whilst at Sites B and C, the moss banks are regularly saturated by the isotopically depleted snow melt streams. Laboratory experiments revealed that evaporative enrichment of C. aciphyllum moss leaf water by 5‰ occurred rapidly following saturation (ecologically equivalent to post-rainfall or snow melt periods). In addition to the recognized source water-cellulose fractionation extent of 27 ± 3‰, such a shift would account for the 32‰ difference measured between δ18O of Signy Island precipitation and cellulose.

Isotopic insights into microbial sulfur cycling in oil reservoirs

PubMed Central

Hubbard, Christopher G.; Cheng, Yiwei; Engelbrekston, Anna; Druhan, Jennifer L.; Li, Li; Ajo-Franklin, Jonathan B.; Coates, John D.; Conrad, Mark E.

2014-01-01

Microbial sulfate reduction in oil reservoirs (biosouring) is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM) is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of −30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters (FW) containing elevated concentrations of volatile fatty acids (VFAs) and injection water (IW) containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures. PMID:25285094

A carbon isotopic and sedimentological record of the latest Devonian (Famennian) from the Western U.S. and Germany

USGS Publications Warehouse

Myrow, P.M.; Strauss, J.V.; Creveling, J.R.; Sicard, K.R.; Ripperdan, R.; Sandberg, C.A.; Hartenfels, S.

2011-01-01

New carbon isotopic data from upper Famennian deposits in the western United States reveal two previously unrecognized major positive isotopic excursions. The first is an abrupt ~. 3??? positive excursion, herein referred to as ALFIE (A Late Famennian Isotopic Excursion), recorded in two sections of the Pinyon Peak Limestone of north-central Utah. Integration of detailed chemostratigraphic and biostratigraphic data suggests that ALFIE is the Laurentian record of the Dasberg Event, which has been linked to transgression in Europe and Morocco. Sedimentological data from the Chaffee Group of western Colorado also record transgression at a similar biostratigraphic position, with a shift from restricted to open-marine lithofacies. ALFIE is not evident in chemostratigraphic data from age-equivalent strata in Germany studied herein and in southern Europe, either because it is a uniquely North American phenomenon, or because the German sections are too condensed relative to those in Laurentia. A second positive carbon isotopic excursion from the upper Chaffee Group of Colorado is recorded in transgressive strata deposited directly above a previously unrecognized paleokarst interval. The age of this excursion, and the duration of the associated paleokarst hiatus, are not well constrained, although the events occurred sometime after the Late Famennian Middle expansa Zone. The high positive values recorded in this excursion are consistent with those associated with the youngest Famennian Middle to Late praesulcata Hangenberg Isotopic Excursion in Europe, the isotopic expression of the Hangenberg Event, which included mass extinction, widespread black shale deposition, and a glacio-eustatic fall and rise. If correct, this would considerably revise the age of the Upper Chaffee Group strata of western Colorado. ?? 2011 Elsevier B.V.

A novel membrane inlet mass spectrometer method to measure ¹⁵NH4₄⁺ for isotope-enrichment experiments in aquatic ecosystems.

PubMed

Yin, Guoyu; Hou, Lijun; Liu, Min; Liu, Zhanfei; Gardner, Wayne S

2014-08-19

Nitrogen (N) pollution in aquatic ecosystems has attracted much attention over the past decades, but the dynamics of this bioreactive element are difficult to measure in aquatic oxygen-transition environments. Nitrogen-transformation experiments often require measurement of (15)N-ammonium ((15)NH4(+)) ratios in small-volume (15)N-enriched samples. Published methods to determine N isotope ratios of dissolved ammonium require large samples and/or costly equipment and effort. We present a novel ("OX/MIMS") method to determine N isotope ratios for (15)NH4(+) in experimental waters previously enriched with (15)N compounds. Dissolved reduced (15)N (dominated by (15)NH4(+)) is oxidized with hypobromite iodine to nitrogen gas ((29)N2 and/or (30)N2) and analyzed by membrane inlet mass spectrometry (MIMS) to quantify (15)NH4(+) concentrations. The N isotope ratios, obtained by comparing the (15)NH4(+) to total ammonium (via autoanalyzer) concentrations, are compared to the ratios of prepared standards. The OX/MIMS method requires only small sample volumes of water (ca. 12 mL) or sediment slurries and is rapid, convenient, accurate, and precise (R(2) = 0.9994, p < 0.0001) over a range of salinities and (15)N/(14)N ratios. It can provide data needed to quantify rates of ammonium regeneration, potential ammonium uptake, and dissimilatory nitrate reduction to ammonium (DNRA). Isotope ratio results agreed closely (R = 0.998, P = 0.001) with those determined independently by isotope ratio mass spectrometry for DNRA measurements or by ammonium isotope retention time shift liquid chromatography for water-column N-cycling experiments. Application of OX/MIMS should simplify experimental approaches and improve understanding of N-cycling rates and fate in a variety of freshwater and marine environments.

[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.

Keratin decomposition by trogid beetles: evidence from a feeding experiment and stable isotope analysis

NASA Astrophysics Data System (ADS)

Sugiura, Shinji; Ikeda, Hiroshi

2014-03-01

The decomposition of vertebrate carcasses is an important ecosystem function. Soft tissues of dead vertebrates are rapidly decomposed by diverse animals. However, decomposition of hard tissues such as hairs and feathers is much slower because only a few animals can digest keratin, a protein that is concentrated in hairs and feathers. Although beetles of the family Trogidae are considered keratin feeders, their ecological function has rarely been explored. Here, we investigated the keratin-decomposition function of trogid beetles in heron-breeding colonies where keratin was frequently supplied as feathers. Three trogid species were collected from the colonies and observed feeding on heron feathers under laboratory conditions. We also measured the nitrogen (δ15N) and carbon (δ13C) stable isotope ratios of two trogid species that were maintained on a constant diet (feathers from one heron individual) during 70 days under laboratory conditions. We compared the isotopic signatures of the trogids with the feathers to investigate isotopic shifts from the feathers to the consumers for δ15N and δ13C. We used mixing models (MixSIR and SIAR) to estimate the main diets of individual field-collected trogid beetles. The analysis indicated that heron feathers were more important as food for trogid beetles than were soft tissues under field conditions. Together, the feeding experiment and stable isotope analysis provided strong evidence of keratin decomposition by trogid beetles.

Tracing the history of submarine hydrothermal inputs and the significance of hydrothermal hafnium for the seawater budget - A combined Pb-Hf-Nd isotope approach

USGS Publications Warehouse

van de Flierdt, T.; Frank, M.; Halliday, A.N.; Hein, J.R.; Hattendorf, B.; Gunther, D.; Kubik, P.W.

2004-01-01

Secular variations in the Pb isotopic composition of a mixed hydrogenous-hydrothermal ferromanganese crust from the Bauer Basin in the eastern Equatorial Pacific provide clear evidence for changes in hydrothermal contributions during the past 7 Myr. The nearby Galapagos Rise spreading center provided a strong hydrothermal flux prior to 6.5 Ma. After 6.5 Ma, the Pb became stepwise more radiogenic and more similar to Equatorial Pacific seawater, reflecting the westward shift of spreading to the presently active East Pacific Rise (EPR). A second, previously unrecognized enhanced hydrothermal period occurred between 4.4 and 2.9 Ma, which reflects either off-axis hydrothermal activity in the Bauer Basin or a late-stage pulse of hydrothermal Pb from the then active, but waning Galapagos Rise spreading center. Hafnium isotope time-series of the same mixed hydrogenous-hydrothermal crust show invariant values over the past 7 Myr. Hafnium isotope ratios, as well as Nd isotope ratios obtained for this crust, are identical to that of hydrogenous Equatorial Pacific deep water crusts and clearly indicate that hydrothermal Hf, similar to Nd, does not travel far from submarine vents. Therefore, we suggest that hydrothermal Hf fluxes do not contribute significantly to the global marine Hf budget. ?? 2004 Elsevier B.V. All rights reserved.

Pb concentrations and isotopic record preserved in northwest Greenland snow.

PubMed

Kang, Jung-Ho; Hwang, Heejin; Han, Changhee; Hur, Soon Do; Kim, Seong-Joong; Hong, Sungmin

2017-11-01

We present high-resolution lead (Pb) concentrations and isotopic ratios from a northwest Greenland snow pit covering a six-year period between 2003 and 2009. Pb concentrations ranged widely from 2.7 pg g -1 to 97.3 pg g -1 , with a mean concentration of 21.6 pg g -1 . These values are higher than those recorded for the pre-industrial period. Pb concentrations exhibit seasonal spikes in winter-spring layers. Crustal Pb enrichment factors (EF) suggest that the northwest Greenland snow pit is highly enriched with Pb of predominantly anthropogenic origin. The 206 Pb/ 207 Pb ratios ranged from 1.144 to 1.169 with a mean value of 1.156, which fall between less radiogenic Eurasian-type and more radiogenic Canadian-type signatures. This result suggests that several potential source areas of Pb impact on northwest Greenland. Abrupt changes in Pb concentrations and Pb isotope ratios were observed and related to seasonal shifts in source regions of aerosol transport. The 206 Pb/ 207 Pb isotope ratio increased gradually between 2003 and 2009. The similarity of the three-isotope plot ( 206 Pb/ 207 Pb versus 208 Pb/ 207 Pb) between some of our samples and Chinese urban aerosols suggests a steadily increasing contribution of Chinese Pb to northwest Greenland snow. Copyright © 2017. Published by Elsevier Ltd.

Ontogenetic dietary shifts and bioaccumulation of diphenhydramine in Mugil cephalus from an urban estuary.

PubMed

Haddad, Samuel P; Du, Bowen; Scott, W Casan; Saari, Gavin N; Breed, Christopher; Kelly, Martin; Broach, Linda; Chambliss, C Kevin; Brooks, Bryan W

2017-06-01

Though bioaccumulation of pharmaceuticals has received attention in inland waters, studies of pharmaceutical bioaccumulation in estuarine and marine systems are limited. Further, an understanding of pharmaceutical bioaccumulation across size classes of organisms displaying ontogenetic feeding shifts is lacking. We selected the striped mullet, Mugil cephalus, a euryhaline and eurythermal species that experiences dietary shifts with age, to identify whether a model base, diphenhydramine, accumulated in a tidally influenced urban bayou. We further determined whether diphenhydramine accumulation differed among size classes of striped mullet over a two year study period. Stable isotope analysis identified that ontogenetic feeding shifts of M. cephalus occurred from juveniles to adults. However, bioaccumulation of diphenhydramine did not significantly increase across age classes of M. cephalus but corresponded to surface water levels of the pharmaceutical, which suggests inhalational uptake to diphenhydramine was more important for bioaccumulation than dietary exposure in this urban estuary. Copyright © 2017 Elsevier Ltd. All rights reserved.

Shifts in bryophyte carbon isotope ratio across an elevation × soil age matrix on Mauna Loa, Hawaii: do bryophytes behave like vascular plants?

PubMed

Waite, Mashuri; Sack, Lawren

2011-05-01

The carbon isotope ratio (δ(13)C) of vascular plant leaf tissue is determined by isotope discrimination, primarily mediated by stomatal and mesophyll diffusion resistances and by photosynthetic rate. These effects lead to predictable trends in leaf δ(13)C across natural gradients of elevation, irradiance and nutrient supply. Less is known about shifts in δ(13)C for bryophytes at landscape scale, as bryophytes lack stomata in the dominant gametophyte phase, and thus lack active control over CO(2) diffusion. Twelve bryophyte species were sampled across a matrix of elevation and soil ages on Mauna Loa, Hawaii Island. We tested hypotheses based on previous findings for vascular plants, which tend to have less negative δ(13)C at higher elevations or irradiances, and for leaves with higher leaf mass per area (LMA). Across the matrix, bryophytes spanned the range of δ(13)C values typical of C(3) vascular plants. Bryophytes were remarkably similar to vascular plants in exhibiting less negative δ(13)C with increasing elevation, and with lower overstory cover; additionally δ(13)C was related to bryophyte canopy projected mass per area, a trait analogous to LMA in vascular plants, also correlated negatively with overstory cover. The similarity of responses of δ(13)C in bryophytes and vascular plants to environmental factors, despite differing morphologies and diffusion pathways, points to a strong direct role of photosynthetic rate in determining δ(13)C variation at the landscape scale.

Oxygen-isotope trends and seawater temperature changes across the Late Cambrian Steptoean positive carbon-isotope excursion (SPICE event)

USGS Publications Warehouse

Elrick, M.; Rieboldt, S.; Saltzman, M.; McKay, R.M.

2011-01-01

The globally recognized Late Cambrian Steptoean positive C-isotope excursion (SPICE) is characterized by a 3???-5??? positive ??13C shift spanning <4 m.y. Existing hypotheses suggest that the SPICE represents a widespread ocean anoxic event leading to enhanced burial/preservation of organic matter (Corg) and pyrite. We analyzed ??18O values of apatitic inarticulate brachiopods from three Upper Cambrian successions across Laurentia to evaluate paleotemperatures during the SPICE. ??18O values range from ~12.5??? to 16.5???. Estimated seawater temperatures associated with the SPICE are unreasonably warm, suggesting that the brachiopod ??18O values were altered during early diagenesis. Despite this, all three localities show similar trends with respect to the SPICE ??13C curve, suggesting that the brachiopod apatite preserves a record of relative ??18O and temperature changes. The trends include relatively high ??18O values at the onset of the SPICE, decreasing and lowest values during the main event, and an increase in values at the end of the event. The higher ??18O values during the global extinction at the onset of the SPICE suggests seawater cooling and supports earlier hypotheses of upwelling of cool waters onto the shallow shelf. Decreasing and low ??18O values coincident with the rising limb of the SPICE support the hypothesis that seawater warming and associated reduced thermohaline circulation rates contributed to decreased dissolved O2 concentrations, which enhanced the preservation/burial of Corg causing the positive ??13C shift. ?? 2011 Geological Society of America.

Constant Chinese Loess Plateau dust source since the Late Miocene

NASA Astrophysics Data System (ADS)

Bird, Anna; Millar, Ian; Stevens, Thomas; Rodenburg, Tanja; Rittner, Martin; Vermeesch, Pieter; Lu, Huayu

2017-04-01

The dramatic deepening of northern hemisphere glaciation at the Pliocene-Pleistocene boundary is accompanied by major changes in global climate. The role of the global atmospheric dust cycle in this event is not clear; in particular, whether, changes in the dust cycle influenced climates change, or resulted from it. Miocene and Quaternary wind-blown Chinese loess records past dust-cycle history, influences of aridification and monsoon circulation. Previous work on the vast Chinese Loess Plateau is in conflict over whether changes in dust source occur at the Pliocene-Pleistocene boundary (2.59 Ma), or at 1.2 Ma, despite these intervals marking major shifts in monsoon dynamics (Sun 2005; Nie et al. 2014a). Here we present Sr, Nd and Hf isotopic data from multiple sites and show that the dust source remains the same across these boundaries. The use of isotope tracers from multiple sites allows us to demonstrate that shifts in sediment geochemistry can be explained by grain-size and weathering changes. Nd and Hf isotopes show that the dust was dominantly sourced from the Tibetan Plateau, with some input from bedrock underlying the Badain Jaran/Tengger deserts. This shows that a major established and constant dust source on the northern Tibetan Plateau has been active and unchanged since the late Miocene, despite dramatically changing climate conditions. Changes in loess accumulation are therefore a function of climate change in the Tibetan Plateau source regions rather than due to expanding source areas controlled by aridification over a widening area over the Pliocene and Quaternary.

Record of the Late Devonian Hangenberg global positive carbon-isotope excursion in an epeiric sea setting: Carbonate production, organic-carbon burial and paleoceanography during the late Famennian

USGS Publications Warehouse

Cramer, Bradley D.; Saltzman, Matthew R.; Day, J.E.; Witzke, B.J.

2008-01-01

Latest Famennian marine carbonates from the mid-continent of North America were examined to investigate the Late Devonian (very late Famennian) Hangenberg positive carbon-isotope (??13 Ccarb) excursion. This global shift in the ?? 13C of marine waters began during the late Famennian Hangenberg Extinction Event that occurred during the Middle Siphonodella praesulcata conodont zone. The post-extinction recovery interval spans the Upper S. praesulcata Zone immediately below the Devonian-Carboniferous boundary. Positive excursions in ?? 13 Ccarb are often attributed to the widespread deposition of organic-rich black shales in epeiric sea settings. The Hangenberg ??13 Ccarb excursion documented in the Louisiana Limestone in this study shows the opposite trend, with peak ??13 Ccarb values corresponding to carbonate production in the U.S. mid-continent during the highstand phase of the very late Famennian post-glacial sea level rise. Our data indicate that the interval of widespread black shale deposition (Hangenberg Black Shale) predates the peak isotope values of the Hangenberg ??13 Ccarb excursion and that peak values of the Hangenberg excursion in Missouri are not coincident with and cannot be accounted for by high Corg burial in epeiric seas. We suggest instead that sequestration and burial of Corg in the deep oceans drove the peak interval of the ??13Ccarb excursion, as a result of a change in the site of deep water formation to low-latitude epeiric seas as the global climate shifted between cold and warm states.

Central depression of nuclear charge density distribution

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

Chu Yanyun; Ren Zhongzhou; Center of Theoretical Nuclear Physics, National Laboratory of Heavy-Ion Accelerator, Lanzhou 730000

The center-depressed nuclear charge distributions are investigated with the parametrized distribution and the relativistic mean-field theory, and their corresponding charge form factors are worked out with the phase shift analysis method. The central depression of nuclear charge distribution of {sup 46}Ar and {sup 44}S is supported by the relativistic mean-field calculation. According to the calculation, the valence protons in {sup 46}Ar and {sup 44}S prefer to occupy the 1d{sub 3/2} state rather than the 2s{sub 1/2} state, which is different from that in the less neutron-rich argon and sulfur isotopes. As a result, the central proton densities of {sup 46}Armore » and {sup 44}S are highly depressed, and so are their central charge densities. The charge form factors of some argon and sulfur isotopes are presented, and the minima of the charge form factors shift upward and inward when the central nuclear charge distributions are more depressed. Besides, the effect of the central depression on the charge form factors is studied with a parametrized distribution, when the root-mean-square charge radii remain constant.« less

High-precision Penning trap mass measurements of 9,10Be and the one-neutron halo nuclide 11Be

NASA Astrophysics Data System (ADS)

Ringle, R.; Brodeur, M.; Brunner, T.; Ettenauer, S.; Smith, M.; Lapierre, A.; Ryjkov, V. L.; Delheij, P.; Drake, G. W. F.; Lassen, J.; Lunney, D.; Dilling, J.

2009-05-01

Penning trap mass measurements of 9Be, 10Be (t1 / 2 = 1.51 My), and the one-neutron halo nuclide 11Be (t1 / 2 = 13.8 s) have been performed using TITAN at TRIUMF. The resulting 11Be mass excess (ME = 20 177.60 (58) keV) is in agreement with the current Atomic Mass Evaluation (AME03) [G. Audi, et al., Nucl. Phys. A 729 (2003) 337] value, but is over an order of magnitude more precise. The precision of the mass values of 9,10Be have been improved by about a factor of four and reveal a ≈ 2 σ deviation from the AME mass values. Results of new atomic physics calculations are presented for the isotope shift of 11Be relative to 9Be, and it is shown that the new mass values essentially remove atomic mass uncertainties as a contributing factor in determining the relative nuclear charge radius from the isotope shift. The new mass values of 10,11Be also allow for a more precise determination of the single-neutron binding energy of the halo neutron in 11Be.

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

Lemonidou, Angeliki A.; Vagia, Ekaterini C.; Lercher, Johannes A.

Reforming of acetic acid was investigated on Rh supported on CeO2-ZrO2 modified with 3 wt % La. The active catalyst converted acetic acid to H-2-rich gas and hardly formed coke. The low rate of coke formation is concluded to be related to the presence of redox-active oxygen limiting the concentration of coke precursors. Temperature-programmed O-18(2)) isotope exchange measurements showed that the La2O3 and Rh enhanced the mobility of lattice oxygen compared with that of the parent CeO2-ZrO2. Ketonization and decarboxylation of acetic acid are the dominating reactions over the latter up to 600 degrees C, whereas above 600 degrees C,more » steam reforming and water gas shift also contribute. Over 0.5 wt % Rh on La2O3/CeO2-ZrO2, reforming and water gas shift reactions dominate, even below 300 degrees C, producing mostly H-2 and CO2. Using isotope labeling, it is shown that acetic acid adsorbs dissociatively on Rh, forming acetates, which sequentially decarboxylate and form surface methyl groups. The latter are in turn converted to CO, CO2, and H-2.« less